1

C s ha hc phn tch
Lm Ngc Th
NXB i hc quc gia H Ni 2005.

T kho: C s ha phn tch, Phn tch nh lng, Chn mu, o mu, Phng php
phn tch.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc

ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc

Chng 1 M u ........................................................................................................ 8
1.1 Lnh vc ng dng phn tch nh lng....................................................... 8
1.2 Thc hnh phn tch nh lng.................................................................... 9
1.2.1 Chn mu.................................................................................................. 9
1.2.2 Chun b mu phn tch.......................................................................10
1.2.3 o mu ....................................................................................................10
1.2.4 Ha tan mu .............................................................................................10
1.2.5 Tch hn hp cn tr ...............................................................................10
1.2.6 Giai on kt thc php phn tch ............................................................10
1.2.7 Chn phng php phn tch ...................................................................11
Chng 2 nh gi tin cy ca nhng s liu phn tch ................................. 12
2.1 Mt s nh ngha.........................................................................................12
2.1.1 Trung bnh v trung v .............................................................................12

2.1.2 lp li .................................................................................................13
2.1.3 ng ...................................................................................................14
2.1.4 lp li v ng ca nhng d kin thc nghim ............................15
2.2 Phn loi sai s.............................................................................................16
2.2.1 Sai s h thng v sai s ngu nhin ........................................................16
2.2.2 Cc loi sai s h thng ...........................................................................16
2.2.3 nh hng ca sai s h thng n kt qu phn tch..............................17
2.3 Biu hin ca sai s h thng .......................................................................18
2.3.1 Pht hin sai s dng c v sai s c bit .................................................18
2.3.2 Pht hin sai s phng php...................................................................18
2.4 nh hng ca sai s ngu nhin .................................................................20
2.4.1 Xem xt nh hng ca sai s ngu nhin ln ng tc chun ho pipet .21
2.4.2 S phn b s liu ca nhng php o song song ....................................22
2.4.3 Nhng khi nim c bn ca thng k c in.........................................25
2.4.4 ng dng nhng phng php thng k ..................................................27
2.4.5 S dng nhng phng php thng k.....................................................29
2.4.6 Khong tin cy .........................................................................................30
2.4.7 Nhng phng php thng k kim tra gi thuyt ...................................36
2.4.8 Loi tr s liu mang sai s th bo.........................................................40
2.1 S lan truyn sai s trn cc php tnh .........................................................42
2.7.2 Php cng sai s h thng ........................................................................42
2.7.2 Cng sai s ngu nhin ............................................................................45
2.7.2 S lan truyn sai s php tnh lu tha .................................................47
2.7.2 S lan truyn sai s php LOGARIT v ANTI LOGARIT ...................49
2.2 iu kin c ngha ca ch s......................................................................50
2.3 Bo him cht lng (QA) v biu kim tra ............................................52
2.7.2 S cn thit ca bo him cht lng.......................................................53
2.7.2 ng dng biu kim tra.......................................................................54
Chng 3 Cc phn ng ha hc trong ha hc phn tch................................. 57
3.1
3.2
3.3
3.4

hon ton ca phn ng ..........................................................................57

Nhng yu cu c th v hon ton ca mt phn ng phn tch nh
lng ............................................................................................................60
Tc phn ng ...........................................................................................61
ngha ca tc phn ng i vi ha hc ...............................................63

Chng 4 Phng php tnh nng cc cht trong nhng dung dch cn bng
n gin...................................................................................................... 65
4.1 Mt s lun im c s ................................................................................65
4.1.1 Thnh phn ho hc ca dung dch ..........................................................65
4.1.2 Tnh cht axit - baz trong cc dung mi khc nhau ................................67
4.2 Phng php tnh nng cc cht trong nhng dung dch cn bng n

gin..............................................................................................................69
4.2.1 Trng thi cn bng..................................................................................69
4.2.2 Biu thc hng s cn bng .....................................................................70
4.2.3 Nhng phng php biu th hng s cn bng........................................70
4.2.4 Biu thc hng s cn bng ca nhng phn ng thng gp nht ..........72
Chng 5 tan ca kt ta ................................................................................... 90
5.1 nh hng ca cn bng cnh tranh n tan ca kt ta .........................90
5.1.1 M t cn bng phc tp ..........................................................................91
5.1.2 S gii bi tp bao gm mt s cn bng ............................................92
5.2 nh hng ca pH n tan ......................................................................93
5.2.1 Tnh tan nng ion hiro bit ...................................................94
5.2.2 Tnh tan nhng nng ion hiro khc nhau...................................96
5.2.3 tan ca hiroxit kim loi trong nc ................................................103
5.3 nh hng ca s to phc n tan.......................................................105
5.4 nh hng ca nng cht in li n tan..........................................110
5.5 Nhng yu t ph nh hng n tan ca kt ta ..................................118
5.6 Phn chia cc ion theo nng cht kt ta (kt ta phn on)................119
Chng 6 Qu trnh to thnh kt ta ................................................................. 123
6.1
6.2
6.3
6.4

Nghin cu thc nghim qu trnh to kt ta............................................123

L thuyt c in v s to thnh cc trung tm kt tinh............................126
L thuyt v s to thnh cc trung tm kt tinh Becker - Doring..............127
L thuyt to thnh cc trung tm kt tinh Christiansen - Nielsen .............129

Chng 7 Phn tch trng lng .......................................................................... 131

7.1 M u .......................................................................................................131
7.2 Tnh kt qu theo d kin phn tch trng lng ........................................131
7.3 Tnh cht ca kt ta v cht to kt ta.....................................................136
7.5.1 Tnh d lc v tinh khit ca kt ta .................................................136
7.5.2 Kt ta v nh hnh...............................................................................139
7.5.3 Nhng kt ta tinh th............................................................................142
7.5.4 Sai s do cng kt ..................................................................................143
7.5.5 Kt ta t dung dch ng th ................................................................144
7.5.6 Sy v nung kt ta ................................................................................144
7.4 V thiu st ca phng php phn tch trng lng .................................146
7.5.1 Thi gian thc hin phn tch trng lng .............................................146
7.5.2 Lnh vc ng dng ca phn tch trng lng .......................................147
7.5 ng dng phng php phn tch trng lng ...........................................147
7.5.1 Cc cht to kt ta v c ......................................................................147
7.5.2 Nhng thuc th c tnh cht kh ..........................................................147
7.5.3 Nhng cht to kt ta hu c ...............................................................147
7.5.4 Xc nh trng lng cc nhm chc hu c.........................................151

7.5.5 Nhng phng php trng lng xc nh cc hp cht hu c

ring l ..................................................................................................152
7.5.6 Phng php chng ct..........................................................................152
Chng 8 M u v phn tch th tch ............................................................... 154
8.1 Nhng khi nim c bn ............................................................................154
8.2 Phn ng v thuc th dng trong phn tch chun ...............................155
8.2.1 Nhng cht chun gc............................................................................155
8.2.2 Dung dch chun ....................................................................................156
8.3 im cui trong cc phng php chun ..............................................156
Chng 9 Chun kt ta................................................................................... 161
9.1
9.2
9.3
9.4
9.5

ng chun kt ta .............................................................................161
ngha ca ch s khi tnh ng chun ..............................................163
Nhng yu t nh hng n tnh r rng ca im cui ...........................163
ng chun hn hp ...........................................................................166
Nhng cht ch th ha hc ca phng php chun kt ta..................169

Chng 10 L thuyt chun Axit Baz i vi nhng h n gin .......... 177

10.1
Thuc th chun chun axit - baz................................................177
10.2
Cht ch th chun axit - baz ........................................................177
10.2.1 L thuyt v tnh cht ca cht ch th ..................................................178
10.2.2 Nhng loi ch th axit - baz ...............................................................179
10.2.3 Sai s chun vi cc ch th axit - baz............................................183
10.2.4 Nhng yu t nh hng ti tnh cht ca ch th .................................183
10.3
ng chun axit mnh hoc baz mnh...........................................183
10.4.1 Chun axit mnh bng baz mnh...................................................183
10.4.2 Chun baz mnh bng axit mnh ...................................................187
10.4
ng chun axit yu hoc baz yu.................................................187
10.4.1 Tnh pH ca dung dch cha mt cp axit - baz lin hp....................187
10.4.2 nh hng ca lc ion n cn bng axit - baz..................................191
10.4.3 Dung dch m .....................................................................................193
10.4.4 ng chun axit yu......................................................................200
10.4.5 ng chun baz yu ....................................................................206
Chng 11 ng chun nhng h Axit Baz phc tp............................ 208
11.1

ng chun hn hp axit mnh v axit yu hoc hn hp baz mnh

v baz yu.............................................................................................208
11.2
Tnh ton nng cn bng ca cc h a axit - a baz........................211
11.2.1 Dung dch mui loi NaHA..................................................................212
11.2.2 Dung dch a axit .................................................................................215
11.2.3 Dung dch a baz................................................................................218
11.2.4 Dung dch m ca cc h axit yu v baz lin hp vi n ................219

11.3
11.4
11.5
11.6

ng chun a axit ..........................................................................221

ng chun a baz.........................................................................227
ng chun cht in li lng tnh ..................................................229
Thnh phn ca dung dch a axit l hm s ca pH...............................231

Chng 12 Chun Axit Baz trong mi trng khng nc..................... 234

12.1
Dung mi chun khng nc.........................................................234
12.1.1 Phn ng axit - baz trong dung mi lng tnh ..................................235
12.1.2 Phn ng axit - baz trong dung mi aproton v dung mi hn hp ....241
12.1.3 Pht hin im cui khi chun trong dung mi hn hp..................241
12.2 ng dng phng php chun trong dung mi khng nc..................242
12.2.1 Chun trong axit axetic bng ...........................................................242
12.2.2 Chun trong dung mi baz.............................................................244
12.2.3 Chun trong dung mi aproton hoc trung tnh ...............................245
Chng 13 Chun to phc ............................................................................. 246
13.1
Chun bng cc thuc th v c ........................................................248
13.2
Chun bng cc axit aminopolicacboxilic ..........................................249
13.2.1 Thuc th .............................................................................................249
13.2.2 Phc ca EDTA vi cc cation kim loi...............................................251
13.2.3 Xy dng ng chun ....................................................................253
Chng 14 Chun Oxi ha kh ....................................................................... 265
14.1
Nhng khi nim c bn .........................................................................265
14.1.1 nh ngha............................................................................................265
14.1.2 Phng trnh Nerst ...............................................................................267
14.2
Nhng yu t nh hng n th oxi ha kh.........................................267
14.2.1 nh hng ca axit .........................................................................267
14.2.2 nh hng ca phn ng to phc .......................................................268
14.2.3 nh hng ca phn ng kt ta ..........................................................269
14.5
Hng s cn bng ca phn ng oxi ha kh ..........................................270
14.5
ng chun oxi ha kh ..................................................................272
14.5
Cc yu t nh hng ln ng chun oxi ha kh..........................274
14.2.1 Nng cht phn ng.........................................................................275
14.2.2 hon ton ca phn ng ..................................................................275
14.2.3 Tc phn ng v th in cc ..........................................................276
14.7
Chun hn hp ...................................................................................277
14.7
Cht ch th oxi ha kh..........................................................................279
14.7.1 Nhng ch th oxi ha kh thng thng..............................................279
14.7.2 Ch th c bit .....................................................................................283
Chng 15 Phn hy v ha tan mu................................................................... 284
15.1

Ngun sai s trong phn hy v ha tan mu..........................................284

15.1.1 S ha tan khng hon ton cc cht cn phn tch..............................285

15.1.2 S mt i mt phn cht cn phn tch do bay hi ...............................285
15.1.3 a cht bn dung mi vo cht cn phn tch.....................................285
15.1.4 a cht bn t phn ng ca dung mi vi thnh bnh vo mu ........285
15.2
Phn hy mu bng axit v c trong bnh m .........................................285
15.2.1 Axit clohiric .......................................................................................286
15.2.2 Axit nitric .............................................................................................286
15.2.3 Axit sunfuric ........................................................................................286
15.2.4 Axit pecloric.........................................................................................286
15.2.5 Cc hn hp oxi ha.............................................................................287
15.2.6 Axit fluoric...........................................................................................287
15.3
Phn hy bng vi sng ............................................................................287
15.4.3 Bnh phn hy mu c iu chnh p sut ............................................289
15.4.3 Bnh vi sng p sut cao.......................................................................289
15.4.3 L vi sng.............................................................................................290
15.4.3 L thiu vi sng....................................................................................290
15.4.3 S dng phn hy vi sng trong bnh ng kn ....................................291
15.4
Phng php t chy phn hy cc mu hu c...............................291
15.4.1 t chy trn ngn la m (tro ha kh)..............................................291
15.4.2 Phng php t trong ng ..................................................................291
15.4.3 Thiu nhit vi oxi trong bnh cha ng kn.......................................292
15.5
Phn hy cc vt liu v c bng cht nung chy ...................................293
15.5.1 Thc hnh nung chy ...........................................................................294
15.5.2 Cc loi cht nung chy........................................................................294
Chng 16 Loi b cc tc dng cn tr.............................................................. 296
16.1 Bn cht ca qu trnh tch.......................................................................296
16.2 Tch bng kt ta......................................................................................297
16.2.1 Tch da trn s kim tra axit .........................................................297
16.2.2 Tch bng sunfua .................................................................................298
16.2.3 Tch bng cc cht kt ta v c khc .................................................299
16.2.4 Tch bng cc cht kt ta hu c........................................................299
16.2.5 Tch cc cht tn ti dng lng vt bng kt ta .............................299
16.3 Tch bng chit.........................................................................................300
16.3.1 L thuyt .............................................................................................300
16.3.2 Cc loi quy trnh chit .......................................................................304
16.4
ng dng cc quy trnh chit ..................................................................306
16.4.1 Chit tch cc ion kim loi dng chelat .............................................306
16.4.2 Chit cc phc clorua kim loi .............................................................310
16.4.3 Chit cc mui nitrat ............................................................................311
16.5
Tch bng trao i ion ............................................................................311
16.5.1 Tch nhng ion cn tr c in tch tri du vi ion cn phn tch .........311
16.5.2 Lm giu vt ca cht in li ..................................................................311

16.5.3 Chuyn ha mui thnh axit hoc baz...................................................312

16.6
Tch cc hp cht v c bng chng ct.................................................312
Ph lc.................................................................................................................313
Ti liu tham kho.............................................................................................337

Chng 1
M u
Ha hc phn tch l khoa hc ca nhng phng php pht hin v xc nh nhng
lng tng i ca mt hoc mt s cu t trong mu ca cht nghin cu. Qu trnh pht
hin cc cht gi l phn tch nh tnh, qu trnh xc nh thnh phn nh lng cc cht gi
l phn tch nh lng. Trong cun sch ny, chng ti ch yu cp vn th hai.
Nhng kt qu phn tch nh lng c din t bng nhng i lng tng i nh
phn trm, phn nghn, phn triu hoc phn t cht cn xc nh trong mu, lng gam cc
cht trong mt mililit hoc mt lt dung dch mu; lng gam cht trong mt tn mu hoc
mol phn ca cu t cn xc nh trong mu.

1.1

Lnh vc ng dng phn tch nh lng

Nhng kt qu phn tch ha hc c ngha thc t ln. Chng ti trch dn mt s v d

ch r, nhng php o nh lng nh hng nh th no n cuc sng ca con ngi hin
i. C nhng thng bo v phn trm hm lng hirocacbon, oxit nit, cacbon oxit trong
kh thi ta c th nh gi cht lng lm vic ca cc thit b trong t. Xc nh nng
ion canxi trong huyt thanh mu l phng php quan trng chun on bnh baz.
dinh dng ca thc phm lin quan trc tip vi hm lng nit ca chng. Phn tch nh
lng theo chu k trong qu trnh luyn thp cho php thu c vt liu c bn, rn,
tnh d rn hoc tnh chng n mn nh trc. S phn tch lin tc cc mecaptan trong
khng kh bo m pht hin r r nguy him trong h thng ng dn kh. Phn tch hm
lng nit, pht pho, lu hunh v m ca t trong thi v pht trin v chn ca cy
trng to cho ta kh nng phn b phn bn v k hoch ha s ti rung vi hiu qu cao
nht, ng thi lm gim ng k nhng chi ph cho phn bn, nc v lm tng nng sut.
Ngoi ngha ng dng, nhng kt qu phn tch nh lng cn rt quan trng trong cc
lnh vc nghin cu ha hc, sinh ha, sinh vt, a cht v cc khoa hc khc. Chng ta xem
xt mt s v d lm dn chng: Khi nim v c ch ca phn ln cc phn ng ha hc c
c t nhng d kin ng hc l nh cc php xc nh nh lng cc cu t trong phn
ng. Ngi ta bit rng, c ch chuyn cc xung ng thn kinh ng vt v s co li hoc
lm yu i cc c do s chuyn ion natri v kali qua mng quyt nh. Hin tng ny c
pht hin nh cc php o nng cc ion ny c hai pha ca mng. S nghin cu tnh
cht ca cc cht bn dn i hi phi pht trin nhng phng php nh lng cc tp cht
trong silic v gecmani tinh khit trong khong 106 1010 %. Trong mt s trng hp, php
phn tch nh lng cc lp b mt ca t cho php cc nh a cht pht hin nhng va
qung tng i su. Phn tch nh lng nhng lng rt nh ca cc mu ly t cc tc

phm ngh thut gip cc nh s hc bit c nguyn liu v k thut ca nhng cng trnh
ca nhng ha s thi trc v cng l phng php quan trng pht hin s gi mo.
Thng khi nghin cu trong cc lnh vc va ha hc, ho sinh v c trong mt s mt
ca sinh hc, phn ln cng vic trong phng th nghim l nhm t ti nhng thng bo v
phn tch nh lng. Phn tch l mt trong nhng phng tin quan trng ca cc nh ha
hc. Do , hiu bn cht phn tch nh lng, bit cch hon thnh chnh xc ng tc phn
tch l nhng yu cu cn thit cho cng cuc nghin cu trong nhiu lnh vc khoa hc. C
th so snh ngha ca ha hc phn tch i vi qu trnh hnh thnh mt nh ha hc hoc
mt nh sinh ha vi ngha ca k thut tnh v i s tuyn tnh i vi tt c nhng ai
mun c thnh cng trong lnh vc vt l l thuyt hoc vi ngha ring ca ting c Hy
Lp v cc ngn ng c khc i vi nh ngn ng hc.

1.2

Thc hnh phn tch nh lng

Thng nhng kt qu phn tch nh lng bao gm nhng d liu ca hai php o hoc
i khi ca hai dy php o: lng ban u ca mu v lng hp phn cn xc nh trong
mu. V d, c th o khi lng, th tch, cng sng, hp th nh sng, cng
pht hunh quang, in lng. Nhng cng cn phi ni rng, nhng php o ch l mt
phn ca php nh lng thng thng. Hon ton khng km phn quan trng l nhng giai
on chun b trc, nhng giai on ny nng nhc lu di hn so vi php o.
Nhng chng u ca cun sch ny ch yu cp ti cc php o giai on kt
thc php phn tch. Cn nhng vn khc ch c cp ti mt cch chi tit cui sch.
Do hp l, ngay by gi cn hnh dung ton cnh php phn tch, tch ra tng giai on
ring bit ca qu trnh phn tch v nh gi ngha ca chng.

1.2.1 Chn mu
thu c kt qu phn tch ng n cn chn mu c thnh phn phn nh ng
thnh phn ton b cht cn phn tch. Nu cht khng ng nht v c khi lng ln, vic
chn mu i din i hi nhiu sc lc. Chng ta xt mt trng hp nh vy. Mt cngten-n cha 25 tn qung bc. Ngi mua v ngi giao hng cn i dn tha thun v gi tr
tng i ca mt hng , trc ht c xc nh bi hm lng bc. Qung khng ng
nht v gm nhng cc nh kch thc khc nhau, hm lng bc khc nhau. Thc t th kt
qu phn tch ton b qung c c l da trn c s phn tch mt khi lng khong 1 g.
Thnh phn ca n phi i din cho thnh phn ca 25 tn qung hoc l khong 22.700.000
g qung hng ha. R rng l, vic la chn mu nh nh th khng th l mt ng tc n
gin, mt giai on. Ni mt cch ngn gn, chn mu khi lng 1 g v tin cy l
thnh phn ca n i din cho 23.000.000 g nguyn liu t n c ly ra, i hi phi x
l s b ton b nguyn liu.
Thng vic chn mu khng phc tp nh ni trn. Hn na, nh ha hc khng th
bt u phn tch khi m cha c trong tay mt phn mu phn nh ng thnh phn ton b
nguyn liu.

10

1.2.2 Chun b mu phn tch

i vi nguyn liu rn thng cn phi nghin v trn m bo ng nht ca
mu. i khi cn phi loi tr m hp ph khi mu rn. S hp ph hoc mt nc dn
ti s ph thuc thnh phn phn trm ca cht vo m trong thi gian phn tch. trnh
sai s lin quan n s dao ng ca m, ngi ta chp nhn phn tch mu sy kh.

1.2.3 o mu
Kt qu phn tch nh lng thng c din t bng n v tng i, ngha l lng
hp phn cn xc nh trong mt n v khi lng hoc th tch mu. Do , khi lng
hoc th tch ca mu cn phi bit trc khi phn tch.

1.2.4 Ha tan mu
Thng php phn tch c tin hnh trong dung dch mu. Trong trng hp l tng,
dung mi cn phi ho tan hon ton mu ban u (ch khng phi ch hp phn cn xc
nh) nhanh v m du khng xy ra s mt mt cht cn xc nh. ng tic l i vi
nhiu hoc chnh xc hn l i vi phn ln cc nguyn liu khng c nhng dung mi nh
vy. Thng nhng nh ha phn tch phi lm vic vi nhng cht kh ch ha nh qung,
cc cht cao phn t, cc t bo sng. Chuyn hp phn cn xc nh ca nhng nguyn liu
nh vy vo trng thi ha tan thng l cng vic phc tp i hi nhiu thi gian.

1.2.5 Tch hn hp cn tr
Ch c rt t nhng tnh cht ha hc v vt l quan trng c s dng lm c trng
trong ha hc phn tch cho mt cht. Ngc li, nhng phn ng c s dng v nhng
tnh cht ca cc cht li c trng i vi c lot cc nguyn t hoc hp cht. S tht l,
khng c nhng phn ng v tnh cht c bit. S thc t cc nh ha phn tch trc
mt kh khn mi: Phi nghin cu nhng s phn tch tch hp phn cn quan tm
khi cc cht l c trong nguyn liu th v c th nh hng n kt qu php o cui cng.
Nhng hp cht hoc nhng nguyn t nh hng n php o trc tip cn xc nh gi l
cht cn tr. Tch cc cht cn tr trc php o l giai on quan trng trong phn ln cc
php phn tch. Khng th chn mt phng php tng qut, cng nhc no loi b hn
hp cn tr v chnh v th nhim v ny l rt quan trng trong ha phn tch.

1.2.6 Giai on kt thc php phn tch

Tt c nhng giai on chun b phn tch cn phi m bo thu c kt qu tin cy
khi o giai on cui cng.
Trong cc chng tip theo s ni ti cc loi php o giai on kt thc v bn lun v
nhng c s ha hc ca nhng phng php .

11

1.2.7 Chn phng php phn tch

Theo cc nh ha hc hoc cc nh bc hc quan tm n nhng d kin phn tch, c c
lot phng php thu c kt qu mong mun. C s chn phng php l cc ch tiu
nh tc , s thun li, chnh xc, s hin c nhng thit b thch hp, s mu phn tch,
lng mu, hm lng hp phn cn xc nh. Phn tch thnh cng hoc khng thnh cng
l ty thuc vo vic la chn phng php. ng tic l khng c mt phng php chung
tng qut. la chn phng php ng cn phi c suy ngh minh mn v trc gic m
iu y ch c c thng qua thc nghim.

12

Chng 2
nh gi tin cy ca nhng s liu phn tch
Mi php o u c sai s, xc nh gi tr sai s ny thng phc tp, i hi nhiu n
lc, sng to v c trc gic. Nhng kt qu phn tch c hon thnh vi tin cy cha
bit s khng c gi tr khoa hc. Ngc li, nhng kt qu phn tch khng chnh xc cng
c th rt quan trng nu c th xc nh c gii hn sai s vi tin cy cao.
Khng c mt phng php tng qut, n gin v chnh xc no nh gi, cho d ch
l nh tnh, nhng kt qu thc nghim. V vy, x l kt qu thng l mt nhim v khng
km phn phc tp so vi vic thu c nhng kt qu . Cng vic bao gm nghin cu
ti liu, chun ho thit b, nhng thc nghim ph c tin hnh mt cch c bit tm
nhng nguyn nhn ca nhng sai s c th c v phn tch thng k nhng d kin thu c.
Mun tng nhy ln mi ln c th phi thm mt cng tc ph trong nhiu gi,
nhiu ngy, thm ch nhiu tun. Do , cn phi xc nh yu cu v tin cy cho mi kt
qu phn tch, khng nn tiu ph nhiu thi gian t nhy cao cho nhng cng vic
khng cn nhy .
Trong chng ny s cp n nhng loi sai s ny sinh khi thc hnh phn tch,
phng php pht hin, phng php nh gi v cch biu din gi tr .

2.1

Mt s nh ngha

Thng thng, nh phn tch phi lp li php phn tch mu t hai n nm ln. Nhng
kt qu ring bit trong dy o song song t khi ph hp vi nhau nn cn phi chn gi tr
trung tm tt nht ca dy. S cn thit ca nhng php o song song l do hai nguyn
nhn. Mt l, gi tr trung tm c la chn ng tin cy hn so vi mi kt qu ring bit
khc. Hai l, s khc nhau v gi tr ca nhng kt qu ring bit khc m bo cho s
nh gi nh tnh v tin cy ca gi tr tt nht c la chn.
C th dng mt trong hai im xut pht t hai i lng, trung bnh v trung v lm
im trung tm ca dy.

2.1.1 Trung bnh v trung v

Trung bnh, trung bnh cng v trung bnh mu, x , l nhng t ng ngha v l thng
s ca php chia tng kt qu ca nhng php o ring bit cho s ln o mu.

13

Trung v ca dy l kt qu gia, c s kt qu c gi tr ln hn v s kt qu c gi tr
nh thua bng nhau. Nu mu c s php o khng chn, c th ly im trung tm l trung v
cn i vi mu c s php o chn, c th ly trung bnh ca cp php o trung tm lm
trung v.
V d, hy tnh trung bnh v trung v ca dy s: 10,06; 10,20; 10,08; 10,10.
Trung bnh = x =

10,06 + 10,20 + 10,08 + 10,10

= 10,11
4

V mu c s php o chn nn trung v l trung bnh ca cp s trung tm:

Trung v = x =

10,08 + 10,10
= 10,09
2

Trong trng hp l tng, trung v v trung bnh phi trng nhau nhng thng iu
khng xy ra, c bit l nu s ln o khng ln.

2.1.2 lp li
Thut ng lp li c dng nh gi nh lng s tn mn ca kt qu. i
lng ny c trng cho s gn nhau theo gi tr tuyt i ca hai hoc mt s php o ln
hn c thc hin trong cng iu kin. lp li c din t bng mt s cch:
Cc cch biu din lp li tuyt i: cch din t lp li n gin nht l bng
lch khi gi tr trung bnh xi x , khng k du. minh ha, chng ti dn ra nhng kt
qu phn tch clorua ca mt mu bng 2.1 di y.
Bng 2.1. Kt qu phn tch clorua mt mu
Cc
Thng s
kt
o mu
[%]

qu

lch khi gi tr trung bnh

xx

lch khi trung v

x1

24,39

0,077

0,03

x2

24,19

0,123

0,17

x3

24,36

0,047

0,00

3 [72,94]

3 [0,247]

3 [0,20]

x = 24,313 = 24,31

lch trung bnh

lch trung bnh khi gi tr
khi trung v 0,067
trung bnh 0,082 0,08
0,07

= xmax xmin = 24,39 24,19 =0,20.

14

Gi tr trung bnh ca cc kt qu l 24,31%; lch ca kt qu th hai khi

gi tr trung bnh l 0,12%; lch trung bnh ca cc kt qu khi gi tr trung bnh l
0,08%. Php tnh lch trung bnh c tin hnh n ch s th ba sau du phy mc d
mi kt qu thu dc ch vi chnh xc n ch s th hai sau du phy. S lm trn gi
tr trung bnh v lch trung bnh n lng con s hp l sau du phy c thc hin sau
khi php tnh kt thc. Bin php cho php lm gim sai s khi lm trn.
Cng c th din t lp li bng lch khi trung v, 24,36% (xem bng trn). S o
lp li cng chnh l bin bin i hoc bin dy s liu, , ngha l hiu s gia kt
qu ln v nh nht (0,20%).
lch tiu chun v phn tn c dng lm hai tiu chun cho lp li. Cch xc
nh cc i lng ny s c cp n trong cc mc tip theo ca chng ny.
lp li tng i
Ngoi lp li tuyt i, thun tin hn, ngi ta cn ngh khi nim lp li
tng i theo s trung bnh hoc theo trung v, biu din bng phn trm. V d, i vi
php o x3:
lch tng i khi gi tr trung bnh =

0,08 100
= 0,32 0,3%
24,31

lch trung bnh tng i khi trung v =

0,067 100
= 0,3%
24,36

2.1.3 ng
ng biu th s gn ng ca gi tr thu c vi gi tr c chp nhn l tht.
ng thng c din t bng sai s tuyt i v c th nh ngha sai s ny nh sau: E = xi
xt.
Sai s tuyt i E l hiu s gia gi tr quan st c, xi v xt l gi tr c chp nhn l
tht. Gi tr c chp nhn l tht cng c th khng ng tin cy. Do vic nh gi sai s
thc s ca php o thng l cng vic kh kh khn.
Tr li v d dn ra trn y, chng ta gi thit rng, kt qu tht ca mu l 24,36%.
Khi sai s tuyt i ca s trung bnh s l:
24,31% 24,36% = 0,05%.
Trong nhng trng hp nh th ny ngi ta thng t du cho sai s ch r kt qu
c nng cao ln hay b h thp xung.
Thng i lng c li hn, khng phi l sai s tuyt i m l sai s tng i, biu
din lch khi gi tr tht bng phn trm. i vi php phn tch xt trn:

15

Sai s tng i =

0,05 100
= 0,21 0,2%
24,36

2.1.4 lp li v ng ca nhng d kin thc nghim

lp li ca php o c th d dng xc nh bng cch lp li thc nghim trong
nhng iu kin ng nht nh gi ng th khng n gin nh vy bi v lm
vic cn phi bit gi tr tht. Theo di mi quan h trc tip gia ng v lp li l
cng vic rt hp dn. S thn trng trong xem xt mi quan h c minh ho trn hnh
2.1. Trn hnh ny ngi ta dn ra nhng kt qu xc nh nit trong hai hp cht tinh khit
ca bn nh phn tch khc nhau. Nhng im phn b trn th xc nhn sai s tuyt i
ca nhng php o song song trong mi mu m mi nh phn tch mc phi.

Hnh 2.1
Sai s tuyt i ca php xc nh vi lng ni t theo phng php Ken-an

Trn mi vch thng ng vi dng ( xi - xt) l lch tuyt i ca gi tr trung bnh

khi gi tr tht
ng ch l nh phn tch th nht t c lp li tng i cao v ng cao.
Ngc li, nh phn tch th hai t lp li xu nhng ng kh. Nh phn tch th ba
t lp li rt cao nhng gi tr trung bnh ca cc kt qu mc sai s rt ng k. Cn nh
phn tch th 4 t lp li v ng u ti.
Cc kt qu phn tch v phn b nh trn hnh 2.1 l do nh phn tch mc phi hai
loi sai s c bn.

16

2.2

Phn loi sai s

2.2.1 Sai s h thng v sai s ngu nhin

C th phn chia nhng sai s sinh ra trong qu trnh phn tch ho hc thnh hai nhm
ln khng ph thuc vo ngun gc ca chng.
Sai s h thng l sai s m gi tr ca n, nu nh khng phi trong thc t th cng l
v nguyn tc, c th o c v tnh ton c.
Sai s ngu nhin l sai s xut hin trong kt qu ca nhng php o lp li nhiu ln.
Ngun gc ca sai s ny khng r, cn gi tr th dao ng ty v khng th o c. S
tn mn ca nhng kt qu gn gi tr trung bnh (hnh 2.1) l h qu trc tip ca sai s ngu
nhin. Ngc li, hiu s gia gi tr tht v gi tr trung bnh thu c ca cc nh phn tch
th 3 v th 4 ( xi xt) l do mt hoc mt s sai s h thng gy nn.

2.2.2 Cc loi sai s h thng

Khng th k tt c mi ngun gc c th c ca sai s h thng nhng c th coi sai s
c bit ca ngi thc nghim, sai s ca thit b o, sai s ca phng php phn tch v c
nhng t hp bt k ca chng l c s ca loi sai s ny.
Sai s c bit: Sai s ny xut hin do khng hiu bit, do cu th, do nh kin hoc do
khuyt tt v sc kho ca ngi thc nghim. V d, chng c th xut hin do vn chuyn
mu khng ng cch, do b qua b chnh nhit i vi thit b o, do ra kt ta hoc do
ghi khng chnh xc ch s ca thit b
Sai s c bit cn thng gp nhng ngi m mu cc mc khc nhau nn kh
thy s chuyn mu. iu ny rt quan trng trong phn tch.
S nh kin c nhn cng l ngun sai s quan trng phi lun lun phng. Ngi
thc nghim v tnh c gng c c nhng ch s ca thit b nhm nng cao lp li ca
dy kt qu hoc l c gng t kt qu cao cho cng gn cng tt vi mt gi tr nh kin
trc c coi l gi tr tht ca php o. trnh sai s h thng loi cn lun nh nhng
khuyt tt ca c th con ngi v c gng khch quan hn khi quan st.
Sai s thit b: Sai s thit b do s khng hon thin ca thit b m nh phn tch s
dng gy nn hoc l do nh hng ca nhng yu t bn ngoi ln thit b. V d, th tch
ca nhng dng c nh mc (buret, pipet, bnh nh mc) thng khc mt cht so vi th
tch c xc nh khi chun ho chng, c bit l nhit ca cc dng c ny khi s dng
khc nhiu vi nhit khi chun ho. C th loi tr sai s h thng loi ny bng cch
chun ha dng c nh mc nhit tng ng
Sai s phng php: Sai s h thng thng xut hin do s sai lch ca tnh cht thuc
th hoc phn ng dng lm c s cho php xc nh khi tiu chun l tng. Nguyn nhn

17

ca nhng sai lch ny c th l: tc phn ng nh, phn ng xy ra khng hon ton, s

khng bn ca cc cht no , s khng c trng ca thuc th v s khng xy ra cc phn
ng ph cn tr qu trnh xc nh. V d, trong phn tch trng lng, nhim v t ra i
vi nh phn tch l tch nguyn t cn xc nh vo dng kt ta cng tinh khit cng tt.
Nu khng ra kt ta tt th kt ta s b bn bi cc cht l v trng lng ca n s
tng ln. Mt khc, s ra cn thit tch cc cht bn c th dn ti s mt i mt lng
ng k kt ta do tan v do xut hin sai s h thng m. Trong bt k trng hp no,
s cn thn thc hin cc ng tc s lm mt i sai s h thng do phng php phn tch
gy nn.
Trong phn tch chun thng gp sai s phng php gn lin vi vic thm d thuc
th so vi lng l thuyt cn thit lm chuyn mu ca ch th l du hiu nh gi im
cui ca phn ng. Kt cc, ng ca ton b php phn tch c xc nh bng chnh
hin tng c trng .
Cn mt loi sai s phng php na c minh ho trn hnh 2.1, php xc nh nit
trong hp cht hu c, theo Ken-an, da trn c s oxi ho mu bng axit sunfuric c, nit
thng chuyn thnh amoni sunfat. Nhng hp cht cha vng piriin, v d, axit nicotinic,
c th khng b oxi ho hon ton trong nhng iu kin phn tch. Sai s m trong nhng kt
qu ca cc nh phn tch th 3 v th 4 chc l gn lin vi s oxi ho khng hon ton.
Sai s phng php l nhm sai s h thng nghim trng nht bi v thng thng
chng khng b pht hin.
2.2.3

nh hng ca sai s h thng n kt qu phn tch

Sai s h thng thng c chia thnh hai loi: loi hng nh v loi bin i. Gi tr
sai s hng nh khng ph thuc vo lng c o. Ngc li, sai s bin i tuyn tnh
gim hoc tng theo gi tr tuyt i, t l vi lng mu ly phn tch.
Sai s hng nh: Trong mt php phn tch c th bt k, sai s hng nh cng ln nu
lng cht c o cng nh, c th dng hin tng mt khi ra kt ta do tan ca n
lm v d.
V d, chng ta gi thit rng theo phng php cn ra kt ta bng 200 ml nc v khi
mt i 0,50 mg kt ta. Nu trng lng kt ta l 500 mg th sai s tng i do tan l
(0,05.100/500) = 0,1%. Mt mt lng cht nh vy khi ra 50 mg kt ta tng ng vi
sai s tng i 1,0%
Th tch thuc th dng d so vi lng cn thit lm i mu trong phn tch chun
l mt v d khc v sai s hng nh. Th tch thng nh v khng ph thuc vo th
tch chung ca thuc th tiu tn cho php chun v mt ln na sai s tng i s cng
ln nu th tch chung cng nh. R rng l, mt trong cc cch h thp sai s hng nh l
la chn mt lng mu hp l, tt nhin l tng ng vi phng php phn tch.

18

Sai s bin i: Nhng hn hp l, nu nh hng ca chng khng b loi tr

bng mt phng php no , s c th dn ti mt trong cc dng ca sai s bin i tuyn
tnh. V d, mt phng php xc nh ng c bit rng ri bao gm phn ng ca ion
ng (II) vi kali ioua v tip sau l php o lng iot tch ra. Nu khi c mt st (III)
th n cng y c iot ra t kali ioua. Nu khng thc hin bin php ngn nga nh
hng ca st (III), php phn tch s cho hm lng phn trm ca ng cao bi v iot tch
ra tng ng vi hm lng tng cng ca ng v st trong mu. Gi tr ca sai s c xc
nh bng nhim bn st ca mu v hiu ng tng i khng ph thuc vo lng mu
phn tch. Nu, v d, tng gp i lng mu th lng iot tch ra do ng cng nh do hn
hp st cng tng gp i. Sai s tuyt i khi tng gp i trong khi sai s tng i
vn gi nguyn

2.3

Biu hin ca sai s h thng

Sai s h thng thng kh ln. Hn na, vic pht hin chng cng kh khn bi v
khng c mt phng php n gin v tin cy no cho php pht hin, c hay khng c loi
sai s ny.

2.3.1 Pht hin sai s dng c v sai s c bit

Ngi ta thng pht hin sai s dng c v b chnh khi chun ho thit b. Tt nht l
chun ho nh k thit b bi v vi thi gian, ch s ca phn ln thit b sai lch do b hao
mn, n mn hoc do s s dng cu th.
C th gim phn ln sai s c bit n cc tiu bng s cn thn trong cng tc v t
kim tra. Nhiu nh nghin cu t rn luyn cho mnh thi quen kim tra cc loi ch s
ca thit b, s ghi chp trong nht k v s tnh ton. Sai s lin quan vi nhng khuyt tt
v th lc ca con ngi c th trnh c bng cch la chn ng phng php, tt nhin l
trong iu kin bit trc.

2.3.2 Pht hin sai s phng php

Pht hin sai s phng php c bit kh khn. Ngoi ra vic b chnh nh hng ca
chng thng cng rt kh. C th pht hin sai s loi ny nh cc bin php di y:
Phn tch cc mu tiu chun. pht hin sai s h thng ca phng php ngi ta
phn tch nhng mu nhn to, c thnh phn bit trc v gn vi thnh phn vt liu cn
phn tch. Mu tiu chun cn phi c chun b rt cn thn nng ca hp phn cn
xc nh c bit trc vi tin cy cao. ng tic l, vic chun b mu c thnh phn
ng ht nh mt cht t nhin phc tp, thng kh khn hoc ni chung khng th lm
c.
Phn tch bng nhng phng php c lp. Hon thnh vic phn tch bng mt phng
php c lp vi chnh xc bit trc song song vi phng php c s dng trong

19

nghin cu l c bit quan trng nu khng c mu vi sch bit trc. Phng php c
lp khng cn gn vi phng php s dng nhm lm gim xc sut nh hng ng nht
ca mt yu t no ln c hai phng php.

Bng 2.2
nh hng ca sai s c nh, bng 2 mg n kt qu xc nh bc trong hp kim

Lng cn, g

Lng bc tm c
g

0,2000

0,0378

18,90

0,5000

0,0979

19,58

1,0000

0,1981

19,81

2,0000

0,3982

19,91

5,0000

0,9980

19,96

Th nghim trng. Thng c th loi tr sai s c nh trong cc php o vt l bng

cch tin hnh th nghim trng, trong tt c cc giai on phn tch u c thc hin
khi khng c cht nghin cu. Kt qu th nghim dng b chnh php o tht. Th nghim
trng c bit c li khi nh gi sai s gn lin vi s ln trong mu th nhng tp cht cn
tr t thuc th v bnh.
Bin i lng mu. C th pht hin sai s c nh bng cch phn tch nhng lng
cht khc nhau. Nhng kt qu phn tch vi gi thit, nhng lng mu hp kim khc nhau
cha chnh xc 20% bc c dn ra bng 2.2. Mi php xc nh c km theo sai s c
nh bng 2 mg v dn ti s h thp kt qu. nh hng ca sai s gim dn khi tng
lng mu.

Bng 2.3
nh hng ca sai s bin i tuyn tnh, bng 0,5%, n kt qu xc nh trong hp kim

Lng cn, g

Tm c

20

0,2000

0,0402

20,10

0,5000

0,1006

20,12

1,0000

0,2009

20,09

2,0000

0,4021

20,11

5,0000

1,0051

20,10

R rng l, t hnh 2.2 ta thy lng mu cng ln kt qu cng gn vi gi tr tht.

Ngc li, s bin i s khng cho php pht hin sai s bin i tuyn tnh. Hnh 2.2
cng minh ho nhng kt qu phn tch nhng mu khc nhau ca cng mt hp kim bng
mt phng php vi sai s bin i tuyn tnh bng 0,5%. Nhng kt qu cng c dn ra
bng 2.2. th l ng thng. R rng l, khng bit c hm lng tht ca bc trong
hp kim c tn ti loi sai s nh vy hay khng? C th l khng nhn bit c.

H m l n g A g %
S a i s b i n i

2 0 ,3

2 0 ,1

G i tr th t

1 9 ,9

S a i s c n h

L n g c n (g )

Hnh 2.2
nh hng ca sai s c nh v sai s bin i tuyn tnh n kt qu xc nh bc (xem bng 2.2 v 2.3)

2.4

nh hng ca sai s ngu nhin

R rng l xut pht t ci tn ca n, sai s ngu nhin xut hin l do nhng sai s
khng bit c v khng kim tra c ca php o, nhng sai s l nguyn nhn ca s
tn mn kt qu khi o lp li, nh c ch r trn hnh 2.1 v d dy th nghim th 4.

21

2.4.1

Xem xt nh hng ca sai s ngu nhin ln ng tc chun ho pipet

nh hng ca sai s ngu nhin ln ng tc chun ho pipet tng i n gin, bao

gm vic xc nh trng lng nc (vi chnh xc n miligam) chy ra t pipet c
minh ha bng 2.4.
Bng 2.4 Nhng kt qu o song song khi chun ho pipet th tch 10 ml
S th Th tch nc S th Th tch nc S
th Th tch nc
nghim chy ra, ml
nghim chy ra, ml
nghim
chy ra, ml
1

9,991

9,988

17

9,978

9,986

10

9,976

18

9,980

9,973

11

9,980

19

9,976

9,983

12

9,973

20

9,986

9,980

13

9,970b

21

9,986

9,988

14

9,988

22

9,983

9,993a

15

9,980

23

9,978

9,970b

16

9,986

24

9,988

Th tch trung bnh = 9,9816 = 9,982 ml

lch trung bnh khi gi tr trung bnh = 0,0054 ml
Bin dao ng = 9,993 9,970 = 0,023 ml
lch tiu chun = 0,0065 ml ?
a

Gi tr ln nht.

Gi tr nh nht.

Cn o nhit ca nc xc nh trng lng ring ca n. Trng lng c xc

nh bng thc nghim, sau tnh ra th tch nc chy ra t pipet. Nu nhng sai s c
pht hin v loi tr, nhng kt qu o ca cng tc vin c kinh nghim snh si trn cn
phn tch chun vi chnh xc 1 mg (tng ng vi khong 0,001 ml) c th c thy
trn hnh 2.3.
Tuy vy, lch trung bnh khi trung bnh s hc ca 24 ln o l 0,0054 ml v bin
dao ng l 0,023 ml. S tn mn kt qu l h qu trc tip ca sai s ngu nhin.

22

C th gii thch c s khng trng lp kt qu ca nhng php o lp li

(bng 2.4) khi gi thit rng mi php o c km theo nhiu sai s khng bit c, gy ra do
s khng trng lp nhng iu kin khng c kim tra thc nghim. Hiu ng tng cng
ca nhng sai s cng l mt i lng ngu nhin. Thng sai s b tr nhau nn tc
dng ca chng l cc tiu. Nhng i khi cng cng hp vi nhau cho sai s dng hoc m
cao hn. Ngun sai s khi chun ho pipet c th l nhng sai s gn lin vi sai s kim tra
bng mt mc cht lng vch, mc thy ngn trong nhit k v ch s ca cn: nhng ngun
sai s khc bao gm s dao ng trong thi gian dc ht nc t pipet, s bin i ca gc
nghing khi nc chy, s dao ng ca nhit ph thuc vo cch cm pipet. Chc chn
rng, ngoi nhng sai s k trn cn tn ti nhiu sai s khc. R rng l, ngay c mt ng
tc gin n nh chun ho pipet cng km theo nhiu bin i khng ln khng kim tra
c. Mc d chng ta khng vch r nh hng ca mi sai s trong s nhng sai s
nhng cng c th din t hiu ng tng cng ca chng di dng sai s ngu nhin phn
nh qua s phn tn s liu quanh gi tr trung bnh.

2.4.2 S phn b s liu ca nhng php o song song

Khc vi sai s h thng, khng th loi tr sai s ngu nhin khi php o. Ngoi ra,
nh nghin cu khng c quyn b qua chng, coi chng l nh. Chc chn l c th cng
nhn rng, gi tr trung bnh ca 24 ln o th tch c dn ra bng 2.4 gn vi th tch tht
hn so vi bt k gi tr ring bit no. Nhng chng ti gi thit rng, ngi ta tin hnh
chun ho ch hai ln v mt cch ngu nhin hai ln o ph hp vi kt qu ca th nghim 1
v 7. Gi tr trung bnh t hai gi tr bng 9,992, khc vi gi tr trung bnh ca 24 php o
l 0,010 ml. Chng ta cng nhn thy rng lch trung bnh ca hai php o khi gi tr
trung bnh ring ca chng ch l 0,0010 ml. Trn c s gi tr lch khi gi tr trung bnh
nh nh vy c th xut hin s lc quan qu ng v sai s ngu nhin. Kt cc nu xut
hin s cn thit gi kim tra gi tr th tch chy ra t pipet vi chnh xc 0,002 ml c
th ngi ta s b qua s thiu chnh xc nghim trng. Trong trng hp ny, s khng bit
gi tr tht ca sai s ngu nhin to ra cm gic gi v tin cy vo cht lng tt ca
pipet. Thc t c th ch ra rng nu s dng pipet 1000 ln th chc chn trong 2 3 trng
hp th tch cht lng chy ra s khc gi tr trung bnh bng 9,982 ml, l 0,002 ml, v hn
100 trng hp l 0,01 ml v ln hn, bt chp tt c mi bin php phng nga ca nh phn
tch.
phn tch nhng sai s nh nh hng nh th no n kt qu ca nhng php o
song song, chng ta xt mt tnh hnh tng tng trong sai s ngu nhin c hnh thnh
t 4 sai s nh vy. Chng ta quy c rng mi loi sai s c c trng bng xc sut
xut hin nh nhau v c th nh hng n kt qu cui cng gy nn sai s dng hoc m
c xc nh bng i lng U l ng nht i vi tt c 4 loi sai s.
Bng 2.5 Nhng phng php t hp c th c 4 loi sai s khc nhau U1; U2; U3 v U4
T hp sai s

i lng sai s ngu nhin

Tn s tng i ca sai s

+ U1 + U2 + U3 + U4

+ 4U

23

U1 + U2 + U3 + U4
+ U1 U2 + U3 + U4
+ U1 + U2 U3 + U4
+ 2U

+ U1 + U2 + U3 U4
U1 U2 + U3 + U4
+ U1 + U2 U3 U4
+ U1 U2 + U3 U4
U1 + U2 U3 + U4
U1 + U2 + U3 U4

+ U1 U2 U3 + U4
+ U1 U2 U3 U4
U1 + U2 U3 U4
U1 U2 + U3 U4
U1 U2 U3 +U4
U1 U2 U3 U4

2U
4U

Tt c cc t hp c th c ca 4 loi sai s c th dn ti sai s ngu nhin ni trn

c dn ra bng 2.5. Ch rng ch c mt t hp c th dn ti sai s dng cc i 4U,
bn t hp dn ti sai s dng 2U v 6 t hp dn ti sai s khng, quan h tng t nh
vy cng xy ra i vi sai s ngu nhin m. l t s 6 : 4 : 1. T s ny phn nh xc
sut sai s ca mi vng. Khi s php o ln c th hy vng s xut hin sai s c phn
b theo tn s tng t nh c m t trn hnh 2.3a. S phn b 10 sai s bng gi tr s
c ch r hnh 2.3b. Mt ln na chng ta thy rng s xut hin "sai s khng" vi xc
sut ln nht trong khi sai s cc i bng 10U rt him hoi xut hin (khong 1 ln cho
500 php o).
Nu chng ta pht trin tip theo nhng bn lun trn y cho s rt ln sai s quy m
ngy cng nh, s ng cong phn b nhn c c dn ra trn hnh 2.3c. ng cong
hnh qu chung c gi l s phn b Gauss hay phn b chun ca sai s (khi xy dng
ng cong Gauss khng cn thit phi gi thit s ng nht ca nhng sai s ring bit.
ng cong c nhng c trng:
1. Tn s xut hin sai s ngu nhin khng l cc i.

24

2. i xng qua cc i, ngha l xc sut hin sai s m v sai s dng

bng nhau.
3. Xc sut xut hin gim dn gi tr sai s ngu nhin ca php phn tch ho hc tin
ti rt gn vi ng cong phn b Gauss. V d, nu xy dng th biu din s ph thuc
tn s xut hin mi lch khi gi tr trung bnh ca hng trm php o pH ca mt mu
vo gi tr lch th thu c ng cong tin gn ti ng cong c din t trn hnh
2.3d.
(b)

Tn s y

-10U -8U

-6U

-4U

-2U

2U

4U

6U

10U

8U

Sai s ngu nhin

Tn s y

S ln o pH
20
(d)

(c)

10

-0,03

-0,02

-0,01

0,01

0,02

0,03

Sai s ngu nhin hoc lch khi gi tr trung bnh

Hnh 2.3
S phn b l thuyt sai s ngu nhin xut hin khi tnh
a) 4 sai s; b) 10 sai s; c) S rt ln sai s

Nhng quan st thc nghim khng nh gi thit cho rng, c th hnh dung sai s ngu
nhin ca php o phn tch di dng tch ly s ln nhng sai s nh c lp v khng
kim tra c. iu quan trng l s phn b phn ln nhng d kin phn tch theo ng
cong Gauss cho php ng dng phng php thng k nh gi gii hn sai s ngu nhin
theo lp li.

25

ng c l ng cong phn b chun hoc phn b Gauss. ng d l ng phn b

thc nghim c th thu c khi t lch khi gi tr trung bnh ca khong 250 php o
pH song song trn trc honh v s php o pH tng ng vi mi lch quan st c trn
trc tung.
2.4.3

Nhng khi nim c bn ca thng k c in

Thng k cho php m t ton hc nhng qu trnh ngu nhin, V d, nh hng ca sai
s ngu nhin n kt qu phn tch ho hc. Nhng iu quan trng l nhn thc rng, ch c
th m t chnh xc bng cc phng php thng k c in khi s quan st ln v hn.

Hnh 2.4
Nhng ng chun phn b sai s c xy dng i vi mt v ch mt i lng c o bng hai phng php.
Phng php 1 tin cy hn do i lng nh hn.

Cn ch n ba loi trc honh:

26

a) i lng o c x vi cc i .
b) i lng Z t phng trnh (2.2).
Trc honh c hp nht hai ng cong lm mt (phng php 1 v 2 cho nhng ng
cong ng nht khi s dng Z lm trc honh).
Phng php cho 2 5 php phn tch song song c mt nh phn tch hon thnh
th nhng kt lun v sai s ngu nhin c th c, c th mc sai lm nghim trng v qu lc
quan. Trong nhng trng hp ny cn thit phi bin dng cc phng php c in. Trc
ht phi xem xt cc loi thc t v v vy xut hin ngh dng li mt cht mt s quy
lut quan trng ca thng k c in.
Tnh cht ca ng cong phn b chun: Hai ng cong trn ca hnh 2.4 l nhng
ng cong phn b sai s chun ca hai phng php phn tch khc nhau. ng cong trn
cng phn nh nhng d kin ca phng php chnh xc hn bi v nhng kt qu c tp
hp li gn vi gi tr trung tm hn.
Nh ch r trn hnh 2.4, c th din t ng cong phn b chun bng ba phng
php khc nhau. Trong mi phng php , trn trc tung t tn s xut hin y ca mi gi
tr t trn trc honh. Trn trc honh a t nhng kt qu o x tm c bng thc nghim;
trong trng hp ny gi tr trung bnh l gi tr trung tm c k hiu l . Trn trc honh b
l nhng lch khi gi tr trung bnh, x . R rng l xc sut xut hin " lch khng" l
ln nht. Chng ta s phn tch ba loi khi nim c dn ra trn trc honh c.
Cn nhn mnh rng, nhng ng cong ang xt l l tng bi v chng l s phn b
l thuyt k vng nhng kt qu thc nghim khi s ln phn tch tin dn ti v hn. i vi
mu thc hin trong thc t, s phn b ri rc nh c m t trn hnh 2.3d l c xc sut
ln. Thng k c in da trn nhng ng cong c dn ra trn hnh 2.4, ch khng phi
da trn nhng ng cong c din t trn hnh 2.3d.
C th m t mt cch ton hc s phn b nhng d kin c dn ra trn hnh 2.4 nh
ba thng s ca phng trnh sau:
( x )

y=

22

Z2
e 2

2
(2.2)

lch tiu chun: T phng trnh 2.2 ta thy rng, mi gi tr lch tiu chun phi
tng ng vi ng cong phn b ca mnh. Tuy vy, c th ni rng, khng ph thuc vo
i lng , 86,30% din tch nm di ng cong trong gii hn mt lch tiu chun
(1) khi gi tr trung bnh . Do 86,30% tt c mi gi tr nm trong gii hn .
Khong 95,50% tt c mi gi tr s 2 ; 99,70% gi tr 3. Nhng gi tr (x ),

27

tng ng 1, 2 v 3 c biu th bng nhng ng thng ng t on trn

nhng ng cong pha trn ca hnh 2.4. Trn ng cong pha di nhng gi tr Z mang
n v c t trn trc honh.
Nhng tnh cht ca ng cong phn b chun rt qu gi, v n cho php rt ra
nhng kt lun v gi tr xc sut ca nhng sai s ngu nhin ca mt php o nu bit c
lch tiu chun ca phng php o. V nu bit i lng th c th khng nh c
rng trong 68,30 trng hp trong s 100 trng hp sai s ngu nhin ca mt php o duy
nht bt k cho s < , 95,5 trng hp trong s 100 trng hp sai s ngu nhin s
< 2,... R rng rng lch tiu chun ca mt phng php o l mt thng s rt qu
nh gi v hnh dung gi tr sai s ngu nhin c th c .
lch tiu chun ca mt s rt ln ln o (n) c din t nh sau :
N

(xi )2

i =1

(2.4)

phn tn: 2 l mt c trng khc ca lp li thng c s dng rng ri trong

thng k. Phn ln cc nh nghin cu a thch dng i lng ch khng phi l 2 bi v
chnh lch tiu chun c din t chnh bng n v ca i lng c o.

2.4.4 ng dng nhng phng php thng k

Ngi ta pht hin rng, ng dng trc tip nhng phng php thng k c in cho
mt s khng ln nhng php o song song (t 2 n 20) thng dn ti kt lun sai lm v
gi tr sai s ngu nhin c th c. Rt may l ngi ta nghin cu c nhng phng
php cho php rt ra nhng kt lun tin cy v sai s ngu nhin m ch cn hai hoc ba php
o l .
i vi mt s khng ln php o lp li khng th dng trc tip cc phng trnh (2.2)
v (2.4) bi gi tr trung bnh ca mt s ln v cng php o, (n l gi tr tht khng cha
sai s h thng) khng bao gi bit c. thay th chng ta phi dng gi tr trung bnh
ca s nh php o x . Trong phn ln trng hp x khc mt cht. Hiu s ny tt nhin
l do sai s ngu nhin gy nn v gi tr c th c ca i lng ny chng ta ang th xc
nh. iu quan trng l cn nhn mnh rng, mt sai s bt k no trong xc nh x cng gy
nn mt sai s tng ng trong i lng (phng trnh (2.4)). Do i vi s nh php
o th khng ch gi tr trung bnh x khc vi m cn mt iu rt quan trng khc l s
nh gi lch tiu chun cng c th khng ng tin cy. Nh vy l, chng ta phi ng
chm ti hai sai s, mt sai s bao hm trong gi tr trung bnh v mt sai s khc bao hm
trong gi tr lch tiu chun. Sai s trong nh gi . S gim s biu l nh hng kp
n lch tiu chun. Th nht l s gi tr rt ln v rt nh tng ln ngha l lp li
ca b xu i. Th hai l lch tiu chun tr thnh s nh gi lp li b dch chuyn

28

v pha m hn. S dch chuyn din t s xut hin vi tn s ln nhng gi tr

nh so vi nhng gi tr ln v s gim gi tr trung bnh khi gim s php o lp li.
S dch chuyn m gi tr i vi s ln o nh l do gi tri trung bnh v lch tiu
chun nhn c t mt v ch mt dy nh d kin. C th ch ra rng, s dch chuyn
mt mc ng k c loi tr khi a vo phng trnh (2.4) s bc t do n 1 thay th
cho n. Nh vy, i vi s ln o nh, lch tiu chun c xc nh theo cng thc:
N

S=

(xi x)2

i =1

(2.5)

n 1

Cn ch ti hai iu khc nhau ca phng trnh (2.5) so vi phng trnh (2.4). Th

nht l, mu s by gi l n 1. Th hai l, thay th cho i lng tht nhng khng bit, ,
l gi tr trung bnh ca s nh cc php o, x . nhn mnh rng lch tiu chun thu
c ch l gn ng vi gi tr tht v c chp nhn k hiu bng ch s S ch khng phi
l . V d, tnh lch tiu chun S i vi dy gm 5 gi tr, Xi c dn ra bng sau:
xi x

(xi x)2

9,990

7,6.103

57,8.106

9,986

3,6.103

13,0.106

9,973

9,4.103

88,4.106

9,983

0,6.103

0,4.106

9,980

2,4.103

5,8.106

x =9,9824; (5 [49,992])

(xi x)2 = 165,4.106

xi

i =1

T phng trnh (2.5) ta c:

S=

165,4.106
= 6,4.103 = 0,006
5 1

S hp l ca s thay th (n 1) vo phng trnh (2.5) c gii thch nh sau. V

khng bit , chng ta phi s dng cch tnh cho dy c s t kt qu thu c hai gi tr
x v S. S cn thit xc nh gi tr trung bnh x dn n s loi tr mt bc t do, ngha l
khi gi nguyn du, tng ca nhng lch ring bit khi x cn phi bng 0. Nu gi tr (n
1) lch c xc nh th lch cui cng tt nhin l cng bit. Do , khi nh gi
lp li ca mu ch (n 1) lch ngi ta a vo nhng i lng c lp.

29

nh gi i lng S theo . i vi dy c s t cc kt qu (n 15) cng c th tnh S,

xut pht t bin dao ng theo cng thc:
S=

(2.6)

y d l h s thng k, ph thuc vo s php o (xem bng 2.5). nh gi S theo phng

trnh (2.6) n gin hn nhng km tin cy hn so vi phng trnh (2.5).
Bng 2.6 H s d tnh lch tiu chun S theo gi tr bin dao ng
n

1,128

2,704

1,693

2,847

2,059

2,970

2,326

10

3,078

2,534

11

3,173

n
12
13
14
15

d
3,528
3,336
3,047
3,472

2.4.5 S dng nhng phng php thng k

Nh thc nghim s dng nhng php tnh thng k hon thin s nh gi ca mnh v
nh hng ca sai s ngu nhin. S nh gi trong gio trnh ny bao gm:
1. Khong xung quanh mu trung bnh, m trong khong vi mt xc sut xc nh c
gi tr trung bnh tht.
2. S php o song song cn thit trung bnh thc nghim vi mt xc sut nht nh
ri vo khong d on xung quanh gi tr trung bnh tht.
3. Gii quyt vn , trong tnh ton mu trung bnh c nn gi li hay loi tr nhng gi
tr ri ra ngoi dy kt qu song song.
4. Xc sut v vic hai mu c phn tch bng phng php tng t nhng do kt qu
khc nhau v thnh phn, ngha l s khc nhau v kt qu thc nghim gy nn bi sai s
ngu nhin hay bi s khc nhau tht s trong thnh phn.
Tip theo chng ta s xt bn im trn.

30

2.4.6 Khong tin cy

Trung bnh tht - mt hng s m gi tr ca n lun lun khng bit c nhng nh
thng k c th xc nh gii hn ca vng xung quanh gi tr trung bnh x tm c bng
thc nghim m trong vng hy vng vi mt xc sut cho tm c gi tr trung bnh
tht. Nh vy, nhng gii hn thu c c gi l gii hn tin cy. Khong gii hn bi
nhng gii hn c gi l khong tin cy. Cn ch mt s tnh cht ca khong tin cy.
i vi mt mu cho, gi tr ca khong ny mt phn c xc nh bng hy vng
cho trc. R rng l d on ng n tuyt i, chng ta cn phi chn mt khong
ln v bao gm trong n cc gi tr c th chp nhn l xi c th c c. Ngc li, nu
chng ta chp nhn rng, xc sut ri vo vng l 99 kt qu ng so vi 100 th khong
khng cn phi ln n nh th v c th lm cho n nh hn nu chp nhn xc sut l 95%.
Ni mt cch gn hn, xc sut d on ng n cng nh th khong gii hn tin cy
cng nh.
Khong tin cy l i lng xut pht t lch tiu chun S ca phng php o, ph
thuc vo tin cy ca cc gi tr o c v t cc gi tr ny S c xc nh. Thng nh
ho hc c quyn khng nh rng gi tr thc nghim S m h tm c l gn nht vi .
Nhng trong mt s trng hp i lng S c th cha sai s ng k. Trong nhng trng
hp khong tin cy cn phi m rng.
Nhng phng php thu c gi tr gn vi . S thng ging khi tnh ton i
lng S theo phng trnh (2.5) b gim i cng vi s tng s ln o n. S tht, c th chp
nhn rng, i vi mc ch thc t S v s l ng nht nu n ln hn 20. iu cho php
nh ho hc thu c gi tr gn ng tt nht i vi S nu phng php khng qu kh
v c c lng mu tng ng. V d, nu trong qu trnh nghin cu cn phi o pH ca
mt s rt ln dung dch th mt cch hp l, c th xc nh S trong dy th nghim u. K
thut thc hin php o rt n gin, ch l nhng cp in cc ra v lm kh vo
dung dch nghin cu; hiu th gia cc in cc c dng lm s o pH. xc nh S c
th o pH trong 20 30 phn ca dung dch vi gi tr pH c nh v xc nh tun theo
trnh t o. Thng c th chp nhn rng, sai s ngu nhin ca dy cng chnh l sai s
ngu nhin ca cc php o tip theo v i lng S c tnh ton theo phng trnh (2.5) l
ng tin cy v l s o chnh xc ca i lng l thuyt.
i vi nhng php phn tch tn nhiu cng sc, cch lm m t trn y khng th
dng c trong thc t. Nhng trong trng hp nhng d kin ca nhng mu khc
nhau c th lin kt li thu c gi tr ng tin cy hn so vi gi tr S ca mu ring l.
V mt ln na phi chp nhn rng nhng nguyn nhn ca sai s ngu nhin trong phn
tch tt c cc mu l nh nhau. S chp nhn thng ng n trong iu kin l cc mu
gn nhau v thnh phn v mi mu u c phn tch trong nhng iu kin gn ging
nhau. thu c s nh gi thng nht ngi ta bnh phng lch khi gi tr trung
bnh ca mi mu sau cng cc bnh phng lch ca tt c cc mu v chia cho s bc
t do tng ng. Ly cn bc hai thng s ta thu c i lng thng nht S. Trong mi
mu mt i mt i lng t do. Do , s bc t do tnh i lng S thng nht bng s
php o tng qut tr i s mu. Di y dn ra v d v cch tnh ton .

31

V d: ngi ta xc nh thu ngn bng phng php hp th nguyn t trong cc

mu t by con c cu c h ERI. Nhng kt qu c dn ra di y. Hy tnh lch
tiu chun ca phng php theo kt qu thng nht.
S
mu

S php Kt qu
o song
(hm lng Hg) n.104 %
song

1,80; 1,58; 1,64

Gi
trung
bnh
n.104%

tr Tng s cc
bnh phng
lch khi gi tr
trung bnh

1,673

0,0259

1,015

0,0115

3,240

0,0242

2,06; 1,93; 2,12; 2,16; 1,98;

2,018
1,95

0,0611

0,570

0,0114

2,482

0,0685

1,130

0,0170

0,96; 0,98; 1,02; 1,10

3,13; 3,35

0,57; 0,58; 0,64; 0,49

2,35; 2,44; 2,70; 2,48; 2,44
1,11; 1,15; 1,22; 1,04

S php o: 28

Tng bnh phng = 0,2196

Gi tr tng cc bnh phng lch khi gi tr trung bnh i vi mu 1 c dn ra

ct 5 thu c nh sau:
xi x

xi
1,80

0,127

1,58

0,093

1,64
3 [5,02]

0,033

(xi x)2

0,0161
0,0087
0,0011
Tng cc bnh phng = 0,0259

xi = 1,673

Mt cch tng t thu c nhng d kin cn li c dn ra ct 5 bng trn.

S=

0,0259 + 0,0115 + 0,0242 + 0,0611 + 0,0114 + 0,0685 + 0,0170

= 0,10.104%Hg
28 7

Khi s bc t do ln hn 20 s nh gi S c th c xem nh rt gn vi .

32

Khong tin cy khi S rt gn vi . Nh ni trc y, chiu rng ca ng

cong phn b chun sai s c xc nh bi i lng . Z cng ng vai tr tng t
trong cc phng trnh (2.2) v (2.3). Theo phng trnh (2.2) c th tnh din tch di
ng cong phn b chun sai s theo din tch chung i vi mi gi tr Z.
Bng 2.7 Xc sut tin cy i vi nhng gi tr Z khc nhau
Xc sut tin cy,%

50

0,67

68

1,00

80

1,29

90

1,64

95

1,96

Xc sut tin cy,%

Z
2,00

96
99
99,7
99,9

2,58
3,00
3,29

T s (thng c din t bng phn trm) c gi l xc sut tin cy v l s o

xc sut ca Z , nh hn lch tuyt i (x ). V d din tch di ng cong Z =
1,96 l 95% din tch, v chng ta c th khng nh rng i vi s ln php o gi tr (x
) tnh ton c s bng hoc nh hn 1,96 trong 95 trng hp trong s 100. bng 2.7
dn ra nhng khong tin cy i vi nhng gi tr Z khc nhau. Gii hn tin cy i vi mt
php o duy nht c th thu c bng cch bin i phng trnh (2.3) v nh rng Z c th
c du cng hoc tr.
Nh vy, gii hn tin cy:
= x Z

(2.7)

Di y dn ra v d v cch s dng phng trnh (2.7).

V d: Hy tnh gii hn tin cy xc sut tin cy 50% v 90% i vi kt qu u tin
(1,80.104% Hg) trong v d trc y.
Chng ta bit rng S = 0,10.104% Hg v cc d kin vi gi thit S l . T bng
2.7 ta thy rng Z = 0,67 v 1,96 tng ng vi hai xc sut tin cy 50 v 95. Do theo
phng trnh (2.8):
Gii hn tin cy vi xc sut tin cy 50%:
= 1,80 0,67.0,10 = (0,80 0,07).104%
Gii hn tin cy vi xc sut tin cy 95%:
= 1,80 1,96.0,10 = (1,80 0,20).104%

33

Trong 50 trng hp trong s 100, trung bnh tht (hoc gi tr tht khng c sai s h
thng) nm trong khong(1,73 1,87).104% Hg. Trong 95 trng hp trong s 100, gi tr
tht ri vo khong (1,60 2,00).104% Hg.
Phng trnh (2.7) c ng dng nh gi kt qu ca mt php o duy nht. C th
ni rng, khong tin cy gim n ln i vi gi tr trung bnh t n php o song song. Nh
vy, dng tng qut hn phng trnh (2.78) c dng:
Gii hn tin cy:
= x

(2.8)

V d: Hy tnh gii hn tin cy ca gi tr trung bnh (1,67.104% Hg) ca mu 1 trong v

d th nht ca chng ny vi xc sut tin cy 50% v 95%.
Mt ln na S = 0,10.
i vi 3 php o:
Gii hn tin cy vi xc sut 50%.
= 0,67

0,67 0,10
3

= (1,67 0,04).104%

Gii hn tin cy vi xc sut 95%

= 1,96

1,96 0,10
3

= (1,67 0,11).104%

Nh vy: Trong 50 trng hp trong s 100, gi tr trung bnh tht s nm trong khong:
(1,63 1,71).104% Hg v trong 95 trng hp trong s 100 n s nm trong khong (1,56
1,78).104% Hg.
V d: Hy tnh s php o song song cn thit lm gim khong tin cy vi xc sut
tin cy 95% n 0,005 ml khi hiu chun pipet th tch 10 ml. K thut hiu chun c
ni r khi thu c nhng s liu bng 2.4.
lch tiu chun ca php o bng 0,0065 ml. V gi tr S thu c t 24 php o nn
c th gi thit rng S =0,0065. Khong tin cy c tnh ton nh sau:
Khong tin cy
0,005 ml =

Z
n

1,96 0,0065
n

; n= 6,5

34

Nh vy, s dng gi tr trung bnh t by php o, chng ta c th thu c th

tch trung bnh tin cy chy ra t pipet vi chnh xc n 0,005 ml vi xc sut tin cy
95%.
Phng trnh (2.8) ch ra rng, lm gim khong tin cy i hai ln cn lm 4 php o.
thu hp gii hn ca n thm hai ln na i hi 16 php o. R rng l khi thu c
nhng s liu b sung, gii hn khong tin cy gim i.
Gii hn tin cy khi cha bit . Thng nh ho hc bt buc phi s dng nhng
phng php phn tch khng c nghin cu trc. Ngoi ra s thiu thn thi gian v s
gii hn lng mu c giao lm kh khn cho vic xc nh chnh xc i lng .
Bng 2.8 Gi tr t nhng xc sut tin cy khc nhau
S bc Xc sut tin cy, %
t do
80
90

95

99

99,9

3,08

6,31

12,7

63,7

637

1,89

2,92

4,30

9,92

31,6

1,64

2,35

3,18

5,84

12,9

1,53

2,13

2,78

4,60

8,60

1,48

2,02

2,57

4,03

6,86

1,44

1,94

2,45

3,71

5,96

1,42

1,90

2,36

3,50

5,40

1,40

1,86

2,31

3,36

5,04

1,38

1,83

2,26

3,25

4,78

10

1,37

1,81

2,23

3,17

4,59

11

1,36

1,80

2,20

3,11

4,44

12

1,36

1,78

2,18

3,06

4,32

13

1,35

1,77

2,16

3,01

4,22

14

1,34

1,64

1,96

2,58

3,29

Trong trng hp ny, theo mt dy php o song song, khng ch cn xc nh gi tr

trung bnh m cn cn nh gi lp li. Nh ni trc y, s tnh ton S theo mt s c

35

hn nhng d kin c th dn ti sai s ng k. Trong trng hp ny gii hn tin cy s

rng ra.
tnh ton nhng gi tr S c th c, ngi ta a vo tiu chun t c xc nh nh
sau:
t=

x
S

(2.9)

Khc vi Z trong phng trnh (2.3), t khng ch ph thuc vo xc sut tin cy cho
m cn ph thuc s bc t do trong cng thc tnh S. Ch l khi s bc t do l v hn,
gi tr t tin ti gi tr Z c dn ra bng 2.7.
C th tnh gii hn tin cy theo gi tr t khi s dng phng trnh tng t (2.8). Nh
vy:
Gii hn tin cy:
= x

tS

(2.10)

V d: Nh phn tch nhn c cc s liu sau v hm lng ru trong mu: etanol

(tnh bng phn trm) = 0,084; 0,089; 0,079. Hy tnh khong tin cy i vi gi tr trung bnh
xc sut tin cy 95%. Gi s rng:
1. Ngi ta khng bit g v lp li v
2. Trn c s ca nhng th nghim s b bit c gi tr S s = 0,005% etanol.
Gii :
1. x =

S=

0,084 + 0,089 + 0,079

= 0,0840
3

(0,00)2 + (0,0050)2 + (0,0050)2

= 0,0050
3 1

T bng 2.7, r rng l hai bc t do, t = 4,30 vi xc sut tin cy 95%.

Khong tin cy xc sut 95% = 0,084

4,3 0,0050
3

= 0,084 0,012

2. V c gi tr tin cy vi xc sut 95%

Khong tin cy xc sut 95% = 0,084

1,96 0,0050
3

= 0,084 0,006

36

R rng l, bit gi tr s thu hp khong tin cy i mt na.

2.4.7 Nhng phng php thng k kim tra gi thuyt

Nhiu nghin cu khoa hc v k thut c thc hin kim tra gi thuyt. hiu r
bn cht nhng quan st m t m hnh l thuyt c hnh thnh cn thc hin nhng
thc nghim kim tra ng n ca n.
Nu kt qu ca nhng thc nghim khng khng nh m hnh th ngi ta b n i v
tm kim m hnh mi.
Ngc li, nu quan st thy s ph hp gia thc nghim v nhng kt qu mong i th
m hnh gi thit c th c dng lm c s cho nhng thc nghim tip theo. Nu gi thit
c khng nh bng mt lng ln nhng d kin thc nghim th gi thit c chp
nhn l l thuyt cho ti khi nhng d kin thc nghim khc khng bc b n.
t khi nhng d kin thc nghim ph hp vi nhng d kin chnh xc ca m hnh. Do
, ngi nghin cu cn thng xuyn quan st khi gii quyt vn , s bt ng l du
hiu sai lm ca gi thuyt hay ch l kt qu ca sai s ngu nhin khng th trnh khi ca
php o. Khi mt s phng php kim tra thng k t ra c ch.
Thuc cc phng php kim tra loi c phng php gi thuyt khng da trn s
so snh nhng gi tr bng s ca hai i lng thc t bng nhau. Sau ngi ta nh gi
xc sut xut hin s khc nhau quan st c do sai s ngu nhin theo nhng quy lut ca
thng k. Nu s khc nhau bng hoc ln hn s khc nhau c th xut hin 5 ln trong s
100, tu thuc vo tin cy i hi ca kt lun.
Nhng nh ho hc rt hay dng cc phng php kim tra, nh so snh hai gi tr trung
bnh ca hai mu (x1 v x2); so snh gi tr trung bnh ca php phn tch x1 v i lng
c chp nhn l tht; so snh nhng lch tiu chun S1 v S2, hoc 1 v 2 ca hai dy
o v c lch tiu chun S ca mu nh v lch tiu chun ca mu ln. Trong cc
mc tip theo chng ta s xt ti nhng phng php thc hin nhng php so snh nh vy.
So snh gi tr trung bnh tm c bng thc nghim vi gi tr tht, ng dng mt
phng php phn tch bit cho mt mu bit chnh xc thnh phn l phng php
thng dng pht hin sai s ngu nhin. Theo tt c mi xc sut, gi tr trung bnh tm
c bng thc nghim x s khc vi gi tr tht .
Vn cn gii quyt l, s khc nhau do sai s h thng ca phng php.
Gii thng k bi ton ny bao hm s so snh hm s (x ) vi hiu s cn phi c
trong nhng iu kin bnh thng c k ti sai s ngu nhin. Nu hiu s quan st c nh
hn hiu s tnh ton xc sut tin cy la chn th xem nh gi thuyt khng (x v
khng khc nhau) c khng nh. V khi c th rt ra kt lun, khng c sai s h thng
trong thc nghim. Ngc li, nu (x ) tng i ln hn so vi gi tr mong i hay gi
tr chun th c th cho rng, hiu s c ngha v sai s h thng c chp nhn.

37

Gi tr chun ph nh gi thuyt khng c th thu c sau khi vit li phng

trnh (2.11) di dng :
x =

tS

(2.11)

y n l s php o song song c thc hin trong kim tra. Nu nh gi c tin

cy , th c th bin i phng trnh (2.11) bng cch thay th t v S bng Z v tng
ng.
V d: Mt phng php mi xc nh nhanh lu hunh trong du ho, c kim tra
bng cch dng phn tch mu c hm lng lu hunh bit trc, bng 0,123%. thu
c nhng kt qu xc nh lu hunh theo phn trm nh sau: 0,112; 0,118; 0,115; 0,119.
C phi chng nhng d kin ch ra sai s h thng m ca phng php mi?
x=

0,122 + 0,118 + 0,115 + 0,119

= 0,116
4

x = 0,116 0,123= 0,007

(0,00040)2 + (0,0020)2 + (0,0010)2 + (0,0030)2

= 0,0032
4 1

S=

T bng (2.8) ta tm thy rng, xc sut tin cy 95% v ba bc t do t c gi tr 3,18. Do

:

tS
n

3,18 0,0032
3

= 0,0059

Nhng x = 0,007.
C th hy vng rng 5 ln trong s 100, trung bnh tm c bng thc nghim s sai lch
0,0059 hoc ln hn. Nh vy l nu chng ta kt lun rng, 0,007 l hiu s c ngha th
trung bnh, kt lun ng trong 95 trng hp v sai trong 5 trng hp trong s 100.
So snh hai trung bnh thc nghim. Nh ho hc thng s dng nhng s liu phn tch
khng nh tnh ng nht hay khng ca hai vt liu. Trong trng hp cn phi bit,
s khc nhau ca kt qu phn tch l do sai s ngu nhin ca c hai dy o hay l do s
khc nhau tht s ca nguyn liu gy nn. thy r chng ta gi thit rng lm n1 php
phn tch song song vt liu 1 v n2 php phn tch vt liu 2. Dng phng trnh (2.10)
chng ta c th vit:
1 = x1

tS

2 = x 2

tS

n1
n2

38

y x1 v x2 l nhng trung bnh tm c bng thc nghim. khng nh,

c tn ti hay khng s khc nhau gia x1 v x2, chng ta phi a ra gi thit khng ngha
l 1 v 2 l ng nht. Sau lm cn bng hai phng trnh ta thu c:
x1 =

tS
n1

= x2

tS
n2

ng thc d dng c chuyn thnh:

x1 x2 = tS

n1 + n2
n1n2

(2.12)

Gi tr bng s ca biu thc bn phi c tnh ton vi s s dng gi tr t ng vi

xc sut tin cy cho (s bc t do tm t bng n1 + n2 2). Nu hiu s x1 x2 tm c
bng thc nghim nh hn i lng tnh ton c th gi thit khng c khng nh v
c th cho rng gia nhng gi tr trung bnh khng c s khc bit c ngha. Ngc li,
nu hiu s tm c bng thc nghim ln hn i lng tnh ton c s dng t th s khc
nhau l c ngha.
Nu tin cy d c nh gi th c th bin i phng trnh (2.12) bng cch thay
th t v S bng Z v .
V d 1: Ngi ta so snh thnh phn sn m vt ca n c pht hin trn qun o ca
nn nhn trong tai nn t vi sn trn chic t m ngi li n b nghi ng l th phm ca
trng hp bt hnh ny. Nhng s liu ca php xc nh quang ph Ti trong sn c dn
ra di y ni c g v s khc nhau trong thnh phn ca hai nguyn liu. Theo nhng s
liu s b, lch tiu chun ca php phn tch c bit trc v bng 0,35% Ti, ngha l S
= 0,35% Ti.
Hm lng Ti, %
Sn trn qun o:
Sn trn t:

4,0; 4,6.
4,5; 5,3; 5,5; 5,0; 4,9.

x1 =

4,6 + 4,0
= 4,3
2

x2 =

4,5 + 5,3 + 5,0 + 4,9 + 5,5

= 5,04
5

x1 x2 = 4,3 5,05 = 0,74% Ti

Ch rng S , bin i phng trnh (2.12) mt cch tng ng v tin hnh tnh
ton vi xc sut tin cy 95 v 99%:

39

n1 + n2
2+5
= 1,96 0,35
= 0,57
n1n2
25
= 2,58 0,35

2+5
= 0,76
25

Chng ta thy rng, ch 5 trng hp trong s 100 kt qu khc 0,57% Ti v ln hn; v

ch c mt trng hp trong s 100 hiu s ln hn 0,76% Ti. Nh vy, hon ton chc chn
rng s khc nhau quan st c 0,74% khng phi l hu qu ca sai s ngu nhin m do
s khc nhau tht s v thnh phn ca hai mu sn gy nn. Do chng ta cn rt ra kt
lun l, ngi li xe b nghi ng khng tham d vo trng hp bt hnh nu trn.
V d 2: Ngi ta phn tch hm lng ru trong ru vang t hai thng g ln
khng nh c phi chng chng c cng mt ngun gc. Hm lng etanol trung bnh trong
thng th nht bng 12,61% c xc nhn trn c s 6 php phn tch. Gi tr trung bnh t
4 php phn tch ru vang trong thng g th hai l 12,53% ru. Gi tr thng nht S i
vi 10 php phn tch bng 0,070%. Phi chng nhng s liu ch ra rng, ru vang hai
thng l khc nhau?
Trong trng hp ny chng ta s dng phng trnh (2.12), dng gi tr t i vi 8 bc
t do (10 2) xc sut tin cy bng 95%.
tS

n1 + n2
6+4
= 2,31 0,70
= 0,10%
n1n2
64

Hiu s quan st c bng:

x1 x2 = 12,61 12,53 = 0,08%

Nm trng hp trong s 100, hiu s 0,10% gy nn bi sai s ngu nhin. Do xc

sut tin cy y s khc nhau khng c xc nhn.
Trong v d cui cng, xc sut tin cy 95% khng pht hin c s khc nhau c ngha
ca nhng kt qu. Cn nhn xt rng, iu khng c ngha l x1 v x2 bng nhau. Cn
phi i hi c nhng bng chng khc v s ng nht ca ru vang hai thng. V thc
cht, hon ton c kh nng, mt l vang mt l vang trng.
xc nhn vi xc sut c th chp nhn c rng, c hai th vang u t cng mt v
ch mt ngun m thi i hi phi kim tra nhiu c tnh khc na nh v, mi, ch s khc
x, hm lng axit axetic, ng v vt cc nguyn t. Nu trong kt qu ca tt c cc c
tnh y v c nhng php th khc khng pht hin thy mt s khc nhau no c ngha th c
th khng nh rng c hai th vang c cng mt ngun gc chung. Ngc li, s pht hin d
ch l mt s khc nhau c ngha cng ch r rng hai th vang c ngun gc khc
nhau. Nh vy, s khng nh mt s khc nhau c ngha trong mt th nghim duy nht tr
thnh tiu biu hn nhiu so vi s khng nh khng c s khc nhau.

40

2.4.8 Loi tr s liu mang sai s th bo

Nu dy s liu cha kt qu vt ra ngoi, ngha l kt qu ny khc gi tr trung bnh
(hoc trung tuyn) tng i nhiu th cn phi quyt nh gi n hoc loi b. La chn tiu
chun loi tr kt qu ng nghi ng c kh khn ca n. Nu ly tiu chun cht ch
loi tr kt qu vt ra ngoi dy s gy kh khn cho vic vt b php o ng nghi ng,
lm cho nhng kt qu sai c th cn li trong dy, nh hng qu ng n gi tr trung bnh
ca dy. Mt khc, nhng i hi mm v lp li cng vi phng php khng cht ch v
loi tr nhng kt qu c th vt b th chng vn tn ti trong mu, ngha l a thm lch
vo dy s liu. ng tic l khng tn ti mt quy lut vn nng c th hng dn gii quyt
vn loi tr kt qu.
T nhiu tiu chun thng k c ngh, ngi ta yu thch tiu chun Q hn c.
Sp xp dy s liu thu c theo trt t, v d, tng dn v tnh Qtn (Q thc nghim) theo
cng thc:
Qtn =

xn xn 1
xmax xmin

trong : xn l gi tr nghi ng, xmax l gi tr ln nht, xmin l gi tr b nht trong dy kt

qu thu c, xn 1 l gi tr ln cn ca xn. Gi tr Qtc (Q tiu chun) xc sut tin cy 90%
c dn ra bng 2.9 so snh Qtn vi Qtc, nu Qtn > Qtc th s liu nghi ng b loi tr v
ngc li.
Bng 2.9 Gi tr chun ca tiu chun Qa
S quan st

Qtc (xc sut 90%)

0,94

0,76

0,64

0,56

S quan st

Qtc

0,51

0,47

0,44

10

0,41

Theo Dean R.B., Dixon W.J. Anal.Chem. 23, 636 (1951)

V d: Khi phn tch mu canxit thu c hm lng CaO (biu din bng phn trm):
55,95; 56,00; 56,04; 56,08; 56,23. Gi tr cui cng dng nh l bt thng. Nn gi hay
nn loi tr n?
Hiu s gia 56,23 v gi tr gn n l 56,08 bng 0,15%; xmax xmin ca mu (56,23
55,95) l 0,28%. Do :

41
Qtn =

0,15
= 0,54
0,28

i vi 5 ln o Qtc = 0,64. V 0,54 < 0,64 nn kt qu cn phi gi li.

Mc d tiu chun Q c u th so vi nhng tiu chun khc nhng vic ng dng n
cng cn phi thn trng. V d, thng xy ra tnh trng c phng sai ca mu, mt cch
ngu nhin, l i lng nh v s ng dng khng chun tiu chun Q dn ti s loi tr
nhng gi tr m thc cht cn phi gi li. S tht l nu trong mu c 3 gi tr m hai gi tr
ng nht th gi tr thc nghim Q tr thnh ln khng xc nh. Mt khc, khi s dng gi
tr ca bng tiu chun Q i vi mu nh nhng s liu sai lm c th vn c gi li.
S ng dng m mm nhng tiu chun thng k gii quyt vn loi tr nhng
php o ng nghi ng t mu nh tt hn mt cht so vi cch gii quyt tu tin. Phng
php trc gic da trn s nh gi lp li mong i, c bit l nu s nh gi da
trn s th ton din phng php phn tch, l phng php chn chn hn. Kt cc, s loi
tr kt qu thc nghim t mu nh cn phi da trn s tin cy chnh xc m bo, nu
khng s dn ti sai lm. Nu tin cy nh vy khng c, s loi tr kt qu cn phi thn
trng.
Chng ti xin trnh by mt s ngh x l mu nh cha kt qu khng th nh gi
c.
1. Kim tra cn thn tt c nhng s liu lin quan n kt qu ng nghi ng xem xt,
c phi chng cho sai s th bo xut hin kt qu ny. Qun l tt nht k phng th
nghim, ghi chp chi tit tt c mi quan st l iu rt c li.
2. Tu theo kh nng hy nh gi c bng chng xc ng v lp li mong i ca
phng php m bo l, kt qu ri ra ngoi qu tht ng b nghi ng.
3. Nu c thi gian v lng mu , hy lp li php phn tch. S tng ng mt ln
na kt qu thu c vi nhng kt qu dng nh l ng n s cng c thm d nh ca
bn v s loi tr kt qu ri ra ngoi. Hn na, kt qu nghi ng dng nh nh hng t
n gi tr trung bnh ca mu ln nu cui cng buc phi gi n.
4. Nu khng c kh nng thu c nhng s liu b sung hy ng dng tiu chun Q cho
mu v trn c s gii quyt vn v s loi tr kt qu nghi ng.
5. Nu theo tiu chun Q, kt qu cn c gi li th khi x l s liu hy s dng trung
v ch khng phi l s trung bnh. Trung v c tin cy ln bi v n gi c gi tr di ra
ngoi trong mu m khng th hin nh hng ng k n n. Ngoi ra, c th ch ra rng
trung v ca mu vi s phn b chun gm 3 php o cho s nh gi kt qu ng, tin cy
hn so vi gi tr trung bnh ca mu sau khi ty loi tr gi tr di ra ngoi.

42

2.1

S lan truyn sai s trn cc php tnh

Nh nghin cu thng nh gi sai s ca kt qu thu c qua php tnh vi hai hoc

mt s kt qu o ln hn m mi kt qu ny u mang theo sai s ca mnh. Phng php
cng cc sai s ring bit ph thuc vo cc php tnh s hc c thc hin vi cc i
lng c bao hm sai s v i lng c tnh ton ra. Ngoi ra nh hng ca sai s h
thng v sai s ngu nhin n i lng tnh ton c cng khc nhau.

2.7.2 Php cng sai s h thng

Phng php nh gi sai s h thng i vi tng hoc hiu khc vi phng php nh
gi chng i vi php nhn hoc chia.
2.5.1.1 Sai s ca tng hoc hiu
Chng ta xt mi quan h:
y=a+bc
y a,b v c l nhng gi tr ca ba i lng o c. Nu a, b v c l nhng sai
s h thng tuyt i gn lin vi nhng php o ca nhng i lng y. Nhng kt qu tht
ca nhng php o bng (a + a), (b + a) v (c + c). Sai s cng trong php xc nh Y khi
bng y v y + y = (a + a) + (b + b) (c + c).
Tr phng trnh th hai cho phng trnh th nht c th thu c sai s trong tnh ton
kt qu, ngha l:
y = a + b c

(2.13)

R rng l khi cng hoc tr, sai s tuyt i ca tng hoc hiu c xc nh bng sai
s tuyt i ca cc s hng.
V d: Hy tnh sai s khi tnh kt qu
+ 0,50 (+ 0,02)
+ 4,10 ( 0,03)
1,97 ( 0,05)
2,63
y s trong ngoc l sai s h thng tuyt i. Sai s ca tng:
y = 0,02 + ( 0,03) ( 0,05) = 0,04

43

2.5.1.2 Sai s nhn hoc chia

u tin chng ta xt php nhn
y = a.b
Mt ln na chng ta gi thit rng, y thu c do sai s h thng a v b. Nh vy:
y + y = (a + a)(b + b) = ab + ab + ba + ab
Tr phng trnh th hai cho phng trnh th nht ta thu c:
y = ba + ab + ab
By gi chia phng trnh ny cho phng trnh th nht, ta c:
y a b ab
=
+
+
y
a
b
ab

Thnh phn th 3 trong v phi ca phng trnh thng nh hn nhiu so vi hai thnh
phn khc bi v t s l tch ca hai s nh v mu s l tch ca hai s rt ln. V ab/ab
<< (a/b+ b/b), nn:
y a b
=
+
y
a
b

(2.14)

Ch l c ba thnh phn u l sai s h thng tng i ch khng phi l sai s tuyt

i nh khi tnh ton sai s ca tng hoc hiu.
Quan h tng t cng c th rt ra i vi sai s ca php chia:
y=

a
b

Khi :
y + y =

(a + a)
(b + b)

thu c kt qu c th vit hai phng trnh trn di dng:

yb = a
yb + by + yb + yb = a + a
T hai phng trnh cui cng ta thu c:

44

by + yb + yb = a
Sau khi chia cho yb = a v bin i ta thu c:
y a b yb
=

y
a
b
yb

Mt ln na chng ta chp nhn rng: (yb/yb) << (a/a b/b).

Khi :
y a b
=

y
a
b

i vi trng hp tng qut hn:

y=

ab
c

Bng cch l lun tng t c th ch ra rng:

y a b c
=
+

y
a
b
c

(2.15)

Nh vy, khi nhn hoc chia sai s tng i ca php nhn hoc chia c xc nh
bng sai s tng i ca cc thnh phn tham gia vo kt qu c tnh ton.
V d: Hy tnh kt qu ca nhng php tnh sau (trong ngoc l nhng gi tr sai s h
thng tuyt i):
y=

4,10( 0,02) 0,0050( +0,0001)

= 0,010406
1,97( 0,04)

Trong trng hp ny, trong tnh ton cn phi tnh sai s tng i. Nh vy:
y 0,02 0,0001 ( 0,04)
=
+

= 0,0049 + 0,020 + 0,020 = 0,035

y
4,10 0,0050
1,97

thu c sai s tuyt i y trong tnh ton y chng ta vit:

y = 0,035.y= 0,035. 0,010406 = 0,0004
y = 0,0104 (+ 0,0004)

45

2.7.2 Cng sai s ngu nhin

Nh chng ta nhn xt trc y, lch tiu chun tuyt i l phng php thun
li nht nh gi sai s ngu nhin ca nhng kt qu thc nghim. Khc vi sai s h
thng khng nn ghi du cho lch tiu chun bi v n c th dng hoc m vi xc sut
nh nhau, do lch tiu chun ca kt qu tnh c nm trong mt s vng.
V d, chng ta xt php cng:
+ 0,50 ( 0,02)
+ 4,10 ( 0,03)
1,97 ( 0,05)
2,63
(Cc s trong ngoc l lch tiu chun). Chng ta nhn xt rng nu hai sai s u l
dng v sai s th ba l m th lch tiu chun ca kt qu phi l:
sy = + 0,02 + 0,03 ( 0,05) = 0,10
Mt khc, trong nhng tnh hung bt ng sai s tng cng c th bng khng. Kt qu s
nh th nu 3 i lng u dng:
sy = + 0,02 + 0,03 (+0,05) = 0,00
Trong bt k trng hp no cng khng nn chp nhn mt t hp bt k ca lch
dn ti mt gi tr no gia cc cc tr lm sai s.
Thng k ch r rng gi tr tt hn hoc ng tin cy hn ca lch tiu chun tuyt
i, sy, ca tng hoc hiu c xc nh bng phng trnh:
s y = sa2 + s2b + s2c + ...

(2.16)

y sa; sb; sc ... l lch tiu chun tuyt i ca nhng s tham gia vo tng hoc
hiu. Chng ta nhn thy rng tn mn tuyt i ca kt qu l tng tn mn tuyt i
thnh phn. Cng c th vit phng trnh (2.16) di dng:
s2y = sa2 + s2b + s2c

Nh vy l khi nhn v chia, lch tiu chun tng i c t hp li. V d, nhn

c lch tiu chun i vi y trong t s:
y=

ab
c

46
2

s s s
= a + b + c
y
a b c

sy

c th vit:

(2.17)

V d: Hy tnh lch tiu chun ca tng dn ra trong v d xt trn. V tnh ton

tng, lch tiu chun tuyt i c t hp li:
s y = ( 0,02)2 + ( 0,03)2 + ( 0,05)2 = 0,06

T :

y = 2,63 ( 0,06)

Trong trng hp ny xc sut tng i nh hn so vi sai s cc i:

(0,02 + 0,03 0,05 = 0,00)
V d: Hy tnh lch tiu chun xc sut i vi kt qu ca php tnh:
y=

(4,10 0,02)(0,0050 0,0001)

= 0,01041 ?
1,97 0,04

Trong trng hp ny chng ta cn phi s dng lch tiu chun tng i. nh vy:

(sy )td =

0,02 0,0001 0,04

2
2
2
4,10 + 0,0050 + 1,97 = (0,0049) + (0,020) + (0,020) = 0,029

lch tiu chun tuyt i c din t nh sau:

sy = y.(sy)td = 0,0104.0,029 = 0,0003
Do :

y = 0,0104 ( 0,0003)

V d: Hy tnh lch tiu chun kt qu ca php tnh:

y=

[14,3( 0,02) 11,6( 0,2)] 50( 0,16) = 3,191 ?

42,3( 0,4)

Ban u cn tnh lch tiu chun i vi hiu t s:

s1 = ( 0,2)2 + ( 0,2)2 = 0,28

Sau phng trnh c vit li thnh:

y=

2,7( 0,28) 50,0( 0,1)

= 3,191
42,3( 0,4)

Tip chng ta tnh lch tiu chun tng i ca thng s:

47
2

0,28
0,1
0,4
2,7 + 50,0 + 42,3 = 0,10

(sy )td =

lch tiu chun tuyt i ca kt qu:

sy = 3,191.0,10 = 0,32
y = 3,2 ( 0,3)
Rt l th nhn xt rng, trong giai on tnh t s, sai s tng.

2.7.2 S lan truyn sai s php tnh lu tha

thy r, sai s trong trng hp khi cn phi nng ly tha gi tr ca kt qu thc
nghim hoc khai cn n th sai s lan truyn nh th no, chng ta xt:
y = ax
y x l ch s lu tha hoc cn s, s khng cha sai s.
Ly vi phn phng trnh :
dy = xa(x1)da
Chia cho phng trnh xut pht ta c:
dy xa(x 1)da
=
y
ax

nhng:
a(x 1)
a

1
a

do :
dy xda
=
y
a

hoc l i vi lng tng hu hn :

y
a
=x
y
a

(2.18)

48

y y l sai s tuyt i ca php xc nh y, sinh ra do sai s a trong php

xc nh a. R rng l, sai s tng i y/y ca kt qu tnh ton l sai s tng i ca gi
tr thc nghim a/a nhn vi ch s lu tha, x. V d, sai s tng i ca s bnh phng
hai ln ln hn sai s ca php xc nh chnh s , cn sai s tng i ca mt s nm
di du cn bc 3 bng mt phn ba sai s ca php xc nh s .
iu quan trng cn ch l, quy lut lan truyn sai s ngu nhin khi tng ch s bng
lu tha khc vi quy lut lan truyn sai s khi nhn bi v trong trng hp khng tn ti
kh nng gin c tng h. Chng ta nh li rng, lch tiu chun ca hai s v c th
tnh gi tr xc sut bng cch ly cn bc hai ca tng bnh phng sai s chng ta p dng
phng php cho php nhn mt s vi chnh n (a.a). y du tt nhin l ng nht
bi v chnh nhng i lng ny l ng nht. Do sai s tng i ca php xc nh a2
phi bng hai ln sai s xc nh a. Phng trnh (2.18) cng c dng tnh sai s ngu
nhin; khi ta thay th y v a bng sy v sa.
V d 1: lch tiu chun khi o ng knh d ca qu cu bng 0,2 cm. lch tiu
chun bng bao nhiu khi tnh th tch qu cu, nu d = 10,0 cm?
3

V=

4 10
= 523, 6 cm3
3 2

C th vit:
s

= 0,06
(sy )td = Vy = 3sdd = 3 0,2
10

Vy lch tiu chun tuyt i ca th tch:

sy = 523,6.0,06 = 31
Do :
V = 524 ( 31) cm3 = 5,2( 0,1).102 cm3
V d 2: Tch s tan (T) ca mui bc AgX bng 4,0 ( 0,4).108.
Sai s tnh ton tan AgX trong nc bng bao nhiu?
Trong trng hp ny (xem chng 3):
tan = (4,0.108)1/2 = 2,0.104.

(sx )td =

0,4 108
4,0 108

49
= 0,05
(sy )td = 12 0,4
4,0

sy = 2,0.104.0,05 = 0,1.104
tan = 2,0 ( 0,1).104 g/l

2.7.2 S lan truyn sai s php LOGARIT v ANTI LOGARIT

thy r sai s php tnh LOGARIT v ANTI LOGARIT c lan truyn nh th
no chng ta ly vi phn phng trnh:
y = loga = 0,434.lna
y ln l logarit t nhin. Nh vy:
dy = 0,434

da
a

Chuyn sang gia lng hu hn, ta c:

y = 0,434

a
a

(2.19)

Ch l, sai s tuyt i ca i lng y c xc nh bng sai s tng i ca i

lng a v ngc li. Cng nh trc y, c th s dng phng trnh (2.19) sau khi thay
th a/a bng lch tiu chun tng i cn y bng lch tiu chun tuyt i ca i
lng y.
V d: Hy tnh lch tiu chun tuyt i cc kt qu ca cc php tnh sau. lch
tiu chun tuyt i i vi mi i lng c cho trong ngoc.
a) y = log[2,00( 0,02).103] = 2,6990 ?
b) a = antlog[1,200 (0,003)] = 15,849 ?
c) a = antlog[45,4 ( 0,3)] = 2,5119.1045 ?
Gii:
a) Theo phng trnh (2.19) chng ta thy rng cn nhn lch tiu chun tng i vi
0,434, ngha l:
y = 0,434

0,02.103
2,00.103

= 0,004 = s y

50

Nh vy:
log[2,00 ( 0,002).103] = 2,699 0,004
b) Bin i phng trnh (2.19) v thay th a v y bng lch tiu chun tng ng:
sy
sa
0,003
=
=
= 0,0069
a 0,434
0,434

sa = 0,0069.a = 0,0069.15,849 = 0,11

Nh vy:
antlog[1,200 ( 0,002)] = 15,8 0,1
c)
sa
0,3
=
= 0,69
a 0,434

sa = 0,69.a = 0,69.2,5119.1045 = 1,7.1045

Do :
antlog[45,4 ( 0,3)] = 2,5 ( 1,7).1045
Cn ch n gi tr ln ca sai s tuyt i trong antilogarit ca s c lng nh s
sau du phy. Sai s ln trong trng hp ny c gii thch l s bn tri du phy (phn
c tnh) ch dng ch ch ca du phy. Trong v d cui cng, sai s ln trong
antilogarit l h qu ca sai s ln trong phn nh tr ca s (ngha l 0,4 0,3).

2.2

iu kin c ngha ca ch s

Trong bo co v php o, nh thc nghim khng nhng cn a ra s liu m h cho l

tt nht, c th l s trung bnh hoc trung v, m cn cn a ra c s nh gi v tin cy
ca n. V tin cy, tt nht l, din t bng lch tiu chun ca kt qu. i khi c th
gp c lch khi gi tr trung bnh, lch khi trung v hoc l bin dao ng bi v
nhng thng s ny ca lp li d tnh hn. S lm trn kt qu thc nghim cng l quy
lut tng qut, nh vy chnh xc l ch cn li nhng gi tr bit, nhng trong mi gi tr
cn c mt ch s ng nghi ng. Quy lut c hiu nh l iu kin c ngha ca
ch s.
V d, gi tr trung bnh ca cc gi tr thc nghim 61,60; 61,46; 61,55; 61,61 bng
61,555. lch tiu chun ca tng l 0,0069. R rng l, s th hai sau du phy trong
phn thp phn l ang nghi ng. Trong trng hp ny ghi tt c cc ch s lin tip khng
c ngha nn chng ta phi lm trn mt cch tng ng s trung bnh. Cn phi bn vn

51

, ly gi tr 61,55 hay 61,56 bi v gi tr 61,555 va ng nm gia chng. C mt quy

lut c ch: lm trn s 5 lun lun dn ti s chn gn nht. Khi xu hng lm trn theo
hng nh trc b loi tr bi v trong tnh hung cho, s chn gn nht s c gi tr ln
hn hoc nh hn c xc sut nh nhau. Nh vy c th cho gi tr s b: 61,56 0,07.
S nh gi tin cy ca lp li. Nu c c s nghi ng 0,07, th c th a ra
kt qu di dng 61,6 0,1
Thng iu kin c ngha ca ch s lm bin i s nh gi c bit i vi lp li
ca kt qu. Trong v d nu trn, kt qu bng 61,6; v thc cht chng ta ni rng, chng ta
bo m cc ch s 6 v 1 nhng gi tr s 6 th hai cn ng nghi ng. Nhng thiu st ca
phng php l hin nhin. Tt nhin c gi c th ngh rng, khong sai s nm t
0,05 n 0,5
Khi s dng iu kin c ngha ca ch s, iu quan trng cn hiu l, s 0 khng ch c
chc nng nh mt ch s m cn c dng ch v tr ca du phy trong nhng s rt
nh v rt ln. C th dng s Avogadro lm v d. Ba s u tin 6, 0 v 2 c bit mt
cch tin cy. Nhng ch s tip theo ng nghi ng nhng c th hn c, l s 3. Bi v
nhng ch s tip sau 6023, khng bit, sau s 3 chng ta t 19 s 0. y nhng s khng
ch ch r trt t ca s thi ch khng c ngha khc. R rng l, cn phn bit nhng ch s
c ngha vt l (ngha l nhng ch s c ngha) v nhng ch s hoc khng bit hoc khng
c ngha do php o khng ng tin cy.
Nhng ch s 0 lin st vi cc ch s ng bn tri cng c th c ngha v khng c
ngha. V d, trng lng ca qu cn l 20 mg, khng cn phi b chnh n phn mi
miligam, c bit vi chnh xc n ba ch s c ngha l 20,0. Nu trng lng c
biu din l 0,0200 g th s ch s c ngha khng thay i. Nu chng ta mun din t th
tch cc hai lt di dng 2000 ml th s ch c mt ch s c ngha. Nhng con s 0 ch
ch r th t ca ch s. Nhng c th xy ra trng hp, th tch ca cc c xc nh bng
thc nghim bng 2,0 l. Trong trng hp ny s 0 sau du phy c ngha v ch r l th tch
c bit vi chnh xc t nht l 0,5 l v cng c th l 0,05 l. Nu nh th tch
c din t bng mililit, s 0 ng sau s 2 l c ngha cn hai s 0 khc khng c ngha. S
thc hin php ghi di dng lu tha loi b c kh khn . Khi chng ta c th din t
th tch di dng 2,0.103 ml.
T nhng iu kin trnh by trn ta thy, s thn trng khi xc nh s ch s c ngha
ca kt qu thu c qua mt php tnh s hc vi hai hoc mt s ln hn s hng m. Khi
cng hoc tr, s ch s c ngha c th xc nh ngay. V d:
3,4 + 0,02 + 1,31 = 4,73
R rng l ch s th hai sau du phy khng c ngha, do sai s tng qut c xc
nh bng sai s s l th nht sau du phy trong s hng 3,4.
Khi nhn hoc chia cc s liu ngi ta thng chp nhn quy tc ly s ch s c ngha
ca kt qu bng s ch s c ngha ca i lng cha s ch s c ngha nh nht. V d:

52
24 0,452
= 0,108 = 0,11
100,0

Trong trng hp ny, s 24 c hai ch s c ngha v kt qu c lm trn tng

ng vi s ny. ng tic quy lut nu trn khng phi lun lun ng dng c. Chng ta
gi thit rng, sai s ca s 24 c th nh, v d l 0,5 hoc ln hn, v d l 5. Sai s ca
php chia i vi gii hn yc xc nh nh sau:
Sai s tuyt i
Sai
gi thit ca s 24
tng i
> 0,5
<5

0,5/24
0,02
5/24 = 0,2

s
=

Sai s tuyt i
ca s 0,108

Lm trn

0,108.0,02 = 0,002

0,108

0,108.0,2 =0,02

0,11

Cn phi thn trng c bit khi lm trn logarit v antilogarit n s c ngha thch hp.
Chng ta ch ti v d dn ra trn v s lan truyn sai s php tnh logarit v
antilogarit; s lm trn tng ng ca i lng log2,00.103 dn ti kt qu 2,699. Th ra
php tnh lm tng ch s c ngha. Nhng thc cht ch s th ba xut pht t kt qu ch
ch r v tr ca du phy trong s xut pht. Thng tin v s 2,00 cho 3 ch s: 0,699. Nh
vy c s tng ng gia s ch s c ngha ca phn ca kt qu v ch s xut pht.
Nh ch r trong v d c dn ra mc 2.5.4 khi tnh antilogarit, c s gim s ch
s c ngha. Nguyn nhn ca hin tng dng nh d thng nm trong chc nng ca
phn c tnh ca logarit.

2.3

Bo him cht lng (QA) v biu kim tra

Khi s dng nhng phng php phn tch gii quyt nhng vn phc tp ca thc
t th cht lng ca nhng kt qu thu c bng nhng phng php ny cng nh ca
nhng dng c v thit b c s dng hon thnh cc php o cn phi c nh gi
lin tc. Chng ta thng gp 3 thut ng trong bn lun v cht lng ca php o: bo him
cht lng, kim tra cht lng v nh gi cht lng. Ba thut ng ny c Taylor nh
ngha trong bi vit ca mnh v ti cht lng ca php o nh sau:
Bo him cht lng (QA): Nhng hot ng ca mt h thng t chc nhm mc ch
chuyn n cho nh sn xut hoc ngi tiu dng mt sn phm hoc mt dch v quyn
c bo him.
Kim tra cht lng (QC): Nhng hot ng ca mt h thng t chc nhm kim tra
cht lng mt sn phm hoc mt dch v theo yu cu ca ngi tiu dng. C th l lm
h mn nguyn mt cch y v ng tin cy.

53

nh gi cht lng: Nhng hot ng ca mt h thng t chc m bo rng cng

vic kim tra c thc hin c hiu qu. Cng vic khng nh s nh gi tip theo l
nhng sn phm c sn xut v s thc hin ca c s sn xut c chp nhn.

2.7.2 S cn thit ca bo him cht lng

o c cc ch tiu ho hc l phc v cuc sng vn rt a dng ca loi ngi v c
gng thc hin nhng nhim v bc thit nh ngn nga v x l mt s bnh tt, bo v mi
trng, bo m an ton cho sn xut v s lu thng nhng vt liu c ch, ng thi thc
thi mt s ln cc nghin cu khoa hc. Nhng s liu v cc ch tiu ho hc phi ng tin
cy v cng phi l bng chng hin nhin v s tn ti ca chng. Nhng nghin cu v
bo him cht lng hon ton khng nh nhng s liu .
C hai cch nh gi cht lng:
Cch th nht l s nh gi ng v chnh xc ca phng php o.
Cch th hai l xem xt cht lng mt sn phm c sn xut mt cch ph bin.
Sau y l v d cho mi loi:
Mt v d v s cn thit phi bo him cht lng phng php o. Cng vic c bt
u bng vic kim tra cc s liu o cc thit b ca bnh vin cung cp xc nh s hiu
ca mu. Cc thit b phi c chun ho cng tn s vi cc mu chun m bo rng
nhng kt qu thu c c ng tin cy v chnh xc hon ton cho bnh vin.
Nu phng php o khng ng v khng chnh xc s dn ti chn on sai, khng
thch hp cho s chm sc bnh nhn hoc thm ch b t vong. l nhng sn phm kt thc
ca phng th nghim, l thc o chnh h.
Mt v d khc v s cn thit phi bo him cht lng: bn v php xc nh florua
trong thuc nh rng. C t nht 3 l do gii thch v sao phi o cn thn v kim tra hm
lng florua trong thuc nh rng; hn na kim tra l cng vic quan trng. u tin l
florua c nng cao nn chnh ph phi iu chnh. Thm vo , tnh hiu qu ca sn
phm thng ph thuc vo s duy tr mt khong nng xc nh ca hp phn c hot
tnh. Nu hm lng florua trong thuc nh rng qu nh th c th khng bo v rng trnh
su c hiu qu. Nu tha nhiu florua s b thi ra ngoi v trong trng hp tha mc
cao, florua s tr thnh nguy him. Cui cng, cng thc c hiu qu c th tr thnh bng
pht minh ca mt nh sn xut hoc cng c th l ca mt ngi trong s nhng ngi
ang cnh tranh nhau. Nu cng thc l bng pht minh ca mt ngi th cng ty ca ngi
mun gi hon ton b mt nng florua, sao cho nng ny khng nm trong cc dy
ca bng pht minh. Nu mt c s sn xut ang nm gi bng pht minh, h c th mong
mun phn tch nhiu mu sn phm ca nhng i th cnh tranh m bo khng c s
xm phm bng pht minh.
nh gi cht lng ngi ta thng s dng biu kim tra. Chng ta cp n
hai v d in hnh, trong cng c thng k c s dng.

54

2.7.2 ng dng biu kim tra

Biu kim tra l th din t s bin i lin tc theo thi gian hoc trong a im
ca mt tiu chun cht lng no c trng v quan trng trong bo him cht lng.
Biu cn ch r gii hn thng k ca dao ng, l s chp nhn i vi mt php o
c th c thc hin.
Biu kim tra gim st chc nng thc hin ca mt thit b phn tch
Trong v d u tin v nh gi cht lng, chng ta s bn v vn , lm th no c
th gim st chc nng thc hin ca mt thit b phn tch rt c s - mt ci cn phn tch.
C th gim st c ng v chnh xc ca cn bng php xc nh nh k trng lng
ca mt mu chun. Sau l nhng php o trong nhng ngy lin tc trong gii hn xc
nh ca mt trng lng mu chun. Nhng gii hn ny c gi l gii hn kim tra trn
(GKT) v gii hn kim tra di (GKD). Chng c nh ngha nh sau:
GKT = +
GKD =

3
N
3
N

l gi tr trung bnh ca php o trng lng a, l lch chun ca php o, N l s

kt qu thu c ca mi mu. Gi tr trung bnh v lch chun ca mt trng lng chun
cn phi c xc nh ngay t nhng nghin cu ban u.
Ngoi lch chun ni trn, cn ghi ch thm rng, GKT v GKD cng l lch
chun trn mt kha cnh khc ca gi tr trung bnh, chng to thnh mt hnh lang thch hp
m trng lng a o c, hy vng nm trong khun kh ti 99,7% thi gian.

55

Hnh 2.5. Biu kim tra mt cn phn tch hin i

Hnh 2.5 l biu kim tra in hnh i vi mt cn phn tch. xy dng biu
ny, chng ti tp trung nhng s liu v trng lng o trong 20 ngy lin tc mt trng
lng chun 20,000 g do Vin Tiu chun v K thut Quc gia cung cp. thu c cc s
liu, cn c a v gi tr 0, trng lng chun c t trn a cn v trng
lng c xc nh. Ton b qu trnh c lp li 4 ln v mi ngy o li 5 ln. T
nhng thc nghim c lp, ngi ta xc nh c gi tr trung bnh = 20,000 g v
lch chun = 0,00012 g, gi tr trung bnh ca nm php o l 3.0,00012 5 = 0,00016 nn
GKT = 20,00016 g v GKD = 19,99984 g. Vi nhng gi tr v gi tr trung bnh trng
lng ca mi ngy chng ta xy dng c biu kim tra c dn ra trn hnh 2.5.
Ghi ch, gi tr trung bnh trng lng ca mi ngy c din t trn th bng mt
chm en. Theo cch , bt k mt xu hng c tnh cht h thng no trong cc php o
cng c th d dng pht hin. V trung bnh trng lng ca mu gia GKD v GKT nn cn
phn tch c coi l qua kim tra thng k. Khi gi tr trung bnh mu nm ngoi gii hn
nh xy ra trong ngy th 17, cn phn tch c coi l khng qua c kim tra. Khi mt
thit b hoc mt h thng thit b khng qua c kim tra, lc chng ta s phi c gng
tm ra nguyn nhn cho tnh hung . V d nh, trong trng hp ca ngy th 17, cn
c pht hin l khng c sch do a cn b bn v cc bc s phi thc hin m
bo s vic s khng ti din. Nhng lch c h thng do gi tr trung bnh s c pht
hin tng i d dng trn biu kim tra trong v d tip theo.
Biu kim tra nh gi cht lng mt dc phm
Nh ni trn y, c th dng biu kim tra kt hp vi k thut phn tch kim
tra qu trnh sn xut. C mt v d rt hay v cch lm ny, c v vic k n v mt loi
thuc c tr cha benzoyl peoxit c dng iu tr mn mt v da. Benzoyl peoxit l
mt loi thuc st trng c ch dn l c hiu qu cho da khi s dng dng kem hay
dng thuc m cha 10% thnh phn hot tnh. V mi loi thuc u c c quan qun l
thc phm v thuc iu chnh nn nng ca benzoyl peoxit cn phi c kim tra v xc
nhn theo kim tra thng k. Benzoyl peoxit l mt cht oxi ha nn c th ho hp vi mt
lng d ioua sinh ra iot. Sau iot sinh ra c chun bng dung dch natri tiosunfat
chun thc hin php o benzoyl peoxit trong mu.
Biu kim tra trn hnh 2.6 ch r, nhng kt qu phn tch 89 sn phm thng qua
nhng php o kem cha 10% benzoyl peoxit danh nh trong nhng ngy lin tip. Mi mu
l mt i din tng trng bng gi tr trung bnh phn trm benzoyl peoxit khc nhau ca
kem thu c t nhng iu kin rt c th d thc hin.

56

Hnh 2.6
S dng biu kim tra gim st nng benzoyl peoxit trong pha ch thuc chng mn da bn
th trng

Biu kim tra cho bit, cho n ngy th 83, qua kim tra thng k vi s thay i
ngu nhin bnh thng v lng benzoyl peoxit, ngha l nm trong vng gia GKD v
GKT. Trc ngy th 83 ch c kt qu ca ngy th 26 lch khi gi tr trung bnh nng
9,94% v tin st ti gii hn kim tra vi s tng h thng t bin cao hn gii hn kim tra
trn. S tng l do iu kin c th ca sn xut gy nn, ch b loi tr khi nguyn nhn
c pht hin v t chc sa sai. Mu ny gn b vi v d v cn phn tch ni trn y,
ch r, s dng biu kim tra thun li ra sao v nhng bin php hu hiu c thc hin
bo him cht lng nhng s liu nhng tnh hung khc nhau.
Nhng v d ny tp trung xc nh ng ca thit b v nhng qu trnh dn ti t
tiu chun. Cng c th s dng biu kim tra gim st chnh xc. Hy c thm
nhng v d b sung v phng php lun bo him cht lng trong sch ca Taylor v ti
liu tham kho trong *.

K.Taylor, Quality Assurance of Chemical Measurements. Chelsea, MI: Lewis,1987.

57

Chng 3
Cc phn ng ha hc trong ha hc phn tch
Cc phn ng ho hc c s dng nhiu trong ho hc phn tch: trong cc phng
php phn tch ho hc c in, trong cc phng php phn tch ho hc v phn tch cng
c hin i, trong cc phng php tch, trong cc php o.
Ha hc ca cc phn ng l c s l thuyt cho s pht trin cc phng php phn
tch cng c v ho hc hin i. V vy, cn phi c bit ch bn lun v cc phn ng
ny.
Mt phn ng ho hc mun c s dng trong ho phn tch trc ht cn phi tho
mn hai iu kin sau:
1. Phn ng phi xy ra hon ton.
2. Tc phn ng phi nhanh.

hon ton ca phn ng

Ni mt cch cht ch th khng c phn ng ho hc no xy ra hon ton, k c phn
ng d th. Phn ng no cng ch t ti trng thi cn bng nhng iu kin c th cho
trc. Chng ta bn v hon ton ca phn ng ho hc trng thi cn bng. Nng lng
Gibbs (nng lng Helmholtz - E) din t trng thi cn bng ca phn ng ng p bng biu
thc nhit ng hc. Nng lng Gibbs l tng cc ho th i = G/ni ca cc cht i tham gia
vo phn ng.
G =

n i i

(3.1)

ni : s mol ca cht i.
i lng Go = n i oi din t entalpi t do chun bng cng c ch chun. Ch s ph
thuc ca ho th vo hot , i vi trng thi cn bng chng ta c:
Go = RTni.lnai = RT.lnK

(3.2)

T phng trnh trn, ch s hng s cn bng ca phn ng, pK, c s dng nh tiu
chun trc tip cho trng thi cn bng.

58
pK = l o g K =

M
Go ;(M = log e)
RT

(3.3)

Trng thi cn bng ca phn ng:

nAA + nBB

nCC + nDD

(3.4)

c biu din bng phng trnh:

pK a = lo g

a cnC a d n D
a A n A a Bn B

(3.5)

Hng s nhit ng ca cn bng Ka hoc ch s cn bng tng ng pKa, nhit nht

nh, khng ph thuc vo nng v in tch ca cc ht c c trng bng trng thi
khng xy ra s bin i hu hiu no i vi thnh phn ca h .
V hot a l i lng tng i nn cn phi xc lp trng thi chun i vi chng.
Cc cht rn hoc cht lng tinh khit mt cch gn ng, c hot khng i c coi nh
bng n v. Ngi ta chp nhn hot ca cht tinh khit bng n v c khi mt phn ca
cht ho tan. Mt cch tng t, c th chp nhn hot ca dung mi trong dung dch
long bng n v. Hot ca cc cht tan c chun ho theo nng mol/l tng ng
vi h thc:
a
=1
lim
c0 c

(3.6)

Nu nng chung c ca tt c cc cht tan tin ti khng th h s hot f =

a
t ti
c

gi tr gii hn, bng n v v hot bng nng phn t a = c. Cc cht tan dng phn
t tng tc yu vi cc ht khc trong h d mang hoc khng mang in tch. Nu nng
ca chng khng qu cao, ngi ta chp nhn f = 1 trong tnh ton. Mt cch tng t, hot
ca cht kh xp x p xut ring phn p ca n. Nu p sut chung ca hn hp kh tin
ti khng thng c th xem a = p.
Khng c kh nng xem xt ring bit h s hot ca anion (f) v cation (f+) nn
ngi ta s dng hot trung bnh (f). i vi cht in li loi AmBn, gi tr f c tnh
theo cng thc sau:
f =

m +n m

fn

(3.7)

H s hot ca cc ion l hm s ca cc cht in li tn ti trong dung dch nn c th

tnh nh hng tng hp ca chng theo phng trnh lc ion ca dung dch:
=

1
Z2ici
2

(3.8)

59

Zi v ci l in tch v nng tng ng ca ion i.

Trong dung dch nc c < 0,01 20oC, c th tnh h s hot theo cng thc
Debye Huckel:
log fi = 0,5Z2i

(3.9)

lc ion cao hn, cc cht in li khc nhau biu din nhng sai lch c bit. = 0,1
c th xc nh h s hot tin cy theo cng thc:
lo g fi = 0,5Z2i

(3.10)

1+

Thay a = fc vo phng trnh (3.5) din t trng thi cn bng ta c:

pK a = l o g

CcnC Cd nD
CA n A CBnB

log

fcnC fd nD

(3.11)

fA n A fBnB

Ch s cn bng nng :
pK c = log

CcnC Cdn D

(3.12)

CA n A CBnB

Ngay c gi tr lc ion tng i thp cng c th khc pKa ng k. Do cn phi

lun lun kim tra xem gi tr ch s hng s cn bng tnh ton c b gim xung bao
nhiu khi thay th hot bng nng phn t. Khi nA = nB = nC = nD = 1, t cc phng
trnh (3.10) v (3.11) ta c :
pK c = pK a + 0,5(Z A 2 + ZB2 ZC2 ZD2 )

1+

(3.13)

Nu phng trnh (3.10) l ng n th hng bin i ca pKc do lc ion gy nn ph

thuc vo tng bnh phng in tch cc ion c hai phn ca phng trnh phn ng.
Gi tr pK c s dng kh thun tin nh gi trng thi cn bng trong h phn ng
lin tip. Chiu ca phn ng do du ca ch s hng s cn bng quyt nh. Ch s hng s
cn bng ca phn ng thun bng gi tr m ca ch s hng s cn bng ca phn ng nghch.
Ch s hng s cn bng t hp ca nhng phn ng lin tip (pKTH) l tng cc ch s hng s
cn bng ca nhng thnh phn.
pKTH = niKi

(3.14)

V tr cn bng ph thuc vo nhit . i vi phn ng ng p, phng trnh Vant

Hoff c nghim ng.

60

ln K a
H
=
T
RT2

(3.15)

Theo nguyn l Le Chatelier, ch s hng s cn bng tng hoc gim tu thuc vo du

ca entalpi (Ho) phn ng. i vi cc tnh ton gn ng pK trong mt khong hp nhit
, c th b qua s ph thuc ca entalpi phn ng vo nhit v s dng phng trnh
tch phn:
pK1 pK 2 =

1
H 1

4,573 T2 T1

(3.16)

Trong ch mt gi tr H ng nht c dng cho c khong nhit t T1 n T2.

Nu cn thit phi xc nh ch s hng s cn bng cho c khong ln nhit cn phi k
n s ph thuc ca H vo nhit . Xut pht t phng trnh c bn v nng lng
Gibbs suy ra t im gc th nht n th hai ca nhit ng hc.
G = H TS

(3.17)

v phng trnh Gibbs - Helmholtz:

G

= S
T p

(3.18)

Ngi ta tm ra nhiu phng php tnh H. R rng l, c entalpi v entropi cng th

hin nh hng ca mnh trn s ph thuc ca pK vo nhit . tnh ton nng cn
bng cc cht trong ho phn tch chng ta ch cn s dng K cn bng (xem tip chng IV).

Nhng yu cu c th v hon ton ca mt phn ng phn tch nh

lng
Sau y l nhng yu cu i vi mt phn ng phn tch nh lng:
1. Phn ng phi hp thc. Nu ngc li s khng c c s tnh ton lng cht sinh
ra trong phn ng.
2. Phn ng phi xy ra nhanh. Nu khng nhanh, thi gian cn thit hon thnh
php phn tch s qu di. Tnh cht c bit quan trng trong cc quy trnh chun ,
bi v phn ng phi hon ton sau mi ln thm cht chun.
3. Phn ng phi nh lng. Ngha l phn ng phi t hon ton t nht l 99,9%.
4. C mt phng php thch hp theo di s tin trin ca phn ng hoc xc nh
khi no phn ng hon thnh.
Chng ta s bn v quy trnh nh lng 1,3-butaien bng cch brom ho lm v d:

61

H2C = CHCH = CH2 + Br H2BrC CH = CHCH2Br + H2BrCCBrHCH = CH2

Phn ng sinh ra 2 sn phm brom ho khc nhau. T s theo lng ca hai sn phm c
th bin i tu thuc vo mi trng thc nghim nhng t s 1 : 1 ca
1,3-butaien
v Br2 c s dng trong phn ng lun l mt hng s. Do c th tnh lng butaien
trong mu.
Mt phn ng xy ra vi t l phn ng c nh v lp li nhng vi sn phm to thnh
l mt hn hp hoc khng hp thc th khng th dng c cho phn tch nh lng. Mc
d mt vi sn phm do kinh nghim m c c s dng thnh cng trong phn tch nh
lng nhng iu ch xy ra khi nhng iu kin thc nghim c kim tra nghim ngt.
V vy, ch nhng phn ng hp thc mi c u tin la chn cho mc ch la chn cc
cht.
Ni chung, mt phn ng ch xy ra hon ton khi cc sn phm sau y c to thnh:
1. To thnh cc phn t t phn li;

2. To thnh kt ta;

3. To thnh phc vng cng;

4. To thnh kh.

Tc phn ng
Khng phi tt c cc phn ng u t ti im cn bng sau cng mt thi gian, ngha
l cng vi mt tc . Tc phn ng l c trng nh lng quan
trng ca n. Cc
phn ng khc nhau din ra vi tc khc nhau. C phn ng nhanh ti mc gn nh tc
khc, th d phn ng phn hu cht n c th kt thc trong 105 giy. Mt s phn ng ion
trong dung dch cng thuc loi v c th cn nhanh hn, th d phn ng in li ca nc
v phn ng ti hp cc ion H+ v OH thnh nc.
Nhiu phn ng khc ko di hng pht, hng gi, hng ngy. a s phn ng hu c
thng chm, c th ko di hng tun, hng thng. Nhng qu trnh trong v qu t c th
ko di hng vn, hng triu nm .
Khng phi ch tc ca cc phn ng khc nhau mi khc nhau nhiu m tc ca
mt phn ng bt k cng c th thay i rt nhiu tu theo ta xt phn ng giai on no.
Nhiu phn ng ng th vi nhng phn t thng thng c tc phn ng gim dn
theo thi gian, cng v cui phn ng cng chm li. Cc phn ng ion trong dung dch cng
tng t .
S nh gi nh lng trng thi cn bng qua Kc cho php bit c phn ng ho hc,
v nguyn tc c c xy ra hay khng nhng s nh gi khng cho mt thng tin no v
tc t ti cn bng. Cng khng cho bit nhng qu trnh nhit ng no s xut hin.

62

Khi nh gi kh nng xy ra phn ng cng nh khi m t trng thi cn bng

hot (ch khng phi l nng phn t) mi c ngha quyt nh. Nu h l tp hp cc
phn t th trong phn ln cc trng hp ngi ta chp nhn a c.
Khi b qua nh hng ca hot th tc phn ng V = dc/dt xy ra thc t v mt
hng v c th din t bng s bin i nng ca mi cht tham gia phn ng.
V=

1 dCi
1 dC j
=
n i dt
n j dt

(3.19)

trong : i l cht tham gia vo phn ng thun; j l cht tham gia vo phn ng nghch; n
l h s hp thc.
Nu phn ng ch xy ra mt phn v gi tr pK ri vo vng +3... 3 th cn phi k ti
phn ng nghch. Mi quan h gia tc phn ng vi hot hoc nng phn t ca
cc cht tham gia phn ng c biu th qua bc phn ng. Tc phn ng xy ra theo
phng trnh (3.4) bng:

dCA
= k CA n A CBnB k ' CCnC CDnD
dt

(3.20)

Nu nng ban u ca cc cht phn ng bng nhau th tc phn ng xy ra t tri

sang phi c xc nh bng phng trnh sau:

dCA
= k CA n
dt

trong tng cc ch s m n = nA + nB l bc phn ng.

Phn ng bc 1, bc 2 thng gp nht, phn ng bc 3 rt t gp. Tc phn ng bc
khng khng ph thuc vo nng cc cht phn ng.
Phn ln cc phn ng xy ra theo tng nc. Quy lut thc nghim v bc phn ng t n
khng cho ta mt thng tin no v c ch phn ng .
Khc vi tc phn ng, tnh phn t ca phn ng m t s xy ra thc s ca nhng
phn ng (ring bit) n l hoc c bn mc phn t v ch r s ht tham gia vo mt va
chm hu hiu. Tc ca mt phn ng phc tp c xc nh bng mt giai on gii hn
trung gian chm nht. Nu tc ca phn ng ni tip khng khc nhau ng k th tp hp
tc ca nhng phn ng thnh phn l tc ca phn ng phc hp ton phn. iu
dn ti s xut hin ch s bc phn ng l phn s. Phn ng dy chuyn l loi phn ng
ni tip c bit. S to thnh nhng ht hot ng, mi trng tng tc c bn dn ti s
lp li c dy phn ng. i vi mc ch phn tch, nhng phn ng mch mi ch c
ngha rt nh.
Nu nhng cht tham gia phn ng tham d vo nhng chuyn ho khc nhau c kh
nng v mt nhit ng lm xy ra trong h ng thi nhng phn ng khng ph thuc ln

63

nhau th nhng phng trnh phn ng tr nn phc tp. Hng s tc ca mt phn ng

xc nh khng bin i do s xy ra cc phn ng song song khc. Nhng s bin i nng
cc cht phn ng do s xy ra cc phn ng khc c phn nh ln tc ca phn ng
song song.
Nhiu phn ng gia cc cht hu c km theo nhng qu trnh xy ra song song. Do
tnh a dng ca nhng phn ng xy ra nn khng c kh nng s dng nhng qu trnh nh
th nh lng mt cht phn ng no . l l do gii thch ti sao cc phng php
phn tch ho hc cc hp cht phn t khng c c ngha ging nh khi phn tch cc h
ion.
Khi tng nhit , tc phn ng thng tng tun theo phng trnh Arrhenius:
E
d ln K
= A
dT
RT2

(3.21)

hoc:
ln K =

EA
+ ln A
RT

Khng phi mi va chm ca cc ht cc cht phn ng u hu hiu v dn ti tng

tc. V vy, cn phi d nng lng so vi gi tr trung bnh mt nhit cho, ngha l
cn nng lng hot ho EA. EA cng nh th s ht c kh nng tham gia phn ng cng
nhiu. Khi nng lng hot ho bng khng, hng s tc c gi tr ln nht. i lng A
c gi l tha s tn s, logA l ch s tn s.
Nhng phn ng ion gia cc ht tch in tri du xy ra thc t l tc thi nn s ng
gp ca nng lng hot ho l rt thp. Ngc li, i vi nhng ion tch in cng tn c
th o c tc phn ng c trng. nh hng rt ng k ca lc ion n tc phn
ng l c im ca cc phn ng ion. Nhiu phn ng ion xy ra rt nhanh v t ti trng
thi cui cng xc nh. l nguyn nhn ch yu lm cho nhng phng php phn tch
ho hc c ph bin rng ri v c u th trong phn tch cc cht v c.
Ngoi nhit , cc cht xc tc cng nh hng nhiu n tc phn ng. Cht xc tc
khng a nng lng vo h phn ng do v tr ca cn bng ho hc c gi khng
i: phn ng thun v phn ng nghch u c tng tc mc bng nhau. Kt cc cht
xc tc khng bin i, s tham gia nht thi ca n vo phn ng to ra c ch phn ng
mi. Trong phn ln trng hp lm tng tc phn ng dn ti kt qu lm gim nng
lng hot ho. Phc trung gian c to thnh vi xc tc i hi nng lng hot ho nh
hn so vi s to thnh sn phm cui cng khi khng c xc tc. Phc ny khng phi hp
cht theo ngha thng thng ca t ny.

ngha ca tc phn ng i vi ha hc
Tc phn ng c ngha ln i vi ho hc phn tch trong mt s vn sau:

64

1. S xy ra chm ca mt phn ng hp thc l mt tr ngi ln cho s s

dng vo phn tch, c bit l trong chun .
2. Xc nh nh lng c th da trn php o tc phn ng, v d nh khi phn tch
hn hp hai cht rt ging nhau, phn ng nh nhau nhng vi tc khc nhau.
3. Tc ca nhng phn ng xc tc ng th thng t l vi nng cht xc tc, do
c th s dng xc nh nng cht xc tc.
4. o hng s ng hc thng cho php hiu c ch phn ng v do gii thch c
nguyn nhn khng hp thc.
Nhng phn ng cng hng thng l ngun sai s rt ng tic, i khi c th chuyn
ho thnh nhng phn ng nh lng c li. Ch c th s dng c nhng phn ng loi
ny bng cch nghin cu ton din hiu c ch ca chng.

65

Chng 4
Phng php tnh nng cc cht trong nhng
dung dch cn bng n gin
4.1

Mt s lun im c s

Phn ln nhng php nh lng c thc hin trong dung dch. Do , i tng ca
ho phn tch bao hm l thuyt v dung dch. Tng quan v nhng lun im c bn ca l
thuyt v dung dch c trnh by trong chng ny v cc chng tip theo.
4.1.1 Thnh phn ho hc ca dung dch
Trong ho hc phn tch ngi ta s dng rng ri c dung mi nc v dung mi
hu c. Nhng dung mi khng phn cc nh tetraclorua cacbon v cc dn xut halogen
ca n c s dng trong trng hp nu chnh cht cn phn tch khng phn cc.
Nhng dung mi hu c vi phn cc trung gian c kh nng to lin kt hiro vi
nhng cht tan (ru, xeton, ete) c s dng ph bin hn so vi nhng hp cht t
phn cc hn, bi v s ln cc cht hu c v cc cht v c u tan c trong chng.
Dng nh cc dung dch nc, trong s c dung dch axit v baz v c c s dng
ph bin nht trong thc t phn tch. Do , trong khi trnh by lun im chng ta c
bit ch n tnh cht ca cc cht tan trong nc. Nhng phn ng trong mi trng
phn cc khng nc s c cp n km chi tit hn.
4.1.1.1

Cc cht in li

Cht in li l nhng cht ion ho trong dung mi to thnh mi trng dn in. Cht
in li mnh ion ho hon ton, nhng cht in li yu ch ion ho mt phn. Nhng cht in
li mnh v yu in hnh c dn ra bng 4.1.

4.1.1.2

Phn loi cc cht in li

Bng 4.1. Nhng cht in li mnh v yu in hnh

Cht in li mnh

Cht in li yu

66

1. Cc axit v c: HNO3, HClO4, 1. Nhiu axit v c nh H2CO3, H3BO3,

H2SO4a, HCl, HI, HBr, HClO3, HB2O3.
H3PO4, H2S, H2SO3.
2. Hiroxit ca cc kim loi kim v 2. Phn ln cc axit hu c.
kim th.

3. Amoniac v phn ln cc baz hu c.

3. Phn ln cc mui

4. Halogenua, xianat, thioxianat

Hg, Zn, v Cd.

H2SO4 phn li hon ton thnh ion HSO4 v H3O+ v do c xp vo cc cht

in li mnh. Nhng cng cn nhn xt rng ion HSO4 l cht in li yu, ch phn li
mt phn.
a

4.1.1.3

Qu trnh ion ho ca dung mi

Nhiu dung mi in hnh l nhng cht in li yu, nhng phn t ca chng phn ng
vi nhau to thnh nhng ion (qu trnh c gi l qu trnh proton phn). Chng ta dn
ra mt s v d:
2H2O

H3O+ + OH

2CH3OH

CH3 OH2+ + CH3O

2HCOOH

HCOOH2+ + HCOO

2NH3

NH4+ + NH2

Ion dng to thnh khi nc t phn li c gi l ion hiroxoni. Proton ny lin kt

vi phn t nc bng lin kt cng ho tr to nn bi i in t khng phn chia ca oxi.
Trong dung dch cn tn ti c nhng ion hirat ho mnh hn nh H5O2+ v H7O3+ nhng
nhng ion ny km bn hn H3O+. Ion hiro khng hirat ho khng th tn ti trong dung
dch nc.
nhn mnh bn cao ca proton hirat ho n gin, khi vit phng trnh phn ng
vi s tham ra ca proton nhiu nh ho hc s dng k hiu H3O+. cho tin li nhng
ngi khc li k hiu proton bng biu tng H+ khng k ti mc hirat ho tht s ca n.
K hiu n gin ho vic vit phng trnh phn ng c proton tham gia.

67

4.1.2 Tnh cht axit - baz trong cc dung mi khc nhau

S phn loi mang tnh lch s cc cht thnh axit v baz c hnh thnh trn c s
nhng tnh cht c trng ca cc dung dch nc ca nhng hp cht y. S hin mu
hoc mu xanh ca qu, mi v xc ca dung dch axit long, v ng v tnh x phng ca
cc dung dch baz, s to mui khi tng tc axit vi kim l nhng tnh cht in hnh .
Cui th k 19, Arrhenius ngh mt cch phn loi cht ch. ng nh ngha axit l
cht cha hiro v phn li trong nc thnh ion hiro v anion; cn baz l hp cht cha
nhm hiroxyl, cho ion hiroxyl v cation khi ho tan trong nc. Khi nim rt b ch
cho php hnh thnh nhng c s nh lng ca thuyt axit - baz. C th nh gi cng
axit - baz theo mc phn li ca chng trong dung dch nc. Ngoi ra, thuyt Arrhenius
t c s cho s m t ton hc cn bng thit lp do kt qu tng tc ca axit v baz.
Thiu st nghim trng ca thuyt Arrhenius l khng nh gi c vai tr ca dung
mi trong qu trnh phn li. Bronsted v mt ngi hon ton c lp vi ng l Lowry (nm
1923) a ra quan nim tng qut hn v axit - baz. Theo thuyt Bronsted - Lowry, axit
l cht c kh nng cho proton. Mt proton, ngha l chuyn thnh baz. Baz c gi l
baz lin hp vi axit ban u. C th dng phn ng gia axit v nc lm v d in hnh.
H2O + axit

Baz lin hp + H3O+

Cn nhn mnh rng, nhng tnh cht axit ca mt cht bt k no ch th hin khi c
mt cht nhn proton v tng t nh vy, mt cht ch th hin tnh baz khi c mt cht cho
proton.
Theo thuyt Bronsted - Lowry, c th din t phn ng trung ho bng phng trnh sau:
Axit1 + Baz2

Baz1 + Axit2
Cl + H3O+

HCl + H2O
HC2H3O2 + H2O

C2H3 O2 + H3O

Al(H2O)36+ + H2O
H2PO4 + H2O

Al(OH)(H2O)52+ + H3O

HPO24 + H3O

NH4+ + H2O

NH3

+ H3O+

H2O + NH3

OH

+ NH4+

H2O + CO32

OH

+ HCO3

68

Ta nhn thy rng axit c th l anion, l cation hoc hp cht trung ho in.
R rng rng, nc ng vai tr cht nhn proton (baz) i vi nm hp cht u v ng
vai tr cht cho proton (axit) i vi hai hp cht cui cng. Nhng dung mi c c tnh axit
v tnh baz c gi l dung mi lng tnh.
Axit (v c baz) khc bit nhau v c mc tng tc vi dung mi.
V d, phn ng gia axit clohiric v nc, thc t xy ra n cng, do axit clohiric
thuc loi axit mnh trong dung mi nc. Axit axetic v ion amoni phn ng vi nc
mc yu hn, do hai cht ny l hai axit yu.
Mc tng tc ca axit tan (hoc baz) vi dung mi, thc cht tu thuc vo kh
nng cho hoc nhn proton ca n. V d, axit pecloric, clohiric, bromhiric trong dung
dch nc thuc loi axit mnh. Nu ly axit axetic (bng axit axetic tinh khit 100%,
thng c gi l axit axetic bng; n c kt tinh 16,7oC dng bng; lng nh tp
cht ca nc lm h im ng bng xung r rt) lm dung mi thay cho nc, l cht
nhn proton yu hn th ch c axit pecloric phn li hon ton trong n thnh ion v l axit
mnh. Qu trnh phn li c th din t bng phng trnh:
HClO4 + HC2H3O2
Axit1

Baz2

ClO4

+ H2C2H3O2+

Baz1 + Axit2

Cc axit clohiric, bromhiric trong axit axetic bng ch phn li mt phn v l cc axit
yu.
Theo thuyt ca Bronsted - Lowry, nhng cht cho proton mnh nht (ngha l nhng
axit mnh nht) cho proton to thnh nhng cht nhn proton yu nht (nhng baz lin
hp yu nht). Tr li phn ng ca axit clohiric, axit axetic v ion amoni vi nc, ta thy
rng ion clorua l baz yu nht, ion axetat l baz mnh hn, cn amoniac l baz mnh
nht.
L thuyt tng qut v dung dch bao hm khng ch cc cht c kh nng cho hoc nhn
proton (axit v baz theo Bronsted - Lowry), m cn c m rng cho c nhng hp cht
khng nht thit phi cha proton. ng dng cho nhng h nh th, l thuyt proton phn t
ra c bit c ch. Trong trng hp ny, axit l cht bt k hoc l c cha trong thnh phn
ca mnh cation c trng i vi mt dung mi nht nh hoc l phn ng vi dung mi
to thnh ion . Mt cch tng t, baz l cht cho anion c trng i vi dung mi
cho.
Cn c mt quan im tng qut hn v bn cht ca axit v baz do Lewis a ra. ng
nh ngha axit l cht nhn i in t v baz l cht cho i in t. Quan im ca Lewis
cn i xa hn, khng gn cht nhng tnh cht axit - baz ca cc cht vi s c mt proton
trong chng v do m rng ng k phm vi ca nhng qu trnh c th xp vo loi phn
ng axit - baz. Quan nim ca Lewis thun li cho vic gii thch c ch phn ng hu c v
phn ng to phc. Cn vi phn ng axit - baz trong ho phn tch, thuyt Bronsted Lowry kh nng gii quyt cc vn l thuyt v thc nghim.

69

Khi xem xt cc vn axit - baz chng ta s da trn nhng khi nim ca Bronsted Lowry v s dng k hiu H3O+. Mt khc, khi vit phng trnh ho hc hoc l trong cc
tnh ton v quan h trng lng, trong proton c ngha H+ l k hiu thun li hn cng
s c s dng.

4.2 Phng php tnh nng cc cht trong nhng dung dch cn bng
n gin
Phn ln cc phn ng c s dng trong ho phn tch u nhanh chng t ti trng
thi cn bng ho hc l trng thi m cc cht phn ng v sn phm ca phn ng c t
l xc nh v khng i. Bit nhng mi tng quan trong nhng iu kin thc nghim
khc nhau, trong phn ln trng hp c th gii quyt c vn , phn ng c thun li
cho mc ch phn tch khng v c vn la chn nhng iu kin cho php lm gim
n cc tiu sai s phn tch.
Biu thc i vi hng s cn bng l phng trnh i s, trong nng ca cc cht
phn ng v sn phm ca phn ng lin h vi nhau qua mt vi i lng gi l hng s
cn bng. Nh ho hc cn phi bit khai thc thng bo c li t hng s cn bng. Trong
chng ny chng ta s nghin cu nhng tnh ton dng cho nhng h c mt cn bng
chim u th. Nhng phng php tnh ton cn bng trong nhng h phc tp s c xt
ti sau.

4.2.1 Trng thi cn bng

V d, chng ta xt cn bng:
2Fe3+ + 3I

2Fe2+ + I3

(4.1)

V tc v chiu su ca phn ng ny v bn phi c th d dng xt on theo mu da

cam, ca ion triioua ( nng thp, ba cht cn li ca phn ng thc t khng mu). Nu, v
d, thm 2 mmol st (III) vo mt lt dung dch cha 3 mmol ioua kali, mu xut hin ngay sau
mt giy hoc t hn, cng mu tr thnh hng nh theo thi gian. iu chng t rng
nng triioua khng bin i.
Dung dch vi cng mu nh vy (v do , vi nng triioua nh vy) c th
iu ch c bng cch thm 2 mmol st (II) vo mt lt dung dch cha 1 mmol ion
triioua. Trong trng hp ny thy cng mu b gim i nhanh chng do kt qu ca
phn ng:
2Fe2+ + I3

2Fe3+ + 3I

(4.2)

C th ly cu t ca phn ng c trong nhng t hp khc nhng nhng dung dch

thu c th ng nht nh va m t. Khi thc hin ch i hi mt iu kin: lng cc
thuc th thm vo trong mt lt dung dch phi c t l sau y:

70

S mmol Fe2+ = 2 s mmol I3

S mmol Fe3+ = 2/3 s mmol I
S mmol Fe3+ + s mmol Fe2+ = 2,00
V d, thu c mt dung dch ng nht vi dung dch m t, c th trn 0,8
mmol st (II), 1,2 mmol st (III), 0,4 mmol ion triioua v 1,8 mmol kali ioua trong mt lt
dung dch.
Nhng v d dn ra ch r mi quan h nng trng thi cn bng ho hc, ngha l
trng thi cn bng khng ph thuc vo con ng t ti trng thi . Mt khc, d dng
ch ra rng, mi quan h nng bin i di tc dng ca mt s yu t. V d, khi bin
i nhit , p sut (nu cht phn ng hoc sn phm phn ng l kh) hoc nng tng
qut ca mt trong s cc cu t. Nhng bin i c th d on mt cch nh tnh trn
c s quy tc Le Chatelier: Cn bng ho hc lun lun chuyn v pha chng li tc dng p
t ln n. V d nh khi nng nhit s dn ti s bin i nng km theo s hp th
nhit; s lm tng p sut s dn ti s to thnh cc cht c th tch chung nh. Trong ho
hc phn tch, hiu ng quan trng nht l hiu ng c gy nn do s thm vo hn hp
phn ng mt lng b sung ca mt trong cc cht tham gia phn ng. Trong trng hp
ny, cn bng chuyn v pha lm mt i mt phn cht thm vo. V d, i vi cn bng ta
ang nghin cu, thm st (III) vo s lm tng cng mu ca ion triioua v lm tng
lng st (II) to thnh; ngc li, thm st (II) vo s gy nn hiu ng ngc li. Chuyn
dch cn bng do bin i lng ca mt trong cc cht tham gia phn ng c gi l hiu
ng tc dng trng lng.
Nu nh c th nghin cu mt h bt k mc phn t chng ta s pht hin c rng,
tng tc gia cc cht tham gia phn ng khng dng li ngay c khi cn bng thit lp.
S hng nh ca t l nng ta quan st thy l kt qu ca s cn bng gia tc phn
ng thun v phn ng nghch. iu c ngha l, cn bng ho hc l qu trnh ng hc.

4.2.2 Biu thc hng s cn bng

m t nh lng nh hng ca nng hoc p sut, nu cc cht phn ng trng
thi kh, n trng thi cn bng ho hc, thun tin nht l s dng hng s cn bng. C th
d dng rt ra biu thc hng s cn bng t nhng khi nim nhit ng. Hng s cn bng
c ngha thc t quan trng bi v n cho php nh ho hc tin on hng v chiu su
ca phn ng ho hc. Nhng cn thit phi nhn xt rng, biu thc hng s cn bng khng
cho mt thng tin no v tc phn ng.

4.2.3 Nhng phng php biu th hng s cn bng

C hai phng php bin th hng s cn bng: cch biu th chnh xc (c gi l cch
biu th nhit ng hc) v cch biu th gn ng, ch ng trong iu kin rt gii hn.

71

Nhng nhng hng s gn ng li c ng dng rng ri bi v s dng chng rt n gin,

mc d c kh nng phm sai s.
4.2.3.1
Nhng gi thit c chp nhn khi rt ra biu thc gn ng
cho hng s cn bng
Khi rt ra h thc gn ng cho hng s cn bng, ngi ta gi thit rng nng ca ion
hoc phn t l yu t ng nht th hin nh hng ca chng n trng thi cn bng, ngha
l mi ht x s mt cch c lp vi ht bn cnh. V d, trong phn ng (4.1) ngi ta gi
thit rng, nh hng ca mi ion st (III) n trng thi cn bng l ng nht trong nhng
dung dch rt long (khi m ion ch yu b bao quanh bi phn t nc trung ho) v c trong
nhng dung dch rt c (khi m ngay st ion c nhng ht tch in khc). Dung dch hoc
kh c nhng ion hoc phn t x s mt cch c lp i vi nhau c gi l dung dch l
tng hoc dung dch tht. Dung dch l tng v tnh cht l tng rt t gp trong thc t.
4.2.3.2

Biu thc gn ng cho hng s cn bng

Chng ta xt trng hp tng qut ca cn bng ho hc:

mM

nN

pP + qQ

(4.3)

y nhng ch hoa k hiu cc cht tham gia phn ng, cn nhng ch thng l h s
hp thc. Phng trnh ch r rng m mol cht M phn ng vi n mol cht N to thnh p mol
cht P v q mol cht Q. Hng s cn bng ca phn ng ny c biu din nh sau:
K=

[P ]p [Q ]q
[ M]m [N ]n

(4.4)

y du ngoc vung l k hiu biu din nng phn t ca cc cht tan hoc p sut
ring phn trong kh quyn nu cht phn ng l kh.
Trong phng trnh (4.4), K l i lng bng s, ph thuc vo nhit , c gi l
hng s cn bng. Nng sn phm phn ng, vit di dng phng trnh (4.3), c t
t s v nng cc cht ban u c t mu s. Mi nng u c nng lu tha
ln bc bng h s hp thc trong phng trnh phn ng. H qu l thuyt ca biu thc
hng s cn bng ch r rng, trong cc du ngoc vung l nng tc thi t c trng
thi cn bng l ng ch khng phi l nng khng thay i. mu s ca biu thc l
nng cht trng thi tiu chun. Dung dch 1,00 mol/l ca cht tan c xem l trng thi
tiu chun ca n. i vi nguyn t hoc cc hp cht tinh khit th l trng thi (rn,
lng hoc kh) ca n 25oC v p sut 1 at. V d, nu P trong phng trnh (4.4) l cht tan:

[P] =

Nng P, mol/l
1, 00 mol/l

72

mu s l nng cht tan trng thi chun. H qu quan trng ca tnh

tng i ca [P] l tnh khng th nguyn ca i lng ny cng nh ca hng s cn bng.
Phng trnh (4.4) c th d dng rt ra t nhng khi nim nhit ng hc vi gi thit l cc
cu t ca phn ng l l tng .
Hng s cn bng nhit ng, phng trnh (4.4), c s dng xc nh thnh phn
gn ng ca cc dung dch long trng thi cn bng. nh gi chnh xc hn cn phi
s dng hng s nhit ng (hng s nhit ng c xt ti chng 5). Nhng tnh ton
theo cc hng s gn ng khng phc tp v trong nhiu trng hp cho cc nh khoa hc
thng tin kh v h.

4.2.4 Biu thc hng s cn bng ca nhng phn ng thng gp nht

Trong mc ny chng ta s xt nhng loi cn bng thng gp nht trong ho phn tch
v nu ln nhng c im ca nhng hng s tng ng .
4.2.4.1

S phn li ca nc

Nhng dung dch nc lun lun c mt lng nh cc ion hiroxoni v hiroxyl do s

phn li ca nc theo phn ng:
2H2O

H3O+ + OH

(4.5)

hnh dung hng s cn bng ca phn ng ny, chng ta s dng phng trnh (4.4):
H3 O+ OH

K=
[H2O]

Trong cc dung dch long trong nc, nng nc rt ln so vi cht tan nn c th

xem l hng nh. V d, nu cho 0,1 mol hiro clorua sc qua mt lt nc [1000 g : 18
g/mol = 55,6 mol H2O], cn bng (4.5) chuyn v bn tri v s mol nc khng phn li tng
t 55,6 n 55,7; nh vy, nu nng axit clohiric khng qu ln, nng nc r rng
khng bin i. Do , [H2O] trong phng trnh (4.5), trong phn ln trng hp c th xem
l i lng hng nh; khi c th vit:
K[H2O]2 = K H2O = [H3O +][OH]

(4.6)

y hng s K H2O c gi l tch s ion nc .

25oC tch s ion nc c gi tr bng s l 1,01.1014 ( thun tin chng ta thng s
dng i lng gn ng K H2O = 1,00.1014). S ph thuc ca hng s vo nhit c
dn ra bng 4.1.

73

Nh tch s ion nc ta d dng tnh c nng cc hiroxyl v hiroxoni (ion hiro)

trong cc dung dch nc.
Bng 4.1
Nhit , oC

K H2O

0,114.1014

25

1,010.1014

50

5,470.1014

100

49,000.1014

V d: Tnh nng ion hiro v ion hiroxyl trong nc nguyn cht 25oC v 100oC.
V OH v H3O+ c to thnh ch l do s phn li ca nc nn nng ca chng
phi bng nhau:
[H3O +] = [OH]
Thay vo phng trnh (4.6) ta c:
[H3O+]2 = [OH]2 = K H2O
[H3O+] = [OH] = K H2O
25oC

[H3O+]2 = [OH]2 = 1,00.1014

100oC [H3O+]2 = [OH]2 = 49.1014

= 1,00.107 ion.g/l
= 7,00.107 ion.g/l

V d: Tnh nng ion hiro v ion hiroxyl trong dung dch NaOH 0,200M trong nc.
V natri hiroxit l cht in li mnh, s ng gp ca n vo nng ion hiroxyl l
0,200M. S phn li ca nc cng to thnh nhng ion hiroxyl lng bng lng ion
hiro. Do c th vit:
[OH] = 0,200 + [H3O+]
y [H3O+] l phn ng gp do dung mi phn li vo nng tng cng ca ion
hiroxyl. So vi 0,200M nng ion OH ca nc nh, do :
[OH] 0,200 ion.g/l
By gi chng ta c th tnh nng ion hiro theo phng trnh (4.6):

74
14

H3O+ = 1,00.10

0,200

= 5,00.1014 ion.g/l

Nhn thy rng, s gn ng:

[OH] = 0,200 + 5,00.1014 0,200 ion.g/l
khng dn n sai s ng k.
4.2.4.2

Cn bng trong dung dch bo ha cht in li t tan

Trong dung dch nc bo ho mui t tan, mt hoc mt s cn bng c thit lp. V

d, trong dung dch bo ho bc clorua:
AgCl(r)

AgCl(n)

AgCl(n)

Ag+ + Cl

y, AgCl(n) l nhng phn t khng phn li trong dung dch. C th din t hng s
cn bng ca qu trnh u tin nh sau:
K=

[ AgCl ]n
[ AgCl ]r

(4.7)

Nng AgCl tng rn l mt hng s bi v nng ca hp cht trng thi rn

khng bin i (gi tr ca hng s ny theo nh ngha, bng 1,00). T y:
K[AgCl]r = K1 = [AgCl]n

(4.8)

T phng trnh (4.8) r rng l nng AgCl trong dung dch bo ho l khng i
mt nhit nht nh.
Hng s cn bng ca phn ng th hai c din t nh sau:
Ag + Cl

K1 =
AgCl
[
]n

(4.9)

thun tin ta nhn phng trnh (4.8) vi (4.9) v rt gn [AgCl]n:

K1K2 = T = [Ag+][Cl]

(4.10)

Tch s ca hai hng s, T, c gi l tch s tan. Nh vy, tch s tan l hng s cn

bng ca phn ng tng cng:
AgCl(r)

Ag+ + Cl

75

Cn nhc mt iu rt quan trng l, cc phng trnh (4.8) v (4.10) ch dng c cho

cc dung dch bo ho nm cn bng vi cht rn d khng tan.
Phn ln cc mui v c t tan, thc t phn li hon ton trong cc dung dch nc, do
so vi nng ca cc ion, nng ca cc phn t khng phn li gn bng khng (1). iu
kin , phn ng tng cng m t mt cch thch hp nht cn bng ca phn ng ho tan.
Do nguyn nhn ny nn i vi phn ln cc cht v c, trong cc ti liu ch dn ra mt
hng s (tch s tan) (xem mc lc). V d, khng c c s cho rng trong dung dch bo
ho bari ioat c Ba(IO3)2 hoc BaIO3+ khng phn li. Do , cn bng:
Ba2+ + 2IO3

Ba(IO3)2 (r)

S l cn bng duy nht tn ti v do ch cn ch ti hng s cn bng , ngha l:

[Ba2+][ IO3 ]2 = T
Di y dn ra nhng v d in hnh s dng biu thc tch s tan. Mt s v d khc
s c xt ti trong chng 5 v 8.
V d 1: C th ho tan bao nhiu gam bari ioat trong 500 ml nc 25oC? Cho bit tch
s tan ca Ba(IO3)2 bng 1,57.109.
Ba(IO3)2

(r)

Ba2+ +

2IO3

[Ba2+][IO3]2 = 1,57.109 = T
T phng trnh m t cn bng, mi mol Ba(IO3)2 tan, phn li to thnh mt mol Ba2+,
ngha l:
tan (tnh bng mol) ca Ba(IO3)2 = [Ba2+]
Mt khc, r rng l, nng ioat ln hn nng bari hai ln.
[ IO3 ] = 2[Ba2+]
Thay nng ioat bng nng Ba2+ vo phng trnh hng s cn bng ta c:
[Ba2+](2[Ba2+])2 = 1,57.109
hoc:

[Ba2+] = (1,57.109/4)1/3 = 7,3.104 mol/l

tan = 7,3.104 M

(1)

Quan im ny rt ph bin, tuy nhin khng phi lc no cng ng. C nhiu mui t tan v t phn li. Trong s , v

d c dy sunfua.

76

bit c tan ca Ba(IO3)2 tnh bng gam trong 500 ml, ta vit:
tan = 7,3.104 [mmol Ba(IO3)2/ml] 500ml [0,487g/mmol Ba(IO3)2] = 0,178g/500ml
y 0,487 l mili trng lng phn t ca Ba(IO3)2 .
V d sau y minh ho nh hng ca ion cng tn c nguyn l Le Chatelier d
on.
V d 2: Tnh tan phn t ca Ba(IO3)2 trong dung dch Ba(NO3)2 0,02M.
Trong trng hp ny cn tnh tan theo [ IO3 ]:
tan ca Ba(IO3)2 =

1
[ IO3 ]
2

Ba(NO3)2 v Ba(IO3)2 cng sinh ra ion bari trong dung dch. Phn ng gp ca cht th
nht l 0,02M, cn phn ng gp ca cht th hai bng tan phn t hoc bng
[Ba2+] = 0,02M +

1
[ IO3 ].
2

1
[ IO3 ]
2

Thay th i lng vo phng trnh tch s tan:

(0,02 +

1
[ IO3 ]) [ IO3 ] = 1,57.109
2

Mun c nng chnh xc [ IO3 ] cn gii phng trnh bc 3. n gin cc php

tnh i s, xut hin tm cch gii gn ng. i lng T nh nn tan ca Ba(IO3)2
nh, do c th gi nh rng, nng ion bari, thu c do s ha tan Ba(IO3)2 rn khng
ng k so vi nng ion bari t Ba(NO3)2. Ni cch khc,
1
[ IO3 ] 0,02.
2

Phng trnh dn ra trn y, lc ny c rt gn :

0,02[ IO3 ]2 = 1,57.109
[ IO3 ] = 2,8.104 mol/l
Gi thit rng:
[0,02 +

1
.2,8.104 ] 0,02
2

1
[ IO3 ] << 0,02, v vy 0,02 +
2

77

khng dn ti sai lm nghim trng, bi v thnh phn th hai ch bng khong 0,7% ca
0,02. Thng gi thit loi ny c th c coi nh l ng n nu s khc bit nh hn 5
10%. Vy:
tan ca Ba(IO3)2 =

1
1
[ IO3 ] = .2,8.104 = 1,4.104 M
2
2

So snh kt qu thu c vi kt qu tan ca ioat bari trong nc nguyn cht, chng

ta nhn thy rng s c mt mt lng nh ion ng dng h thp tan phn t ca
Ba(IO3)2 xung khong 5 ln.
V d 3: Ly mt v d khc phc tp hn, tnh tan ca Ba(IO3)2 trong dung dch thu
c bng cch trn 200 ml dung dch Ba(NO3)2 0,01M vi 100 ml dung dch NaIO3 0,1M.
Trc ht chng ta cn xc nh xem trong s cc thuc th, thuc th no d? Lng
ban u ca cc thuc th l nh sau:
Lng mmol Ba2+ = 200ml.0,01mmol/ml = 2,00
Lng mmol IO3 = 100ml.0,1mmol/ml = 10,00.
Sau khi kt ta Ba(IO3)2:
IO3 d = 10,0 2(2,00) = 6,00 mmol

T y:

[ IO3 ] = 6,00mmol/300ml = 0,02 M

Cng nh trong v d u tin:

tan phn t ca Ba(IO3)2 = [Ba2+]
Nhng trong trng hp ny:
[ IO3 ] = 0,02 + 2[Ba2+]
y 2[Ba2+] l phn ng gp ca tan kt ta vo nng ioat. Sau khi gi thit
rng:
[ IO3 ] 0,02
C th nhn c li gii s b:
tan ca Ba(IO3)2 = [Ba2+] =

T
IO3

1,57.109
2

0,02

= 3,9.106

Gi thit ra khi tnh ton l hon ton chp nhn c.

78

So snh nhng kt qu thu c trong hai v d trn, ta nhn thy rng d ioat
lm gim tan Ba(IO3)2 mc ln hn so vi s d nh vy ca ion bari.
4.2.4.3

S phn li ca axit yu v baz yu

Khi ho tan axit yu hoc baz yu trong nc, xy ra s phn li mt phn. V d i vi

axit nitr ta c th vit:
H3O+ + NO2

HNO2 + H2O

H3 O+ NO2

Ka =
[HNO2 ]

y Ka l hng s phn li axit ca axit nitr. Hng s phn li baz ca amoniac c

biu din tng t:
NH4+ + OH

NH3 + H2O

NH4 + OH

Kb =
NH
[ 3]

Ta nhn thy rng, nng nc khng tham gia vo mt phng trnh no trong s cc
phng trnh trn. Cng nh i vi tch s ion nc, ngi ta chp nhn rng nng dung
mi l i lng ln v hng nh, do bao gm hm trong hng s cn bng Ka v Kb .
Quan h gia hng s phn li ca mt cp axit - baz lin hp. Chng ta xt biu thc
hng s phn li ca amoniac v axit lin hp ca n l ion amoni. C th vit:
NH3 + H2O

NH4+ + OH

NH4 + OH

Kb =
[NH3 ]

NH4+ + H2O
Ka =

Nhn hai biu thc, ta c:

NH3 + H3O+

[NH3 ] H3O+
NH4 +

79
K aK b =

[NH3 ] H3O+
NH4 +

NH4 + OH

= H O+ OH

NH
[ 3]

Bi v:
[H3O+][OH] = Kn KaKb = Kn

(4.11)

Mi quan h ng i vi tt c cc cp axit - baz lin hp. Trong phn ln cc bng

hng s phn li, ngi ta a ra hoc hng s axit hoc hng s baz lin hp, bi v d dng
tnh mt trong hai hng s theo gi tr ca hng s kia bng phng trnh (4.11).
ng dng ca hng s phn li axit. Hng s phn li ca nhiu axit yu ph bin nht
c dn ra ph lc IV.
Nhng hng s ny c s dng ph bin tnh nng ion hiro v hiroxyl trong
dung dch ca cc axit v baz yu.
V d, khi ho tan mt axit yu HA trong nc ta c, cn bng:
HA + H2O

H3O+ + A

A H3 O+

Ka =
[HA ]

Ngoi ra ion hiro cn phn li t nc:

2H2O

H3O+ + OH

Thng nhng ion hiro sinh ra do phn ng th nht ngn cn s phn li ca nc n

mc c th b qua, nng ion hiro v hiroxyl phn li ra t nc. iu kin , r rng
l, axit phn li, c mi ion H3O+ to thnh mt ion A:
[H3O+] [A]

(4.12)

Ngoi ra, tng nng phn t ca axit yu v baz lin hp ca n phi bng nng
ca phn t axit ban u bi v trong dung dch khng c cc cht khc cho A. Do :
CHA = [A] + [HA]

(4.13)

Sau khi thay phng trnh (4.12) vo (4.13) v chuyn v ta c:

[HA] = CHA [H3O+]

(4.14)

Nu thay th [A] v [HA] bng cc biu thc ca chng t cc phng trnh (4.12) v
(4.14) th hng s phn li axit c dng:

80
2

H O+
3
Ka =
CHA H3O+

(4.15)

Phng trnh (4.15) c th chuyn thnh:

[H3O+]2 + Ka[H3O+] KaCHA = 0
Gii phng trnh bc hai trn ta thu c:
H3 O+ =

K a + (K a + 4K aCHA
2

(4.16)

Gi thit rng [H3O+] nh hn rt nhiu so vi CHA th phng trnh (4.15) c th rt gn:

[H3O+] = K aCHA
(4.17)
Sai s gy ra do gi thit ny s cng ln nu nng axit cng nh v hng s phn li
cng ln. S khng nh ny c chng minh bng nhng d liu ca bng 4.2. Ta nhn
thy rng, sai s do gi thit nu trn gy ra khong 0,5% khi t s (CHA/Ka) = 104. Sai s
ny tng n khong 1,6% khi t s ny bng 103 v n 5% nu t s bng 102 v n
17% nu t s bng 10. Nhng d kin ny c dn ra bng th trn hnh 4.1.
ng ch l, khi t s (CHA/Ka) << 1, nng ion hiro tnh c theo phng trnh gn
ng s khng dn ti sai s c ngha.
Trong thc t, thng ngi ta thc hin s rt gn gi thit v thu c gi tr gn ng
ca [H3O+], sau cn phi so snh gi tr ny vi nng CHA trong phng trnh (4.15).
Nu gi tr [H3O+] thu c lm bin i [HA] mt i lng nh hn sai s cho php trong
cc php tnh (trong sch ny, phn ln trng hp l 5 10%).

81

Sai s tng i gy nn do gi thit CHA [H3O+] CHA (phng trnh (4.15)) c th

xem nh tho mn. nhn c gi tr [H3O+] chnh xc hn cn gii phng trnh bc 2.
V d: Hy tnh nng ion hiro trong dung dch axit nitr 0,12 M trong nc. Cn
bng c bn trong dung dch:
HNO2 + H2O

H3O+ + NO2

Trong ph lc IV ta tm thy:
H3 O+ NO2

= 5,1.104
Ka =
[HNO2 ]

[H3O+] = [ NO2 ]; [HNO2] = 0,12 [H3O+]

V:
T :
2

H3 O+

= 5,1.104
+
0,12 H3O

Gi thit rng [H3O+] << 0,120 mol/l ta tm c:

H3 O+ = 0,120 5,1.104 = 7,8.103 M

By gi cn kim tra tnh ng n ca gi thit (0,12 0,0078) 0,12; s khc nhau

khong 7%. Sai s tng i cho php tnh [H3O+] nh thua i lng , v log(CHA/Ka) =
2,4. T hnh 4.1, ta thy rng sai s khong 3%. Nu cn chnh xc cao hn, cn phi gii
phng trnh bc hai v ta thu c gi tr 7,6.103M.
Bng 4.2 Sai s gy ra do gi thit cho rng H3O+ nh so vi CHA khi s dng phng
trnh (4.15)
i
Ka

lng i
CHA

1,00.102

i lng [H3O+] Sai s

lng i lng [H3O+]
tnh theo phng
tnh theo gi thit
(%)
trnh chnh xc

1,00.103

3,16.103

0,92.103

244

1,00.102

1,00.102

0,62.102

61

1,00.101

3,16.102

2,70.102

17

82

1,00.104

1,00.106

1,00.104

1,00.104

0,62.104

61

1,00.103

3,16.104

2,70.104

17

1,00.102

1,00.103

0,95.103

5,3

1,00.101

3,16.103

3,11.103

1,6

1,00.105

3,16.106

2,70.106

17

1,00.104

1,00.105

0,95.105

5,3

1,00.103

3,16.105

3,11.105

1,6

1,00.102

1,00.104

9,95.105

0,5

1,00.101

3,16.104

3,16.104

0,0

V d: Tnh nng ion hiro trong dung dch hiroclorua anilin C6H5NH3Cl 2,0.104 M.
Trong dung dch nc, hp cht phn li hon ton ra Cl v C6H5NH3+ . Axit yu
C6 H5 NH3+ phn li nh sau:
C6H5NH3+ + H2O

C6H5NH2 + H3O+

H3O+ [C6 H5NH2 ]

Ka =
C6 H5NH3+

Trong ph lc IV khng c hng s phn li ca C6H5NH3+ nhng trong ph lc V ta tm

thy hng s baz ca anilin C6H5NH2.
C6H5NH2 + H2O

C6 H5 NH3+

+ OH

Kb = 3,94.1010
tnh Ka chng ta s dng phng trnh (3.11):
Ka =

1,00.1014
3,94.10

10

= 2,54.105

Lm nh trong v d trc:

83

[H3O+] = [C6H5NH2]
[C6H5NH2] = 2,0.104 [H3O+]
Gi thit rng [H3O+] << 2,0.104. Thay gi tr gn ng ca [C6H5NH2] vo biu thc
hng s phn li:
2

H3 O+

= 2,54.105
4
2,0.10

Ta tm thy:

[H3O+] = 7,1.105 mol/l.

So snh nhng i lng 7,1.105 v 2,0.104 ta thy rng, khi tnh [H3O+] ta b qua
sai s ln (s dng hnh 4.1 ta tm thy sai s ln hn 20%). Sai s ln n nh vy nn phi
s dng phng trnh chnh xc hn.
2

H3 O+

= 2,54.105
2,0.104

Sau khi bin i thnh:

[H3O+]2 + 2,54.105[H3O+] 5,08.109 = 0
Gii ra ta thu c:
5
5 2
9
H3 O+ = 2,54.10 + (2,54.10 ) + 4 5,08.10

[H3O+] = 6,0.105 mol/l

ng dng hng s phn li ca baz yu. Nhng tnh ton dn ra trong cc phn trc
c th d dng vn dng tnh nng ion hiroxyl trong cc dung dch baz yu.
Dung dch nc ca amoniac biu l tnh baz trong phn ng:
NH3 + H2O

NH4+ + OH

D dng ch ra rng, ht chim u th trong dung dch l NH3. Hn na, i khi ngi ta
gi nhng dung dch l dung dch hiroxit amoni theo thut ng cn c cng nhn cho
n khi NH4OH cn c coi l dng cha phn li ca baz ch khng phi l NH3. Theo
nh lut tc dng khi lng:
NH4 + OH

Kb =
[NH3 ]

84

Gi tr hng s cn bng tan khng ph thuc vo cng thc ca hp cht mu

s, l NH3 cng thc ng hn hay NH4OH l cng thc dng trc y.
V d: Hy tnh nng ion hiro trong dung dch NH3 0,075M.
Cn bng chim u th trong dung dch l:
NH3 + H2O

NH4+ + OH

T cc bng ta tm thy hng s phn li ca baz (ph lc V):

NH4 + OH

= 1,76.105
[NH3 ]

T phng trnh phn li trn:

[NH4+] = [OH]
v
[NH4+] + [NH3] = CNH3 = 0,075
Thay th [OH] bng [NH4+] v bin i phng trnh th hai ta tm c:
[NH3] = 0,075 [OH]
Thay cc gi tr vo phng trnh hng s phn li:
2

OH

= 1,76.105
2

7,5.10 OH

Nu gi thit rng [OH] << 7,5.102, phng trnh trn c rt gn:

[OH]2

(7,5.102)(1,76.105)

[OH] = 1,15.103 mol/l

V d: Tnh nng ion hiroxyl trong dung dch hippoclorit natri 0,01M.
T phn ng tng tc gia OCl v nc:
OCl + H2O
c th vit:

HOCl + OH

85
Kb =

[HOCl ] OH
OCl

Trong ph lc V khng gi tr Kb nhng trong ph lc IV chng ta tm c hng s phn

li axit ca HClO l 3,0.108. S dng phng trnh (4.11) chng ta c:
Kb =

K n 1,00.1014
=
= 3,3.107
8
Ka
3,0.10

Gii nh trong v d trn:

[OH] = [HOCl]
[OCl] + [HOCl] 0,01
nn:
[OCl] = 0,01 [OH] 0,01 mol/l
Gi thit rng [OH] << 0,01 mol/l v thay vo phng trnh hng s cn bng ta c:
2

OH

= 3,3.107
0,01

[OH] = 5,7.105 mol/l

R rng l, gi thit khng dn ti sai s ln.
4.2.4.4

S to phc

Phn ng to phc ca cc ion phc tan l loi phn ng phn tch quan trng. Chng ta
dn ra hai v d:
Fe3+ + SCN

Fe(SCN)2+

Fe(SCN)2+

K=
Fe3 + SCN

Zn(OH)2 (r) + 2OH

Zn(OH)24

86
Zn(OH)24

K=
2

OH

K l hng s to phc hoc hng s bn ca phc. Hng s khng bn m t cn bng

phn li ca ion phc. Hng s khng bn l nghch o ca hng s bn, v d:
K kb

3+
1 Fe SCN
= =
K
Fe(SCN)2+

Cn nhn xt rng, hng s bn ca Zn(OH)24 ch dng cho dung dch bo ho hiroxit

km t tan. ng thi cng cn nu r nng hiroxit km khng tham gia vo phng trnh
hng s bn bi v nng cht rn l hng nh v bao hm trong hng s bn. Vi quan
im nh vy, tt c mi lp lun tng t s c vn dng i vi phng trnh tch s tan.
Hng s bn ca nhiu ion phc bit c dn ra trong ph lc VI. ng dng hng s
bn s c minh ha bng v d sau y:
V d: C th nhn thy mu thng thng ca FeSCN2+ trong dung dch nc nng
phc 6.106M hoc ln hn. Nng KSCN nh nht, cn thit l bao nhiu pht hin
1 mg/ml st (III) trong nc t nhin. Chng ta tm c trong ph lc VI.
Fe3+ + SCN

Fe(SCN)2+

K = 1,4.102
ngha l:
FeSCN2+

= 1,4.102
3
+
Fe SCN

Chng ta biu din nng st (III) bng mol:

CFe3+ =

1mg
1
1
=
=
= 1,8.105 M
1
1000mg/g 55,8g/trng lng mol

iu kin gii hn pht hin ca phc [FeSCN2+] = 6.106 M. trng thi cn bng, st
(III) hai trng thi: Fe3+ v FeSCN2+. Do :
5

3+

2+

CFe3 + = 1,8.10 M = [Fe ] + [FeSCN ]

[Fe3+] = 1,8.105 [FeSCN2+] = 1,8.105 6.106 = 1,2.105 M

87

Thay nng tm c vo phng trnh hng s bn ta xc nh c nng SCN

cn thit.
6.106

= 1,4.102 [SCN ] = 0,0036M

5

1,2.10
SCN

Nh vy, nh dung dch KSCN c nng 0,0036 M hoc ln hn c th pht hin st

(III) c nng 1 mg/ml hoc ln hn theo phn ng to thnh FeSCN2+.
4.2.4.5

Phn ng oxi ho kh

C th biu din hng s cn bng ca phn ng oxi ho kh bng phng php thng
thng. V d:
6Fe2+ + Cr2O72 + 14H3O+
6

K=

Fe3+ Cr3 +

6Fe3+ + 2Cr3+ + 21H2O

14

Fe2+ Cr2O72 H3 O+

Nh trc y chng ta nhn xt, nng nc khng tham gia vo phng trnh. Ni
chung, cc bng hng s cn bng ca cc phn ng oxi ho kh khng c thit lp bi v
d dng thu c cc hng s ny t cc hng s c bn hn l th in cc tiu chun.
Nhng tnh ton chi tit s c xt ti trong chng 13.
4.2.4.6

S phn b cht gia hai cht lng khng ho ln

Cn mt dng cn bng na c s dng trong phn tch l s phn b cht gia hai
tng lng. V d, nu ta ly dung dch it trong nc vi mt dung mi hu c khng ho
tan trong nc nh hexan hoc clorofom th mt phn iot c chit vo lp hu c. Cui
cng cn bng c thit lp gia hai tng v c th hnh dung cn bng nh sau:
I2 (n)

I2 (hc) ;

K=

[I2 ]hc
[I2 ]n

K, hng s cn bng ca phn ng ny, thng gi l hng s phn b hoc h s phn

b. Cn bng phn b c ngha ln trong nhiu qu trnh phn chia.
4.2.4.7

Cn bng tng nc

Nhiu cht in li yu lin hp hoc phn li tng nc, c th vit hng s cn bng i
vi mi nc. V d, nu thm amoniac vo dung dch ca ion bc th cui cng hai cn bng
c thit lp, Ag+ v NH3 tham gia vo cc cn bng sau:

88
AgNH3+

Ag+ + NH3

AgNH3+

K1 =
+
Ag [NH3 ]

AgNH3+ + NH3

Ag(NH3 )2+

Ag(NH3 )2+

K2 =
+
AgNH3 [NH3 ]

y K1 v K2 l nhng hng s bn tng nc ca hai phc cht. Nu nhn hai s K1, K2

vi nhau ta thu c hng s bn tng qut ca phc:
Ag(NH3)2+

Ag+ + 2NH3

Ag(NH3 )2+

2 = K1K 2 =
+
Ag [NH3 ]2

Hng s bn tng qut c k hiu l n, y n l s mol ca thuc th to phc lin

kt vi mt mol cation. V d:
Cd(CN)3

Cd2+ + 3CN
3 = K1K 2K 3 =

Cd(CN)3

Cd2+ CN

Cd2+ + 4CN
4 = K1K 2K 3K 4 =

Cd(CN)24
Cd(CN)24

Cd2+ CN

y K1, K2, K3 ,K4 l nhng hng s tng nc tng ng.

Nhiu axit v baz rt quen bit, phn li tng nc. V d, trong dung dch axit photphoric
tn ti nhng cn bng sau y:
H3PO4 + H2O

H2PO4 + H3O

89
H3O+ H2PO4

= 7,11.103
K1 =
H
PO
[ 3 4]
H2PO4 + H2O

HPO24 + H3O

H3 O+ HPO42

= 6,34.108
K2 =
H2PO4

HPO24 + H2O

PO34 + H3O

H3O+ PO34

= 4,2.1013
K3 =
HPO24

T v d dn ra, r rng l gi tr bng s Kn ca mi nc phn li lin tip ca axit hoc

baz gim dn. Cn bng loi ny c xt chng 10.

90

Chng 5
tan ca kt ta
Nhng phn ng to nhng hp cht t tan c nhiu ng dng rng ri trong ba qu trnh
ho phn tch quan trng:
1. Trong qu trnh tch cht cn xc nh di dng kt ta khi cc cht tan cn tr cho
php o giai on kt thc.
2. Trong phn tch trng lng da trn s to thnh kt ta m trng lng ca n c
trng cho lng cht cn xc nh.
3. Trong phng php phn tch chun da trn s o th tch ca dung dch thuc th
chun tiu tn cho s kt ta nh lng cu t cn xc nh.
ng dng thnh cng phn ng ny trong mi trng hp, kt ta cn phi c tan
tng i nh, tinh khit v gm nhng ht c kch thc thch hp. Trong chng ny
chng ta s xt nhng yu t nh hng n tnh cht th nht trong s nhng tnh cht vt l
ca kt ta nu trn.
Nhng v d v s dng tch s tan tnh ton tan trong nc ca kt ta c cu to
ion, k c khi c mt ion ng dng c bn lun chng IV. Sinh vin cn lm quen
tt vi nhng ti liu y trc khi bt u nghin cu chng ny. Trong chng ny chng
ta s xem xt nhng yu t nh pH, nng thuc th to phc v nng ca nhng cht
in li nh hng nh th no n tan ca kt ta.

5.1

nh hng ca cn bng cnh tranh n tan ca kt ta

tan ca kt ta tng ln khi c mt nhng ion hoc phn t ca cc cht to vi cc

ion kt ta nhng hp cht tan hoc phc cht. V d, tan ca florua canxi trong mi
trng axit cao hn trong mi trng trung tnh bi ion flo phn ng vi ion hiro. Do ,
trong dung dch bo ho florua canxi, hai cn bng c thit lp:

91
CaF2 (rn)

Ca2+

+ 2F
+
2H3O+

2HF + 2H2O

Ph hp vi nguyn l Le Chatelier, khi thm axit s dn ti s tng nng hiro

florua. S h thp nng ion florua gy ra bi hin tng iu chnh mt phn do s
chuyn dch cn bng u tin v bn phi v do tan kt ta tng ln.
Nhng phng trnh sau y:
AgBr (rn)

Ag+

+ Br
+
2NH3

Ag(NH3)2

l mt v d khc v s tng tan khi c mt cc cht phn ng vi ion kt ta.

Nhng phn t amoniac lm h thp nng ion bc trong dung dch. Do cn bng ca phn
ng ho tan chuyn dch v pha phi nn tan ca bromua bc tng ln.

5.1.1 M t cn bng phc tp

Chng ta thng ng chm ti vn tnh ton nng ca cc hp cht trong dung
dch m trong ng thi thit lp hai hoc mt s ln hn cn bng cnh tranh. S ho tan
florua canxi hoc bromua bc l nhng v d. Trong trng hp tng qut hn, chng ta xt
hp cht t tan AB ho tan thnh cc ion A v B:
AB (rn)

A
+
C

AC

B
+
D

BD

Nu A v B phn ng vi C v D to thnh cc hp cht tan AC v BD th vic a C

hoc D vo dung dch gy nn s chuyn dch cn bng ho tan v hng lm tng tan ca
AB.

92

xc nh tan ca AB trong h cn phi bit nng ca cc cht C v

D thm vo v hng s cn bng ca ba cn bng. Ni chung, m t hon ton h thc
nng trong dung dch cho cn phi thit lp mt s phng trnh i s. tnh tan
cn phi gii h phng trnh. thng l nhim v kh khn hn nhiu so vi vic thit
lp chng.
Khi m t nhng cn bng phc tp cn phi lun bit rng gi tr v dng din t hng s
ca mt cn bng cho, bng bt c cch no cng khng ph thuc vo s xy ra trong
dung dch nhng phn ng cnh tranh ph. Nh trong v d ta ang xt, tch s tan AB m t
h thc gia nhng nng cn bng A v B v khng ph thuc vo vic trong dung dch c
hay khng c nhng ion C v D. Ni cch khc, nhit khng i trong dung dch bo ho
AB, tch s [A][B] l mt i lng hng nh. Tt nhin l khi c mt C hoc D, lng AB b
ho tan tng ln nhng iu xy ra khng phi do s bin i tch s ion [A][B], m do s
chuyn mt phn kt ta thnh AC v BD.
Di y l s gip gii quyt cc bi tp v mt s cn bng. Sau s s c
minh ha bng mt s v d.

5.1.2 S gii bi tp bao gm mt s cn bng

1. Vit cc phng trnh ca tt c mi phn ng c th c quan h vi bi tp.
2. Xc nh nng cn bng ca nhng cht cn phi tm.
3. Vit cc biu thc cho hng s cn bng ca tt c cc phn ng vit (im 1). Tm
cc gi tr hng s cn bng trong cc bng tng ng.
4. Vit cc phng trnh cn bng vt cht ca h, cc phng trnh lin kt nng cn
bng ca cc dng khc nhau ca cc cht, lin kt gia nng cn bng mi dng vi nng
tng qut ca n trong dung dch. Cc iu kin cn bng.
5. Vit phng trnh trung ho in. Trong mt dung dch bt k, tng s in tch dng
ca cation phi bng tng s in tch m ca anion, ngha l trung ho in. Nhng h thc
c din t bng phng trnh trung ho in (1).

(1)

Chng ta xt dung dch thu c bng cch ho tan NaCl trong nc. V ton cc, in tch ca dung

dch bng khng mc d rng trong dung dch c cc ion tch in dng v m. iu kin trung ha in
+

cn c thc hin trc tip t h thc: [Na ] + [H3O ] = [Cl ] + [OH ]. Dung dch NaCl trung ha, bi v
tng nng cc ht tch in dng bng tng nng cc ht tch in m. By gi chng ta xt dung dch
2+

nc MgCl2. i vi dung dch ny cn phi vit: 2[Mg ] + [H3O ] = [Cl ] + [OH ]. tnh in tch ion
bng hai, chng ta nhn nng ca ion magie vi 2. Cn bng in tch s c tun theo bi v nng

2+

ca ion clorua gp i nng ca ion magie ([Cl ]=2[Mg ]). Theo nguyn nhn y, nng ca ion 3 in
tch c nhn vi 3. V d, i vi dung dch cha Al2(SO4)3, MgCl2 trong nc ta c phng trnh trung
ha in nh sau:

93

6. m s n s trong cc phng trnh c thit lp theo cc im 3, 4, 5 v so snh n

s vi s phng trnh c lp. Nu s n s v s phng trnh bng nhau th c th gii
bi tp mt cch chnh xc nh nhng php tnh i s tng ng. Nu s phng trnh t hn
s n th hy th c gng thit lp nhng phng trnh c lp ph. Nu nh khng lm c
iu th cn phi tha nhn rng khng th gii chnh xc c, nhng c th gii gn
ng.
7. Lm cc gi thit cn thit gii bi tp vi mc ch n gin nhng phng trnh
i s hoc gim n s.
8. Gii nhng phng trnh i s tng i theo nhng nng cn bng cn phi xc
nh (im 2).
9. S dng nng cn bng thu c im 8 kim tra ng ca nhng gi
thit ra im 7.
Trong s ngh cn c bit ch ti im 6 bi v im ny ni v kh nng chnh
gii chnh xc bi tp. Nu s phng trnh c lp bng s n s, bi tp tr thnh hon
ton i s, ngha l i ti gii h mt s phng trnh. Ngc li, nu s phng trnh nh
hn s n s th cn thit phi tm nhng phng trnh khc hoc ra nhng gi thit c th
lm gim s n s. Sinh vin khng cn tn thi gian tm gii nhng bi tp phc tp v
cn bng trc khi khng nh c rng c s liu gii hay cha.

5.2

nh hng ca pH n tan

tan ca nhiu kt ta c ngha quan trng trong phn tch nh lng, ph thuc
trc ht vo nng ion hiro trong dung dch. Trong phn t ca nhng kt ta cha
hoc anion c tnh baz, hoc cation c tnh axit, hoc ng thi c hai. Baz tham gia vo
thnh phn canxi florua l ion florua, phn ng vi ion hiro to thnh axit flohiric. Do
tan ca florua canxi tng ln khi axit ho. Chng ta ly bismut ioua lm v d v hp cht
trong thnh phn c cation c tnh axit tham gia. Trong dung dch bo ho BiI3 cn bng sau
c thit lp:
BiI3 (rn)

Bi3+ + 3I

Bi3+ + H2O

BiOH2+ + H3O+

Chng ta nhn thy rng, khc vi tan ca canxi florua, tan ca bismut ioua gim
khi axit tng.

3+

2+

3[Al ] + 2[Mg ] + [H3O ] = 2[SO4 ] + [HSO4 ] + [Cl ] + [OH ]

94

5.2.1

Tnh tan nng ion hiro bit

Trong thc t phn tch thng cn phi kt ta nng ion hiro xc nh cho sn.
Chng ta minh ha php tnh tan trong nhng iu kin nhng v d sau y.
V d: Tnh tan ca CaC2O4 nng ion hiro bng 1,00.104 mol/l.
Giai on 1. Thit lp nhng phng trnh ho hc:
Ca2+ + C2O24

CaC2O4 (rn)

(5.1)

V H2C2O4 l axit yu, nhng ion oxalat lin kt mt phn vi ion hiro c thm vo
to axit nu trn.
C2O42 + H3O

HC2O4 + H3O

HC2O4 + H2O

(5.2)

H2C2O4 + H2O

(5.3)

Giai on 2. Xc nh n s. S tht cn tm ci g ? Chng ta mun xc nh tan ca

CaC2O4 biu din bng mol/l. V CaC2O4 l hp cht ion, nng ca n bng nng ca
ion canxi v cng bng nng cn bng nhng dng khc nhau ca ion oxalat.
tan = [Ca2+] = [ C2O24 ] + [ HC2O4 ] + [H2C2O4]
iu c ngha l, nu chng ta c th tnh mt i lng bt k no trong nhng i
lng y, chng ta s gii c bi tp.
Giai on 3. Biu din hng s cn bng.
T = [Ca2+][ C2O42 ] = 2,3.109

(5.4)

D dng hnh dung phng trnh (5.2) nh phn ng phn li ca HC2O4 . Do lin
h gia [ C2O24 ] v [ HC2O4 ] c th s dng gi tr K2 ca axit oxalic.
H3 O+ C2O42

K2 =
HC2O4

(5.5)

Mt cch tng t i vi phng trnh (5.3) :

H3O+ HC2O4

= 5,36.102
K1 =
[H2C2O4 ]

(5.6)

95

Giai on 4. Thit lp phng trnh cn bng vt cht CaC2O4 tan l ngun duy nht ca
Ca2+ v cc dng khc ca oxalat. Do :
[Ca2+] = [ C2O42 ] + [ HC2O4 ] + [H2C2O4]

(5.7)

Ngoi ra, theo iu kin ca bi tp, khi cn bng:

[H3O+] = 1,0.104 mol/l

(5.8)

Giai on 5. Thit lp phng trnh trung ho in. i vi h ny khng nn vit

phng trnh trung ho in ngay, bi v to ra [H3O+] = 1,0.104 mol/l phi a vo
mt lng axit cha bit HX. Phng trnh da trn iu kin trung ho in ca dung dch
cn phi bao hm c nng ion ca axit cha bit. S thit lp phng trnh nh th cha mt
thnh phn ph cha bit nh vy ni chung l khng bt buc.
Giai on 6. So snh s phng trnh v s n s. Chng ta c 4 n s: [Ca2+], [ C2O24 ],
[ HC2O4 ] v [H2C2O4]. Chng ta cng c 4 h thc i s c lp: cc phng trnh (5.4),
(5.5), (5.6), (5.7). Do , v nguyn tc c th gii chnh xc v bi tp c quy v php
bin i i s.
Giai on 7. S gn ng. V cc s liu nn c th gii chnh xc.
Giai on 8. Gii phng trnh. S thay th tng ng vo phng trnh (5.7) lin kt
[Ca ] v [ C2O42 ] l phng php thun li gii. Ban u chng ta cn din t [ HC2O4 ]
2+

v [H2C2O4] qua [ C2O24 ].

Sau thay vo phng trnh (5.5) gi tr [H3O+] = 1,00.104 mol/l:
(1,00.104 ) C2O42

= 5,42.105

HC2O4

T :
HC2O4

(1,00.104 ) C2O42

= 1,84.102 C O2
=
5
2 4
5,42.10

Sau khi thay th cc h thc thu c v nng ion hiro vo phng trnh (5.6) ta thu
c:
1,00.104 1,84 C2O24

= 5,36.102
[H2C2O4 ]

T :

96
1,00.104 1,84 C2O42

= 0,0034 C O2
[H2C2O4 ] =
2
2 4
5,36.10

Thay th nhng gi tr [H2C2O4] v [ HC2O4 ] tm c vo phng trnh (5.7):

[Ca2+] = [ C2O42 ] + 1,84 [ C2O42 ] + 0,0034 [ C2O42 ] = 2,84 [ C2O42 ]
Vy:
Ca2+

C2O24 =

2,84

Thay [ C2O42 ] bng kt qu trn vo phng trnh (5.4):

Ca2+
= 2,3.109 mol / l
Ca2+

2,84

[Ca2+]2 = 6,53.109 mol/l

[Ca2+]

8,1.105 mol/l

T , sau khi nh li giai on 2 chng ta i ti kt lun l:

tan ca CaC2O4 = 8,1.105M

5.2.2 Tnh tan nhng nng ion hiro khc nhau

Nhng kt ta cha anion baz, v d canxi oxalat hoc cation axit, v d nh bismut
ioua ng gp phn ca mnh vo nng ion hiro trong dung dch nc. Do , nu
nng ion hiro khng c gi hng nh nh mt cn bng no n s ph thuc vo
tan ca kt ta. V d, dung dch bo ho ca canxi oxalat c phn ng kim v tn ti
nhng cn bng:
CaC2O4 (rn)

Ca2+ + C2O42

C2O24 + H2O

HC2O4 + OH

HC2O4 + H2O

H2C2O4 + OH

Khc vi trng hp trn, nng ca ion hiroxyl trong trng hp ny cha bit nn
cn thit phi thit lp phng trnh i s ph.

97

Trong phn ln trng hp khng nn b qua tng tc ca kt ta vi nc, v khng

chp nhn c nhng sai s trong cc php tnh. Theo bng 5.1, gi tr sai s ph thuc vo
tan ca kt ta v hng s phn li baz ca anion. tan ca kt ta MA c k ti phn
ng ca A vi nc c gii thiu ct th t. ct th nm dn ra nhng kt qu tnh
khng k tnh baz ca A; tan trong trng hp ny, mt cch n gin, bng cn bc hai
ca tch s tan. Nhng tnh ton c thc hin i vi hai kt ta vi tch s tan 1,0.1010
v 1,0.1020 mt gi tr hng s baz ca A. R rng l s b qua tng tc ca anion vi
nc dn ti sai s m; sai s ny cng tr thnh r rng hn khi tan ca kt ta cng ln,
ngha l T cng ln v anion ca kt ta l baz cng mnh.
Bng 5.1 tan ca kt ta MA, c tnh nhng gi tr T v Kb khc nhau
Hng s Hng s baz tan ca MA
Tch s
phn li ca ca A
tnh
c,
tan MA
HA, KHA
mol/l
Kb = Kw/KHA

tan ca MA tnh
c khi khng k ti
phn ng vi nc,
mol/l

1,0.1010

1,0.1020

1,0.106

1,0.108

1,02.105

1,0.105

1,0.108

1,0.106

1,2.105

1,0.105

1,0.1010

1,0.104

2,4.105

1,0.105

1,0.1012

1,0.102

10.105

1,0.105

1,0.106

1,0.108

1,05.1010

1,0.1010

1,0.108

1,0.106

3,3.1010

1,0.1010

1,0.1010

1,0.104

32.1010

1,0.1010

1,0.1012

1,0.102

290.1010

1,0.1010

Thit lp nhng phng trnh i s tch s tan ca kt ta khng c g kh khn

nhng gii chng tn nhiu cng sc. Rt may mn l n gin nhng php tnh i s,
thng c th thc hin mt trong hai gi thit. Gi thit th nht c ng dng i vi
nhng kt ta c tan trung bnh, anion tham gia vo thnh phn kt ta phn ng vi nc.
Trong trng hp ny, gi thit rng nng ion hiroxyl c th b qua nng ca ion
hiro trong cc php tnh, ni mt cch khc nng ca ion hiroxyl c xc nh mt
cch c bit bng phn ng ca anion vi nc, cn s ng gp ion hiroxyl do s phn li
ca nc c th b qua.
Gi thit loi th hai dng cho kt ta c tan rt thp, c bit l cc kt ta cha
anion phn ng yu vi nc. Trong nhng trng hp c th gi thit rng s ho tan kt
ta lm bin i nng ion hiro hoc hiroxyl trong dung dch mt i lng khng ng
k v nng thc t bng 107 M. Php tnh tan khi tr thnh tng t nh lm
trong v d trc y.

98

Di y dn ra cc v d tnh ton theo mi loi ca nhng loi k trn.

V d 1. Hy tnh tan ca PbCO3 trong nc. gii bi tp chng ta thit lp nhng
phng trnh m t h:
Pb2+ + CO32

PbCO3

(5.9)

CO32 + H2O

HCO3 + OH

(5.10)

HCO3 + H2O

H2CO3 + OH

(5.11)

2H2O

H3O+ + OH

(5.12)

tan ca PbCO3 c th din t nh sau:

tan = [Pb2+] = [ CO32 ] + [ HCO3 ] + [H2CO3]
Nhng hng s cn bng c din t nh sau:
[Pb2+][ CO32 ] = T = 3,3.1014

(5.13)

HCO3 OH K

= H2O = 2,13.102
2
K2
[CO3 ]

(5.14)

[H2CO3 ] OH
[HCO3 ]

K H2O
K1

1,00.1014
4,45.107

= 2,25.108

(5.15)

Ngoi ra:
[H3O+][OH] = 1,00.1014

(5.16)

Chng ta vit phng trnh cn bng vt cht:

[Pb2+] = [ CO32 ] + [ HCO3 ] + [H2CO3]

(5.17)

i vi h cng c th thit lp phng trnh trung ho in:

2[Pb2+] + [H3O+] = 2[ CO32 ] + [ HCO3 ] + [OH]

(5.18)

Nh vy, chng ta c su phng trnh vi su n s, chnh l: [Pb2+], [ CO32 ],

[ HCO3 ], [H2CO3], [OH], [H3O+]. gii h phng trnh cn nhng php tnh i s rt
phc tp. iu bt buc chng ta phi tm cch gii d dng hn nh mt s php gn
ng. Trong v d ny, phn xt theo gi tr hng s cn bng ca cc phn ng (5.13), (5.14),

99

(5.15) ta thy, kt ta kh tan, cha anion d dng phn ng vi nc. Do chng ta c th

hi vng rng khi ho tan kt ta nng ca ion hiroxyl tng ln ng k v nng ca ion
hiro b gim i tng ng. Sau , r rng l trong phng trnh (5 .18) [H3O+] << 2[Pb2+]
v nng ca ion hiro c th b qua. Gi thit th hai da trn s kin l cn bng to
thnh H2CO3 (phng trnh (5.11)) tng i khng ng k so vi cn bng to thnh HCO3
(phng trnh (5.10)). Do nng H2CO3 nh hn rt nhiu so vi nng HCO3 . Gi
thit hon ton c c s v i lng K H2O /K1 bng K H2O /10000 K2 (xem phng trnh
(5.14) v (5.15)).
Nu [H3O+] thc t nh hn mt thnh phn bt k trong phng trnh (5.18), v [ HCO3 ]
>> [H2CO3] th phng trnh (5.17) c n gin:
[Pb+] = [ CO32 ] + [ HCO3 ]

(5.19)

Phng trnh (5.18) c dng sau:

2[Pb2+] = 2[ CO32 ] + [ HCO3 ] + [OH]

(5.20)

S cn thit ca cc phng trnh (5.15) v (5.16) by gi khng cn na. Nh vy

chng ta n gin s phng trnh v s n s n 4.
Nhn phng trnh (5.19) vi 2 v tr i phng trnh (5.20):
0 = [OH] [ HCO3 ]
hoc l:
[OH] = [HCO3]

(5.21)

Thay [OH] bng [ HCO3 ] vo phng trnh (5.14):

2

HCO3

= K H2O
2
K2
[CO3 ]

HCO3 =

K H2O
K2

CO32

Phng trnh thu c cho php loi tr [ HCO3 ] ca phng trnh (5.19):
Pb2+ = CO32 +

K H2O
K2

CO32

(5.22)

100

T phng trnh (5.13) chng ta thu c:

T
CO32 =

Pb2+

Thay phng trnh i vi [ CO32 ] vo phng trnh (5.22).

K H2O .T
T
Pb2+ =
+

Pb2+
K 2 Pb2+

ng mu s v sp xp li cc thnh phn:
K H2O .T Pb2+

T = 0

K2

2+

Pb

V cui cng, sau khi thay th gi tr bng s ca cc hng s ta c:

[Pb2+]2 2,65.109.[Pb2+]1/2 3,3.1014 = 0
D dng gii phng trnh c rt ra bng phng php gn ng lin tip. V d,
chng ta gi thit rng [Pb2+] = 0, khi phn bn phi ca phng trnh c gi tr 3,3.1014.
Mt khc nu [Pb2+] = 105 M chng ta thu c gi tr 9.1011. Thc cht:
(105)2 (2,56.109) (105)1/2 3,3.1014 = 9.1011
Nu [Pb2+] = 106 M th:
(106)2 (2,56.109) (106)1/2 3,3.1014 = 2.1012
R rng l, [Pb2+] nm gia 106 v 105 M. Gi tr th [Pb2+] = 5.106 M cho gi tr +
1,9.1011 M. y du cng ch r rng l gi tr th qu ln. Nhng sai s gn ng tip
theo dn ti gi tr [Pb2+] = 1,9.106 M.
tan PbCO3 = 1,9.106 M
kim tra ng n ca nhng gi tr cn thit nu chng ta cn phi tnh nng
ca phn ln cc ion trong dung dch. Tnh [ CO32 ] t phng trnh (5.13):
14
CO2 = 3,3.10
= 1,7.108 M
3

1,9.106

Sau t phng trnh (5.19) ta c:

[ HCO3 ] = 1,9.106 1,7.108 1,9.106 M

101

v t phng trnh (5.21):

[OH] = [HCO3] = 1,9.106 M
Theo phng trnh (5.15):

[H2CO3 ].1,9.106
1,9.10

= 2,25.108

[H2CO3] = 2,25.108 ion.g/l

Cui cng, tng ng vi phng trnh (5.16)
[H3O+ ] =

1,00.1014
1,9.10

= 5,3.109 ion.g / l

Chng ta thy rng nhng gi thit c chng ta chp nhn khng dn ti sai s ng
k. [H2CO3] bng khong 1/90 [ HCO3 ], cn [H3O+] r rng nh hn nhiu nng tng
cng ca cc ion cacbonat v hirocacbonat trong phng trnh (5.18).
V cui cng, nu nh khng k ti tnh cht baz ca CO32 chng ta thu c tan
1,8.107 ch bng mt phn mi i lng tnh bng phng php chnh xc hn.
V d 2. Tnh tan ca bc sunfua trong nc tinh khit. Nhng phng trnh c bn l:
Ag2S (rn)

2Ag+ + S2

(5.23)

S2 + H2O

HS + OH

(5.24)

HS + H2O

H2S + OH

(5.25)

2H2O

H3O+ + OH

(5.26)

C th hnh dung tan nh sau:

tan =

1
[Ag+] = [S2] + [HS] + [H2S]
2

Cc phng trnh cho cc hng s cn bng:

[Ag+]2 [S2] = 6.1050

(5.27)

HS OH K
14

= H2O = 1,0.10
= 8,3
K2
S2
1,2.1013

(5.28)

102

[H2S] OH
HS

K H2O
K1

1,0.1014
5,7.10

= 1,8.107

(5.29)

Nhng phng trnh cn bng vt cht v trung ho in:

1
[Ag+] = [S2] + [HS] + [H2S]
2

(5.30)

[Ag+] + [H3O+] = 2[S2] + [HS] + [OH]

(5.31)

Tch s tan ca Ag2S rt nh, do chc chn l s ho tan kt ta khng gy nn mt s

bin i ng k nng ion hiroxyl trong dung dch. V vy, chng ta chp nhn rng khi
cn bng:
[OH] [H3O+] = 1,0.107 ion.g/l
Gi thit ng iu kin l trong phng trnh (5.31):
[Ag+] << [H3O+] v (2[S2] + [HS]) << [OH]
Chng ta thay [OH] trong cc phng trnh (5.28) v (5.29) bng gi tr 1,0.107:

[H2S] =
S2

[H2S]
HS

1,0.1014
1,2.10

13

.10

1,0.1014
5,7.108.107

= 8,3.107

= 1,8

Sau khi thay th nhng h thc vo phng trnh (5.30) ta c:

1
[Ag+] = [S2] + 8,3.107 [S2] + 14,9.107 [S2]
2

[S2] = 2,16.109 [Ag+]

Thay h thc cui cng vo phng trnh tch s tan ta c:
2,16.109 [Ag+]3 = 6.1050
[Ag+] = 3,0.1014 ion.g/l
tan =

1
[Ag+] = 1,5.1014 M
2

103

Gi thit cho rng [Ag+]nh hn nhiu so vi [H3O+] r rng l c c s. Chng ta c th

d dng tnh (2[S2] + [HS]) v khng nh c rng tng s cng nh hn [OH] rt
nhiu. T chng ta i n kt lun l nhng gi thit nu l chp nhn c v cch gii
gn ng l tho mn.

5.2.3 tan ca hiroxit kim loi trong nc

xc nh tan ca hiroxit kim loi cn xt hai cn bng. V d, i vi hiroxit kim
loi ho tr (II) M2+:
M2+

M(OH)2 (rn)

+ OH

H3O+ + OH

2H2O

c th d dng m t qu trnh bng phng trnh i s:

[M2+] [OH]2 = T

(5.32)

[H3O+] [OH] = Kn

(5.33)

v phng trnh cui m t theo iu kin trung ho in:

2[M2+] + [H3O+] = [OH]

(5.34)

Nu hiroxit tan kh, nng ion hiro s nh v phng trnh (5.34) c n gin
ho:
2[M2+] [OH]
Thay h thc vo phng trnh (5.32) v sau khi bin i ta c:
[M2+] = (T/4)1/3 = tan

(5.35)

Mt khc, tan rt thp ca M(OH)2, i lng 2[M2+] nh hn [H3O+] rt nhiu v

phng trnh (5.34) tr thnh:
[H3O+] [OH] = 1,00.107 M
Thay kt qu thu c vo phng trnh (5.32) mt ln na v sp xp li cc thnh phn
ca phng trnh:
[M2+ ] =

T
2

[OH ]

T
1,0.1014

= tan

V d: Tnh tan Fe(OH)3 trong nc.

(5.36)

104

Chng ta chp nhn rng phng trnh trung ho in c th n gin n

phng trnh sau:
3[Fe3+] + [H3O+] 3[Fe3+] = [OH]
lm gi thit gii.
Thay [OH] vo phng trnh tch s tan:
[Fe3+] (3[Fe3+])3 = 4.1038
[Fe3+] = (4.1038/27)1/4 = 2.1010 M
tan = 2.1010 M
Nhng chng ta gi thit rng:
[OH] 3[Fe3+] = 3.2.1010 = 6.1010 M
T suy ra rng:
[H3 O+ ] =

1,00.1014
6.10

10

= 1,7.105 M

R rng l khng nn xem [H3O+] nh hn 3[Fe3+] rt nhiu. S tht, trong trng hp

ny quan st thy hin tng ngc li:
3[Fe3+] << [H3O+]
v phng trnh trung ho in c quy v phng trnh sau:
[H3O+] = [OH] = 1,0.107 M
Sau khi thay [OH] vo phng trnh tch s tan ta c:
[Fe3+ ] =

4.1028
[1,00.10

7 3

= 4.1017 M

tan = 4.1017 M
Gi thit cho rng 3[Fe3+] << [H3O+] r rng l ng n. Cn nhn mnh rng, trong
php tnh u, khi a ra mt gi thit khng ng tin cy th nhn c sai s rt ln.
V d trn y ch r tan ca hiroxit kim loi c tnh ton tng t cch tnh tan
ca hp cht cha baz yu. Sau khi chp nhn mt trong hai php tnh gn ng th nhng
php tnh c th c n gin ho. Nhng chc chn l s c mt vng gi tr tch s tan,
khng mt php tnh gn ng no ng dng c v i vi trng hp cn phi

105

gii cc phng trnh (5.32), (5.33) v (5.34) theo ba n s, bng 5.2 ch ra nhng gii hn
ca vng i vi nhng kt ta loi M(OH)2.

Bng 5.2 Sai s tng i ca nhng php tnh gn ng tan ca kt ta

tan tnh
Gi tr T
c khng
c
s
dng
chp
php
gn
nhn
ng

Sai s gy ra
tan tnh
tan tnh Sai s gy ra
do s dng
c
theo
c
theo do s dng
phng
phng trnh
phng trnh phng trnh
trnh

1,00.1018 6,3.107

6,3.107

1,00.1020 1,24.107

(5.36)

(5.36), %

0,00

1,00.104

1,6.104

1,36.107

9,7

1,00.106

7,1.102

1,00.1022 8,4.109

2,92.108

2,5.102

1,00.108

1,9.101

1,00.1024 1,00.1010

6,3.109

6,2.103

1,00.1010

0,00

1,00.1026 1,00.1012

1,36.109

1,4.105

1,00.1012

0,00

5.3

(5.35)

(5.35), %

nh hng ca s to phc n tan

tan ca kt ta c th bin i nhiu khi c mt mt s cht to phc tan vi anion v

cation ca kt ta. V d s kt ta nhm bng baz khng bao gi hon ton khi c mt ion
florua mc d tan ca hiroxit nhm cc nh. Phc florua nhm kh bn cn tr s xut
hin nh lng cation Al3+ trong dung dch. Khi thit lp nhng cn bng sau:
Al(OH) 3 (rn)

Al3+
+
6F

AlF6

+ 3OH

Nh vy, ion florua y cnh tranh thng li vi ion hiroxyl phn ng vi nhm (III).
Nng ion florua cng cao th tan ca kt ta cng ln do s to thnh [AlF6]3.
Nu bit hng s bn ca phc, c th tnh tan ca kt ta khi c mt thuc th to
phc. Khi nhng bin php c s dng tng t nhng phng php c m t
trong phn trn.

106

V d: Hy tnh tan ca AgBr trong dung dch NH3 0,1 M. Nhng cn bng
trong dung dch:

AgNH3+

AgBr (rn)

Ag+ + Br

Ag+ + NH3

AgNH3+
+

Ag ( NH3 )2

+ NH3

NH3 + H2O

NH4+ + OH

Chng ta xc nh n s:
tan ca AgBr = [Br] = [Ag+] + [ AgNH3+ ] + [ Ag ( NH3 )2+ ]
Nhng hng s cn bng tng ng:
[Ag+] [Br] = T = 5,2.1013

(5.37)

AgNH3+

= K = 2,0.103
1
+
Ag [NH3 ]

(5.38)

Ag ( NH )+
3 2

= K = 6,9.103
2
+
AgNH3 [NH3 ]

(5.39)

NH4+ OH

= K = 1,76.105
b
[NH3 ]

(5.40)

Phng trnh cn bng vt cht:

[Br] = [Ag+] + [ AgNH3+ ] + [ Ag ( NH3 )2+ ]

(5.41)

V nng u ca amoniac bng 0,10 M, nn c th vit:

0,10 = [NH3] + [ AgNH3+ ] + 2[ Ag ( NH3 )2+ ] + [ NH4+ ]

(5.42)

Ngoi ra, trong tng tc ca amoniac vi nc, c mi ion NH4+ xut hin, mt ion OH
c to thnh. Nh vy:
[OH] [ NH4+ ]

(5.43)

107

Phng trnh trung ho in:

[ NH4+ ] + [Ag+] + [ AgNH3+ ] + 2[ Ag ( NH3 )2+ ] = [Br] + [OH]

(5.44) (1)

S nghin cu cn thn tm phng trnh trn ch r rng, 7 trong s l phng trnh

c lp v phng trnh (5.44) suy ra c t phng trnh (5.41) v (5.43). Nhng v s n
s bng 7 nn c th gii c.
Gi thit:
a/ [ NH4+ ] nh hn rt nhiu so vi cc thnh phn khc ca phng trnh (5.42). Gi thit
l c c s nu k ti gi tr bng s kh nh ca hng s baz ca amoniac (phng trnh
(5.40)).
b/ [ Ag ( NH3 )2+ ] >> [ AgNH3+ ] v [Ag+]. Loi tr nhng dung dch amoniac rt long, gi
thit l c c s. iu c suy ra t gi tr hng s cn bng ca cc phng trnh
(5.38) v (5.39).
Thc hin nhng gi thit y dn ti s n gin cc phng trnh.
[Br] [ Ag ( NH3 )2+ ]

(5.45)

[NH3] 0,10 2[ Ag ( NH3 )2+ ]

(5.46)

Sau khi thay phng trnh (5.45) vo phng trnh (5.46) ta c:

[NH3] = 0,10 2[Br]

(5.47)

Nhn phng trnh (5.38) vi (5.39):

Ag ( NH )+
3 2

= K K = 1,38.107
1 2
Ag + [NH3 ]2

(5.48)

Thay th cc phng trnh (5.47) v (5.45) vo phng trnh cui cng ta c:

[Br ]
+

[Ag ](0,10 2[Br ])

= 1,38.107

Thay th [Ag+] bng gi tr tng ng t phng trnh (5.37) vo phng trnh trn ta
c:

(1)

Chng ta b qua [H3O ] bi v nng ca ion hidro trong dung dch amoniac 0,10 M l khng ng k.

108
[Br ]
= 1,38.107
5,2.1013

0,10 2[Br ]

[Br ]

hoc:
[Br ]2

(0,10 2[Br ])

= 7,2.106

C th bin i phng trnh thu c phng trnh bc hai:

[Br]2 + 2,88.106[Br] 7,2.108 = 0
T :
[Br] = 2,7.104 mol/l
tan = 2,7.104 mol/l
S kim tra ch r rng nhng gi thit ra l c c s.
S to phc vi ion cng tn ca kt ta. Nhiu kt ta c th phn ng vi mt trong s
nhng ion ca kt ta to thnh nhng phc tan. V d, bc clorua to nhng phc clorua c
thnh phn AgCl2 , AgCl32 ..., nhng nng ion cng tn cao nhng phn ng ny lm
tng tan ca kt ta. S tng tan khi c d ion cng tn hon ton khng phi l him
hoi. Ngi ta c bit ch ti nhng hiroxit lng tnh nh hiroxit nhm v km. Nhng
hiroxit ny dng kt ta t tan, di tc dng ca baz tr thnh nhng dung dch ion.
Chng ho tan khi d ion hiroxyl to thnh phc hiroxo ca nhm v km. i vi nhm
c th hnh dung cn bng nh th ny:
Al3+ + 3OH

Al(OH)3 (rn)

Al(OH)3 (rn) + OH

Al(OH)4

Nh trong trng hp bc clorua, tan ca hiroxit nhm v km tri qua cc tiu v

sau tng ln t ngt khi tng nng ion cng tn. C th d dng tnh nng ion
hiroxyl tng ng vi tan cc tiu khi bit cc hng s cn bng ca phn ng.
V d: nng OH bng bao nhiu th tan ca Zn(OH)2 l cc tiu. Hy tnh tan
cc tiu.
Cc cn bng:
Zn(OH)2 (rn)

Zn2+ + 2OH

109
Zn(OH)24

Zn(OH)2 (rn) + 2OH

Chng ta k hiu tan ca Zn(OH)2 l S. Khi :

S = [Zn2+] + [ Zn(OH)24 ]

(5.49)

Hng s cn bng:
T = [Zn2+] [OH]2 = 1,2.1017

(5.50)

Zn(OH)24
= 0,13
K=
2
OH

(5.51)

Thay phng trnh (5.50) v (5.51) vo phng trnh (5.49):

S=

OH

+ K OH

(5.52)

thu c tan cc tiu chng ta ly vi phn phng trnh (5.52) v cho o hm ca

S theo [OH] tin ti khng:
dS

d OH

2T
OH

2K OH

Nu:
dS
d OH

=0

2T

th:

OH

= 2K OH

T :
1/ 4

OH = 2T

2K

1/ 4

1,2.1017
=

0,13

= 9,8.105

Ngi ta thu c tan cc tiu khi thay th nng ion hiroxyl tnh ton c vo
phng trnh (5.52):

110

1,2.1017
5 2
9
Scc tiu =
+ 0,13(9,8.10 ) = 2,5.10
5 2
(9,8.10 )

5.4

nh hng ca nng cht in li n tan

Bng thc nghim ngi ta pht hin rng, kt ta thng tan trong dung dch cht in li
nhiu hn so vi trong nc, tt nhin l iu kin cht in li khng cha ion cng tn vi
kt ta. Hnh 5.1 minh ha nh hng ca cht in li n tan ca ba kt ta.
Khi tng nng kali nitrat trong dung dch t 0 n 0,02 M, tan ca bari sunfat tng
gp i. tan ca bari ioat cng khong bin i nng cht in li nh vy ch tng
1,25 ln v ca bc clorua tng 1,20 ln.
nh hng ca cht in li ti tan c gii thch bng sc ht tch in gia cc ion
ca kt ta v cc ion l tch in tri du. Nhng tng tc gy nn s chuyn dch cn
bng ca phn ng ho tan. iu quan trng l, cn hiu rng hin tng khng ch quan
st thy trong cc cn bng ho tan - kt ta m cn trong tt c cc dng cn li ca cn
bng. V d, nhng d kin trong bng 5.3 ch r rng, khi c mt natri clorua mc phn li
ca axit axetic tng ln ng k. Nhng hng s phn li dn ra thu c bng cch o thc
nghim nhng nng cn bng ca ion hiro v ion axetat trong dung dch cha mui
nng nu. Trong trng hp ny, s chuyn dch cn bng r rt cng c th c xp
vo loi do lc ht ca ion cht in li vi nhng ion hiro v ion axetat.

111
Hnh 5.1
nh hng ca nng cht in li n tan ca mt s mui

T nhng d liu c th rt ra mt kt lun: nh lut cn bng cng thc c

dn ra trc y c gii hn v chng ta ch ng dng cho nhng dung dch rt long, trong
nng cht in li khng ng k (ngha l dung dch l tng, xem chng IV). By
gi xt ti cng thc cht ch hn ca nh lut c th dng cho nhng dung dch khng l
tng.
Bng 5.3 Hng s phn li ca axit axetic trong cc dung dch natri clorua 25oC
Nng NaCl, M

K 'a biu kin

0,00

1,75.105

0,02

2.29.105

0,11

2,85.105

0,51

3,31.105

1,01

3,16.105

Nhiu cng trnh nghin cu nh hng ca nng cht in li n cn bng ho hc

cho php rt ra nhng khi qut quan trng. Mt trong nhng khi qut l, hiu ng nng
cht in li ph thuc nhiu vo in tch ca cc ht tham gia vo cn bng. Nu cc ht
trung ho in th hng s cn bng bin i t nhng khi in tch ca cc ht tham gia phn
ng hoc sn phm ca phn ng cng ln th hiu ng cng tr nn r rt. V d, khi thm
lng va phi kali nitrat th trong hai cn bng:
AgCl (rn)
BaSO4 (rn)

Ag+ + Cl
Ba2+ + SO24

cn bng th hai chuyn mnh v bn phi hn cn bng th nht (xem hnh 5.1).
iu khi qut quan trng th hai l nh hng ca cht in li trong mt khong rng
nng thc t khng ph thuc vo bn cht ca n m ch ph thuc vo thng s nng
ion ca dung dch qua lc ion :
Lc ion =

1
(m1Z12 + m2Z22 + m3Z32 +.. .)
2

(5.53)

112

y m1, m2, m3... l nng phn t ca cc ion khc nhau trong dung dch;
cn Z1, Z2, Z3 l in tch ca cc ion tng ng.
V d: Lc ion ca dung dch KNO3 0,1 M ca dung dch Na2SO4 0,1 M l bao nhiu?
Trong dung dch KNO3, mK + v mNO u bng 0,1 v:
3

1
(0,1.12 + 0,1.12) = 0,1
2

Trong dung dch Na2SO4, mNa+ = 0,2 v mSO2 = 0,1, do :

4

1
(0,2.12 + 0,1.22) = 0,3
2

V d: Lc ion ca dung dch KNO3 0,05 M v Na2SO4 0,1 M bng bao nhiu?
=

1
(0,05.12 + 0,05.12 + 0,2.12 + 0,1.22) = 0,35
2

T cc v d ta thy rng, lc ion ca cc dung dch cht in li mnh c to thnh

t cc ion mt in tch bng nng phn t ca chng. Trong cc dung dch ca cc hp
cht to thnh t nhng ion nhiu in tch, lc ion ln hn nng phn t.
Ngi ta pht hin rng trong cc dung dch c lc ion nh hn 0,1, nh hng ca cht
in li khng ph thuc vo bn cht ion v c xc nh ch bng lc ion. Do , phn li
ca axit axetic l ng nht khi c mt natri clorua, kali nitrat hoc bari ioua iu kin
nng ca cc cht in li m bo lc ion ng nht. Cn nhn xt rng, quy lut
lc ion cao b ph v.
Hot v h s hot . m t nh lng nh hng ca lc ion n cn bng, cc
nh ho hc s dng thng s hot . Hot c xc nh nh sau:
aa = [A].fA
y aa l hot ca cht A, [A] l nng phn t, fA l i lng khng th nguyn,
c gi l h s hot . H s hot (v do , c hot ) ca cht A bin i khi lc ion
bin i. Nh vy l khi thay th [A] bng a trong phng trnh hng s cn bng, gi tr bng
s ca hng s cn bng khng ph thuc vo lc ion. Chng ta minh ha iu v d v
s phn li ca axit axetic:
Ka =

aH

3O

a Ax

aHAx

H3 O+ Ax f
f

H3O+ Ax
=
fHAx
[HAx ]

113

y fH O+ , fAx v fHAx bin i theo s bin i ca lc ion cho Ka hng nh trong

3

mt khong rng gi tr lc ion, khc vi K 'a biu kin c dn ra bng 5.3.

Nhng tnh cht ca h s hot . H s hot c nhng tnh cht sau:
1. C th hnh dung h s hot nh thc o s tham gia ca cc cht in li vo cn
bng ho hc. Trong cc dung dch rt long, khi lc ion nh nht, i lng tr thnh
hng nh v h s hot nhn gi tr bng n v, iu kin hot v nng phn
t l ng nht. Khi tng lc ion, s tham gia ca ion vo cn bng gim xung v h s hot
ca n gim xung. Tng kt v s dng nhng i lng a vo phng trnh (5.54) c
th ni: lc ion va phi fA < 1; khi pha long v hn fA 1 v do aA [A]. nhng
lc ion cao, h s hot i vi mt s cht tng ln v thm ch c th tr thnh ln hn
n v; gii thch tnh cht ca cc dung dch trong vng kh phc tp. Chng ta gii hn
trong phn ln nhng bn lun trong vng gi tr lc ion (khi M < 0,1) thp hoc va. Nhng
ng cong in hnh biu din s ph thuc ca h s hot vo lc ion c dn ra trn
hnh 5.2.
2. Trong nhng dung dch khng qu m c, h s hot ca mt cht cho khng
ph thuc vo bn cht cht in li v c xc nh ch bng lc ion.
3. lc ion cho in tch ca ion cng ln th h s hot ca n khc n v cng
ln. iu c minh ha trn hnh 5.2. H s hot ca nhng phn t khng tch in
gn nh khng ph thuc vo lc ion.

Hnh 5.2
S ph thuc ca h s hot vo lc ion

4. lc ion xc nh, h s hot ca nhng ion c s in tch ging nhau xp x bng

nhau. S sai lch khng ln gn lin vi kch thc hiu dng ca ion hirat ho.

114

5. H s hot m t tnh cht thc s ca mt ion trong cn bng m n

tham gia. V d, lc ion xc nh mt v ch mt h s hot m t nh hng ca ion
xianua n cn bng bt k trong s nhng cn bng c dn ra di y:
HCN + H2O

H3O+ + CN

Ag(CN) (rn)

Ag+ + CN

Ni(CN)24

Ni2+ + 4CN

Tnh h s hot . Nm 1923, P. Debye v E. Huckel a ra phng trnh l thuyt

sau y cho php tnh h s hot ca ion:
lg fA =

0,5085 Z2A

(5.55)

1 + 0,3281 a A

y: fA l h s hot ca A, ZA l in tch ca A, l lc ion ca dung dch, aA l

bn knh hiu dng ca ion hirat ho o bng anstron, (1 anstron = 108 cm). Nhng hng
s 0,5085 v 0,3281 ng vi dung dch 25oC, nhng nhit khc th phi s dng
nhng gi tr khc.
ng tic l gi tr aA trong phng trnh (5.55) mang tnh khng xc nh ln. Gi tr aA
ca phn ln cc ion mt in tch gn vi 3 , do i vi nhng hp cht tng ng, mu
s ca phng trnh Debye - Huckel c n gin n (1 + ). aA ca cc ion in tch cao
c th t ti 10 . Cn nhn xt thm rng, lc ion nh hn 0,01, thnh phn th hai
mu s tr thnh nh so vi thnh phn th nht. Trong iu kin tnh khng xc nh
trong gi tr aA khng nh hng ln trong tnh ton h s hot .
Kielland tnh gi tr aA cho s ln ion t nhiu d kin thc nghim. Nhng gi tr tt
nht ca bn knh ion hiu dng c dn ra bng 5.4. y cng gii thiu c h s hot
c tnh ton theo phng trnh (5.55) c s dng cc kch thc .
S kim tra thc nghim nhng gi tr h s hot ca nhng ion ring bit c dn ra
bng 5.4, rt ng tic l khng th thc hin. Tt c cc phng trnh thc nghim ch cho
gi tr h s hot trung bnh ca cc ion tch in dng v m trong dung dch. Nhng cn
ch rng h s hot trung bnh tnh ton c nh cc d kin ca bng 5.4 kh ph hp
vi nhng gi tr tm c bng thc nghim.
H s hot trung bnh ca cht in li AmBn c xc nh nh sau:
H s hot trung bnh f+ = (fAm.fBn)1/(m+n)
Bng 5.4 H s hot ca cc ion 25oC
Ion

Bn knh H s hot lc ion tng ng

115

hiu
dng aA, 0,001

0,005

0,01

0,05

0,1

H3O+

0,967

0,933

0,914

0,860

0,830

Li+, C6H5COO

0,965

0,929

0,907

0,840

0,800

0,964

0,928

0,902

0,820

0,780

OH, F, SCN, HS, ClO3

, ClO4 , BrO3, IO4, 3,5
MnO4

0,964

0,926

0,900

0,810

0,760

K+, Cl, Br, I, CN, NO2,

3
NO3 , HCOO

0,964

0,925

0,899

0,800

0,760

Rb+, Cs+, Tl+, Ag+, NH4+

2,5

0,964

0,924

0,898

0,800

0,750

Mg2+, Be2+

0,872

0,755

0,690

0,520

0,450

Ca2+, Cu2+, Zn2+ Sn2+,

Mn2+, Fe2+ Ni2+, Cs2+, 6
Phtalat2

0,870

0,749

0,675

0,480

0,400

Sr2+, Ba2+, Cd2+, Hg2+, S2

0,868

0,744

0,670

0,460

0,380

Pb2+, CO32, SO32 CrO42

4,5

0,868

0,742

0,665

0,460

0,370

Hg2+,
SO42,
CrO42, HPO42

4,0

0,867

0,740

0,660

0,440

0,360

Al3+, Fe3+, Cr3+ La3+ Ce3+

0,738

0,540

0,440

0,240

0,180

PO43, Fe(CN)63

0,725

0,500

0,400

0,160

0,095

Th4+, Zn4+, Ce4+ Sn4+

11

0,588

0,350

0,255

0,100

0,065

Fe(CN)64

0,570

0,310

0,200

0,048

0,021

Na+,
IO3,
HCO3,
H2AsO4, Ax

HSO3,
H2PO4, 4 4,5

S2O32,

C th o c h s hot trung bnh bng mt s phng php nhng khng nn quy

gi tr thc nghim tm c lm h s hot cho mt ion ring bit fA hoc fB. V d, i
vi kt ta AmBn c th vit:

116

T = [A]m [B]n fAm fBn = [A]m [B]n f(m +n)

o tan ca AmBn nng cht in li tin ti khng, ngha l fA v fB 1 chng
ta c th thu c gi tr T. o tan ln th hai lc ion ta c gi tr [A] v [B]. Nhng
d kin thu c cho php tnh fAm. fBn = f(m +n) lc ion . iu quan trng l cn hiu
rng, nhng d kin thc nghim khng tnh gi tr ring fA v fB v cng khng th
thu c mt thng bo thc nghim ph no cho php nh gi nhng gi tr . C mt quy
lut tng qut: Xc nh bng thc nghim h s hot ring c l l khng thc hin ni.
Nh cng thc Debye - Huckel v nhng d kin ca bng 5.4 c th tnh ton c h
s hot lc ion nh hn 0,1. gi tr cao hn s tnh ton theo cng thc dn ti sai
s v cn phi s dng nhng gi tr h s hot trung bnh tm c bng thc nghim.
Tnh ton tan c s dng h s hot . S dng hot thay th cho nng phn t
khi tng hng s cn bng cho php ta thu c thng bo chnh xc hn. Nu khng c
nhng quy c c bit trc nhng gi tr T trong bng thng l tch s hot . (Nhng
hng s c din t bng hot , i khi ngi ta gi l hng s nhit ng hc). Nh vy,
i vi kt ta AmBn c th vit:
T = aAm bBn = [A]m [B]n fAm fBn
hoc:
T

[A]m [B]n =
fA

fBn

= T'

y, trong ngoc vung l nng phn t ca A v B. Khi chia hng s nhit ng T

cho tch s h s hot ca cc ion A v B (hoc cho h s hot trung bnh) c hng s
nng T dng cho cc dung dch vi lc ion xc nh. C th s dng hng s tnh
cn bng ang xt trong chng ny. Chng ta trnh by mt lot php tnh v d sau.
V d: Hy tnh tan ca Ba(IO3)2 trong dung dch Mg(IO3)2 0,033 M. Tch s tan ng
hc ca Ba(IO3)2 bng 1,57.109.
Trc ht ta vit :
9
2
Ba2+ IO3 = 1,57.10
= T'

fBa2+ f 2
IO3

Sau tnh h s hot ca Ba2+ v IO3 theo gi tr lc ion ca dung dch.

=

1
m 2+ 22 + mIO 12

3
2 Mg

117
1
[0,33.4 + 0,066.1 ] = 0,099 0,1
2

Khi tnh chng ta gi thit rng, cc ion Ba2+ v IO3 t kt ta khng th hin nh
hng ng k n lc ion ca dung dch. S n gin l c c s bi v bari ioat c
tan nh. Trong nhng trng hp, khi gi thit l khng tha mn cn tnh gn ng nng
ca c hai ion bng cch thng thng vi gi thit l hot v nng ph hp vi
nhau. Cn tnh nhng nng khi thu c nhng gi tr xc nh hn.
Theo bng 5.4 chng ta tm thy l lc ion 0,1.
fBa2+ = 0,38 ;

fIO = 0,78
3

Nu gi tr lc ion tnh ton c khng ph hp vi mt trong s nhng gi tr c dn

ra trong bng tnh fBa2+ v fIO th cn phi s dng phng trnh (5.55).
3

By gi c th vit:
1,57.109
= 6,8.109 = T'
(0,38) (0,78)

[Ba2+] [ IO3 ]2 = 6,8.109

Chng ta lm tip nh thng l khi tnh tan (chng IV).
tan S
[IO3]

= [Ba2+]
0,066

S (0,066)2 = 6,8.109

S = 1,56.106 M

Rt l th nhn thy rng, tan tnh ton c khng k lc ion bng 3,60.107 M.
B qua h s hot trong cc php tnh cn bng. Mt cch n gin thng chng ta
b qua h s hot trong cc phng trnh cn bng, s dng nng phn t. iu lm
n gin cc php tnh v lm gim i ng k lng thng tin cn thit. Trong phn ln
trng hp sai s gy nn do vic cho h s hot bng n v khng ln n mc lm sai
lch kt qu tnh ton. Nhng t v d trn r rng l, s b qua h s hot trong cc tnh
ton loi c th dn n sai s ng k. Sai s tng i 100% hoc ln hn trong trng
hp ny khng phi l him hoi.
Sinh vin cn ch trong tnh ton bi v i khi s thay th hot bng nng c th
dn ti nhng sai s ln. S khc bit ln c quan st thy trong trng hp lc ion ln
(0,01 v ln hn) hoc ion nhiu in tch (xem bng 5.4). i vi cc dung dch long (lc
ion < 0,01) ca cc cht khng in li hoc cc ion mt in tch, vic s dng nng trong
tnh ton theo nh lut tc dng trng lng thng cho kt qu kh chnh xc.

118

Cng cn nhn mnh rng, s gim tan khi c mt ion cng tn vi ion ca kt
ta c b tr mt phn bng s tng tan ng thi do nng ln ca cc cht in li cha
ion cng tn. Hin tng c minh ha trong v d va phn tch.

5.5

Nhng yu t ph nh hng n tan ca kt ta

Nhit , phn ln cc cht rn khi tan hp th nhit. Do , khi tng nhit thng
tan v tch s tan tng ng ca phn ln cht t tan tng ln.
Thnh phn dung mi. tan ca phn ln cc cht v c trong hn hp nc vi cc
dung mi hu c nh hn r rt so vi nc tinh khit. Nhng d kin v tan ca canxi
sunfat c dn ra bng 5.5 l in hnh i vi loi nh hng ny.
Bng 5.5 tan ca canxi sunfat trong cc dung dch ru etylic trong nc
Nng

ru
etylic
tan,
theo phn trm trng lng
g CaSO4/100 g dung mi
0

0,208

6,2

0,100

13,6

0,044

23,8

0,014

33,0

0,0052

41,0

0,0029

Tc to kt ta. Cn nhn mnh rng, khng nn suy on v tc phn ng. Nhiu

phn ng t ti trng thi cn bng vi hng s ln nhng vi tc rt nh.
Phn ng kt ta thng xy ra chm. t ti cn bng cn mt s pht, thm ch mt
vi gi. i khi nh ho hc c th c li trong cc phn ng kt ta chm v s phn chia
khng th thc hin c trong cc phn ng t cn bng nhanh. V d, c th tch canxi
khi magie bng cch kt ta oxalat, mc d magie cng to thnh oxalat c tan khng
khc nhiu vi tan ca canxi oxalat.
S phn chia c th thc hin c nh tc thit lp cn bng to magie oxalat nh
hn rt nhiu so vi tc to canxi oxalat. Nu lc canxi oxalat ngay sau khi kt ta th kt
ta thc t s khng b ln magie, nhng nu kt ta trong dung dch th s b ln magie.

119

5.6

Phn chia cc ion theo nng cht kt ta (kt ta phn on)

Nu hai ion phn ng vi mt ion th ba no to thnh nhng kt ta c tan khc

nhau, th hp cht t tan hn s kt ta nng thuc th thp hn. Khi tan khc nhau
ln c th tch nh lng ion u ra khi dung dch trc khi ion th hai bt u kt ta.
phn chia nh vy, cn thit gi cn thn nng cht kt ta gii hn c xc nh
trc. Mt lot phng php phn chia phn tch quan trng, da trn bin php ny trong
c phng php phn chia bng ion sunfua, bng ion hiroxyl v cc thuc th hu c.
nh gi kh nng phn chia da trn phn ng kt ta nng thuc th c kim
tra trc l mt ng dng quan trng ca quy lut tch s tan. Quy lut ny cn c s dng
tnh ton nhng iu kin ti u cho s phn chia. iu c minh ha bng hai v d
sau y.
V d 1. C kh nng v mt l thuyt phn chia nh lng Fe3+ v Mg2+ bng kt ta
phn on bng OH t dung dch 0,1 M cho mi ion hay khng? Nu s phn chia y l c
kh nng th gii hn nng OH cho php l bao nhiu?
Tch s tan ca cc hiroxit tng ng bng:
[Fe3+] [OH]3 = 4.1038
[Mg2+] [OH]2 = 1,8.1011
Tt nhin l c th cho rng Fe(OH)3 s kt ta nng OH thp hn bi v T ca
Fe(OH)3 nh hn rt nhiu so vi T ca Mg(OH)2.
tr li vn c nu trn, cn tnh ton nng OH cn thit kt ta nh
lng Fe3+ t dung dch cho, xc nh nng OH khi Mg(OH)2 bt u kt ta. Nu
nng OH trong trng hp th nht nh hn so vi trng hp th hai th s phn chia l
c kh nng v khong nng OH c s dng s l p s ca bi ton th nht v bi
ton th hai.
xc nh gi tr th nht, chng ta cn bt u bng vic xc lp tiu chun tch nh
lng Fe3+ t dung dch. Bi v khng iu kin no c th t c vic kt ta tt c cc
ion st (III) nn chng ta cn phi xc nh gii hn, m di gii hn , s c mt ca ion
ny thc t l c th b qua. Nu nng ca n h thp n
106 mol/l, trong dung
dch ch cn bng 1/100.000 lng ban u v trong phn ln trng hp, s kt ta nh th
c th xem nh l nh lng.
D dng tnh c nng OH nm cn bng vi 1,0.106 mol/l Fe3+ trong phng trnh
tch s tan.
1,0.106 [OH]3 = 4.1038
[OH] = 3,4.1011

120

11

3+

Nh vy, nu gi nng OH mc 3,4.10 mol/l, nng Fe h n

1,0.106 ion.g/l. Rt l th nhn xt rng, Fe(OH)3 kt ta nh lng trong dung dch kh
axit.
By gi chng ta ch n i lng th hai, ngha l ti nng OH ln nht m
Mg(OH)2 cn cha to thnh. cho Mg(OH)2 bt u kt ta, tch s nng Mg2+ v nng
OH bnh phng phi ln hn tch s tan 1,8.1011. Sau khi thay th 0,1 (nng phn t
ca Mg2+ trong dung dch) vo phng trnh tch s tan, c th tnh c nng OH cc
i cho php m d Mg(OH)2 cn cha to thnh.
0,1 [OH]2 = 1,8.1011
[OH] = 1,3.105 ion.g/l
Nu nng OH cao hn gi tr dung dch tr thnh qu bo ho Mg(OH)2 v kt ta
bt u lng xung.
Nhng php tnh thc hin ch r rng, s tch nh lng Fe(OH)3 xy ra nng OH
ln hn 3,4.1011 mol/l v cho ti khi nng OH cha t ti 1,3.105 mol/l th Mg(OH)2 s
cn cha kt ta. Do tch Fe3+ v Mg2+ cn gi nng OH khong gia cc gi tr
.
V d 2. Phn chia di dng sunfua. Trong mt lot phng trnh quan trng dng
tch cc ion kim loi, ngi ta gi nng cn thit ca cht kt ta amoni bng cch iu
chnh nng ion hiro trong dung dch. Nhng phng php nh th c sc hp dn c
bit, bi v trong cc phng php ny tng i d gi nng ion hiro mc xc nh
nh dung dch m thch hp (1). C l phng php c bit ti nhiu nht trong s cc
phng php l phng php da trn s ng dng hiro sunfua lm cht kt ta.
Hiro sunfua l axit yu phn li nh sau:
H2S + H2O

H3O+ + HS

H3 O+ HS

= 5,7.108
K1 =
H2S

HS + H2O

H3O+ + S2

H3 O+ S2

= 1,2.1015
K2 =

[HS ]

(1)

iu ch v tnh cht ca cc dung dch m c xt ti chng IX. Kh nng gi nng ion hidro
mc xc nh khng bin i l tnh cht quan trng ca dung dch m.

121

Cng nhng phng trnh , ta thu c phng trnh tng cng ca s phn li sunfua
hiro n ion sunfua.
2H3O+ + S2

H2S + H2O

H3 O+ S2

= 6,8.1023
K 1K 2 =
[H2S]

Ngi ta thu c hng s ca phn ng cui cng bng cch nhn K1 vi K2.
Khi phn chia di dng sunfua, ngi ta thng lm dung dch bo ho hiro sunfua
lin tc cho ti khi phn ng kt ta kt thc. V vy, nng ca thuc th trong qu trnh
kt ta thc t l khng i. V hiro sunfua l axit yu, nng cn bng xp x bng tan
trong nc ca n, bng khong 0,1 M. Nh vy chng ta c th gi thit rng, trong qu
trnh kt ta mt sunfua no :
[H2S] 0,1 M
Thay th gi tr vo phng trnh hng s phn li ta c:
2

H3 O+ S2

= 6,8.1023
0,10
24
S2 = 6,8.10
2

H3 O+

Do , nng ca ion sunfua t l ngc vi bnh phng nng ion hiro. H thc
c ng dng tnh iu kin ti u cho kt ta cc cation di dng sunfua.
V d 3. Hy tm nhng iu kin tch nh lng Pb2+ v Tl+ bng cch dng H2S kt ta
t dung dch cha mi ion 0,1 mol/l.
Hng s cn bng ca hai phn ng chnh:
PbS (rn)

Pb2+ + S2

[Pb2+] [S2] = 7.1028

Tl2S (rn)

2Tl+ + S2

[Tl+]2 [S2] = 1.1022

PbS kt ta nng S2 nh hn nng S2 kt ta Tl2S. Chng ta gi thit rng s
h thp nng ion Pb2+ n 106 mol/l hoc thp hn c ngha l tch nh lng n ra

122

khi dung dch v chng ta thay gi tr vo phng trnh tch s tan. Khi c
th tnh c nng ion sunfua cn thit:
106 [S2] = 7.1028
[S2] = 7.1022
By gi cn so snh gi tr thu c vi nng S2 m s kt ta Tl2S t dung dch
0,1 M bt u.
(0,1)2 [S2] = 1.1022
[S2] = 1.1020
Nh vy, mun phn chia cn gi nng S2 gia 7.1022 v 1.1020 mol/l. Chng ta cn
tnh nng H3O+ m nng S2 s nm trong gii hn ni trn. Thay vo h thc
rt ra trc y:
24
S2 = 6,8.10
2

H3O+

Ta thu c hai gi tr nng gii hn ca S2:

[H3O+] =

6,8.10 24
7.10 22

= 0,97.10 2 mol / l

[H3O+] = 0,0097 0,01 mol/l

[H3O+]2 =

6,8.10 24
1.10 20

[H3O+] = 0,026 0,03 mol/l

Khi gi nng [H3O+] gia 0,03 v 0,01 mol/l c th kt ta c PbS trc khi kt ta
Tl2S bt u. Nhng vi quan im thc t, tht ng ng kh nng kim tra axit chnh
xc phn chia c.

123

Chng 6
Qu trnh to thnh kt ta
C ch qu trnh to thnh kt ta l ti tranh lun trong nhiu nm. C nhiu kin
rt khc nhau v vn ny. V vy, chng ta bt u nhng quan st thc nghim, sau
xem xt nhng gii thch l thuyt nhng quan st .

6.1

Nghin cu thc nghim qu trnh to kt ta

C th xem thi k tip xc ko di t lc trn cc thuc th n khi xut hin kt ta

nhn thy c, l giai on lun xy ra v l hin tng ng ch nht. Thi lng ca thi
k tip xc thng rt khc nhau: khi kt ta bari sunfat thi k tip xc rt di trong khi kt
ta bc clorua giai on li rt ngn. Hai mui ny c nghin cu rt cn thn, v chng
c tan tnh theo mol gn nh ng nht. iu to nn mi quan tm ln khi nghin cu
so snh hai kt ta.
Nielsen so snh nhng thi k tip xc ca nhng kt ta khc nhau theo nhng d kin
ca nhiu nh nghin cu v rt ra c phng trnh thc nghim sau:
tiCon = k

(6.1)

ti l thi k tip xc;

Co l nng ban u ngay sau khi trn ln cc thuc th;
n, k l cc hng s thc nghim.
i vi cc kt ta AgCl, Ag2CrO4, CaF2, CaC2O4 v KClO4, gi tr n thu c t nhiu
nh nghin cu kh ph hp v bng cc gi tr tng ng 5; 4,7; 9; 3,3 v 2,6; cn i vi
bari sunfat nhng gi tr thu c rt khc nhau.
Thi lng ca thi k tip xc khng ph thuc vo phng php quan st. Khi quan st
trc tip bng mt cng thu c kt qu ging nh khi s dng cc thit b quang hc c
nhy cao hoc o dn in. Theo cc s liu ca Johnson v ORourke, dn in trong
thi k tip xc hu nh khng bin i. Do vy, trong thi gian ch mt phn nh cht tan
dng cp ion hoc nhng lin hp ion ln hn.
Khi kt ta bari sunfat, thi lng ca thi k tip xc ph thuc vo phng php trn
thuc th. T nhng s liu ca Lamer v Dinegar c th rt ra kt lun, trong trng hp
iu ch ion sunfat trong dung dch ng th theo phn ng:

124

S2O8

+ 2S2O3

2SO4

+ S4O6

(6.2)

Khi c mt ion Ba2+, dung dch to thnh mc qu bo ha xc nh khng sinh ra

kt ta trong khong thi gian tng i di so vi chnh dung dch nhng c iu ch
bng cch trn trc tip cc thuc th. S dng phng php kt ta ng th, Lamer v
Dinegar i n kt lun, kt ta ch xut hin khi qu bo ho t mc xc nh:
aBa2+ .aSO2
4

KM

= 21,5

khng ph thuc vo nng ion bari hoc tc to thnh ion sunfat.

Trong cng trnh mun hn, Collins v Leineweber ch r rng gi tr mc qu bo
ha chun ph thuc vo tinh khit ca thuc th. Khi kt tinh li nhiu ln v lc cc
dung dch thuc th, cc tc gi trn thu c gi tr mc qu bo ha chun bng 32.
Cc tc gi rt ra kt lun, trong trng hp ny khng to thnh cc trung tm kt tinh
ng th v s kt tinh bt u trn nhng trung tm l, c th l lu hunh nguyn t tn ti
trong dung dch tiosunfat l trung tm kt tinh. Nielsen cho rng, khi lm sch cn thn bnh
kt ta bng cch x l hi trong thi gian di, lng tinh th bari sunfat trn mt n v th
tch gim i 10 ln v c th trn 10 ln. Do ng ta qu quyt rng, nhng iu kin kt
ta bnh thng, phn ln trung tm kt tinh c to thnh trn thnh bnh thy tinh.
Ngoi ra, nhiu bng chng ng tin cy v s to thnh nhng trung tm kt tinh l
trong cc dung dch bari clorua va mi c iu ch c cng b v s khng nh v
s gim lng, ng thi tng kch thc ht bari sunfat c to thnh khi s dng cc dung
dch bari clorua gi ha v c lc cng c xc nhn. Cn c mt nhm quan st rt
quan trng khc v s ph thuc ca kch thc v lng ht kt ta vo nng cht kt ta.
Von Weimarn hon thnh cng trnh nghin cu c in v s to thnh kt ta: o kch
thc tinh th bari sunfat thu c bng cch trn nhanh nhng dung dch bari tioxianat v
mangan(II) sunfat c nng phn t bng nhau. long 104 M, ni chung kt ta
khng xut hin. Khi tng nng trong gii hn 104 103 M, kt ta c to thnh, ban
u l nhng ht v nh hnh, sau chuyn t t thnh tinh th. Nhng nhng bin i
ny ca kt ta xy ra rt chm, n mc to thnh nhng tinh th hon chnh cn ti 6
thng. Kch thc ca nhng ht to thnh ban u tng ln cng vi s tng nng , ngc
li, kch thc ca nhng tinh th cui cng gim i khi nng ban u tng.
Tnh cht ca mt s kt ta in hnh nht trong nhng khong thi gian khc nhau tng
t t1 n t5 c dn ra trn hnh 6.1. Khi nng ban u bin i t 103 n 1 M, nhng
tinh th mi c to thnh km hon chnh, xut hin nhng tinh th ln c dng hnh kim
v hnh b khung; nng ln hn 1 M, ban u to thnh mt khi ng t, khi ny dn
dn chuyn thnh kt ta ht nh c th tch ln. T u th k 20, Weimarn khng nh
rng, nhng kt ta c gi l v nh hnh v thc cht cng ch l kt ta tinh th nhng
bao gm nhng ht cc k nh dng cha hon chnh, sau c xc nhn nh nhng
nghin cu ph Rnghen. Nhng nghin cu ny ch r rng, nhng nh Debye ca nhng
kt ta mi v nhng kt ta c gi ha thng l ng nht; s khc nhau duy nht l
nhng vch trn nh Debye ca nhng kt ta mi c c tnh khuch tn hn. Weimarn

125

khng hnh dung c mt cch r rng nhng khc nhau gia s to thnh cc ht kt ta v
nhng s bin i tip theo vi chng m ngy nay chng ta gi l hin tng gi ha.

Hnh 6.1
Kch thc ht l hm s ca nng (theo Weimarn)

Oden v Werner o kch thc tinh th bari sunfat bng phng php trm tch. Cc tc gi
rt ra kt lun, trong gii hn nng 103 101, kch thc ht tng cng vi s pha long
v ng thi ng nht ca s phn b kch thc cng tng ln.
Mt khc, nhng iu kin xc nh, kch thc ht c th tng cng vi s tng nng
. Quy lut Weimarn pht hin khi kt ta t nhng dung dch rt long. ORourke v
Johnson nhn thy rng, khi trn nhanh cc dung dch bari clorua v natri sunfat gi ha,
tng lng cc ht bari sunfat to thnh khng ph thuc vo nng u ca bari sunfat trong
gii hn 2,5 25.104 M. Fisher v Rhinehammer ch r rng, khi kt ta t dung dch HCl
pH = 1, kch thc ht bari sunfat tng cng vi s tng nng trong gii hn 2,6 26.103
M. Cc tc gi nhn xt rng, trong nhng iu kin nhng tinh th kh ln (4,3 16 m)
c to thnh. nhng pH cao hn, kch thc tinh th tng ln nhng nhng tinh th ny
l nhng lin hp ln ca nhng ht nh.
S tng kch thc ht cng vi s tng nng c quan st thy c khi kt ta bc
cromat, bc tioxyanat v niken imetylglioximat.
ng ch l nhng kt qu nghin cu kt ta bari sunfat ca Turnbull. Tc gi nghin
cu mc kt ta X nh l hm s ca thi gian t sau khi trn nhanh cc dung dch.
Turnbull a vo h s t l f l h s t l ca thi gian c c s ph thuc: X =
F(ft). Mc d h s t l bin i t th nghim ny n th nghim khc i khi n 5 ln,
hm s F theo thang chun thi gian vn c gi khng i trong tt c cc th nghim. Hm
s F loi tr qu trnh ln ln ca ht tinh th, cn h s t l f loi tr s trung tm kt tinh,
bin i t th nghim ny n th nghim khc.

126

Khc vi bari sunfat, bc clorua kt ta nhanh ngay c trong cc dung dch qu

bo ho khng ln. Davies v Jones tm thy gii hn di ca s qu bo ho; di gii hn
di ny, cc trung tm kt tinh c l ni chung khng c to thnh. Phng php ca hai
tc gi trn l quan st tc bin i dn in theo thi gian nh hm s ca nng
dung dch, sau ngoi suy n gi tr khng ca tc bin i. Cc tc gi ch r rng, gi
tr bo ho gii hn ph thuc vo t s nng ca ion bc v clorua v t s bng n v,
gi tr gii hn t cc tiu 1,32. Nhng s dng phng php ngoi suy gy nn nhng
nghi ng bi v tc bin i dn in ng ra lin quan n ln ca tinh th ch
khng phi vi qu trnh to thnh cc trung tm kt tinh. Bc clorua v bc halogenua khc
thng c gi l kt ta sa ng cc (kt ta phomat) bi v c to thnh t s tch
gp cc ht keo, cn tri li bari sunfat li c to thnh t nhng tinh th ring bit, bt k
lc no nu kt ta t cc dung dch long.

6.2

L thuyt c in v s to thnh cc trung tm kt tinh

R rng l, hp phn nhng ht nh ca kt ta c quyt nh bi tc tng i ca

2 qu trnh:
1. Qu trnh to thnh cc trung tm kt tinh.
2. Qu trnh ln ln ca cc trung tm kt tinh.
Theo Ostwald, dung dch qu bo ho c th l gi bn nn vn trng thi ng th lu v
hn. Cho n khi ngi ta cho vo mui thch hp vi cc trung tm kt tinh. Khi s qu bo
ho cao hn mt gi tr xc nh (gii hn gi bn) dung dch c xem nh bn, ngha l c
kh nng t kt tinh. Mt s nh bc hc u th k 20, c bit l Miers, ngh a vo cm
t ng cong siu tan. Nhng trng thi bn v gi bn l hm s ca nhit c cc
ng cong siu tan phn chia thnh nhng vng ring bit. Nhng ng cong v nhng vng
nh vy c dn ra trn hnh 6.2 v 6.3.
Da trn nhng quan im , c th gii thch s to thnh kt ta nh sau: Nu nhit
A, ta tng dn nng cht b kt ta, v d nh bng cch va khuy mnh va thm dn
dn cht kt ta vo (hoc l tng dn nng cc cht kt ta c to thnh do mt phn
ng ng th) th cho n im C trn ng cong siu tan kt ta khng c to thnh. Nu
thi im tng ng vi im C ta dng thm thuc th, nng ca n s b h thp n
im B trn ng cong tan. Thm thuc th tip tc cng khng dn ti s to thnh cc
trung tm kt tinh mi nu nng lc khng t ti im C. Do , kt ta to thnh
khi phi l ht tng i ln v ng nht v kch thc.
Nu do thm thuc th kt ta nhanh hoc do khuy khng nhanh, nng im
mt lc no vt qu C th trong qu trnh kt ta nhng trung tm kt tinh mi c th
c to thnh v do s ht tng ng thi kch thc v ng nht ca chng gim.
Nu nhng ng cong tan v siu tan kh gn nhau nh trn hnh 6.3 th hon ton chc
chn rng kh c th thu c kt ta c ht to v ng nht.

127

Hnh 6.3
ng cong qu bo ho tng ng vi vng gi bn hp

Hnh 6.3
ng cong qu bo ho tng ng vi vng gi bn hp

Ni chung, tnh cht ca bari sunfat tng ng vi nhng ng cong trn hnh 6.2. Nh
ni trn y, nhng dung dch vi qu bo ho tng i ln c th tn ti trong thi
gian kh lu mi xut hin kt ta v bari sunfat thu c t dung dch rt long thc t bao
gm nhng ht tng i ln v ng nht. Trong khi bc clorua c tan tnh theo mol/l
cng gn nh th nhng biu l khuynh hng to thnh dung dch qu bo ho kh nh v
nhng ht s cp ca kt ta v c khi kt ta t dung dch long cng b khuch tn rt mn.

6.3

L thuyt v s to thnh cc trung tm kt tinh Becker - Doring

C th xem xt qu trnh to thnh cc trung tm kt tinh di quan im ca nhit ng

hc v ng hc. Nhng kin gii nhit ng hc u tin ca Gibbs c Rudebush s

128

dng gii thch s to thnh git nc t hi nc. i lc ln ln (lm gim

nng lng t do b mt) ca tp hp phn t cn bng vi i lc phn li (lm ln entropi)
ca trung tm ng t c c chnh xc ln ca tp hp l 100 phn t. Kch thc
ca tp hp phn t hoc gi tr chun ca trung tm ng t c c trng bng nng lng
t do cc i xy ra 1 mol, do nhng tp hp phn t nh hn s hng ti s phn li,
cn nhng tp hp ln hn s hng ti s pht trin.
Khi to thnh cc trung tm kt tinh, v c bn tnh hung cng nh th nhng cn phc
tp hn. Trung tm kt tinh c kch thc xc nh ch c th ln ln khi ng thi xy ra qu
trnh ehirat ha tng phn nhng ion ang tham gia lin kt vi trung tm kt tinh hoc
nm trong trung tm kt tinh. Nh vy l, nng lng ca h thot ra tng ng vi nng
lng mng li tinh th v nng lng tiu ph (qu trnh khng t din bin) tng ng vi
nng lng ehirat ha. Hng ti qu trnh tng cng xp xp li khi kt tinh km theo
qu trnh gim entropi v ng thi xy ra qu trnh tng entropi do mc mt trt t trong
chuyn ng ca cc phn t dung mi tng ln. V vy, c th cho rng, c mt thng s
nng lng v mt thng s entropi c kh nng lm cho ht ln ln v mt cp thng s
tng t nh vy c kh nng tng cng s phn li. mt kch thc chun xc nh ca
ht, nng lng t do t gi tr cc i.
C th xem qu trnh to thnh cc trung tm kt tinh ging nh qu trnh trnh by
trn y vi quan im ng hc.
Volmer, Werber v Becker, Doring xem xt qu trnh to thnh cc trung tm ngng
t khi chuyn mt cht t trng thi hi v trng thi lng. Cc tc gi ny xem qu trnh
bao hm mt lot cc phn ng bc lng phn t dn ti s to thnh cc tp hp v cc tp
hp ny cng trong thi gian c th t lm gim kch thc ca mnh do mt i nhng
phn t ring bit. T y, tn s to thnh cc trung tm ngng t chnh l tc to thnh
cc trung tm ngng t c kch thc chun khi cc tp hp phn t va chm vi cc phn t
ring bit. Volmer v Werber cho rng nng ca cc phn t tng ng vi mt s trng
thi cn bng. Nhng Becker v Doring hon chnh thm l thuyt v cho rng, khng
phi xut hin trng thi cn bng m l trng thi dng. Do nhng trung tm ngng t c
kch thc chun pht trin nhanh v to thnh cc git trong lc nng tng ng vi
trng thi dng thp hn rt ng k so vi nng n cn phi c tng ng vi trng
thi cn bng nu c.
Theo l thuyt ca Becker v Doring, tc to thnh cc trung tm ngng t ph thuc
nhiu vo nng v do ph thuc vo bo ho chun. Kch thc chun ca trung tm
ngng t cht lng th hin gn nh ng nht i vi cc cht khc nhau, khong 50 100
phn t.
so snh l thuyt vi thc nghim, ngi ta tm c gi tr chun ca mc qu
bo ho. Gi tr chun ny cng vi phng trnh Gibbs - Tomson c s dng tnh
sc cng b mt ca trung tm ngng t v so snh gi tr thu c vi sc cng b mt thng
thng. Turnbull trong mt trong nhng cng trnh cui cng ca mnh so snh nhng d
kin thc nghim vi l thuyt v i n kt lun, s ph hp ca cc kt qu xu hn so
vi nhng g c chp nhn trn c s cng trnh c in ca Volmer v Flood v s to
thnh cc trung tm ca nhng git nc nhng khng c mt l thuyt khc c xy

129

dng tt hn. Kh khn ng k l ch, cho n by gi cha c mt l thuyt m t s ph

thuc ca bin i sc cng b mt vo bin i cong ca ht.
Becker s dng gi nh hp phn ln cn gn nht. Gi nh ny k ti s khc
nhau v s phi tr gia cc phn t trn b mt v cc phn t bn trong tng. Trong cc
tp hp phn t nh, s phi tr ca cc phn t b mt bng s phi tr ca cc ion nm trn
mt phng. Theo cc d kin ca Benson v Shuttle-worth khi nghin cu cc tng tc th
cp, sc cng b mt ca cc tp hp khng ln phn t c th thp hn sc cng b mt
phng 15%.
Lin quan n cc ht rn, vn sc cng b mt cn phc tp hn nhiu do kh khn
v phng php o i lng ny ngay c i vi cc tinh th ln. Hn na trong trng hp
ny l thuyt gn ng ca Becker cng c s dng v kt qu thu c mt ln na khng
nh rng, kch thc chun ca trung tm kt tinh c gi tr khong 100 ion. T cn thit
phi rt ra kt lun, tc to thnh trung tm kt tinh l hm bc cao ca nng . Nhng
quan im ca Turnbull ph hp vi l thuyt . ng ch r rng, thi k tip xc (cng
hng) khi kt ta bari sunfat c c tnh biu kin hn l hin thc; thi k tng ng vi
thi k pht trin rt chm v b gii hn bi b mt nh. Turnbull cho rng, trung tm kt
tinh c to thnh thi im trn ln thuc th cc im m nng cao hn nng
chun to thnh cc trung tm kt tinh. Gi tr khc nhau ca thng s quy m ( c
ni n trn y) l do lp li khng t yu cu ca qu trnh trn ln. Thi k cng
hng tng i di khi cht kt ta c cung cp mt cch ng th c th c gii thch
nh l thuyt khng nh rng, s ln ln ca ht ch xy ra khi c mt nhng trung tm kt
tinh l. gii thch kt qu thu c mt lng ng nht ht trong kt ta theo quan st ca
ORourke v Johnson, chc l phi gi thit rng, trong mt th tch dung dch xc nh c
mt lng khng i trung tm kt tinh l khng ph thuc vo nng cht tan trong vng
dung dch rt long. Nhng kt qu khc ca nhng nh nghin cu khc cng c gii thch
bng nhng lng trung tm kt tinh l khc nhau.

6.4

L thuyt to thnh cc trung tm kt tinh Christiansen - Nielsen

Christiansen v Nielsen a ra l thuyt to thnh cc trung tm kt tinh trn c s gii

thch thi gian ca thi k cng hng. Hai ng cho rng, thi k cng hng lin quan cht
ch vi bc ca phn ng to thnh cc trung tm kt tinh. Tng t nh Becker v Doring,
h cho rng, cc tp hp ion c to thnh nh cc phn ng lng phn t cho ti khi to
thnh trung tm c kch thc chun ri sau cc trung tm ny t pht trin. Nhng v thi
k cng hng l hm s bc khng cao (bc 3 9) ca nng nn dn ti kt qu l, trung
tm kt tinh chun ch bao gm mt s tng i khng ln ion.
Johnson v ORourke chnh xc ha l thuyt . Ch ti c im, nng trong thi
k cng hng c gi hng nh, hai tc gi ny i n kt lun, tc to thnh cc
trung tm kt tinh cng cn phi khng i trong sut thi k . Ch cui thi k cng
hng mi cn ch ti s ln ln ca ht cn trong sut thi k cng hng cn ch ti
s to thnh trung tm kt tinh cng nh s pht trin ca chng. Hai ng rt ra mt kt
lun rt hay l, tng s cc trung tm kt tinh bari sunfat khi kt ta t cc dung dch rt long
khng nht thit ph thuc vo nng . Tng kt c rt ra trn c s, tc to thnh

130

trung tm kt tinh t l thun vi nng theo bc 4 v tr thnh hng nh trong

sut thi k cng hng. Thi gian ca thi k cng hng t l nghch vi gi tr nng
theo bc 4. Nh vy, c th d dng gii thch, s ht hng nh trong kt ta thu c c
quan st thy trong thc nghim. Theo cc s liu ca Christiansen v Nielsen, s ion trong
cc trung tm kt tinh chun ca BaSO4, Ag2CrO4 v CaF2 tng ng l 8, 6 v 9. Peisach v
Brescia cng b, trung tm kt tinh chun ca oxalat magi c thnh phn (MgC2O4)2.
Duke v Brown khng nh rng, s ht b kt ta ph thuc vo nng u ca ion
cht kt ta. Xut pht t kt qu, tc to thnh cc trung tm kt tinh v tc ln ln ca
n quyt nh s ht cui cng, cc tc gi trn ngh mt vi quy lut v s pht trin v
a ra kch thc ca trung tm kt tinh chun. V cng trong chnh cng trnh , xut pht
t bc khng cao ca s ph thuc s ht vo nng cc thuc th, mt kt lun kh logic
v kch thc khng ln ca trung tm kt tinh chun c rt ra.
Nu chp nhn rng, s ln ln ca ht xy ra theo quy lut bc nht th trung tm chun
ca tetraphenylasoni peclorat phi bao gm cc cp triion, cn nu chp nhn s ln ln ca
ht tun theo quy lut bc 2 th trung tm kt tinh chun ca cht phi c to thnh t
cc cp tetraion. Rt ng ch n nhn xt cho rng, thnh phn trung tm niken nioximat
chun ph thuc vo iu kin, trong hai ion phn ng, nioxim v niken, ion no d. Khi chp
nhn quy lut ln ln l bc nht iu kin d ion nioxim, thnh phn ca trung tm chun
tng ng vi cng thc (NiNiOX)3. Cn khi d ion niken, cng thc tng ng l
Ni(NiOX)3. Thuyt ca Duke v Brown cho rng, sau khi to thnh cc trung tm kt tinh ban
u, nhng trung tm mi s khng c to thnh na.
Quan im v trung tm chun khng ln c a ra theo linh cm, n ch c chp
nhn trong nhng trng hp khi s bc to thnh trung tm kt tinh khng ln. Nhng
Turnbull bc b gi thuyt c bn ca thuyt Christiansen-Nielsen bi v ng ta cho rng, s tn
ti ca trung tm chun khng ln c kch thc khng ph thuc vo qu bo ho khng c
mt cht c s l thuyt no c.
Nhng phn tch v trung tm ln v trung tm nh dn ti vn bc ln hay nh
ca s ph thuc tc to thnh cc trung tm vo qu bo ho. Nu s to thnh cc
trung tm l qu trnh bc cao th qu trnh y ch xy ra trong trng hp nng cc b cao
hn nng chun. Trong trng hp khc, s ln ln ca tinh th c th bt u trn cc
trung tm l, Turnbull a ra dn chng sau: thng nhng git nh ca cht lng hoc ca
dung dch nc c th chm ng ng k so vi lng ln ca chnh cc cht lng y. Hin
tng y xy ra l do t kh nng c, d ch l mt trung tm l trong mt git nh cht lng.
Chc chn l, trn c s nghin cu k dng ng cong dn in trong thi k ln ln
ca tinh th cng c th rt ra kt lun r rng v c ch kt tinh. Nhng c hai thuyt u
ging nhau im l, trong sut thi k cng hng, s ln ln ca cc mm ban u chm
chp v ch cui giai on phn ln cc ion t do mi tch khi dung dch.

131

Chng 7
Phn tch trng lng
7.1

M u

Phn tch trng lng da trn php o trng lng ca hp cht c thnh phn bit,
lin quan v mt ha hc vi cu t cn xc nh. C hai nhm cc phng php phn tch
trng lng: nhm cc phng php kt ta v nhm cc phng php chng ct. Trong
nhm cc phng php kt ta, cu t cn xc nh tham gia vo phn ng ha hc vi thuc
th to thnh sn phm t tan; sau lc v thc hin nhng ng tc cn thit khc v cui
cng cn kt ta rn c thnh phn ha hc bit. Trong nhm cc phng php chng ct,
cu t cn xc nh c tch ra khi mu dng kh: trong trng hp ny, php phn tch
hoc l da trn php xc nh trng lng cht c ct ra, hoc l da trn php xc nh
trng lng cht cn li. Chng ta s ch yu xem xt phng php kt ta bi v phng
php ny thng c s dng.

7.2

Tnh kt qu theo d kin phn tch trng lng

Phng php phn tch trng lng bao gm hai php o thc nghim: cn mu v cn
sn phm bit thnh phn ha hc, thu c t lng mu . Trn c s ca nhng d
kin , bng nhng php tnh n gin, ta thng thu c hm lng theo phn trm ca
cu t cn xc nh.
Nu A l cu t cn xc nh th c th vit:
%A =

Trng lng A
.100
Trng lng mu

(7.1)

Thng dng hn c l khng o trc tip trng lng ca A. Thay th cho ng tc

ngi ta tch v cn cht hoc cha A hoc lin quan v mt ha hc vi A. Trong trng
hp no i na cng cn dng h s chuyn tnh trng lng ca A tng ng vi trng
lng kt ta. C th thy r bn cht ca h s chuyn mt cch thun tin qua nhng v d
sau:
V d 1: C bao nhiu gam Cl cha trong 0,2040 g kt ta AgCl?
T cng thc r rng l:

132

S mol AgCl =

1
s mol Cl2;
2

v
S mol AgCl =

1
0,2040
= s mol Cl2
t AgCl
2
Khi lng phan

nn:
Trng lng ca Cl = 0,2040

t Cl2
1/2 trng lng phan
t AgCl
Trng lng phan

= 0,2040

35,45
= 0,2040.0,2474 = 0,0505 (g)
143,3

V d 2: Trng lng AlCl3 tng ng vi 0,2040 g AgCl bng bao nhiu?

Chng ta bit rng, t mi phn t AlCl3 thu c 3 phn t AgCl.
Do : s phn t AlCl3 =

1
1
0,2040
t AgCl =
s phan
tAgCl
3
3 Trng lng phan

Thc hin nhng php tnh tng t nh m t trn chng ta c:

Trng lng AlCl3 = 0,2040

t AlCl3
Trng lng phan
t AgCl
3 trng lng phan

= 0,2040

133,3
= 0,0633 (g)
3 143,3

Chng ta nhn thy s ging nhau ca nhng php tnh dn. Trong c hai v d, trng
lng ca mt cht c din t qua tch s trng lng bit ca mt cht khc vi t s
trng lng phn t tng ng vi hai cht . T s c gi l h s chuyn. Trong v
d th hai, cn phi nhn trng lng phn t ca bc clorua vi 3 lm cho lng clorua
t s v mu s ca h s chuyn bng nhau.
V d 3: C th thu c bao nhiu gam Fe2O3 t 1,63 g Fe3O4? Hy tm h s chuyn K.
Trong trng hp ny cn thit phi gi thit rng, Fe3O4 chuyn nh lng thnh Fe2O3
v c hon ton oxi chuyn:
2Fe3O4 + [O] = 3Fe2O3
Chng ta thy rng, t mt mol Fe3O4 thu c 3/2 mol Fe2O3. Nh vy, s mol Fe2O3
ln hn s mol Fe3O4 3/2 ln hoc l:

133

S mol Fe2O3 = 3/2 s mol Fe3O4;

Trng lng Fe2O3
Trng lng Fe3 O4
3
=
t Fe2O3 2 Trng lng phan
t Fe3O4
Trng lng phan

Trng lng Fe2O3 =

Trng lng Fe3 O4

3
trng lng phn t Fe2O3
t Fe3 O4
2 Trng lng phan

Sau khi bin i ta c:

Trng lng Fe2O3 = trng lng Fe3O4

t Fe2O3
3 Trng lng phan
t Fe3 O4
2 Trng lng phan

v thay cc gi tr bng s ta c:
Trng lng Fe2O3 = 1,63

3 159,7
= 1,687 = 1,69 g
2 231,5

Trong v d ny:
H s chuyn =

t Fe2O3
3 Trng lng phan
= 1,035.
t Fe3 O4
2 Trng lng phan

Trong trng hp tng qut, h s chuyn K c xc nh nh sau:

H s chuyn =

t ca cht cn xc nh
a Trng lng phan
.
t ca cht c can

b Trng lng phan

y a v b l nhng h s nguyn khng ln, cn phi nhn trng lng phn t vi

nhng s ny cho s mol trong t s v mu s tng ng v mt ha hc.
By gi c th hnh dung phng trnh (7.1) di dng thun tin hn cho vic vn dng
thc t:
a Trng lng phan
t ca cht cn xc nh
Trng lng

t ca cht c can

b Trng lng phan

100
%A=

Trng lng can

Mt s h s chuyn c dn ra bng 7.1. Trong phn ln cc s tra cu ha hc u

c cc bng cc h s chuyn v logarit ca chng.

134
Bng 7.1 Nhng v d in hnh v h s chuyn

Cht cn xc nh

Dng cn

H s chuyn

In

In2O3

2 Trng lng mol In

Trng lng mol In2O3

HgO

Hg5(IO6)2

5 Trng lng mol HgO

Trng lng mol Hg5 (IO6 )2

Hg5(IO6)2

2 Trng lng mol I

Trng lng mol Hg5 (IO6 )2

K3PO4

K2PtCl6

2 Trng lng mol K 3 PO4

3 Trng lng mol K 2PtCl6

V d 4: Chng ta xem xt php xc nh gin tip st trong st (III) sunfat bao gm php
kt ta v php cn bari sunfat. Trong trng hp ny t s v mu s ca cng thc h s
chuyn khng c nguyn t chung v chng ta phi tm mt cch khc din t s tng
ng ha hc gia cc i lng . Chng ta nhn thy rng.
2 mol Fe 1 mol Fe2(SO4)3 3 mol BaSO4
H s chuyn tnh ton phn trm hm lng st s c din t nh sau:
H s chuyn =

2 Trng lng mol Fe

3 Trng lng mol BaSO4

Nh vy, mc d hp cht ng trong cng thc tnh h s chuyn khng c lin quan
trc tip qua nguyn t chung, chng ta vn c th xc nh s tng ng ca chng, khi
bit quan h hp thc gia chng.
Chng ta minh ho vic p dng h s chuyn tnh kt qu phn tch qua nhng v d
sau y:
V d 5: Ngi ta nung 0,703 g mt sn phm c ra sch ph hy cht hu c.
Sau ch ha phn cn li bng HCl nng chuyn P thnh H3PO4. Kt ta pht pht di
dng MgNH4PO4.6H2O bng cch thm Mg2+ vo v trung ho tip theo bng dung dch nc
ca NH3. Sau khi ra v lc, kt ta chuyn thnh Mg2P2O7 bng cch nung 1000oC. Trng
lng ca kt ta thu c l 0,432 g. Hy tnh hm lng phn trm P trong mu:
2 Trng lng mol P
0,432

Trng lng mol Mg 2P2O7 100

%P =
0,703

135

0,432 0,2783 100

= 17,1
0,703

V d 6: nhit cao natri oxalat chuyn thnh cacbonat:

Na2C2O4 Na2CO3 + CO
Khi nung 1,3906 g natri oxalat bn thu c trng lng cht cn li l 1,1436 g. Hy xc
nh tinh khit ca mu.
Trong trng hp cho cn gi thit rng s khc nhau gia trng lng ban u v
trng lng cui cng tng ng vi s mt oxit cacbon khi nung. o lng mt i l c
s ca php phn tch. T phng trnh phn ng chng ta thy rng:
S mol CO = s mol Na2C2O4
Nh vy:
Trng lng mol Na 2 C 2 O 4
Trng lng mol CO
100

Trng lng can

Trng lng CO
%Na 2 C 2 O 4 =
=

(1,3906 1,1436) 4,784 100

= 84,97
1,3906

V d 7: Ngi ta t 0,2795 g mu thuc tr su ch cha lindan C6H6Cl6 (trng lng

mol = 290,8) v DDT C14H9Cl5 (trng lng mol = 354,5) trong dng oxi trong ng thch anh
v sn phm (CO2, H2O v HCl) c cho qua dung dch NaHCO3. Sau khi axit ha, tch Cl
ra khi dung dch di dng AgCl c trng lng 0,7161 g. Hy tnh hm lng phn trm
lindan v DDT trong mu.
y c hai n s, do chng ta cn thit lp hai phng trnh c lp v gii chung:
Trng lng C6H6Cl6 + trng lng C14H9Cl5 = 0,2795 g v
Trng lng AgCl t C6H6Cl6 + trng lng AgCl t C14H9Cl5 = 0,7161 g
hoc:
Trng lng C6H6Cl6.2,957 + trng lng C14H9Cl5.2,021 = 0,7161
Chng ta thay trng lng ca C14H9Cl5 rt ra t phng trnh th nht:
2,957.trng lng C6H6Cl6 + 2,021(0,2795 trng lng C6H6Cl6) = 0,7161
T , trng lng C6H6Cl6 = 0,1616 g v

136

% C6H6Cl6 =

0,1616
100 = 57,82 ;
0,2795

% C14H9Cl5 = 42,18.

7.3

Tnh cht ca kt ta v cht to kt ta

Cht to kt ta l tng trong phn tch trng lng cn phi phn ng vi cu t cn

xc nh, to kt ta tha mn cc iu kin sau:
1. C tan thp c th b qua s mt i do tan.
2. D lc v d ra cc cht bn km theo.
3. Khng b tc dng ca mi trng xung quanh v c thnh phn bit sau khi sy
kh hoc sau khi nung nu cn thit.
Ch c s rt t kt ta v cht to kt ta tho mn tt c cc yu cu , do nh ha
hc thng phi s dng nhng sn phm hoc phn ng cn xa mi t tiu chun l tng
phn tch.
Nhng yu t nh hng n tan ca kt ta c xt trong chng 5. By gi
chng ta cn bn lun, lm th no thu c kt ta tinh khit v d lc.

7.5.1 Tnh d lc v tinh khit ca kt ta

Kch thc ht ca tng rn quyt nh tnh d lc v tnh d tinh ch. Gia kch thc
ht v tnh d lc c mi quan h trc tip. Kt ta ht ln d b cc vt liu xp gi li; iu
m bo lc nhanh. Khi phi lc kt ta nh, phn tn phi dng giy lc mn v do tc
lc b gim xung. nh hng ca kch thc ht n tinh khit ca kt ta cn phc
tp hn. Thng khi tng kch thc ht km theo s gim bn ca kt ta.
ni ti vn tinh khit ca kt ta, chng ta s dng t cng kt. Danh t c
trng cho qu trnh ko vo kt ta nhng cu t, trong iu kin thng cng tn ti trong
dung dch. Sinh vin cn hnh dung r rng rng s lm bn kt ta do cc cht c tch s tan
t ti, ng ra khng phi l hin tng cng kt.
Nhng yu t quyt nh kch thc ht kt ta. Kch thc ht kt ta khc nhau rt
nhiu tu thuc vo cu trc v iu kin to thnh n. mt u ca thang kch thc l h
keo. Nhng ht ring bit ca h ny nh n mc khng th phn bit c bng mt thng
(bn knh 106 104 mm). Nhng ht nh vy khng kt ta c t dung dch v khng gi
li c bng cc giy lc thng thng. mt u khc ca thang l nhng ht kch thc
c mt vi chc milimet. H khng bn theo thi gian cha nhng ht phn b trong pha
lng c gi l huyn ph tinh th. Nhng ht huyn ph tinh th nhanh chng lng xung
v d lc.

137

Khi chuyn t keo sang tinh th in hnh khng c mt s bin i t ngt no v tnh
cht vt l, ch tu thuc vo kch thc ht tng rn. Trong thc t tn ti nhng kt ta
c tnh cht trung gian in hnh. Nhng c th d dng sp xp phn ln kt ta vo loi tnh
keo chim u th hoc vo loi tnh tinh th chim u th. Nh vy, mc d tnh khng trit
ca cch phn loi vn c th s dng thnh cng cho phn ln tng rn.
Mc d hin tng kt ta t lu thu ht s ch ca cc nh ha hc, nhiu vn
quan trng c lin quan n c ch ca qu trnh vn cn cha hon ton sng t (xem
chng 6). V li c th xem, kch thc ht tng rn c to thnh mt phn c quyt
nh bi nhng iu kin thc nghim c thit lp nh nhit , tan trong mi trng
cho, nng v tc khuy thuc th. C th gii thch nh hng ca cc yu t ny,
trong mi trng hp mt cch nh tnh. Khi gi thit rng kch thc ht gn lin vi mt
trong cc tnh cht ca h gi l tnh qu bo ho tng i.
Tnh qu bo ho tng i =

Q S
Q

(7.2)

y Q l nng cht tan mt thi im no ; S l tan ca n lc cn bng.

L thuyt qu bo ho tng i v nh hng ca n n kch thc ht gn lin vi
tn tui ca Phn Veimarn. T l thuyt ca Veimarn, ngi ta rt ra c nhng iu
kin c bn thu c kt ta vi kch thc ht tho mn yu cu. Qu trnh kt ta
c nghin cu chi tit hn trn c s cc l thuyt khc nhau.
Trong qu trnh to thnh kt ta t tan, s thm mi phn cht to kt ta dn ti s qu
bo ho chp nhong ca dung dch (ngha l Q > S). Trong phn ln trng hp trng thi
khng bn , qua mt thi gian ngn s b ph hy do to thnh kt ta. Nhng quan st thc
nghim ch r rng, kch thc ht ca kt ta thu c t l nghch vi hin tng qu bo
ho tng i trung bnh sau khi thm mi phn thuc th. Nh th l, nu (Q S)/S ln, kt
ta biu l khuynh hng to thnh keo; nu t s nh th s thu c tng rn tinh th.
C ch to kt ta. gii thch nh hng ca hin tng qu bo ho tng i n
kch thc ht, chng ta tch qu trnh kt ta thnh hai giai on: giai on to thnh cc
trung tm kt tinh v giai on ln ln ca ht. Kch thc ht ca cht va mi kt ta c
quyt nh bi s kin l, giai on no trong hai giai on chim u th.
S to thnh cc trung tm kt tinh l qu trnh hp nht mt s cc tiu ion hoc phn t
(c th n bn nm c thy) to thnh tng th hai bn vng. S kt ta tip theo c th
c thc hin hoc l bng cch to thnh nhng trung tm mi hoc l bng cch chuyn
kt ta n nhng mm tinh th c to thnh. Nu s kt ta xy ra theo con ng th
nht l ch yu th kt ta thu c l s ln cc ht nh; nu qu trnh ln ln ca tinh th
chim u th th s thu c s nh cc ht ln.
Gi thit rng tc to thnh cc trung tm kt tinh tng vi s tng ca qu trnh qu
bo ho tng i theo quy lut hm s m, trong khi tc ln ln ca ht li lin quan
vi thng s bng quan h gn nh tuyn tnh:

138
n

Q S

Tc to thnh mm = k1

Q
y n khong 4 v:
Q S

Tc ln ln ca ht = k2
.
Q
Thng k2 ln hn k1, do khi s qu bo ho tng i thp th qu trnh pht trin
tinh th chim u th. Nu s qu bo ho ln, nh c tnh hm s m, qu trnh to trung
tm kt tinh c th thc t ln t qu trnh ln ln ca ht. Hnh 7.1 minh ha hin tng .

Hnh 7.1
nh hng ca hin tng qu bo ha tng i n qu trnh kt ta

S iu chnh kch thc ht. S nng nhit ( tng S), s pha long dung dch
gim Q v s thm cht to kt ta chm trong iu kin khuy mnh ( gim gi tr Q trung
bnh) l nhng iu kin thc nghim cho php lm cho qu bo ho gim n cc tiu v
cng chnh l nhng iu kin thu c kt ta tinh th.
tng kch thc ht kt ta c tan ph thuc vo pH mi trng, thng ngi ta
lm tng S trong qu trnh kt ta. V d, thu c nhng tinh th canxi oxalat ln, d lc,
phn ch yu ca kt ta cn c to thnh trong dung dch axit, khi mui tan kh. cui
qu trnh kt ta ngi ta thm chm dung dch amoniac n pH m xy ra s tch nh
lng canxi oxalat. Kt ta c to thnh giai on c chuyn ln nhng ht rn
c to thnh.
Lm vic vi kt ta tinh th thun li hn so vi kt ta v nh hnh. V nguyn nhn
, qu trnh ln ln ca tinh th thng c a thch hn qu trnh to nhng trung tm kt

139

tinh mi trong qu trnh kt ta. Nhng nu tan S ca kt ta rt nh, trnh hin tng
qu bo ho chp nhong tng i ln trong khi khuy dung dch thc t l khng c kh
nng. V d, trong nhng iu kin phn tch hiroxit st (III), nhm, crom (III) v c sunfua
ca phn ln kim loi nng, do tan ca chng nh nn ch c th thu c trng thi keo.
Cc halogenua bc cng thuc loi kt ta ny (nhn tin cng cn ni, v d bc clorua,
nhng thiu st ca thuyt qu bo ho tng i c thy r, kt ta thng c to thnh
dng keo; trong khi tan ca n khc bit khng ng k tan ca cc hp cht khc
bit, v d nh bari sunfat li thng c to thnh dng tinh th).

7.5.2 Kt ta v nh hnh
Nhng ht keo ring bit nh n mc khng gi c khi lc, chuyn ng Brao cng
cn tr s kt ta chng t dng dch nh tc dng ca trng lc (s lng ng). May mn l
c th lm ng t hoc l lm ln ln nhng ht ca phn ln h keo v khi trng lng
khng phi l tinh th lng xung nhanh v d lc.
S ng t keo l qu trnh ng t c lm nhanh ln khi un nng, khuy v thm
cht in li. hiu tc dng ca nhng yu t cn thit phi phn tch nguyn nhn tnh
bn vng ca nhng h keo.
Do s hp ph trn b mt ca mnh nhng cation hoc anion nn mi ht keo u mang
in tch dng hoc m. C th d dng theo di bng thc nghim s c mt ca in tch
bng cch quan st s in chuyn ht di tc dng ca dng in mt chiu.
S hp ph cc ion trn kt ta rn c cu trc ion c gy nn bi chnh nhng lc to
ra s pht trin tinh th. Nh ion bc phn b trn b mt ht bc clorua mang mt phn in
tch khng c b tr. Nhng ion tch in m b ko v pha nhng phn bi chnh
nhng lc gi ion clorua trong mng li bc clorua. Nhng ion clorua trn b mt ht th
hin tc dng tng t ln cation c mt trong dung dch.
Bn cht v gi tr in tch ca ht keo ph thuc mt cch phc tp vo mt lot yu t.
Nhng i vi nhng h keo ng ch trn quan im phn tch th c th d dng d on,
nhng cht no s b hp ph v do xc nh c in tch ca ht khi s dng quy lut
thc nghim. Nhng ion tham gia vo thnh phn mng li tinh th thng b hp ph mnh
hn so vi nhng ion l. V d, ht bc clorua s tch in dng trong dung dch cha d ion
bc nh s hp ph u tin ion . Do nguyn nhn n s mang in tch m khi d ion
clorua. Rt l th nhn xt rng nhng ht bc clorua to thnh khi xc nh trng lng
clorua, ban u mang in tch m v sau khi thm d cht kt ta tr thnh in tch dng.
Mc hp ph tng ln nhanh vi s tng nng ion hp ph. Nhng cui cng b mt
ca mi ht c bo ho, trong iu kin s tng tip tc nng hoc l khng nh hng
n mc hp ph hoc l nh hng rt khng ng k.
Trn hnh 7.2 dn ra hnh nh din t bng s ht keo bc clorua trong dung dch cha
d ion bc. Nhng ion bc lin kt trc tip vi b mt to thnh lp hp ph th nht. Xung
quanh ht tch in to thnh mt lp i ion, trong cha lng d ion m lm trung

140

ho in tch ca cc ion dng b hp ph trn b mt. Lp ion i c to thnh

di tc dng ca lc tnh in.

Hnh 7.2
Ht keo AgCl trong dung dch AgNO3

Nhng ion b hp ph u tin v nhng ion i ca chng nm trong dung dch to

thnh lp in kp quyt nh bn vng ca h keo. Nh s c mt ca lp , nhng ht
keo y ln nhau, lc ht gia cc ht vi nhau khng ln thng lc y ca lp in
kp. Mun lm ng t keo cn phi lm gim lc y n cc tiu.
D dng ch ra nh hng ca lp in kp n bn ca h keo v d kt ta ion
clorua bng ion bc. u qu trnh kt ta, khi thm bc nitrat vo, bc clorua c to
thnh iu kin nng ion clorua cao, do trn nhng ht bc clorua xut hin in tch
m cao. Kch thc ca lp in tch dng ca ion i bao quanh mi ht cn phi tng i
ln v cha mt lng ion dng, v d ion hiro hoc natri, trung ho in tch m ca
ht. S ng t trong nhng iu kin khng xy ra. Theo mc thm ion bc, in tch
ca ht thp dn v nng ca ion clorua b gim xung v s ht tng ln, tc dng y ca
lp in kp khi gim xung. Khi thm lng thuc th ta quan st thy s ng t keo
xy ra nhanh chng. Khi s ion clorua b hp ph trn ht b gim nhanh v lp in kp b
gim xung n mc l nhng ht ring bit c th tin gn li nhau n khong cch m
c kh nng xy ra s kt t. ng ch l qu trnh kt t l thun nghch, khi thm d
nhiu ion bc, s to keo li mt ln na xy ra. Tt nhin in tch ca lp in kp by gi
bin i v lp ion i tch in m.

141

S ng t thng xy ra khi un nng trong mt thi gian ngn, c bit l km theo

khuy. S nng nhit lm gim s hp ph v do lm gim in tch chung ca ht;
ngoi ra cc ht c c nng lng ng hc vt qua hng ro ngn cn chng tin
gn li nhau.
S lm tng nng cht in li trong dung dch bng cch thm hp cht c c tnh ion
thch hp l phng php ng t hiu qu hn. Trong trng hp ny, trung ho in tch
ca ht i hi mt th tch nh dung dch cha ion tch in ngc du. Do s thm cht
in li gy nn s bp mo lp ion i v do kt qu in tch trn b mt ht c trung
ho hon ton hn. S h thp in tch hiu dng dn ti s xch li gn nhau ca cc ht.
Cng kt trn kt ta v nh hnh. Nhng kt ta v nh hnh b lm bn ch yu do
cng kt theo c ch hp ph. i vi nhng kt ta tinh th nhng dng cng kt khc l c
trng.
Kt ta v nh hnh gm nhng ht c cu trc khng trt t to thnh khi rng, ti,
xp. Kt ta c b mt bn trong ln nm tip xc vi nc ci (xem hnh 7.3). B mt
gi phn ln ion b hp ph ban u trn b mt nhng ht keo khng ng t. Mc d lp
ion i bao quanh ht keo ban u, ni ng ra l mt phn ca dung dch, nn cn ni rng
bo m tnh trung ho in ca h trong qu trnh ng t v lc cn phi gi mt lng
tng i ion ln gn cc ht (lp cht lng bao quanh n). Do kt qu ca s hp ph,
cc cht trong nhng iu kin cho ng l phi tn ti trong dung dch li ri vo kt ta
v lm bn b mt.

Hnh 7.3
Cu to ca kt ta v nh hnh

S peptit ha keo. Peptit ha l qu trnh lm cho keo ng t li c chuyn thnh

trng thi khuch tn ban u. Hin tng peptit ha thng c quan st thy khi ra kt
ta v nh hnh bng nc tinh khit. Mc d ra khng phi l phng php c hiu qu
tch cht bn, hn na n cn dn ti s tch cht in li lm ng t t lp cht lng nm
tip xc vi tng rn. Theo mc tch cht in li, kch thc ca lp ion i c tng
ln. Lc y gy nn s to thnh keo c phc hi v cc ht c tch ra t khi c

142

ng t. Cht lng ra tr nn c bi v nhng ht khuch tn li mt ln na i

qua giy lc.
Khi lm vic vi nhng kt ta keo, nh ha hc phi ng chm ti mt tnh hung kh
x: cn phi lm sch kt ta khi cc cht bn nhng ng thi khng lm mt i mt phn
kt ta do hin tng peptit ha. C th gii quyt tnh hung kh x bng cch chn ng
cht lng ra cho kt ta v nh hnh. Thng ngi ta s dng dung dch cht in li bay
hi, n c tch ra khi nung nng tip theo. V d, thng ra bc clorua bng dung dch
axit nitric long. Kt ta ra cn nhim bn nhiu axit nhng iu khng nh hng
n kt qu phn tch bi v axit nitric bay hi khi sy kt ta 110oC.
Tch nh lng kt ta v nh hnh.
Thng khi khuy, kt ta v nh hnh c to thnh t dung dch nng c cht in
li ng t keo. Trong nhiu trng hp, hon thin nhng tnh cht vt l ca kt ta
ng t tng rn, ngi ta gi kt ta tip xc vi dung dch nng m t qu trnh kt ta
c tin hnh. Trong thi gian ca qu trnh c gi l gi ha , chc l nc lin kt
yu c tch ra t kt ta v do kt ta tr thnh mn hn v d lc hn.
Khi lc kt ta ngi ta ra bng dung dch long cht in li bay hi. Nhng ion b hp
ph trc t b tch ra khi ra bi v chng lin kt cht vi cht kt ta rn. Nhng gia
nhng ion i trong kt ta v mt trong nhng ion ca cht lng ra c th trao i. Khi k
ti tt c nhng iu , kh m hy vng rng kt ta khng b bn n mc no thm
ch c ngay sau khi ra tch cc. Sai s phn tch do nguyn nhn c th dao ng t (1
2).104% (v d nh bc nitrat cng kt trn bc clorua) n nhng i lng khng th chp
nhn c (v d nh hiroxit cc kim loi nng cng kt trn oxit hirat ha st ha tr ba
hoc nhm).
Kt ta li l bin php hiu qu nht lm gim hp ph. Trong trng hp ny ngi
ta ho tan kt ta c lc v kt ta li mt ln na. Nh thng l, kt ta thu c ngay
t u ch cha mt phn nh lng cht bn tng qut tn ti ban u. Do , nng hn
hp bn trong dung dch thu c khi ho tan kt ta s nh hn rt r rt so vi nng cht
bn trong dung dch ban u. Khi lp li ng tc kt ta c th mong i s hp ph thp.
Kt ta li lm ko di ng k ng tc phn tch, nhng mc d vy, ng tc y hu nh
khng th trnh khi i vi nhng kt ta nh hiroxit st (III) v nhm c khuynh hng
hp ph c bit ln cc hiroxit cc kim loi nng nh km, cadimi v mangan.

7.5.3 Nhng kt ta tinh th

Ch ha cc kt ta tinh th ni chung d hn so vi kt ta v nh hnh. Trong trng
hp ny c th iu chnh kch thc ht kt ta n mt mc nht nh. Nh vy, nh ha
hc c th iu khin nhng tnh cht vt l v tinh khit ca kt ta thng qua nhng iu
kin thc nghim.
Nhng bin php lm cho ht ln v nng cao tnh d lc ca kt ta: Theo thng l, c
th lm tng kch thc ht kt ta tinh th khi gi trng thi qu bo ha tng i trong qu

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trnh kt ta mc thp. Nh thy trn hnh 6.2, c th t ti iu bng cch h

thp Q hoc nng cao S hoc iu chnh c hai yu t .
Dng dung dch long, thm cht kt ta chm v khuy mnh ngi ta c th lm gim
s qu bo ha tng ni trong dung dch. Thng c th nng cao S khi kt ta t dung dch
nng. Nh bin php n gin , hon ton c th thnh cng v kch thc ht.
sch ca cc kt ta tinh th: B mt ring ca kt ta tinh th (c xc nh bng
din tch cho mt n v trng lng tnh theo cm2/g) thng nh, do s cng kt theo c
ch hp ph khng ng k. Nhng nhng dng khc ca s cng kt lin quan n s lm
bn bn trong tinh th c th dn n sai s nghim trng.
Ngi ta bit c hai loi cng kt trn kt ta tinh th: loi hp tng v loi hp lu;
chng khc bit nhau c tnh phn b tp cht bn trong tng rn. Tp cht hp tng
dng cc ion hoc phn t n l c phn b ng th trn ton tinh th. Ngc li, s hp
lu l s phn b khng ng u, nhiu ion hoc phn t tp cht ri vo tinh th do s
khng hon chnh ca mng li tinh th.
S hp lu xut hin trong nhng trng hp khi m nhng git nh hon chnh ca
dung dch cha tp cht gy bn b ko vo v b bao quanh rt nhanh chng bi s ln ln
ca tinh th. V tp cht nm bn trong tinh th nn kh tch chng bng cch ra, c th
gim mc hp lu ng k bng cch kt ta chm hn cho nhng ht nh tp cht kp
tch ra khi b mt tng rn trc khi chng b ri vo bn trong tinh th. Cn mt phng
php hiu qu hn lm gim tp cht hp lu l phng php lm gi kt ta.
Lm gi nhng kt ta tinh th: un nng nhng kt ta tinh th (khng khuy) trong mt
thi gian sau khi kt ta thng cho php ta thu c sn phm tinh khit v kh d lc.
Khng cn nghi ng g na, s lm sch kt ta gn lin vi nhng qu trnh ho tan v kt
tinh li xy ra lin tip m tc ca chng tng ln khi nhit tng. Trong thi gian
nhiu l hng ca tinh th c dung dch hon chnh, kh nng tch cht bn khi tng rn
xut hin v do tinh th tr thnh hon chnh hn.
S ho tan v kt tinh li khi lm gi cn to kh nng nng cao tnh d lc. S xut hin
cu gia nhng ht gn nhau dn ti s thu c nhng lin hp (chm tinh th) tinh th d
lc hn. Gi thit khng nh rng s khuy kt ta vi dung dch khi lm gi thc t
khng nh hng n tnh d lc ca kt ta.

7.5.4 Sai s do cng kt

S cng kt tp cht c th lm nng cao hoc h thp kt qu phn tch. Nu tp cht
khng to hp cht vi ion cn xc nh, sai s s lun lun dng. V d, khi xc nh ion
clorua s thy sai s dng do hp ph bc nitrat trn kt ta bc clorua v nh hnh. Ngc
li, nu tp cht cha ion cn xc nh, sai s c th l dng hoc m. V d, khi xc nh
bari bng cch kt ta di dng bari sunfat ngi ta quan st thy s hp lu mui bari. Nu
bari clorua l tp cht b hp lu th xut hin sai s m bi v phn t lng ca n nh hn
phn t lng ca bari sunfat.

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7.5.5 Kt ta t dung dch ng th

Khi kt ta t dung dch ng th s sinh ra cht kt ta trong dung dch phi chm
s qu bo ho tng i lun lun thp. V cht kt ta c phn b u trong ton b th
tch dung dch nn s qu bo ho mt ch khng xy ra. Theo thng l, nhng kt ta c
v nh hnh v tinh th thu c t dung dch ng th c nhng tnh cht phn tch qu gi
hn so vi nhng kt ta thu c bng cch thm trc tip cht kt ta vo.
Thng thu c ion hiroxyl ng th ngi ta dng ure cho phn ng theo phng
trnh sau:

( NH2 )2 CO + 3H2O

CO2 + 2NH4+ + OH

nhit thp hn nhit si mt cht, phn ng ny xy ra chm. Thng thng,

c lng thuc th kt ta hon ton phi cn t mt n hai gi. Phng php c
bit thun tin khi kt ta hiroxit hoc mui baz. V d, hiroxit st (III) v nhm c kt
ta bng cch thm baz trc tip vo l mt khi keo xp rt bn v kh lc. Ngi ta thu
c cng chnh nhng sn phm nhng mn hn, d lc hn v tinh khit hn rt nhiu
nu php kt ta c thc hin bng nhng ion hiroxyl t dung dch ng th.
S kt ta cc kt ta tinh th t dung dch ng th cng dn ti s tng kch thc tinh
th ln r rt: s pht trin tinh th thng km theo tinh khit cao. Nhng v d v nhng
php xc nh da trn s kt ta t dung dch ng th c dn ra bng 7.2.

7.5.6 Sy v nung kt ta
Sau khi lc kt ta ngi ta nung n khi trng lng khng i. Mc ch ca ng tc
nung l tch dung mi v nhng cht in li bay hi b kt ta ng thi vi kt ta. Ngoi ra,
php ch ha i khi dn ti s phn hy kt ta vi s to thnh sn phm c thnh phn
bit.

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Hnh 7.4
nh hng ca nhit n trng lng kt ta

Nhit cn thit thu c sn phm mong mun ph thuc vo bn cht ca kt ta.

Trn hnh 7.4 gii thiu s ph thuc ca s mt trng lng vo nhit i vi mt s kt
ta thng dng trong phn tch. Nhng d kin thu c trn cn nhit t ng, cn lin
tc, lin tc o trng lng ca cht theo nhit trong l tng vi tc khng i. Khi
nung ba kt ta: bc clorua, bari sunfat v nhm hiroxit, nc b tch ra v c th c nhng
cht in li bay hi b kt ta trong qu trnh thu c kt ta. a nhng kt ta c
kh nc n trng lng khng i ngi ta s dng mt khong rng nhit . Nh tch
hon ton m khi bc clorua i hi nhit t 110 n 120oC; s ehirat ha hon ton
nhm hiroxit t c nhit cao hn 1000oC. Rt l th nhn xt rng, nhm hiroxit
thu c bng phng php kt ta ng th t dung dch ure, c th mt nc hon ton
nhit khong 650oC.
R rng l nhit trng lng ca canxi oxalat phc tp hn nhiu nhit trng lng
ca cc cht khc c din t trn hnh 6.4. nhit thp hn 135oC m hp ph
c tch ra, monohirat CaC2O4.H2O c to thnh v 225oC n chuyn thnh oxalat
khan. khong 450oC s bin i t ngt trng lng ch r s phn hy canxi oxalat, to
thnh canxi cacbonat v oxit cacbon. Bc cui cng trn nhit trng lng tng ng vi
s chuyn cacbonat thnh canxi oxit v kh CO2. Hin nhin l dng trng lng c s
dng i vi canxi oxalat ph thuc vo iu kin nung.

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7.4

V thiu st ca phng php phn tch trng lng

Hin nay mt s nh ha hc c khuynh hng lm gim ngha ca nhng phng

php trng lng, vin c rng chng c hiu sut thp v gi ci. Chng ti cho rng,
nhng phng php trng lng c mt mnh, mt yu v n thc hin mt s kh ln
nhng nhim v phn tch (v c nhng nhim v khc na, khi m phn tch trng lng l
phng php tt nht gii quyt nhng nhim v ).

7.5.1 Thi gian thc hin phn tch trng lng

Kt cc, trong tt c cc phng php phn tch ngi ta u o mt tnh cht vt l M
no bin i theo s bin i lng hoc nng CA ca cu t cn xc nh A trong mu
u. Trong trng hp l tng, nhng hon ton khng phi l lun lun, s ph thuc hm
s gia CA v M l tuyn tnh, ngha l:
CA = kM
Trong phn ln cc phng php phn tch cn thit phi xc nh k bng cch chun ha
hoc l bng ng chun thc nghim trong ngi ta o M i vi mt hoc mt s ln
hn mu chun c CA bit. C hai ngoi l c bit lch ra khi quy lut : phng php
phn tch in trng lng v culng (cc phng php phn tch cng c). Trong cc phng
php ny c th tnh k trc tip t nhng hng s tng qut bit. Nh vy, s cn thit phi
hiu chnh hoc chun ha khng cn na.
Trong phn tch trng lng k l yu t lng c th tnh c theo bng phn t lng.
Nh s c ch r sau y, i khi tnh hnh lm cho phn tch trng lng tr thnh
phng php hiu qu nht gii quyt nhng nhim v phn tch.
Khi cp n vn thi gian thc hnh phn tch, cn thit phi phn bit thi gian
xc nh v thi gian nh phn tch tiu ph cho php xc nh. Thi gian xc nh l s gi
hoc pht k t lc bt u phn tch n khi thu c kt qu. Cn thi gian nh phn tch
tiu ph l thi gian thc t tiu ph cho s hon thnh cc ng tc cn thit hon thnh
php phn tch v tnh ton kt qu. Khi so snh vi cc phng php khc, ta thy phng
php phn tch trng lng c c im l c s khc nhau ln gia thi gian xc nh v thi
gian nh phn tch tiu ph, bi v phn ln nhng giai on phn tch di khng cn thit phi
lun lun ch . V d, nhng ng tc nh a cht n trng lng khng i, lm bay hi
dung dch, lm gi kt ta v nung sn phm chim mt mt s gi nhng nh phn tch tiu
ph cho tt c nhng ng tc nhiu nht cng ch l mt s pht v do thi gian cn li
c th dng hon thnh nhng nhim v khc.
Nu so snh vi nhng phng php khc, v nguyn tc, vic hnh thnh mt php xc
nh no theo thi gian m nh phn tch phi tiu tn cho vic thc hin chng th phn
tch trng lng thng t ra hiu qu nht c bit l khi ch phn tch mt hoc hai mu bi
v khng cn tn thi gian cho ng chun hoc chun ha (ngha l xc nh k). Khi tng s
mu phn tch thi gian tiu tn cho ng chun tnh cho mt mu trong nhng phng
php khng trng lng tr nn ngy cng nh hn v thng khi phn tch 8 n 10 mu ni

147

chung l c th b qua. (Tt nhin l gi thit rng mt ng chun phn tch tt c cc

mu). Khi phn tch mt s ln mu, lc kt ta, ra v cn c th cn thi gian ln hn so
vi vic thc hin nhng ng tc tng ng trong cc phng php khng trng lng.
Do , nu phi phn tch mt s ln mu, phng php trng lng thng (nhng khng
phi l lun lun) khng thch hp.

7.5.2 Lnh vc ng dng ca phn tch trng lng

Nhng phng php trng lng c nghin cu cho phn ln cc anion v cation v
c v c cho cc hp cht trung ha nh nc, ioxit lu hunh, kh CO2 v it. C mt lot
cc hp cht hu c cng d dng xc nh bng phng php trng lng, v d nh xc
nh lactoza trong cc sn phm sa, salixilat trong dc phm, phenolphtalein trong thuc
s, nicotin trong ha cht c, cholesterol trong huyt thanh v benzanehit trong dch chit
qu hnh nhn. Phn tch trng lng l mt trong nhng phng php phn tch c s
dng rng ri nht.

7.5

ng dng phng php phn tch trng lng

7.5.1 Cc cht to kt ta v c
Bng 7.3 lit k nhng cht kt ta v c thng dng nht. Nhng thuc th ny thng
c s dng iu ch nhng mui v hiroxit t tan. Hoc l chnh mui hoc l oxit c
dng lm dng cn. Nhiu hp cht c gch di trong bng ch r tnh khng chn lc
ca phn ln cc thuc th v c.

7.5.2 Nhng thuc th c tnh cht kh

Bng 7.4 dn ra mt s thuc th kh cu t cn xc nh n nguyn t l dng c
dng lm dng cn.

7.5.3 Nhng cht to kt ta hu c

Mt lot cc cht hu c c ngh xc nh trng lng cc cht v c. Nhng
thuc th loi ny c la chn cao hn so vi nhiu thuc th v c c dn ra bng
7.3.
Bng 7.3 Mt s cht to kt ta v c

Cht kt ta

Nguyn t b kt ta

NH3 (nc)

Be (BeO), Al (Al2O3), Sc (Sc2O3), Cr (Cr2O3)*, Fe (Fe2O3), Ga

(Ga2O3), Zn (ZnO2), In (In2O3), Sn(SnO2), U(U3O8),

148

H2S

Cu(CuO)*, Zn (ZnO hay ZnSO4), Ge (GeO2), As (As2O3 hay

As2O5), Mo (MoO3), Sn(SnO2)*, Sb (Sb2O3) hay Sb2O5), Bi
(Bi2S3)

(NH4)2S

Hg (HgS), Co (Co3O4).

(NH4)2HPO4

Mg (Mg2P2O7), Al (AlPO4), Mn (Mn2P2O7), Zn (Zn2P2O7), Zr,

(Zr2P2O7), Cd (Cd2P2O7), Bi (BiPO4).

H2SO4

Li, Mn, Sr, Cd, Pb, Ba (tt c dng sunfat)

H2PtCl6

K (K2PtCl6), hoc Pt) rb (Rb2PtCl6), Cs (Cs2PtCl6)

H2C2O4

Ca(CaO), Sr (SrO), Th (ThO2)

(NH4)2MoO4

Cd (Cd MoO4)*, Pb (PbMoO4)

HCl

Ag (AgCl), Hg (Hg2Cl2), Na ( dng NaCl trong butanol), Si

(SiO2)

AgNO3

Cl (AgCl), Br (AgBr), I (AgI)

(NH4)2CO3

Bi (Bi2O3)

(NH4)2SCN

Cu [Cu2(SCN)2]

NaHCO3

Ru,Os, Ir (kt ta di dng hiroxit b kh n trng thi kim

loi, H2)

HNO3

Sn (SnO2)

H5IO6

Hg[Hg5(IO6)2]

NaCl, Pb(NO3)2

F, (PbClF)

BaCl2

SO42 (BaSO4)

MgCl2, NH4Cl

PO43 (Mg2P2O7)

Ch m k hiu trong bng 7.3 ch nguyn t hoc ion m i vi chng phng php
trng lng l phng php xc nh chim u th nht. Dng cn ca chng c ch ra
trong ngoc. Du sao c ngha l phng php trng lng t c dng. Gch di ch dng
cn thch hp nht.
C hai loi thuc th hu c. Nhng thuc th loi th nht to phc cht t tan c c
tnh kh ion ha gi l cc hp cht phi tr. Nhng thuc th loi th hai to nhng sn

149

phm trong lin kt gia nhng ion v c v thuc th mang c tnh ion mc ng
k.
Nhng thuc th hu c to nhng hp cht phi tr t tan thng cha t nht hai nhm
to phc, trong mt nhm c kh nng cho cation kim loi i in t khng phn chia.
Nhng nhm to phc phn b trong phn t nh th no cho kt qu phn ng l
vng nm hoc su thnh phn. Nhng hp cht to phc loi c gi l nhng thuc th
to vng cng. Cn sn phm tng tc gia chng vi cc cation kim loi c gi l phc
vng cng (chelat).
Bng 7.4 Mt s cht kh c ng dng trong phn tch trng lng

Cht kh

Nguyn t cn xc nh

SO2

Se, Au

SO2 + NH2OH

Te

NH2OH

Se

H2C2O4

Au

H2

Re, Ir

HCOOH

Pt

NaNO2

Au

TiCl2

Rh

SnCl2

Hg

Kh bng in phn

Cs, Ni, Cu, Zn, Ag, In, Sn, Sb, Cd, Re, Bi

Nhng hp cht phi tr khng tch in c phn cc tng i thp, do chng t

tan trong nc v tan tt trong dung mi hu c. Thng cc phc vng cng c phn t gam
ln v c mu m. Nhng hp cht phi tr khng b tm t bng nc v do d mt
m nhit thp nhng ng thi nhng kt ta k nc ca chng biu l tnh cht khng
th chp nhn c theo quan im phn tch, l tnh cht bm vo thnh giy lc khi ra.
V vy, nu khng thc hin nhng bin php ngn nga c th mt kt ta theo c ch c
hc. Di y chng ta xt 3 thuc th to phc vng cng.
8-oxiquinolin: thuc th ny cn c tn oxin, to hp cht phi tr t tan vi hn hai chc
cation:

150

N
OH

Dng hp cht ca oxin vi magie lm v d in hnh:

O
N Mg

tan ca oxiquinolinat kim loi bin i trong mt gii hn rng tu thuc vo bn

cht ca cation v gi tr pH, bi v phn ng to phc km theo s y ra proton. Do , iu
chnh pH khi kt ta 8-oxiquinolinat c th t c la chn kh.
1-nitrozo-2-naphtol: l mt trong nhng thuc th hu c la chn u tin, c
ngh nm 1885; cng thc ca n nh sau:
NO
OH

Khi tng tc vi coban (II) n to thnh phc vng cng ca coban (III) khng dn in
c thnh phn CoA3, y A l baz lin hp ca thuc th. Chng ta nhn thy rng, s to
kt ta km theo s oxi ha coban bng 1-nitrozo-2-naphtol nn kt ta thng b bn bi sn
phm kh ca thuc th. Do , nu chp nhn nung phc vng cng trong kh quyn oxi ha
th n Co3O4; cn nu nh dng coban trng thi nguyn t l dng cn th phi nung trong
kh quyn kh.
Xc nh coban khi c mt niken l trng hp quan trng nht ca 1-nitrozo-2-naphtol.
Mt s ion khc bao gm bismut (III), crom (III), thy ngn (II), thic (IV), titan (III),
vonfram (VI), uran (VI), vanai(V) cng to kt ta vi thuc th ny.
imetylglyoxim:
H3C
HO

CH3
OH

151

l thuc th hu c c la chn rt cao. V d, trong mi trng axit ch c palai to

hp cht phi tr t tan vi thuc th ny, cn trong mi trng kim yu ch c hp cht ca
niken lng xung. Kt ta imetylglyoximat niken c mu hng ti, c cu to nh sau:
H 3C
O

CH3
O

Ni
O

H 3C

O
CH3

v c th tch ln n mc l c th kt ta c mt lng niken rt nh. Kt ta ny c

mt tnh cht ng ght l b ln thnh giy lc khi ra. Hp cht phi tr ny b sy kh
110oC v tng ng vi thnh phn trong cng thc nu trn.
Natri tetraphenylborat: natritetraphenylborat l mt i din quan trng ca cc cht
kt ta hu c to kt ta dng mui. Trong cc dung dch axit v c lnh, thuc th thc
t c tc dng c trng vi cc ion kali v amoni.
Nhng kt ta ca mui kali hoc amoni l hp thc, d lc trong chn khng v t
trng lng khng i nhit 105 120oC. Ch c thy ngn (II), rubii v xezi cn tr
php xc nh nn cn phi tch trc.
Benzidin:

l mt thuc th to mui khc. Benzidin kt ta ion sunfat trong mi trng axit yu di

dng C12H12N2.H2SO4. tan ca kt ta tng nhanh khi nng nhit v axit ha; phi kim
tra nghim ngt c hai yu t . C th thay ng tc cn kt ta bng ng tc chun
bng dung dch NaOH chun. Theo mt phng php khc, php phn tch c kt thc
bng cch chun benzidin bng dung dch chun pemanganat. Nhng phng php kt ta s
dng benzidin c p dng thnh cng khi c mt cc ion ng, coban, niken, km, mangan
(II), st (II), crom (III) v nhm. Phng php nu trn c dng xc nh nhanh hng
lot mu sunfat.

7.5.4 Xc nh trng lng cc nhm chc hu c

Hng lot thuc th phn ng la chn vi mt s nhm chc hu c c ngh.
iu cho php xc nh phn ln cc hp cht c cha trong thnh phn ca mnh cc
nhm chc . Danh sch cc thuc th kt ta cc hp cht c cc nhm chc tng ng
c dn ra bng 7.5. Nhiu phn ng trong s nhng phn ng nu c th c s dng

152

trong cc phng php phn tch chun v o mu. Khi thc hin nhng php
phn tch n nht, phng php trng lng thng chim u th bi v trong trng hp
ny khng cn thit lp ng chun.
7.5.5

Nhng phng php trng lng xc nh cc hp cht hu c ring l

Nhng v d in hnh xc nh mt s hp cht hu c c m t trong phn ny.

Xc nh axit salixilic: Ha tan axit salixilic trong dung dch natri cacbonat v sau khi
thm iot vo, yn. Khi xy ra phn ng:
-

COO

OH
2

+ 68I2 + OH

O + 8I- + 2 HCO3- + 6 H2O

O
I

lc, sy v cn kt ta vng ca tetraiotphenylenquinon. Bng phng php ny c th

xc nh axetylsalixilic axit (aspirin) sau khi thy phn n n axit salixilic.
Xc nh nicotin: Sau khi ct li cun hi nc nicotin khi mu, c th xc nh hp
cht ny trong cc ha phm c hoc trong cc sn phm ca cng ngh thuc l bng cch
kt ta vi axit silicovonphramic. Lc, ra, nung kt ta n hn hp oxit SiO2.12WO3 v sau
cn.
Xc nh phenolphtalein: Phng php chun xc nh phenolphtalein trong thuc ty bao
gm ng tc chit bng ru v lm bay hi tip theo n kh. Sau ha tan phenolphtalein
trong dung dch kim long v kt ta di dng tetraioua bng cch thm dung dch iot vo.
C th sy sn phm n trng lng khng i 110oC.

7.5.6 Phng php chng ct

Hai phng php trng lng ph bin nht da trn php chng ct l php xc nh
nc v php xc nh kh CO2.
Nc b tch nh lng ra khi phn ln cc cht v c khi nung chng. Phng php
xc nh trc tip da trn s tng trng lng cht lm kh ri suy ra trng lng nc.
Phng php gin tip da trn s mt trng lng mu khi nung cho kt qu km tho
mn hn. Trong trng hp ny buc phi gi thit, nc l cu t duy nht b tch. Gi thit
thng khng c c s bi v khi nung, nhiu cht b phn hy v khi dn ti s mt
trng lng khng lin quan vi s c mt ca nc.

153

Cc cacbonat thng b phn hy bi cc axit to thnh kh CO2 d dng tch ra khi

dung dch khi un nng. Nh trong phng php trc tip xc nh nc, trng lng kh
CO2 c xc nh theo s tng trng lng ca cht hp th rn. Askanit v amiang tm
kim natri c dng lm cht hp th kh CO2.
2NaOH + CO2 Na2CO3 + H2O

ng hp th kh cng cn cha cht ht nc ngn nga s mt nc tch ra.

Cng c th xc nh sunfua v sunfit bng phng php chng ct. Trong trng hp
ny, sau khi ch ha mu bng axit, sunfua hiro hoc ioxit lu hunh c tch ra t dung
dch, c hp th bng cht hp th thch hp.

154

Chng 8
M u v phn tch th tch

Trong nhiu trng hp, gii quyt nhim v phn tch, phng php phn tch trng
lng l phng php tt nht. Tuy vy, thi gian thc hin php phn tch trng lng
thng qu di nn nhiu khi khng p ng nhu cu ca sn xut cng nghip. l l do ra
i ca phng php phn tch th tch.
Phng php nh lng da trn php o th tch c gi l phng php phn tch th
tch hay phng php chun . Phng php chun c s dng rng ri hn phng
php trng lng v phng php ny nhanh hn, thun tin hn m nhy li khng thua
km.

8.1 Nhng khi nim c bn

Chun l qu trnh nh lng cht cn phn tch theo lng thuc th tiu chun tiu
tn. Php chun c thc hin bng cch thm mt cch thn trng dung dch thuc th
bit nng vo dung dch cht cn xc nh cho ti khi phn ng gia chng kt thc,
sau o th tch dung dch thuc th chun. i khi, nu iu khng thun tin hoc cn
thit, ngi ta thm d thuc th v sau chun ngc bng mt thuc th khc bit
nng xc nh lng d thuc th th nht khng tham gia phn ng.
Dung dch thuc th c nng chnh xc bit dng chun c gi l dung
dch chun. chnh xc ca nng dung dch chun hn ch chnh xc chung ca
phng php, do cn c bit ch vic iu ch cc dung dch chun. Nng dung dch
chun c xc nh hoc trc tip hoc gin tip:
1. Trc tip bng cch ho tan hon ton mt lng cn chnh xc thuc th chun gc v
pha long n th tch chnh xc bit bng nc ct.
2. Chun dung dch cha mt lng cn xc nh ca mt hp cht tinh khit bng
dung dch thuc th chun l cch gin tip.
Hp cht ha hc c dng lm cht chun phi c tinh khit cao c gi l cht
chun gc. Qu trnh xc nh nng dung dch chun theo cch chun bng dung dch
cht chun gc c gi l php chun ha.

155

Mc ch ca mt php chun bt k no cng l tm lng dung dch chun tng

ng v mt ha hc vi lng cht phn ng vi n (cht cn xc nh). iu t c
im tng ng. V d, trong php chun dung dch natri clorua bng dung dch bc
nitrat, im tng ng t c khi mt mol bc nitrat c thm vo mt mol natri clorua
trong mu. Khi chun axit sunfuric bng natri hiroxit im tng ng l lc thm hai
phn t gam kim vo mt phn t gam axit.
im tng ng l mt khi nim l thuyt. xc nh v tr thc t ca n, phi
quan st s bin i tnh cht vt l lin quan vi im tng ng. Nhng bin i ch
tr thnh r rng im cui ca php chun. Thng ngi ta cho rng hiu s th tch
im tng ng v im cui nh nhng lun tn ti do s khng tng ng gia qu
trnh bin i tnh cht vt l v phng php chng ta quan st n; do xut hin sai s
chun .
Thng thng, xc nh im cui php chun ngi ta s dng ha cht ph c
kh nng bin i mu ca mnh theo s bin i nng gn im tng ng. Nhng
cht nh vy gi l cht ch th.

8.2 Phn ng v thuc th dng trong phn tch chun

Ty thuc vo loi phn ng dng lm c s cho mi phng php ngi ta chia cc
phng php chun thnh 4 loi: phng php kt ta, phng php trung ha (axit baz), phng php complexon v phng php oxi ha kh. Cc phng php ny khc
nhau v bn cht ca cn bng c s dng, v ch th, v thuc th, v cht chun gc.

8.2.1 Nhng cht chun gc

ng ca kt qu phn tch chun ph thuc rt nhiu vo cht chun gc c
dng thit lp (trc tip hoc gin tip) nng dung dch chun. Cc cht c chp nhn
l cht chun gc tt cn phi tho mn mt lot nhng i hi quan trng:
1. Chng phi c tinh khit cao nht, hn na phi c nhng phng php n gin,
tin cy khng nh tinh khit ca chng.
2. Phi bn, ngha l khng tc dng vi cc cu t ca kh quyn.
3. Khng cha nc hirat. Khng phi l cht ht m hoc c xu hng phong ho kh
lm kh v kh cn.
4. Phi d kim (gi thnh va phi).
5. C phn t gam mol cao. Khi lng cht cn thit chun ha hoc iu ch
dung dch c nng cho s cng ln nu phn t gam ca n cng ln. Khi khi lng
tng sai s ca php cn s gim, phn t gam cng cao c kh nng lm gim sai s cn cng
ln.

156

Ch c mt s t cht tha mn hoc hu nh tho mn cc yu cu v do

s cht quy cch dng lm cht chun gc b hn ch.
Trong mt s trng hp, thay th cho cht chun th nht phi dng cht km tinh khit
hn. tinh khit ca cht chun th hai cn phi c xc nh bng con ng phn
tch cn thn.
Vic s dng cc t ng cht chun th nht v th hai l ngun gc s bt ng
gia cc nh ha hc. Mt s gi mt s tng i t hp cht c cc tnh cht c k ra
u mc ny l cc cht chun gc v cc cht chun c thnh phn c bit mt cch tin
cy l cht chun th hai. Mt s khc a thch xem tt c cc cht loi bit l cc cht
chun th nht v cc dung dch vi nng bit l cc cht chun th hai. Chng ta chn
h cc thut ng th nht.

8.2.2 Dung dch chun

Dung dch chun l tng phn tch chun cn phi c nhng tnh cht sau:
1. Sau khi iu ch nng ca n phi khng bin i trong thi gian bo qun lu
(trong mt vi thng hoc hng nm), khng cn phi chun ha li.
2. Phn ng nhanh vi cht cn xc nh thi gian ch i sau khi thm tng phn nh
thuc th phi ngn.
3. Phn ng gia thuc th v cht cn xc nh cn phi xy ra hon ton c th
xc nh im cui tho mn.
4. Phn ng gia thuc th v cht cn xc nh cn phi xy ra hp thc, nu khc i th
khng th tnh trc tip khi lng cht cn xc nh.
5. Cn phi c phng php xc nh im tng ng ca phn ng gia thuc th vi
cht cn xc nh, ngha l c phng php xc nh im cui tho mn.
Hin nay, ch c mt s t trong nhng thuc th c s dng tho mn hon ton tt
c cc yu cu .
8.3

im cui trong cc phng php chun

Ngi ta xc nh im cui ca php chun bng cch quan st s bin i mt tnh

cht vt l no im tng ng. C th xc nh im cui theo s bin i mu ca
thuc th, ca cht cn xc nh hoc ca ch th. tm im tng ng ngi ta s dng
s bin i c ca cc tnh cht vt l khc nh th in cc, dn, nhit v ch s khc
x.
S bin i nng trong qu trnh chun

157

im cui ca php chun xy ra s bin i nng rt ln t nht ca mt trong

cc cht phn ng. Trong phn ln (nhng khng phi l tt c) trng hp, xc nh im
cui ngha l xc nh nhng bin i xy ra vng ln cn im tng ng l c bit
quan trng. minh ho ny trong ct th hai v th ba ca bng 8.1 dn ra nhng d kin
ch r s bin i nng ion hiro v hiroxyl khi chun 50,0 ml dung dch axit clohiric
0,100 M bng dung dch NaOH 0,100 M. nhn mnh rng, chng ta c bit ch ti
nhng bin i nng ng k, nn ta thm vo tng th tch thuc th gy nn s tng
hoc gim 10 ln nng cht phn ng.
lm gim nng ion hiro t 0,100 M n 0,0100 M cn phi thm vo 40,9 ml
kim. h thp nng n 0,00100 M i hi ph thm 8,1 ml. giai on sau, lm
gim nng 10 ln ch cn phi thm vo 0,89 ml ... ng thi quan st thy s bin i
tng t nng ion hiroxyl. T cc d kin ca bng 8.1, ta thy gn im tng ng s
bin i nng cc cht phn ng l cao nht. Trong nhiu trng hp, s xc nh thnh
cng im cui c thc hin nh chnh gi tr ca s bin i . Trn hnh 8.1 dn ra
th bin i c xy dng theo cc d kin ca bng 8.1. Mi chia trn h trc ca th
c gi tr ln ton thang bao trm mt khong ln ca s bin i nng thuc th.
Do , nhng bin i quan st c trong vng chng ta quan tm nht - vng im tng
ng - cn cha c r rng.
a

Bng 8.1 S bin i nng khi chun

Th tch dung
NaOH 0,100 M, ml

Nng OH
dch Nng
pH
H3O+, mol/l
mol/l

pOH

0,0

1,0.101

1,0.1013

1,00

13,00

40,9

1,0.102

1,0.1012

2,00

12,00

49,01

1,0.103

1,0.1011

3,00

11,00

49,90

1,0.104

1,0.1010

4,00

10,00

49,990

1,0.105

1,0.109

5,00

9,00

49,9990

1,0.106

1,0.108

6,00

8,00

50,0000

1,0.107

1,0.107

7,00

7,00

50,0010

1,0.108

1,0.106

8,00

6,00

50,010

1,0.109

1,0.105

9,00

5,00

50,10

1,0.1010

1,0.104

10,00

4,00

51,01

1,0.1011

1,0.103

11,00

3,00

158

1,0.1012

61,1

1,0.102

12,00

2,00

Nhng d kin trong bng 8.1 ch dng minh ha nn cng d dng hiu rng: khng
c kh nng thu c nhng d kin nh th trong phng th nghim bi v o th tch v
nng dung dch n 6 ch s c ngha thng l iu khng th lm c.
hnh dung r rng hn s bin i trong vng , biu din nng khng phi
dng tuyn tnh m dng logarit s thun li hn. V chng thng nh hn n v nn s
dng logarit m l hp l v v vy hm s din t nng di dng s dng nh.
Logarit m (c s 10) ca nng phn t c bit di dng hm s p. Nhng gi tr pH
v pOH c a ra 2 ct cui ca bng 8.1.

Hnh 8.1
S bin i nng cc cht phn ng khi chun 50,00 ml dung dch HCl 0,0100 M bng dung dch NaOH 0,100 M

V d: Hy tnh hm s p ca mi ion trong dung dch 0,020 M theo NaCl v 0,0054 M

theo HCl.
1.

[H3O+] = 0,0054 = 5,4.103

pH = log[H3O+] = log[5,4.103] = 2,27

Cn nh rng trong kt qu tm c c 3 ch s c ngha xy dng th theo hm
s p (hnh 8.2) mc d i vi [H3O+] ch c 2 ch s.
2.

[Na+] = 0,020 = 2.102

pNa = log(2.102) = 1,70.

159

[Cl] = 0,020 + 0,0054 = 0,0254

3.

pCl = log(2,54.102) = 1,6.

V d: Hy tnh [Ag+] trong dung dch nu pAg = 6,372.
pAg = 6,372 = 7,000 + 0,628
[Ag+] = antlog(7,000).antlog(0,628) = 107.4,246 = 4,25.107.
Nu nng ion ln hn 1 mol/l, hm s p ca n s l s m. V d, trong dung dch
HCl 2,0 M:
[H3O+] = 2,0 ion.g/l
pH = log[H3O+] = log2,0 = 0,30.
Nu nhng gi tr pH v pOH c dn ra bng 8.1 c mang ln th theo th tch
thuc th thm vo th thu c ng cong cho bc tranh r rng hn v s bin i nng
xy ra trong dung dch gn im tng ng: y quan st thy s tng t ngt pH
v s gim tng ng pOH.
Nhng ng cong tng t nh ng cong c din t trn hnh 8.2 c gi l
ng chun . th c xy dng theo nhng d kin tng t i vi cc php chun
oxi ha kh, kt ta hoc complexon cng c nhng c tnh y. Trong cc chng sau s dn
ra v bn lun nhng v d in hnh v ng chun .

Hnh 8.2

160
ng chun 50,0 ml dung dch HCl 0,100 M bng dung dch NaOH 0,100 M

iu ch ln nht i vi nh ha hc phn tch l dng ng chun v c bit l

gi tr bc nhy, trong trng hp ny l bc nhy pH im tng ng, bi v chnh
yu t quyt nh c th xc nh im cui ng v d dng n mc no. C th d dng
pht hin s bin i tnh cht vt l v do pht hin chnh im cui, im thng gn
lin trc tip vi gi tr v tc bin i hm s p. Theo l thng, xc nh im cui d
hn c l khi hm s p bin i ln trong mt vng nh th tch thuc th.

161

Chng 9
Chun kt ta
Nhng phng php chun da trn s to thnh mui bc t tan l nhng phng
php phn tch c bit t lu. Cho n by gi, nhng phng php vn thng c
s dng xc nh bc v nhng ion nh clorua, bromua, ioua v tioxianat. ng dng
nhng phng php chun kt ta trong cht chun khng phi l mui bc m l
nhng hp cht khc cn tng i hn ch.

9.1 ng chun kt ta
Trc khi nghin cu chng ny, sinh vin cn n li nhng lun im c s v tan
ca kt ta chng 5.
ng chun c ch cho vic la chn ch th v c php tnh sai s trong chun . V
d sau y s ch r cch xy dng ng chun kt ta xut pht t tch s tan ca kt ta
to thnh.
V d: Hy dng ng chun 50 ml dung dch KBr 0,005 M bng dung dch AgNO3
0,010 M.
Chng ta tnh pBr v pAg mc d thng ch cn tnh mt trong 2 i lng y l (la
chn i lng no l do nh hng ca cc ion n tnh cht ca ch th quyt nh).
im u: u php chun chng ta c dung dch Br 0,00500 M, Ag+ cha c. Do
pBr = log(5,00.103) = 2,30; gi tr pAg khng xc nh c.
im sau khi thm 5 ml thuc th: Nng ion bromua trong trng hp ny h thp do
kt ta c to thnh v do c s pha long dung dch. Do :
CNaBr =

50,00 0,005 5,00 0,010

= 3,64.103 M
50,00 + 5,00

Thnh phn u t s l lng milimol NaBr ban u, thnh phn th 2 l lng

milimol AgNO3 thm vo. Ion bromua tn ti trong dung dch do phn NaBr cha b chun v
do tan ca AgBr, do nng chung ca Br ln hn nng NaBr cha b chun mt
lng bng tan ca kt ta, ngha l:
[Br] = 3,64.103 + [Ag+]

162

S hng th 2 trong tng s phn nh s ng gp ca AgBr vo nng

Br , m mi ion Br c to thnh t mt ion Ag+. Nu nng NaBr khng qu nh th c
th b qua s hng th 2, ngha l nu:

[Ag+] << 3,64.103 ion.g/l

th
[Br] 3,64.103 ion.g/l
pBr = log(3,64.103) = 2,439 = 2,44
C th tnh i lng pAg mt cch thun tin khi s dng logarit m din t tch s
tan ca AgBr:
log([Ag+][Br]) = logT = log(5,2.1013);
log[Ag+] log[Br] = logT = 12,28
hoc
pAg + pBr = pT =12,28
pAg = 12,28 2,44 = 9,84
C th tnh mt cch tng t nng Br v Ag+ cc im khc ca ng chun
cho n im tng ng.
im tng ng: im ny khng c d c AgNO3 v NaBr, do :
[Ag+] = [Br]
Thc hin nhng php thay th tng ng trong phng trnh tch s tan chng ta c:
[Ag+] = [Br] = 5,2.1013 = 7,21.107 mol/l
pAg = pBr = log(7,21.107) = 6,14
im sau khi thm 25,10 ml thuc th: Trong dung dch c d AgNO3, do :
CAgNO3 =

25,10 0,010 50,00 0,005

= 1,33.105 M
75,10

v
[Ag+] = 1,33.105 + [Br] 1,33.105 ion.g/l

163

Thnh phn th 2 bn phi phn nh lng ion Ag+ i vo dung dch do tan ca AgBr,
thng c th b qua i lng :
pAg = log(1,33.105) = 4,876 = 4,88
pBr= 12,28 4,88 = 7,40
Nhng im b sung xy dng ng chun sau im tng ng c th thu c
bng cch tng t.

9.2 ngha ca ch s khi tnh ng chun

Tnh ng chun gn im tng ng thng khng c chnh xc cao bi v
n da trn c s s dng hiu s hai s ln gn nhau v gi tr. V d, khi tnh nng
AgNO3 sau khi thm 25,10 ml dung dch AgNO3 0,010 M; t s trong cng thc tnh (0,2510
0,2500) ch cha 2 ch s c ngha. Do , nng AgNO3 trong trng hp tt nht cng
ch c th tnh vi chnh xc n 2 ch s c ngha. Hn na lm gim sai s khi lm
trn, chng ta kim tra php tnh vi chnh xc n 3 s l v lm trn sau khi tnh pAg.
Khi lm trn hm s p, cn nh rng (chng 2) logarit gm c phn c tnh (nhng ch
s bn tri du phy ngn cch vi s l thp phn) v phn nh tr; phn c tnh c
din t ch bng s s nguyn trong gi tr ly logarit. Do ch c th lm trn phn nh tr
n s tng ng ca ch s c ngha.
Trong v d c phn tch trn y, cc im ca ng chun tch bit khi
bc nhy chun . Chng ta c kh nng tnh bc nhy vi chnh xc cao. Chng ta c
th a ra pAg im u bng 2,301, nhng chnh xc t c ngha bi v, trc ht
chng ta quan tm n vng gn im tng ng. Do , y cng nh khi xy dng cc
ng chun khc, chng ta s lm trn hm s p n 2 s sau du phy. chnh xc
khng cao cng hon ton tha mn bi v iu quan trng cn bit l s bin i ca hm s p
ch khng phi l gi tr tuyt i ca n. Nhng bin i ln v t ph thuc vo sai s
trong php tnh.

9.3 Nhng yu t nh hng n tnh r rng ca im cui

c s r rng v do d dng xc nh c im cui ca php chun, iu cn
thit nht cn bit l gn im tng ng ch cn thm mt lng nh cht chun cng
lm cho hm s p bin i r rt. Do , cn thit phi xt nhng yu t nh hng n gi tr
bc nhy ca hm s p trong qu trnh chun .
Nng thuc th: bng 9.1 dn ra nhng kt qu tnh theo phng php c phn
tch trong v d dn ra trn y. Tnh ton c tin hnh i vi 3 nng ion bromua v
ion bc khc nhau 10 ln. Nhng kt qu tnh ton pAg i vi c 3 trng hp c din t
trn hnh 9.1, minh ha r rng nh hng ca nng n ng chun . Khi tng nng

164

cht cn chun v cht chun, s bin i pAg vng gn im tng ng

tr nn r hn.
1. Chun dung dch Br 0,0500 M bng dung dch Ag+ 0,100 M.
2. Chun dung dch Br 0,00500 M bng dung dch Ag+ 0,0100 M.
3. Chun dung dch Br 0,000500 M bng dung dch Ag+ 0,00100 M.
Hin tng tng t cng c quan st thy nu thay th pAg trn trc tung bng pBr.

Hnh 9.1
nh hng ca nng thuc th n ng chun 25,0 ml dung dch NaBr

Bng 9.1 S bin i pAg v pBr trong qu trnh chun nhng dung dch c nng
khc nhau

Chun 25,0 ml Br Chun 25,0 ml Br Chun 25,0 ml Br

0,0500
M
bng 0,00500 M bng 0,00500 M bng
Th
tch
AgNO3 0,100 M
AgNO3 0,010 M
AgNO3 0,001 M
AgNO3 (ml)
pAg

pBr

pAg

pBr

pAg

pBr

0,00

1,30

2,30

3,30

10,00

10,68

1,60

9,68

2,60

8,68

3,60

20,00

10,13

2,15

9,13

3,15

8,13

4,15

23,00

9,72

2,56,

8,72

3,56

7,72

4,56

24,90

8,41

3,87

7,41

4,87

6,50

5,78a

165

24,95

8,10

4,18

7,10

5,18

6,33

5,95a

25,00

6,14

6,14

6,14

6,14

6,14

6,14

25,05

4,18

8,10

5,18

7,10

5,95

6,33b

25,10

3,88

8,40

4,88

7,40

5,78

6,50b

27,00

2,58

9,70

3,58

8,70

4,58

7,70

30,00

2,20

10,08

3,20

9,08

4,20

8,08

Trong trng hp ny gi thit [Ag+] <<CNaBr khng ng

Trong trng hp ny gi thit [Br] << CAgNO3 khng ng

Hiu ng c ngha thc t khi chun ion bromua. Nu nng bromua ln s

dng dung dch bc nitrat 0,100 M th im cui c xc nh d dng v sai s chun s
cc tiu. Ngc li, i vi cc dung dch c nng 0,001 M, s bin i pAg hoc pBr nh
n mc l, kh khn xc nh im cui. Trong trng hp sai s chun phi ln.
Nng thuc th nh hng tng t n bc nhy ca php chun theo cc loi
phn ng khc.
xy ra hon ton ca phn ng: Hnh 9.2 minh ha nh hng ca tan ca sn
phm phn ng n ng chun khi dng dung dch AgNO3 0,1 M lm cht chun. R
rng l s bin i pAg ln nht c quan st thy khi chun ion ioua. Ion ioua to hp
cht vi bc t tan nht so vi tt c cc anion ang nghin cu. iu m bo phn ng
xy ra hon ton nht. Bc nhy km t ngt nht c quan st thy phn ng xy ra
km hon ton nht ngha l php chun ion bromat. Bc nhy trn ng chun
theo phn ng m sn phm l hp cht ca bc c tan trung gian, cng s c gi tr trung
gian. Mt ln na, chng ta nhn xt rng, nh hng l c trng i vi ng chun
theo cc loi phn ng khc.

166

Hnh 9.2
nh hng ca hon ton ca phn ng xy ra n ng chun 25,0 ml dung dch anion 0,050
M bng dung dch AgNO3 0,100 M

9.4 ng chun hn hp
Nhng phng php c xt trong mc trc c th m rng cho hn hp ion to vi
cht chun nhng kt ta c tan khc nhau. Chng ta xt php chun 50,0 ml dung dch
cha 0,080 M ioua v 0,100 M clorua bng dung dch bc nitrat 0,200 M.
V bc ioua t tan hn nhiu so vi bc clorua nn khi thm cht chun vo, u php
chun ch ring bc ioua to thnh. ng chun s tng t ng chun ioua
c m t trn hnh 9.2. Cn c bit ch n vic thit lp gii hn m , kt ta bc
ioua xy ra khi s to thnh bc clorua khng ng k.
Khi xut hin nhng phn u tin ca kt ta bc clorua th tch s tan ca c 2 kt ta
t c. Chia h thc ny cho h thc kia, ta c:
[I ]

[Cl ]

8,3.1017
1,82.10

10

= 4,56.107

[I] = 4,56.107.[Cl]

167

v thu c h thc
[I] = 4,56.107.[Cl]
R rng l trc khi kt ta bc clorua xut hin, nng ca ion ioua phi h thp n
gi tr ch bng mt phn rt nh nng ion clorua. Ni mt cch khc, bc clorua khng
c to thnh gn nh n chnh im tng ng ca ion ioua hoc cho ti khi thm
khong 20 ml cht chun. Trong trng hp ny nng ion clorua c k ti c s pha long
bng khong:
CCl [Cl ] =

50,0 0,100
= 0,0714 mol/l
70,0

v
[I] = 4,56.107.0,0714 = 3,26.108 mol/l
Phn trm ioua khng kt ta im c th tnh nh sau:
Lng milimol ban u ca I = 50,0.0,080 = 4,00
% I khng kt ta =

3,26.108 70,0 100

= 5,7.105
4,0

Nh vy l cho n khi nng ioua cha b chun bng khong 6.105% lng ban
u, bc clorua vn cha to thnh nn ng chun phi tng t ng chun mt
mnh ioua. Xut pht t , na u ca ng chun c dn ra bng ng m nt
trn hnh 9.3.
Ngay khi kt ta AgCl bt u xut hin, s gim nhanh chng pAg t ngt dng li.
Thun tin nht l tnh pAg t tch s tan ca bc clorua:
[Cl] 0,0714
10

Ag + = 1,82.10

0,0714

= 2,55.109 mol/l

pAg = log(2,55.109) = 8,59

Tip tc thm bc nitrat s lm gim nng ion clorua v ng cong chuyn thnh
ng cong c trng cho php chun mt mnh clorua. V d, sau khi thm 25,00 ml cht
chun:
CCl [Cl ] =

50,0 0,10 + 50,0 0,080 25,0 0,200

75,0

168

Hai s hng u tin t s l s milimol ca clorua v ioua tng ng, cn

s hng th 3 l s milimol cht chun thm vo. Nh vy:
[Cl] = 0,0533
[Ag + ] =

1,82.1010
= 3,41.109 mol / l
0,0533

pAg = 8,47
C th tnh phn cn li ca ng cong nh trng hp chun mt mnh clorua.

Hnh 9.3
Nhng ng chun 50 ml dung dch cha 0,100 M Cl v 0,0800 M Br hoc I

Hnh 9.3 ch r rng, ng chun hn hp l lin hp hai ng chun ring bit.

Trn ng cong ta thy hai bc nhy chun . C th hy vng rng, s bin i pAg gn
im tng ng th nht s cng nh nu tan ca hai kt ta cng gn nhau. Hin tng
c quan st thy khi chun hn hp cc ion clorua v bromua. iu c thy r
rng trn hnh v. Trong trng hp ny gi tr pAg u php chun s thp hn bi v
tan ca bc bromua cao hn tan ca bc ioua. Sau im tng ng, hai ng cong
trng nhau. Nhng ng cong thc nghim tng t c din t trn hnh 9.3 c th thu
c bng cch o th ca in cc bc nhng vo dung dch. Bng phng php c th
xc nh nhng cu t ring bit trong hn hp.

169

9.5 Nhng cht ch th ha hc ca phng php chun kt ta

Tc dng ca cht ch th ha hc thng da trn s xc nh bng mt s bin i mu
hoc c ca dung dch. Cht ch th phn ng la chn hoc l vi cht chun hoc l vi
cht cn chun hoc l vi sn phm ca phn ng chun . V d, khi chun cht A bng
thuc th B vi cht ch th (In) c kh nng phn ng vi B, cc phn ng c th xy ra nh
sau:
A+B

AB

In + B

InB

Tt nhin l tnh cht ca InB cn thit phi khc bit ng k vi tnh cht ca In. Ngoi
ra mt phi nhn bit c mt lng InB nh n mc l sau khi to thnh InB, s tiu tn B
khng nhn thy c v cui cng hng s cn bng ca phn ng vi s tham gia ca ch
th cn phi c mt gi tr nh th no gn im tng ng, khi [B] (hoc pB) bin
i s xy ra s bin i t ngt [InB]/[In]. iu kin cui cng d thc hin nht khi pB
bin i ln.
Chng ta xt s chun 3 dung dch (bng 9.1 v hnh 9.1) vi cht ch th bin i
hon ton mu trong vng pAg = 7 5 lm v d. R rng l chim vng pAg nu,
trong mi trng hp i hi mt th tch cht chun khc nhau. Nh, t nhng d kin ca
h chun ct th 2 bng 9.1, r rng l ch cn t hn 0,10 ml dung dch AgNO3 0,100 M,
ngha l s bin i mu bt u sau khi thm 24,95 ml cht chun v kt thc trc khi thm
vo 25,05 ml. Khi c th hy vng s bin i mu t ngt v sai s chun cc tiu.
Ngc li, khi chun bng dung dch AgNO3 0,001 M s bin i mu bt u khi thm
vo khong 24,5 ml v khi kt thc thm vo 25,8 ml. Trong trng hp ny khng c kh
nng xc nh im tng ng. Khi chun bng dung dch 0,010 M, mu bin i
im cui i hi mt lng nh hn 0,2 ml mt cht, trong trng hp ny c th dng cht
ch th nhng sai s xc nh im tng ng s kh ln.
By gi chng ta xt, cng chnh cht ch th i vi cc trng hp ca nhng php
chun c m t bng cc ng cong trn hnh 9.2, s thun tin v c hiu qu n
nhng no. Khi chun cc ion bromua v ioua, ch th s v c bn di dng AgIn, do
sau khi thm nhng phn bc nitrat u tin, s bin i mu khng quan st thy.
V bc bromua v ioua c tan thp nn n trc im tng ng khng xy ra s
to thnh mt lng ng k AgIn. Theo hnh 9.2, pAg cn thc t ln hn 7 n tn trc
im tng ng khi chun bromua v thm ch sau im tng ng khi chun ioua.
Trong c 2 trng hp, s d ion bc l cn thit mu bin i hon ton tng ng vi t
hn 0,01 ml cht chun. Do sai s chun khng ng k.
Cht ch th vi khong pAg = 5 7 khng thch hp chun clorua bi v s to thnh
mt lng ng k AgIn bt u khong 1 ml trc im tng ng v tip tc cho ti
khi thm vo d khong 1 ml. Trong trng hp ny khng c kh nng xc nh chnh xc
im cui ca php chun . Ngc li, vi khong ch th pAg t 4 n 6 hon ton thch

170

hp. Khng c ch th ha hc thch hp chun ioat v bromat bi v bc

nhy chun qu nh (hnh 9.2).
Nhng v d v s dng cc cht ch th chun kt ta bng ion bc c dn ra
trong cc mc sau.
S to thnh kt ta th 2 - phng php Mohr: S to thnh kt ta th 2 c mu khc
vi mu ca hp cht kt ta l c s xc nh im cui theo phng php Mohr.
Phng php Mohr c ng dng rng ri khi chun clorua v bromua bng dung dch
bc nitrat chun. Ion cromat c dng lm ch th, im cui php chun xut hin kt
ta bc cromat Ag2CrO4 mu gch.
tan ca bc cromat cao hn nhiu tan ca bc halogenua. Do , khi chun theo
phng php Mohr, bc cromat cha c to thnh khi thc t tt c halogenua cha kt ta
ht. iu chnh nng cromat c th ngn nga s to thnh bc cromat cho ti khi nng
ion bc cha t ti nng tnh ton l thuyt i vi vng im tng ng khi chun
halogen.
V d: Sai s 0,1% tng ng vi 0,025 ml i vi th tch 25 ml cht chun. Nng
ion bc c tnh ton nh chng 5 bng 4,78.106 mol/l sau khi thm 24,975 ml dung
dch Ag+ 0,100 M v bng 3,81.105 mol/l sau khi thm 25,025 ml cng dung dch vo
dung dch Cl 0,05 M. C th thay i nng ion cromat cn thit to thnh Ag2CrO4
trong khong no chun qu hoc chun cha ti khng ln hn 0,025 ml.
Khi thm 24,975 ml cht chun, kt ta Ag2CrO4 c th xy ra nu:
[ CrO24 ][Ag+]2 T
Nu:

12
CrO24 = T > 1,1.10
= 0,048 mol / l

[Ag]2 (4,78.106 )2

v khi thm 25,025 ml cht chun, nu:

12
CrO24 1,1.10
= 7,6.104 mol / l

(3,81.105 )2

Nhng tnh ton ch r rng, chun chnh xc theo phng php Mohr, c th
gi nng cht ch th trong mt khong kh rng, gia 0,0008 v 0,05 M. Nhng trong
thc t nng ln hn 0,005 M mu vng m ca ion cromat s cn tr mu ca bc
cromat. Ngi ta thng s dng nng cromat nh hn 0,005 M mt cht. Khng th tnh
ton lng ti thiu cromat cn phi c to thnh m mt c th nhn bit m ch xc nh
c bng thc nghim. Trc khi pht hin mu ca bc cromat, dung dch b chun
qu trung bnh 0,05 ml dung dch 0,1 M. Ch sai s trong sai s kt qu ca php
chun , nn trong thi gian phn tch ngi ta thng lm th nghim trng. t mc
ch ngi ta xc nh s tiu tn ion bc cho mt th tch nh vy huyn ph canxi

171

cacbonat khng cha ion clo vi chnh cht ch th . Dung dch v kt ta thu c sau
php chun trng c dng lm chun rt thun tin chun lp li. Php chun ha
dung dch bc nitrat bng cch chun natri clorua tinh khit theo phng php Mohr l mt
bin php khc lm gim i ng k sai s ch th. Xc nh "nng ng lng chun
" nh vy s khng nhng gip tnh ton s tiu tn qu dung dch chun m cn cn nhc
c nhng kh nng khc xc nh s i mu ca nh phn tch.
Cn ch n axit ca mi trng bi v khi tng nng ion hiro, cn bng:
2CrO24 + 2H

Cr2O72

+ H2O

s chuyn dch v bn phi. tan ca icromat bc cao hn kh nhiu tan ca

cromat bc, do i vi phn ng ch th trong mi trng axit i hi nng ion bc ln
ng k nu phn ng ni chung c th xy ra. Trong mi trng kim c th lng xung oxit
bc:
2Ag+ + 2OH

2AgOH(rn)

Ag2O(rn, en) + H2O

Nh vy, php xc nh clorua theo phng php Mohr cn phi c tin hnh trong
mi trng trung tnh hoc gn trung tnh (pH = 7 10). C th gi nng ion hiro trong
khong mt cch thun tin bng cch thm vo natri bicacbonat, canxi cacbonat hoc
natri tetraborat.
S to thnh phc mu - phng php Volhard: chun bc theo phng php Volhard
c th s dng dung dch tioxianat chun:
Ag+ + SCN

AgSCN(rn)

Ion st (III) lm cho dung dch c mu khi thm nhng git dung dch tioxianat d u
tin c dng lm ch th:
Fe3+ + SCN

Fe(SCN)2+

Php chun cn c thc hin trong mi trng axit ngn nga s kt ta st (III)
di dng hiroxit. C th d dng tnh c nng ch th m sai s chun tin ti
khng nh s c ch r trong v d sau y.
V d: Bng thc nghim ngi quan st c th pht hin mu Fe(SCN)2+ nng
trung bnh l 6,4.106 M. Cn to ra nng Fe3+ bng bao nhiu khi chun 50 ml dung
dch Ag+ 0,050 M bng dung dch KSCN 0,100 M, sai s chun tin ti khng?
sai s chun bng khng, mu ca Fe(SCN)2+ cn phi xut hin nng Ag+,
cn trong dung dch bng nng tng cng ca tioxianat:
[Ag+] = [SCN] + [Fe(SCN)2+] = [SCN] + 6,4.106
hoc:

172
T
[SCN ]

1,1.1012
[SCN ]

= [SCN ] + 6,4.106

Bin i:
[SCN]2 + 6,4.106 [SCN] 1,1.1012 = 0
[SCN] = 1,7.107 ion.g/l
Hng s bn ca Fe(SCN)2+:
K = 1,4.102 =

[Fe(SCN)2+ ]
[Fe3+ ][SCN ]

By gi chng ta thay th nng [SCN] bo m to thnh mt lng Fe(SCN)2+

nhn bit bng mt im tng ng vo phng trnh hng s bn:
1,4.102 =

6,4.106
[Fe3+ ] 1,7.107

[Fe3+] = 0,27 mol/l

Khi chun theo phng php Volhard, nng khng bt buc phi cht ch. Tht
vy, nhng tnh ton tng t nh va c tin hnh ch r rng nng st (III) trong
khong 0,002 1,6 mol/l mt cch l thuyt, sai s s khng vt qu 0,1%. Trong thc t
ngi ta cng pht hin rng, nng vt qu 0,2 mol/l, mu ring ca cht ch th gy tr
ngi cho s pht hin phc tioxianat. Do ngi ta to ra nng st (III) thp hn (thng
l khong 0,01 mol/l).
ng dng phng php Volhard xc nh ion clorua: Thng ngi ta ng dng
phng php Volhard xc nh gin tip clorua. Thm vo mu clorua d mt lng xc
nh dung dch bc nitrat chun v lng d ion bc c xc nh bng php chun
ngc bng dung dch tioxianat chun. u th c bit ca phng php Volhard trc cc
phng php xc nh clorua khc l kh nng chun trong mi trng axit mnh bi v
nhng ion nh cacbonat, oxalat v asenat (to mui bc t tan trong mi trng trung tnh)
khng cn tr.
Khc vi cc halogenua bc khc, bc clorua tan nhiu hn bc tioxianat. Do phn
ng:
AgCl(rn) + SCN

AgSCN(rn) + Cl

(8.1)

gy tr ngi cho s pht hin im cui php chun theo Volhard. V vy ta quan st
thy s tiu tn qu mc ion tioxianat v xut hin sai s phn tch m. Gi tr sai s ph
thuc vo nng cht ch th.

173

trnh sai s lin quan vi phn ng gia tioxianat v bc clorua ngi ta s dng ch
yu hai bin php. Bin php th nht l to ra nng cht ch th cc i c php
(khong 0,2 M st (III)). Bin php th hai ph bin hn l tch kt ta bc clorua trc khi
chun ngc bng dung dch tioxianat. Php chun mt phn nc lc sau khi lc bc
clorua cho kt qu tt nht trong iu kin kt ta ng t tt. S tiu tn thi gian cho php
lc tt nhin l nhc im ca phng php ny. Dng nh phng php c ng dng
rng ri nht l phng php Caldwell v Moyer. Theo phng php ny, ngi ta ph ln
kt ta bc clorua mt lp nitrobenzen ngn nga n tip xc vi dung dch. C lp kt ta
bng cch lc hn hp vi mt vi mililit nitrobenzen trc khi chun ngc.
Cht ch th hp ph: Cht ch th hp ph l nhng cht hu c b kt ta hp ph hoc
c gii hp t b mt kt ta c to thnh trong qu trnh chun . Trong trng hp l
tng, s hp ph hoc gii hp c quan st thy gn im tong ng v km theo
khng ch s bin i mu ca dung dch m cn c s to thnh hp cht mu trn b mt
kt ta. Phng php da trn s s dng cht ch th hp ph i khi c ngi ta gi l
phng php Fajans k nim nh bc hc cng hin nhiu cho s pht trin phng
php ny.
Cht mu hu c fluoretxein c dng khi chun ion clorua bng nitrat bc l mt
cht ch th hp ph in hnh. Trong dung dch nc, fluretxein phn li mt phn thnh ion
hiro v ion fluoretxeinat tch in m, lm cho dung dch c mu vng lc. Ion fluoretxeinat
to mui bc c mu m t tan. Nhng khi s dng cht mu lm ch th, nng ca n
khng bao gi t tch s tan ca fluoretxeinat bc.
u php chun clorua bng cc ion bc theo phng php Fajans, cc anion cht
mu hu nh khng b kt ta hp ph. Thc t chng y b mt kt ta tch in m do hp
ph cc ion clorua. Sau im tng ng, nhng ht kt ta mang in tch dng do s hp
ph mnh cc ion bc d; trong nhng iu kin ion fluoretxeinat i vo lp ion i. V
vy, trn b mt kt ta xut hin mu c trng cho fluoretxeinat bc. Cn nhn mnh
rng, s bin i mu xy ra do qu trnh hp ph (ch khng phi do qu trnh kt ta), bi
v tch s tan ca fluoretxeinat bc khng t c trong thi gian chun . S hp ph l
thun nghch: cht mu b gii hp khi chun ngc bng ion clorua.
ng dng thnh cng cht ch th hp ph th cht kt ta v ch th cn c nhng tnh
cht sau:
1. Nhng ht kt ta phi c c kch thc ca ht keo bi v b mt ca kt ta pht trin
mnh, hp ph c lng ln cht ch th.
2. Kt ta phi hp ph bn cc ion ring bit. Chng ta thy (chng 7) tnh cht
l c trng i vi kt ta keo.
3. Cht mu dng lm cht ch th cn phi c gi chc trong lp ion i bao quanh
nhng ion b hp ph u tin. Ni chung s hp ph loi c quyt nh bi tan thp
ca mui to thnh gia cht mu vi cc ion ca mng li tinh th. ng thi nhng hp
cht phi c tan ln khng xy ra s kt ta chng.

174

4. pH ca dung dch cn phi c gi mc xc nh. Ion dng lm dng

hot ng ca phn ln cc cht ch th hp ph l axit hoc baz lin hp vi phn t cht
mu nn c kh nng lin kt vi ion hiro hoc ion hiroxil to thnh phn t ban u khng
hot ng. Do , ngi ta to ra gi tr pH no m dng ion ca cht ch th chim u
th.
Php chun vi cht ch th hp ph nhanh, chnh xc, ng tin cy nhng ng dng
ca n tng i b hn ch bi s t phn ng kt ta c kt ta v nh hnh c to thnh
nhanh chng. Khi c mt cht in li nng cao, im cui ca php chun vi cht
ch th hp ph tr nn km r rng do s ng t kt ta lm gim b mt trn xy ra qu
trnh hp ph. Phn ln cc cht ch th hp ph l axit yu, do lnh vc ng dng ca
chng b gii hn trong cc dung dch trung tnh hoc axit yu v cht ch th ch yu tn
ti dng anion. Ngi ta bit mt s ch th hp ph cation chun trong cc dung dch
axit mnh. Vi nhng cht ch th , s hp ph cht mu v s nhum mu kt ta c
quan st thy khi c d anion kt ta, ngha l khi cc ht mang in tch m.
Bng 9.2 Nhng phng php kt ta o bc in hnh

Phng php xc nh
Ghi ch
im cui

Cu t cn xc nh
AsO43,
Br,
CNO, SCN

I,

Phng php Volhard

CO32, CrO42, CN,

Cl, C2O42, PO43, Phng php Volhard
S2

Khng cn tch mui bc

Trc khi chun ngc lng
Ag+ d, cn tch mui bc
Chun tip theo lng Ag+ d
trong phn ng:

BH4

Phng php Volhard

BH4 + 8Ag+ + 8OH
bin dng

8Ag(rn) + H2BO3 + 5H2O

Chun lng Cl d sau khi ch
ha bng hiro clorua

Epoxit

Phng php Volhard

K+

Kt ta K+ bng lng d
Phng php Volhard B(C6H5)4 bit, thm d Ag+ to
bin dng
kt ta AgB(C6H5)4 v chun
ngc Ag+ d

Br, Cl

Phng php Mohr

Br, Cl, I, SeO32

Ch th hp ph

175

V(OH)4+, cc axit Phng php phn tch Chun trc tip bng dung dch
bo, cc mecaptan
in ha
Ag+
Kt ta di dng ZnHg(SCN)4.
Phng php Volhard
Lc v ha tan trong axit, thm d
bin dng
Ag+; chun ngc Ag+ d

Zn2+

Kt ta di dng PbClF. Lc ha
Phng php Volhard
tan trong axit thm d Ag+; chun
bin dng
ngc Ag+ d

Cui cng, cn ch mt s cht ch th hp ph phn ng vi kt ta cha bc c tnh

cht nhy sng gy tr ngi khi lm vic vi chng.
Nhng phng php khc xc nh im cui: Trong gio trnh cc phng php phn
tch cng c c m t nhng phng php in ha pht hin im cui trong mt s phng
php chun kt ta.
ng dng ca phng php chun kt ta: Trong phn ln trng hp, php chun
kt ta da trn s s dng dung dch bc nitrat chun, i khi phng php ny gi l
phng php o bc. bng 9.2 dn ra nhng v d in hnh v ng dng phng php o
bc. Chng ta nhn thy rng, nhiu phng php xc nh trong nhng php xc nh nu
da trn php kt ta cu t cn xc nh bng mt lng d chnh xc dung dch bc nitrat
v chun tip theo bng dung dch kali tioxianat chun theo Volhard. C hai thuc th
c th dng c di dng cht chun u nhng kali tioxianat ht m mt cht gy kh
khn cho php cn m cao. Nhng dung dch bc nitrat v kali tioxianat bn trong thi
gian lu khng gii hn.
Bng 9.3 lit k nhng phng php chun khc dng cc thuc th khc thay th cho
mui bc.
Bng 9.3 Nhng phng php chun kt ta khc

Cht chun

Ion cn xc nh

Sn phm phn ng

Cht ch th

K4[Fe(CN)6]

Zn2+

K2Zn3[Fe(CN)6]2

iphenylamin

Pb(NO3)2

SO42

PbSO4

Eritrozin B

MoO42

PbMoO4

Eosin E

PO43

Pb3(PO4)2

ibromfluoretxein

C2O42

PbC2O4

Fluoretxein

ThF4

Alizarin

Pb(CH3COO)2

Th(NO3)4

176

Hg2(NO3)2

Cl, Br

Hg2X2

Bromophenol chm

NaCl

Hg22+

Hg2X2

Bromophenol chm

177

Chng 10
L thuyt chun Axit Baz i vi nhng h
n gin

Chun axit - baz l vic xc nh im cui da trn s bin i pH t ngt quan st

thy gn im tng ng. Ging nh nhng trng hp chun khc, bn cht v nng
ca c cht b chun v cht chun quyt nh khong bin ii pH. la chn cht ch
th thch hp v xc nh sai s chun cn phi bit s bin i pH trong qu trnh chun
. Nh vy, ngha l cn phi bit ng chun trong phng php axit - baz c xy
dng nh th no.
Trong chng ny s xt nhng axit v baz n gin, chng phn li tch ra mt ion
hiro hoc mt ion hiroxyl. Trong chng 11 s bn ti nhng ng chun nhng axit
hoc baz nhiu nc v hn hp axit.
chun b cho nhng bn lun sp ti, sinh vin cn xem li nhng kin thc v axit,
baz v phng php tnh ton cn bng axit - baz (chng 4).

10.1 Thuc th chun chun axit - baz

Trong phng php chun axit - baz, cc axit hoc baz mnh lun lun c dng
lm thuc th chun bi v phn ng vi s tham gia ca chng xy ra hon ton hn so vi
phn ng vi s tham gia ca axit hoc baz yu. Cng nh trong php chun kt ta,
phn ng xy ra cng hon ton, hm s p bin i cng ln v cng d xc nh im cui.

10.2 Cht ch th chun axit - baz

Nhiu hp cht tng hp cng nh t nhin c mu khc nhau ty thuc vo pH ca dung
dch. Mt s trong cc cht t lu c s dng ch r tnh kim hoc tnh axit ca
nc. Chng cng quan trng c i vi nhng nh ha hc hin i trong vic dng chng
xc nh pH ca dung dch v pht hin im cui trong chun axit - baz.

178

10.2.1 L thuyt v tnh cht ca cht ch th

Nhng ch th axit - baz l nhng hp cht hu c biu l tnh axit yu hoc baz yu.
Phn ng phn li hoc lin hp ca cht ch th km theo s chuyn v cu to bn trong dn
ti s bin i mu. Chng ta a ra phn ng in hnh ca ch th axit - baz di dng sau:
H2O + HIn

H3O+ + In

(mu axit)

(mu kim)

hoc
In + H2O
(mu kim)

InH + OH
(mu axit)

Trong cc dung dch axit mnh, ch th dng HIn l dng chim u th, tng ng vi
"mu axit" v In s l "mu kim" ca n. Trong cc dung dch kim, cc ht In s chim u
th tng ng vi "mu kim" ca cht ch th .
Khi cn bng, nhng qu trnh c c trng bng nhng hng s:
Ka =

[H3 O+ ][In ]
[InH][OH ]
v K b =
[HIn]
[In ]

C th bin i nhng phng trnh nh sau:

Kb
K [H O+ ]
Ka
[InH]
[In ]
v
=
=
= b 3
[HIn] [H3 O+ ]
K H2O
[In ] [OH ]

Khi pH bin i, dung dch cha cht ch th bin i lin tc thnh phn phn trm dng
mu ca mnh. Nhng mt ngi rt khng nhy vi nhng bin i . Thng mt dng
phi hn t 5 n 10 ln dng kia th ngi quan st mi nhn bit c mu ca n; tip tc
tng lng d ca dng s kh nhn bit. S bin i mu ca ch th ch c nhn bit
trong vng m mt dng hn dng kia 5 10 ln. Nh vy "s bin i mu" quan st
c phn nh s chuyn dch cn bng ca ch th. Xt HIn lm v d, c th ni rng, ch th
th hin mu axit hon ton ca mnh c ngi quan st nhn bit khi:
[In ] 1
[In ] 10

v mu hon ton kim khi

[HIn] 10
[HIn] 1

Bn trong khong c xc nh bng nhng i lng , mu l mu hn hp ca ch

th. Nhng gii hn bng s nu tt nhin phn nh tnh cht trung bnh ca ch th. Mt s
cht ch th bin i mu trong khong hp hn i vi nng dng axit v dng kim, mt

179

s khc li bin i trong khong rng hn. Hn na, kh nng ca ngi quan st phn bit
mu cng khng ng nht. Nhng ngi m mu khng phn bit c mt s sc thi mu.
Nu thay hai t s nng vo phng trnh hng s phn li ca ch th th c th tnh
khong nng ion hiro cn thit chuyn mu ch th. i vi mu hon ton axit:
[H3 O+ ][In ] [H3O+ ] 1
+
=
= K a [H3O ] = 10.Ka
[HIn]
10

v mt cch tng t i vi mu hon ton kim:

[H3 O+ ] 10
K
= K a [H3O+ ] = a
1
10

thu c khong chuyn mu ca ch th chng ta tm logarit m ca c hai phng

trnh.
Khong pH chuyn mu ca ch th:
t log10Ka n log

Ka
= t 1 + pKa n (1) + pKa = pKa 1.
10

Nh vy, s chuyn mu ca ch th vi hng s phn li axit 1.105 c quan st thy

khi pH ca dung dch bin i t 4 n 6. D dng rt ra nhng h thc tng t vi ch th
loi kim.

10.2.2 Nhng loi ch th axit - baz

Danh sch nhng hp cht c tnh cht ch th axit - baz l danh sch nhng cht hu
c. Thng c th tm ch th c mu bin i trong khong pH cn thit bt k. Mt s ch
th c dn ra bng 10.1.
Bng 10.1 Mt s ch th axit - baz quan trng

Tn

Khong bin i pH

S bin i mu

Loi ch th
a

Dng axit

Dng kim

1,22,8

Vng

8,0 9,6

Vng

Xanh bin

Metyl vng

2,9 4,0

Vng

Metyl da cam

3,1 4,4,

Vng

Timol chm

180

Bromcresol lc

3,8 5,4

Vng

Xanh bin

Metyl

4,2 6,3

Vng

Clophenol

4,8 6,4

Vng

Bromtymol
xanh

6,0 7,6

Vng

Xanh bin

Phenol

6,4 8,0

Vng

trung tnh

6,8 8,0

Vng da cam

7,4 9,0

Vng

gch

1,2 2,8

Vng

Phenolphtalein

8,0 9,6

Khng mu

Tymolphtalein

9,3 10,5

Khng mu

Xanh bin

Alizarin vng

10,1 12,0

Khng mu

Tm

Crezol

1. Ch th axit

: HIn + H2O

2. Ch th kim : In + H2O

H3O+ + In,
InH + OH.

Phn ln nhng ch th axit - baz c cu to c trng c chia thnh 6 loi. Ba trong

s cc loi c cp ti di y.
Nhng ch th phtalein: Phn ln nhng ch th phtalein khng mu trong dung dch axit
v c mu trong mi trng kim. Trong mi trng kim mnh mu ca chng b mt chm.
Trong mt s trng hp iu l khng thun li. Thng nhng ch th phtalein tan va
phi trong nc. chun b dung dch ch th ngi ta thng dng etanol. C th biu din
phenolphtalein theo cng thc cu to nh sau:

181
OH

OH

OH

OH

+ 2H2O
C

O
C

H3O+

OH

O
O

Khng mu

Khng mu

OH

OH

+
C

OH
C

C
O
O

Khng mu

H3O+

O
O

y l ch th ph bin nht trong s nhng ch th phtalein.

Chng ta nhn thy rng, cn bng th hai dn ti s to thnh vng quinon v s c mt
ca vng ny trong phn t hp cht thng quyt nh mu ca n. Nng ng k ca ion
mu c quan st thy vng pH = 8,0 9,6; pH m quan st thy s xut hin mu
ph thuc vo nng ch th v vo s nhy cm ca th gic ngi quan st.
Nhng ch th phtalein khc, khc vi phenolphtalein l c trong vng phenol cc nhm
chc; v d trong phn t tymolphtalein hai nhm alkyl c gn vo mi vng. Nhng bin
i cu trc c bn gn lin vi s chuyn mu ca ch th , tng t nh m t i vi
phenolphtalein.
Nhng ch th sulfophtalein: c trng ca nhiu ch th sulfophtalein l c hai khong
chuyn mu; mt khong c quan st thy trong dung dch kh axit, mt khong khc trong
mi trng trung tnh hoc kim va phi. Khc vi cc cht mu phtalein, cc ch th loi ny
c dng kim mu rt bn trong mi trng kim mnh.
chun b cc dung dch ch th, ngi ta thng s dng mui natri ca sulfophtalein
bi v bn thn ch th c tnh axit r rt. C th iu ch dung dch trc tip t mui natri
hoc bng cch ha tan sulfophtalein trong mt th tch tng ng dung dch natri hiroxit
long trong nc.
Phenolsulfophtalein c bit di tn phenol l ch th n gin nht. Nhng cn
bng quan trng nht i vi ch th l nh sau:

182
OH

OH

OH

-1,5

H2O

Ka = 10

H3O+

H3O+

SO3

SO3

OH

Vng
O

O
+

H2O

Ka = 10-7,9

SO3

SO3

Vng

S qu gi thc t ch l khong chuyn mu th hai trong hai khong chuyn mu quan

st thy khong pH = 6,4 8,0.
Thay th cc nguyn t hiro vng phenol ca hp cht ban u bng cc halogen hoc
cc nhm alkyl s thu c nhng sunfophtalein khc nhau v mu sc v khong pH chuyn
mu.
Nhng ch th azo: Khi tng kim ca mi trng mu ca phn ln cc ch th azo
bin i t mu sang vng; im chuyn mu ca ch th chuyn dch mt cht v vng
axit. Metyl da cam v metyl l nhng i din ph bin nht ca loi ch th . C th m
t tnh cht ca metyl da cam nh sau:

O3S

O3S

H+
N N

H+
N(CH3)2
+ H2O
N(CH3)2

O3S

N(CH3)2 + H3O+

Vng

Metyl c c trng bng cng thc tng t cng thc ca metyl da cam, ch loi
tr nhm sunfo trong vng v thay th bng nhm cacboxyl. Thay th cc nhm th nit

183

ca nhm amino v trong vng s thu c hng lot ch th c tnh cht khc nhau mt
cht.

10.2.3 Sai s chun vi cc ch th axit - baz

Cn phn bit hai loi sai s chun . Sai s h thng do pH chuyn mu ca ch th
khc vi pH im tng ng ca phn ng ha hc dng chun l sai s loi th
nht. C th gim sai s n cc tiu bng cch la chn cn thn ch th. Th nghim trng
s cho b chnh tng ng.
Sai s ngu nhin do kh nng ca ngi quan st phn bit mt cch lp li thi im
chuyn mu b hn ch l loi sai s th hai. Gi tr ca sai s ph thuc vo s bin i
pH trn mt mililit thuc th im tng ng, nng ch th v phng php nh phn
tch dng phn bit hai mu ca ch th. Khi quan st bng mt vi ch th axit - baz sai s
trung bnh khong 0,5 n v pH. So snh mu ca dung dch b chun cha lng ch th
"i chng" gi tr pH tng ng thng cho php h thp sai s n 0,1 n v pH hoc
nh hn. R rng, l nhng gi tr gn ng v mc ng k chng ph thuc vo bn
cht ca ch th cng nh vo trnh ca ngi thc hin.

10.2.4 Nhng yu t nh hng ti tnh cht ca ch th

Nhit , lc ion, s c mt ca nhng dung mi hu c v cc ht keo nh hng n
gi tr khong pH chuyn mu ca mt s cht ch th nht nh. Mt s trong nhng yu t
, c bit l hai yu t cui cng c th lm chuyn dch khong i mu i mt hoc mt
s ln hn n v pH.

10.3 ng chun axit mnh hoc baz mnh

Nu c cht chun v cht b chun l axit mnh v baz mnh th c th hnh dung phn
ng axit - baz tng th bng phng trnh:
H3O+ + OH = 2H2O
v c th xy dng ng chun trong trng hp ny tng t nh lm trong
phng php chun kt ta.

10.4.1 Chun axit mnh bng baz mnh

Nhng ion hiro trong cc dung dch nc ca axit mnh xut pht t hai ngun:
1. Do tng tc ca axit tan vi nc;

184

2. Do s phn li ca chnh nc. Trong cc dung dch khng qu long phn

ng gp ca phn ng gia cht tan vi dung mi vo axit tng cng ln hn nhiu phn
ng gp do dung mi phn li. Do , i vi dung dch HCl c nng ln hn 1.106 M:
[H3O+] = CHCl

(10.1)

Nu nng dung dch thp hn 1.106 M, tnh [H3O+] c th s dng phng trnh
chnh xc hn, thu c t iu kin trung ha in tch:
[H3O+] = [Cl] + [OH] = CHCl +

K H2O

[H3 O+ ]

(10.2)

Thnh phn u tin phn bn phi ca phng trnh l lng ion hiro to thnh do
HCl phn li, cn thnh phn th hai l lng ion hiro to thnh do nc phn li.
Nhng lp lun tng t cng ng n i vi dung dch baz mnh, v d i vi natri
hiroxit:
[OH] = CNaOH
R rng l i vi baz phn li hon ton, Ba(OH)2:
[OH] = 2 CBa(OH)2
C th thu c phng trnh thun tin tnh pH ca cc dung dch kim bng cch ly
logarit phng trnh biu thc tch s ion nc:
l og K H2O = l og([H3 O+ ][OH ]) = l og[H3O+ ] log[OH ]
pK H2O = pH + pOH

25oC, pK H2O = 14,00.

Nh s c ch r trong v d dn ra di y, vic xy dng ng chun axit mnh
bng baz mnh khng kh khn g bi v nng ion hiro hoc ion hiroxyl c tnh ton
trc tip t nng chung hoc axit d hoc baz d.
V d: Hy xy dng ng chun 50,00 ml dung dch HCl 0,050 M bng dung dch
NaOH 0,100 M. Nhng gi tr pH thu c c lm trn n s l th hai sau du phy.
Gi tr pH u: Chng ta c dung dch HCl 5.102 M. V HCl phn li hon ton:
[H3O+] = 5.102 mol/l,
pH = log(5,00.10 2 ) = log 5,00 lo g102
= 0,699 + 2 = 1,301 = 1,30

185

Gi tr pH sau khi thm 10,00 ml dung dch NaOH: Th tch dung dch tr thnh 60,00
ml v mt phn HCl c chun , do :
50,00 0,050 10,00 0,100
= 2,50.102 mol / l
60,00
pH = 2 l og 2,50 = 1,60

[H3O+ ] =

Bng cch tng t, ngi ta tnh pH cho n tn im tng ng. Nhng kt qu tnh
ton c gii thiu trong ct 2 ca bng 10.2.
Gi tr pH sau khi thm 25,00 ml dung dch NaOH: thi im trong dung dch
khng cn d HCl v cng khng d NaOH v pH c xc nh bng s phn li ca nc:
[H3O+ ] = [OH ] = K H2O = 1,00.107 mol / l;pH = 7

Gi tr pH sau khi thm 25,10 ml NaOH:

CNaOH =

25,10 0,100 50,00 0,0500

= 1,33.104 M
75,10

Gi thit rng nng OH to thnh do s phn li ca nc nh hn so vi CNaOH.

[OH] = 1,33.104 ion.g/l
pOH = 3,88
pH = 14,00 3,88 = 10,12
Trong ct th hai ca bng 10.2 dn ra nhng d kin b sung ca php chun trn,
c tnh ton tng t.
Bng 10.2 S bin i pH khi chun axit mnh bng baz mnh

pH
Th tch dung dch
Chun
25,0
NaOH, ml
HCl 0,050 M
NaOH 0,100 M

ml
Chun 25,0 ml HCl 0,0005 M
bng
bng NaOH 0,0010 M

0,00

1,30

3,30

10,00

1,60

3,60

20,00

2,15

4,15

24,00

2,87

4,87

186

24,90

3,87

5,87

25,00

7,00

7,00

25,10

10,12

8,12

26,00

11,12

9,12

30,00

11,80

9,80

nh hng ca nng : Hai lot d kin c dn ra bng 10.2 phn nh nh hng

ca nng cht chun v cht b chun n dng ca ng chun axit - baz. S din t
bng th cc d kin c gii thiu trn hnh 10.1.

Hnh 10.1
Nhng ng chun HCl bng dung dch NaOH chun
1. Chun 25,0 ml HCl 0,0005 M bng NaOH 0,0010 M.
2. Chun 25,0 ml HCl 0,050 M bng NaOH 0,100 M.

Khi chun bng dung dch NaOH 0,100 M (ng cong 1) vng im tng ng,
quan st thy bc nhy pH ln, trong trng hp chun bng dung dch NaOH 0,001 M
bc nhy pH nh hn nhiu nhng rt cuc vn hon ton nhn thy c.
T hnh 10.1 r rng l nng cht chun 0,100 M, vic la chn ch th khng kh
khn. Trong trng hp hiu s th tch cht chun tiu tn cho php chun khi dng c ba
ch th c nu ln trn hnh v ch bng sai s c trn buret v do khng ng k. Mt
khc, bromcrezol lc r rng l khng thch hp cho php chun bng dung dch chun

187

0,001 N, khng ch v s chuyn mu ch th c quan st thy trong mt khong ln th tch

cht chun m cn v s chuyn ch th thnh dng kim thc t xy ra rt sm trc khi t
ti im tng ng v do xut hin sai s xc nh ln. Cng do chnh nguyn nhn
m ny sinh s bt ng v s s dng phenolphtalein. Trong s ba ch th xt ch c
bromtimol xanh cho php xc nh im cui vi sai s nh nht.

10.4.2 Chun baz mnh bng axit mnh

Tnh hnh tng t c quan st thy khi chun baz mnh bng axit mnh. gn im
tng ng, dung dch l kim mnh v nng ca ion hiroxyl bng nng ca kim
mnh cha c chun . Mt cch chnh xc, cng theo nhng nguyn nhn xt trn
y, dung dch im tng ng tr thnh trung ha. Cui cng, dung dch sau im
tng ng tr thnh axit v trng hp ny ngi ta tnh pH theo lng axit mnh d thm
vo. ng chun baz mnh bng HCl 0,100 M c gii thiu trn hnh 10.5. Ngi ta
chn ch th cng nh trng hp chun axit mnh bng baz mnh.

10.4 ng chun axit yu hoc baz yu

Khi xy dng ng chun axit yu cn phi tnh pH ca dung dch chnh axit lin
hp vi baz ca n v hn hp ca chng. Nhng tnh ton tng t cng cn thit khi xy
dng chun baz yu. Nhng phng php tnh pH ca dung dch axit yu v baz lin
hp c xem xt chng 4. Tnh pH ca cc dung dch cha mt lng ng k cp
axit - baz lin hp s c xem xt trong chng sau.

10.4.1 Tnh pH ca dung dch cha mt cp axit - baz lin hp

Dung dch cha mt cp axit - baz lin hp c th l axit, kim hoc trung tnh ty
thuc vo hai cn bng cnh tranh tn ti trong dung dch. i vi axit yu HA v mui natri
NaA ca n, nhng cn bng l:
HA + H2O
A+ H2O

H3O+ + A ; K a =
OH + HA

; Kb =

[H3 O+ ][A ]
[HA]
[OH ][HA]
[A ]

(10.3)

(10.4)

Nu cn bng th nht chuyn dch v bn phi mnh hn cn bng th hai th dung dch
s axit. Ngc li, nu cn bng th hai chim u th th dung dch s kim. T cc phng
trnh hng s cn bng y, r rng l nng tng i ca ion hiro v hiroxyl ph thuc
khng ch vo cc i lng Ka v Kb m cn ph thuc vo t s nng ca axit v baz
lin hp vi n.

188

Dung dch baz yu cng hon ton tng t. Trong dung dch cha amoniac
v amoni clorua, cc cn bng sau y c thit lp:
NH3 + H2O
Kb =

NH4+ + OH,

[NH4 + ][OH ]
= 1,76.105
[NH3 ]

NH4+ + H2O
Ka =

[NH3 ][H3 O+ ]
[NH4+ ]

NH3 + H3O+,
=

K H2O
Kb

1,00.1014
1,76.10

= 5,68.1010

V Kb ln hn Ka nhiu nn trong dung dch cn bng th nht chim u th v dung dch

s kim. Nhng nu nng NH4+ ln hn nng NH3 khong 200 ln, s khc nhau v gi
tr hng s cn bng c b tr v dung dch trong trng hp s axit.
Tnh pH ca dung dch cha axit yu v baz lin hp vi n: Chng ta xt dung dch c
nng axit chung CHA v nng baz lin hp chung CNaA. Nhng cn bng quan trng
nht v nhng h thc hng s cn bng y c m t bng cc phng trnh (10.3) v
(10.4).
Do kt qu ca phn ng (10.3), nng axit HA gim xung mt gi tr bng [H3O+]; mt
khc, do kt qu ca phn ng (10.4) nng axit HA tng mt gi tr bng [OH]. Nh vy, c
th din t nng cn bng ca axit HA bng phng trnh:
[HA] = CHA [H3O+] + [OH]

(10.5)

Mt cch tng t, do kt qu ca phn ng (10.3) [A] tng ln mt gi tr bng [H3O+],

trong khi do kt qu ca phn ng (10.4) [A] gim i mt gi tr bng [OH]:
[A] = CNaA + [H3O+] [OH]

(10.6)

Di y s ch r rng, phng trnh (10.5) c th d dng thu c t phng trnh cn

bng vt cht v iu kin trung ha in. Trong dung dch, [HA] v [A] c to thnh t hai
ngun HA v NaA m nng chung ca chng bit, do :
CHA + CNaA = [HA] + [A]
iu kin trung ha in i hi:
[Na+] + [H3O+] = [A] + [OH]
nhng v:
[Na+] = CNaA

(10.7)

189

nn:
CNaA + [H3O+] = [A] + [OH]

(10.8)

Sau khi bin i phng trnh , chng ta i ti phng trnh (10.6):

[A] = CNaA + [H3O+] [OH]
Ly phng trnh (10.8) tr phng trnh (10.7) v bin i ta thu c:
[HA] = CNaA [H3O+] + [OH]
ngha l mt phng tnh tng t phng trnh (10.5).
Trong phn ln trng hp chng ta s ng chm ti vn l hiu s
([H3O+]

[OH ]) nh hn rt nhiu so vi c hai nng chung. Trong cc iu kin cc phng

trnh (10.5) v (10.6) c n gin ha:
[HA] CHA

(10.9)

[A] CNaA

(10.10)

Thay cc phng trnh thu c vo phng trnh hng s phn li, sau khi bin i ta
c:
[H3O+ ] = K a

CHA
CNaA

(10.11)

Trong cc ti liu v sinh vt v ha sinh thng gp mt s dng khc ca phng trnh

(10.11). Dng thu c khi din t mi thnh phn ca phng trnh di dng m logarit
v chuyn ch t s nng :
log[H3O+ ] = log K a lg

CHA
CNaA

T :
pH = pK a + lg

CNaA
CHA

(10.12)

Biu thc ny c tn l phng trnh Henderson-Schwazenbach.

Gi thit dn ti phng trnh (10.9) v (10.10) i khi khng c gi tr i vi axit hoc
baz c hng s phn li ln hn 103 hoc l trong trng hp nu nng chung ca axit
hoc baz lin hp ca n (hoc c hai cu t ca cp axit - baz lin hp) rt nh. Nh trong
cc tnh ton trc y, sau khi thc hin cc gi thit tng ng, nhng gi tr [H3O+] v

190

[OH ] tm c trong cc tnh ton s b, cn c s dng kim tra ng

n ca nhng gi thit (1).
T phng trnh (10.11) ta thy rng, trong dung dch cha axit yu v baz lin hp vi
n, nng ion hiro ch ph thuc vo t s nng chung ca cc cht ny; iu ng
trong khong nng tha mn nhng gi thit, t rt ra phng trnh (10.11) cn c
ngha. Ngoi ra, gi tr h thc khng ph thuc vo s pha long dung dch, bi v khi
bin i th tch dung dch, nng ca mi cu t bin i mt s ln nh nhau. Nh vy,
nng ion hiro trong dung dch cha mt lng ng k axit yu v baz lin hp vi n,
khng ph thuc vo pha long v c xc nh ch bng t s nng chung ca c hai
cht tan. S khng ph thuc ca pH vo long l mt trong nhng biu hin tnh cht
m ca nhng dung dch .
V d: pH ca dung dch cha 0,400 M axit focmic v 1,00 M natri focmiat bng bao
nhiu ?
Nng ca ion hiro trong dung dch c xc nh bng cn bng ca phn ng:
H2O + HCOOH

H3O+ + HCOO

hng s cn bng ca cn bng l:

Ka =

[H3 O+ ][HCOO ]
= 1,77.104
[HCOOH]

Theo iu kin bi tp:

[HCOO] C HCOO = 1,00 M
[HCOOH] CHCOOH = 0,400 M
v:
[H3 O+ ] 1,00
= 1,77.104
0,400

t :
[H3O+] = 7,08.105 mol/l
pH = log(7,08.105) = 4,150 = 4,15
(1)

Nu [H3O+] c gi tr ln, dung dch s axit v c th b qua gi tr [OH]. Ngc li nu

dung dch l kim s c [OH] l ch yu v c th khng cn k ti gi tr [H3O+].

191

Nu chng ta so snh pH ca dung dch vi pH ca dung dch axit focmic 0,400 M th

thy rng, khi thm natri focmiat, nh hng ca ion cng tn dn ti s tng pH t 2,08 n
4,15.
Tnh pH ca dung dch baz yu v axit lin hp vi n: Tnh pH ca mt dung dch cha
baz yu v axit lin hp vi n khng c g khc vi v d phn tch trn.
V d: Tnh pH ca dung dch cha NH4Cl 0,28 M v NH3 0,070 M.
Cn bng chng ta ch l:
NH4+ + OH

NH3 + H2O

c c trng bng hng s Kb =1,76.105.

Nh thng l, chng ta c th gi thit rng :
[NH3] CNH3 = 0,070
[NH4+ ] CNH+ = 0,28
4

Thay th nhng gi tr vo phng trnh hng s cn bng chng ta c:

[OH ] 0,28
= 1,76.105
0,070

[OH] = 4,40.106 mol/l

pOH = log(4,40.106) = 5,36;
pH = 14 5,36 = 8,64.

10.4.2 nh hng ca lc ion n cn bng axit - baz

Trong chng 4 ch r mc phn li ca axit yu, v d axit axetic tng ln cng vi
s tng ca lc ion. Nguyn nhn ca hin tng tng t nguyn nhn gy nn s chuyn
dch cn bng kt ta-dung dch. V dng khng phn li ca axit khng tch in nn s bin
i lc ion t nh hng n tnh cht ca n; mt khc, v s bin i lc ion nh hng n
tnh cht cc ion ca cht in li, khuynh hng cc ion hiro v ion axetat ti lin hp b
gim xung.
V d dn ra di y ch r rng c th tnh ton nh hng ca lc ion nu bit h s
hat ca cc ion.

192

V d: Tnh pH ca dung dch m cha 0,0400 M axit focmic v 0,100 M

natri focmiat, theo hot . So snh kt qu thu c vi kt qu tm c khi s dng nng
thay th cho hot .
Gi thit mt cch hp l rng, lc ion ca dung dch c xc nh bng nng
natri focmiat, ngha l nng H3O+ v ion focmiat to thnh khi axit focmic phn li nh:
=

1
(0,100.12 + 1,00.12) = 0,100.
2

T bng 5.4 (xem chng 5) chng ta tm thy rng i vi = 0,1:

fH

3O

= 0,83;

fHCOO = 0,76

Nh vy:
Ka =

[H3 O+ ][HCOO ] fH3O+ fHCOO

= 1,77.104
[HCOOH]
fHCOOH

Hp nht h s hot i vi Ka chng ta tnh c hng s nng ca cn bng K 'a :

K a' =

1,77.104 fHCOOH 1,77.104 1,0

[H O+ ][HCOO ]
=
= 2,81.104 = 3
fH O+ fHCOO
0,83 0,76
[HCOOH]
3

Chng ta nhn thy rng h s hot ca HCOOH khng tch in c chp nhn
bng 1,0. Gi thit i vi ht trung ha thng l ng.
Sau ny, tnh ton chng ta s dng hng s cn bng nng Ka':
[HCOO] = 0,100 M
[HCOOH] = 0,0400 M
[H3 O+ ] 0,100
= 2,81.104
0,0400

[H3O+] = 1,12.104 mol/l;

pH = log(1,12.104) = 3,95.
Ch rng, nu khng tnh h s hot chng ta thu c pH = 4,15.

193

10.4.3 Dung dch m

Dung dch m l dung dch c pH khng bin i trong cc trng hp:
1. Khi pha long;
2. Khi thm vo mt lng nh axit hoc baz. Dung dch c nng axit v baz lin
hp vi n cao v xp x bng nhau l tt nht.
nh hng ca s pha long: Gi tr pH ca dung dch m thc t khng bin i khi
pha long cho ti khi nng ca n khng gim ti mc l, s gn ng c s dng
rt ra phng trnh (10.9) v (10.10), tr thnh mt gi tr. V d dn ra di y minh ha
tnh cht in hnh ca dung dch m khi pha long.
V d: Hy tnh pH ca dung dch m c pH = 4,15 khi pha long dung dch m (xem
v d mc 10.4.1):
1. 50 ln;
2. 10.000 ln.
Gii:
1. Sau khi pha long 50 ln:
CHCOOH = 0,400/50 = 8,00.103 M
CHCOONa = 1,00/50 = 2,00.102 M
Nh trc y, nu gi thit rng, hiu s [H3O+] [OH] nh so vi CHCOOH v CHCOONa
ta c:
[H3 O+ ] 2,00.102
8,00.103

= 1,77.104

[H3O+] = 7,08.105 mol/l; pH = 4,15.

Trong trng hp :
[OH ] =

1,00.1014
7,08.10

= 1,41.1010 mol / l

Nh vy gi thit (7,08.105 1,41,1010) << 8,00.103 v 2,00.102 c c s.

2. Sau khi pha long 10.000 ln:
CHCOOH = 4,00.105 M

194
4

CHCOONa = 1,00.10 M
Trong trng hp ny cn s dng phng trnh (10.5) v (10.6), chng cho nhng kt
qu chnh xc hn:
[HCOOH] = 4,00.105 [H3O+] + [OH]
[HCOO] = 1,00.104 + [H3O+] [OH]
V dung dch l axit nn chc chn phi c [H3O+] >> [OH], nh vy:
[HCOOH] 4,00.105 [H3O+];
[HCOO] 1,00.104 + [H3O+]
Thay th cc gi tr vo phng trnh hng s cn bng ta c:
[H3 O+ ] (1,00.1014 + [H3O+ ])
4,00.10

[H3O ]

= 1,77.104

a phng trnh n dng bc hai:

[H3O+ ]2 + 2,77.104 [H3O+ ] 7,08.109 = 0

v gii ra:
[H3O+] = 2,36.105 mol/l; pH = 4,63.
Nh vy, khi pha long 10.000 ln pH tng t 4,15 n 4,63 v khi pha long 50 ln pH
thc t khng bin i.
Trn hnh 10.2 dn ra s so snh nh hng ca s pha long n pH ca cc dung dch
m v khng m vi nng u ca mi dung dch bng 1,00 M. T hnh v thy r rng
l nhng dung dch m t bin i pH.
Thm axit v baz vo dung dch m: Kh nng ca dung dch m gi khng i gi tr
pH khi thm axit hoc baz vo c chng ta minh ha v d sau.
V d: Hy tnh xem pH bin i nh th no nu thm vo 400 ml dung dch m cha
NH3 0,200 M v NH4Cl 0,300 M.
1. 100 ml NaOH 0,0500 M;

2. 100 ml HCl 0,500 M.

Chng ta tnh gi tr pH ban u, khi gi thit rng:

[NH3] CNH3 = 0,200 M

195
[NH4+ ] CNH4Cl = 0,300 M

v thay th nhng gi tr vo phng trnh hng s phn li:

[OH ] 0,300
= 1,76.105
0,200

[OH] = 1,17.105 mol/l; pH = 14,00 (log1,17.105) = 9,07

Hnh 10.2
nh hng ca s pha long n pH ca cc dung dch m v khng m.

Hng s phn li HA bng 1,00.104. Nng u i vi tt c cc trng hp bng 1,00

M.
1. Thm NaOH vo gy nn s chuyn dch mt phn NH4+ thnh NH3:
NH4+ + OH

NH3 + H2O

Nng chung ca NH3 v NH4Cl sau khi thm kim vo tr thnh nh sau:
CNH3 =

400 0,200 + 100 0,0500

= 0,170 M
500

CNH4Cl =

400 0,300 100 0,0500

= 0,230 M
500

196

Sau khi thay th nng tm c vo phng trnh hng s phn li ca

NH3 ta thu c:
[OH ] =

1,76.105 0,170
= 1,30.105 mol / l
0,230

pH = 14 (log1,30.105) = 9,11
pH = 9,11 9,07 = 0,04
2. Thm HCl gy nn s chuyn mt phn NH3 thnh NH4+ , do :
CNH3 =

400 0,200 100 0,0500

= 0,150 M
500

CNH4Cl =
[OH ] =

400 0,300 + 100 0,0500

= 0,250 M
500

1,76.105 0,150
= 1,06.105 mol / l
0,250

pH = 14 (log1,06.105) = 9,02
pH = 9,02 9,07 = 0,05
V d: Hy so snh tnh cht ca dung dch khng m c pH = 9,07([OH] = 1,17.105
mol/l), khi thm vo cng mt lng kim v axit nh trong v d trn.
1. Sau khi thm kim:
[OH ] =

400 1,17.105 + 100 0,0500

= 1,00.102 mol / l
500

pH = 14 (log1,00.102) = 12,00
pH = 12,00 9,07 = 2,93
2. Sau khi thm axit clohiric:
[H3O+ ] =

100 0,05 400 1,17.105

= 1,00.102 mol / l
500

pH = log(1,00.102) = 2,00
pH = 2 9,07 = 7,07

197

Khi lng m: nhng v d xt ch r rng dung dch cha cp axit - baz lin hp
c kh nng gi pH n nh khi pH ca dung dch b bin i. Tnh cht gi pH n nh ca
dung dch m i vi s bin i ng k ca pH ph thuc c vo nng chung ca cc
cu t ca dung dch m c vo t s ca chng. V d, nu thm vo 400 ml dung dch m
thu c bng cch pha long 10 ln dung dch m m t trong v d trn, cng mt
lng nh th natri hiroxit hoc axit clohiric th pH ca n bin i khong 0,5 n v;
i vi dung dch m c hn, s bin i pH ch khong 0,04 n v.
Ngi ta o khi lng m ca dung dch bng s mol axit mnh hoc baz mnh cn
thit phi thm vo mt lt dung dch m lm bin i pH ca n mt n v. Chng ta
cng thy rng, khi lng m ph thuc vo nng cp axit - baz lin hp ng thi
c vo t s nng ca cp axit - baz lin hp v t ti gi tr cc i khi t s bng
n v.
Chng ta xt dung dch m cha a mol axit HA v b mol baz lin hp NaA. Nu thm
vo dung dch n mol axit mnh, nng chung ca axit v baz lin hp s nh sau:
a+n
;
v
bn
=
v

CHA =
CNaA

y v l th tch dung dch. Chng ta xc nh pH ca dung dch theo phng trnh

(10.12):
pH = pK a + log

CNaA
bn
= pK a + log
= pK a + log(b n) log(a + n)
CHA
a+n

Ly vi phn phng trnh theo n ta c phng trnh m t tc bin i pH ca dung

dch m khi thm axit:
dpH
1
1
= 0,434
0,434
dn
bn
a+n

Cho vi phn bc hai bng khng chng ta tm c cc tiu ca hm pH = F(n).

d 2 pH
dn

= 0,434

1
2

(b n)

0,434

1
(a + n)2

=0

Sau khi bin i ta c:

1
2

(b n)

1
(a + n)2

Khai cn bc hai c hai phn ca phng trnh v sp xp li ta c: b = a.

198

Nh vy, tc bin i pH cc tiu khi thm axit c quan st thy trong

trng hp nu s mol baz lin hp b bng s mol axit lin hp a. Ta cng c c mi
quan h nh vy nu thm baz vo dung dch m c iu ch t baz yu v axit lin
hp vi n.
Gii hn ng dng phng trnh Henderson-Schwazenbach.
Phng trnh Henderson-Schwazenbach:
pH = pK a + log

CNaA
CHA

(10.12)

c s dng rng ri tnh pH v iu ch dung dch m. Trong phng trnh trn

pKa l hng s nn t s

CNaA
quyt nh gi tr pH ca dung dch, nhng trong thc t, iu
CHA

ch ng trong mt khong xc nh. Khi t s ny rt ln hoc rt nh, phng trnh trn

tr thnh khng ng v khng th p dng c. V d, khi

CNaA 1.101
=
= 1.106 th i
7
CHA
1.10

vi h NaCH3COO - CH3COOH, pH ca dung dch s l:

pH = 4,76 + log106 = 4,76 + 6,00 = 10,76
Kt qu trn l khng th chp nhn c v ln hn nhiu pH ca dung dch
NaCH3COOH 0,100 M, ng thi cng chnh l pH im rt gn vi im tng ng
trong php chun dung dch CH3COOH 0,200 M bng dung dch NaOH 0,200 M (xem mc
10.4.4 di y). V lc ny [NaCH3COO] >> [CH3COOH] nn:
[OH ] = K bCb =

K H2O
Ka

CNaCH3COO =

1014
10

4,76

101 = 1.105,12

pOH = 5,12
do
pH = 14,00 5,12 = 8,88
Ngc li, khi

CNaA 107
=
= 106 th i vi h NaCH3COO - CH3COOH ta ang xt
1
CHA
10

pH s l:
pH = 4,76 + log106 = 4,76 6,00 = 1,24
Kt qu ny cng khng th chp nhn c v dung dch ny thc t l dung dch
CH3COOH 0,100 M, ng thi pH ca n cng chnh l pH im u, chnh xc hn l
im "cc k st" vi im u ca ng chun dung dch CH3COOH 0,100 M bng
dung dch NaOH 0,100 M (v [CH3COOH >> [NaCH3COO]) nn:

199
[H3O+ ] = K CH3COOH CCH3COOH = 104,76 101 = 102,88 (xem 10.4.4)

pH = 2,88.
Khi sinh vin mun tnh pH im "v cng st" vi im u v im "v cng st" vi
im tng ng ca php chun axit yu bng baz mnh nhng li bng phng trnh
phng trnh Henderson-Schwazenbach th phm phi nhng sai lm nh trn.
S tht l h m axit yu v baz lin hp vi n c khi lng m (xem khi lng
m 10.4.3) cc i khi CHA = CNaA v khi lng m gim dn v c hai pha khi CHA v
CNaA gim dn. Khi CHA = 107 ngha l CHA 0 v CNaA = 107 ngha l CNaA 0 l lc
khi lng m ca h tin ti khng nn h khng cn l h m na v do khng th
dng cng thc ca Henderson-Schwazenbach tnh pH.
iu ch dung dch m: V nguyn tc c th iu ch dung dch m c pH cn thit
bt k bng cch trn nhng lng c tnh ton trc ca nhng cp axit - baz lin hp
thch hp.
V d: Hy trnh by cch iu ch dung dch m c pH = 5,00 t dung dch axit axetic
(Ka = 1,75.105) 0,500 M v dung dch NaOH 0,426 M.
Ta tm c t s nng axit axetic v anion axetat pH = 5,00 t phng trnh hng
s phn li:
[OAx ] K HOAx 1,75.105
=
=
= 1,75
[HOAx] [H3 O+ ] 1,00.105

c c t s cn trn VHA ml axit axetic vi VOH ml NaOH 0,426 M. Sau khi trn,
nng axit v baz lin hp s tng ng bng:
COAx =
CHOAx =

0,426 VOH
VHA + VOH

[OAx ]

0,500 VHA 0,426 VOH

VHA + VOH

[HOAx]

Nu thay th [OAx] v [HOAx] bng nhng nng vo t s ban u th mu s

c n gin ha:
0,426 VOH
0,500 VHA 0,426 VOH

= 1,75

v sau khi sp xp li chng ta thu c:

200
VOH
VHA

= 0,747

Nu cn thit iu ch 100 ml dung dch m th chng ta lm nh sau:

VOH + VHA = 100
0,747VHA + VHA = 100
VHA = 57,2 ml; VOH = 100 57,2 = 42,8 ml
Nh vy, nu thm 57,2 ml dung dch axit axetic vo 42,8 ml dung dch NaOH th v
nguyn tc phi thu c dung dch c pH cn thit. Bng cc tnh ton loi tng t c th
hng dn vic iu ch cc dung dch m c pH xp x pH tng ng cn thit. Thng
khng nn mong i cc gi tr chnh xc bi v gi tr ca nhiu hng s phn li c sai s.
Cn mt iu quan trng hn na l lc ion ca cc dung dch m thng ln dn n mc
l khng th thu c gi tr h s hot tin cy ca cc ion trong cc dung dch t
phng trnh Debye-Huckel. Nh trong v d xt, lc ion khong 0,18 v vy hng s phn
li nng K 'a cn phi ln hn 1,75.105 ng k nhng cha c xc nh chnh xc
(khong 3.105).
Nhng hng dn iu ch cc dung dch m c pH bit trc c trong cc s tay tra
cu ha hc. Cn c bit nh hai h m ph bin nht: dung dch m Makilvein i vi
khong pH = 2 8 c iu ch bng cch trn dung dch axit xitric v natri hiro-photphat
v dung dch m Klark v Labo i vi khong pH = 2 10 c iu ch bng cch s
dng ba h: axit phtalic-kali biphtalat, kali ihiro photphat-kali hiro photphat, axit boric v
natri borat.

10.4.4 ng chun axit yu

xy dng ng chun axit yu (hoc baz yu) cn phi thc hin bn loi php
tnh tng ng vi bn phn ca ng cong:
1. Trc khi chun, dung dch ch cha axit yu, nn pH ca dung dch c tnh theo
nng cht b chun.
2. Sau khi thm mt phn bt k thuc th (mt lng cho ti trc im tng ng
nhng cha bng lng tng ng), cc dung dch s l mt lot h m; i vi mi h
m c th tnh pH theo nng chung ca sn phm phn ng v ca axit hoc baz
cha b chun.
3. im tng ng dung dch cha hp cht lin hp vi axit yu hoc baz yu b
chun v pH c tnh theo nng chung ca hp cht .

201

4. Cui cng, sau im tng ng lng d axit mnh hoc baz mnh c dng lm
cht chun ti mc ngn cn phn ng ca sn phm to thnh nn pH ch yu c xc nh
theo nng lng d cht chun.
Xy dng ng chun : Chng ta xt nhng tnh ton v d xy dng ng
chun 50,00 ml dung dch axit axetic (Ka = 1,75.105) 0,100 M bng dung dch NaOH
0,100 M.
Gi tr pH ban u: S dng phng php m t trc y chng 4 cho dung dch
HOAx 0,100 M chng ta c pH = 2,88.
Gi tr pH sau khi thm 10,00 ml cht chun: Trong trng hp ny chng ta thu c
dung dch m gm c NaOAx v HOAx. Ta phi tm nng ca c hai cu t ca dung
dch m:
5 0, 0 0 0,1 000 1 0, 0 00 0,100 0
4, 00 0
=
60, 00
6 0, 0 0
10, 00 0,1 00 0 1, 000
C N aO A x =
=
6 0, 0 0
60, 00
CH O Ax =

Thay th nhng gi tr tm c vo phng trnh hng s phn li HOAx chng ta thu

c:
[H 3 O + ] 1, 00 0
60, 00
= K a = 1,75.10 5
4, 0 00
60, 00

[H3O+] = 7,00.105 mol/l pH = 4,16

Bng 10.3 S bin i pH khi chun axit yu bng baz mnh

pH
Th tch dung dch
Chun 50,00 ml CH3COOH Chun 50,00 ml CH3COOH
NaOH ml
0,100 M bng dung dch 0,00100 M bng dung dch
NaOH 0,100 M
NaOH 0,00100 M
0,00

2,88

3,91

10,00

4,16

4,30

25,00

4,76

4,80

40,00

5,36

5,38

49,00

6,45

6,45

202

49,90

7,46

7,46

50,00

8,73

7,73

50,10

10,00

8,00

51,00

11,00

9,00

60,00

1196

9,96

75,00

12,30

10,30

Nhng tnh ton loi tng t, thch hp xy dng ng chun sut c vng
m. Nhng kt qu ca nhng tnh ton c gii thiu ct th hai ca bng 10.3. Ch
l nu axit b chun 50% (i vi php chun cho, iu tng ng vi s thm vo
chnh xc 25 ml dung dch kim) nng chung ca axit v baz lin hp bng nhau; trong
gii hn ca nhng gi thit thng thng, ngi ta cng nhn nng cn bng bng nhau
ca chng. Do trong phng trnh hng s phn li nhng i lng c n gin
ha v nng ion hiro bng tr s hng s phn li, ngha l pH bng pKa. Bng cch tng
t khi chun baz yu, nng ion hiroxyl thi im 50% baz c chun bng tr s
hng s phn li baz.
Gi tr pH im tng ng: im tng ng, axit axetic chuyn thnh natri
axetat ngha l chng ta c dung dch ch cha baz . Sau khi tnh nng tng qut ca
ion axetat ngi ta tnh pH nh m t i vi baz yu (chng 4). Trong v d cho,
nng baz NaOAx l 0,0500 M, do :
[OH ]

K H2O
Ka

0,0500 =

1,00 1014 0,0500

1,75.105

[OH ] = 5,34.106 mol / l

pH = 14,00 ( log 5,34.106 ) = 8,73

Gi tr pH sau khi thm 50,10 ml baz mnh: Sau khi thm 50,10 ml kim, ion hiroxyl
c to thnh do s phn li ca baz d v do tng tc ca ion axetat vi nc. S ng
gp ca phn ng sau qu nh bi v lng d baz mnh cn tr s phn li baz yu v c
th khng cn k ti n. iu tr thnh r rng khi chng ta tnh c nng ion
hiroxyl im tng ng trong php chun cho l 5,34.106 mol/l. S ng gp
[H3O+] do phn ng phn li ca axit axetic khi va xut hin lng d baz mnh s cn b
hn do :
[OH ] CNaOH =

50,10 0,1000 50,00 0,1000

= 1,0.104 mol / l
100,1

pH = 14,00 ( log1,0.104 ) = 10,00

203

Chng ta nhn thy rng ng chun axit yu bng baz mnh sau im tng
ng ging vi ng chun axit mnh bng baz mnh.
nh hng ca nng : Trong cc ct th hai v th ba ca bng 10.3 dn ra nhng d
kin thu c khi chun cc dung dch axit axetic 0,100 M v 0,001 M bng dung dch
NaOH c cng nng . V d dn ra di y ch r rng khi xy dng ng chun cc
dung dch long cn tnh ton nng ion hiro bng nhng phng trnh chnh xc hn.
V d: Hy tnh pH ca dung dch to thnh khi trn 50,00 ml dung dch axit axetic 0,001
M vi 10,00 ml dung dch NaOH 0,001 M.
Chng ta tnh nng HOAx v NaOAx:
50,00 0,001 10,00 0,001
= 6,67.10 4 M
60,00
10,00 0,001
=
= 1,67.10 4 M
60,00

CHOAx =
CNaOAx

Nu chng ta tnh [H3O+] bng chnh nhng phng trnh c s dng trong trng
hp chun bng cc dung dch thuc th 0,100 M th tm thy: [H3O+] = 7,00.105 mol/l. R
rng l gi tr [H3O+] tm c by gi c th snh vi CHOAx v CNaOAx do cn ng dng
cc phng trnh (9.5) v (9.6):
[HOAx] = CHA [H3O+] + [OH]
[OAx] = CNaA + [H3O+] [OH]
C th b qua gi tr [OH] bi v dung dch l axit. Thay th cc gi tr tm c vo
phng trnh hng s phn li ta c:
Ka =

[H3 O+ ] CNaA + [H3O+ ]

(CHA [H3O ])
+

v sau khi chuyn thnh phng trnh bc hai:

[H3O+]2 + (CNaA + Ka).[H3O+] Ka.CHA = 0
i vi v d cho:
[H3O+]2 + 1,84.104.[H3O+] 1,17,108 = 0;
[H3O+] = 5,00.105 mol/l;
pH = 4,30

204

Gi tr pH i vi nhng thi im chun tng ng vi s thm vo t 10,00

n 49,00 ml dung dch baz mnh (bng 10.3, ct 3) c tnh ton tng t.
S din t bng th nhng d kin ca bng 10.3 c gii thiu trn hnh 10.3.
Chng ta nhn thy rng i vi dung dch long hn, gi tr pH ban u cao hn v pH
im tng thp hn so vi trng hp dung dch 0,100 M. cc im tng ng vi s
thm vo mt th tch trung gian cht chun, pH bin i t hn. Trong vng ca php
chun, dung dch m cha axit axetic v natri axetat c to thnh. Hnh 10.3 khng nh
li rng, s pha long t nh hng n pH ca dung dch m.
Trn hnh 10.4 dn ra nhng ng chun cc dung dch axit 0,100 M c cng
khc nhau. R rng l khi lm gim cng axit, s bin i pH trong vng im tng
ng tr nn t r rng hn bi v phn ng gia axit v baz xy ra km hon ton hn.
nh hng ca nng thuc th n hon ton ca phn ng (hnh 10.3) tng t
nh c m t trc y i vi ng chun kt ta (chng 9).

Hnh 10.3

Hnh 10.4

Nhng ng chun axit axetic bng dung dch

NaOH

nh hng ca cng axit n c im ca ng

chun .

1. Chun axit 0,100 M bng NaOH 0,100 M.

Mi ng cong tng ng vi php chun 50,00 ml axit

0,1000 M bng NaOH 0,1000 M

2. Chun axit 0,00100 M bng NaOH 0,00100 M

La chn ch th: Hnh 10.3 v 10.4 ch r rng, s la chn ch th cho php chun axit
yu b hn ch hn so vi php chun axit mnh. V d, brom crezol lc hon ton khng
thch hp cho php chun axit axetic 0,100 M; c brom timol chm cng t thch hp i vi
php chun axit axetic 0,100 M bi v s bin i mu ca n c quan st thy trong
khong t 47 n 50 ml baz mnh 0,100 M. Nhng c th dng brom timol chm nu chun

205

n mu hon ton kim; bin php i hi phi dng dung dch kim chun cha cng
mt lng ch th v dung dch b chun (i chng) so snh. chun , nhng ch th
c s chuyn mu trong mi trng kim nh phenolphtalein thch hp hn.
S bin i pH im cui khi chun axit axetic 0,00100 M (ng cong 2 trn hnh
10.3) nh n mc l c th gy sai s chun ln. xc nh im cui vi lp li mt
vi phn trm cn s dng ch th vi s chuyn mu trong vng chuyn mu t
phenolphtalein n brom timol chm v ngoi ra cn dng i chng.
T hnh 10.4 r rng l, nhng vn tng t ny sinh theo mc gim cng axit.
Khi chun axit 0,100 M vi hng s phn li 108 c th thu c chnh xc 2% iu
kin c i chng thch hp. C th chun nhng dung dch c hn ca nhng axit tng i
yu vi chnh xc kh.
Sau y xin dn ra mt v d v cch tnh bc nhy pH khi chun 20,00 ml dung dch axit
0,100 M c K a = 1.108 bng dung dch NaOH 0,100 M lm minh chng.
u bc nhy l lc php chun ang cn thiu 0,10 ml NaOH 0,100 M, ngha l
mt dung dch m nn pH = pK a log

0,1
= 8,00 + 2,30 = 10,30.
19,9

Ti im tng ng php chun thm 20,00 ml NaOH 0,100 M, h tr

thnh dung dch baz lin hp ca HA l NaA c V= 40,00 ml nn [NaA] = 5.102 M,
K b = 1.106 , OH = 1.106.5.102 = 2,24.104 M , pOH = 3,65, pH = 10,35.

Cui bc nhy l lc php chun tha 0,10 ml NaOH 0,100 M nn [OH] do

NaOH d to ra l:
O H - = 0,100 0,10

40,10
+
O H

= 2,50.10 4 M v O H do A to ra l

1.10 6 .5.10 2 = 2, 24.10 4 M

O H

= 4,74.10 4 M

pOH = 0,68 + 4,00 = 3,32

pH = 10,68

Vy bc nhy c pH = 0,38.
Vi bc nhy nh trn, kt hp vi khong chuyn mu ca ch th v iu kin c i
chng c th t chnh xc 2% nu trn l hp l.

206

10.4.5 ng chun baz yu

Xy dng ng chun baz yu khng c g khc vi xy dng ng chun axit
yu.
V d: Chun 50,00 ml dung dch NaCN 0,050 M bng dung dch HCl 0,100 M. Hy tnh
pH sau khi thm:
1. 00,00 ml;

2. 10,00 ml;

3. 25,00 ml;

4. 26,00 ml axit.

1. Thm 0,00 ml dung dch chun. Ion xianua l baz yu; tnh pH c tin hnh nh
ch ra chng 4.
[OH ] K b CNaCN

Kb =

y:

KH2O
KHCN

1,00.1014
2,1.10

= 4,76.106

Gi tr pH tm c l 10,69.
2. Thm 10,00 ml dung dch chun: s thm axit dn ti s to thnh dung dch m
cha:
50,00 0,050 10,00 0,100 1,500
=
60,00
60,00
10,00 0,100
1,00
=
=
60,00
60,00

CNaCN =
CHCN

Thay th cc gi tr vo phng trnh hng s phn li ca HCN ta c:

2,1.109 1,00
60,00
= 1,4.109 mol / l
[H3O+ ] =
1,500
60,00

pH = 8,85.
3. Thm 25,00 ml dung dch chun: thm vo mt th tch nh vy cht chun cho php
t ti im tng ng; by gi trong dung dch c axit yu HCN:
CHCN =

25,00 0,100
= 0,03333 M v do (xem chng 4)
75,00

207
[OH ] K b CNaCN

= 2,1.109 0,03333 = 8,37.106 mol / l

pH = 5,08

4. Thm vo 26,00 ml cht chun: lng d axit mnh ngn cn s phn li HCN n mc
l s ng gp ca n vo gi tr pH khng ng k v do :
[H3O+ ] = CHCl =

26,00 0,100 50,00 0,050

= 1,32.103 mol / l
76,00

pH = 2,88

Trn hnh 10.5 dn ra nhng ng chun baz yu c cng baz khc nhau. R
rng l khi chun baz yu c th s dng nhng ch th vi s chuyn mu trong vng axit.

Hnh 10.5
nh hng ca cng baz n dng ca ng chun .
Mi ng cong tng ng vi php chun 50,00 ml dung dch baz 0,1000 M bng HCl 0,1000 M

208

Chng 11
ng chun nhng h Axit Baz phc tp
Trong chng ny chng ta s xem xt nhng cn bng c thit lp trong dung dch c
hai axit hoc hai baz khc nhau v hng s phn li. ng ch l hai loi dung dch:
Dung dch hn hp n axit hoc n baz;
Dung dch hn hp a axit hoc a baz.

11.1 ng chun hn hp axit mnh v axit yu hoc hn hp baz

mnh v baz yu
Xy dng ng chun hn hp axit mnh v axit yu c thc hin trn v d chun
hn hp axit clohiric v axit yu HA.
giai on u ca php chun , nng ion hiro c din t bng phng trnh:
[H3O+] = CHCl + [A] + [OH]
trong s hng u th hin s ng gp ca axit mnh, s hng th hai l s ng gp
ca axit yu, s hng th ba l s ng gp do s phn li ca dung mi vo axit tng cng
ca dung dch. Trong phn ln cc dung dch axit, s ng gp do s phn li ca dung mi
qu nh nn c th b qua trong cc php tnh.
giai on u ca php chun, axit clohiric ngn cn s phn li ca axit yu nn c
th chp nhn [A] << CHCl v do nng ion hiro ca hn hp bng nng ca axit
mnh.
V d: Tnh pH ca dung dch c [HCl] = 0,120 M v [HA] = 0,080 M (Ka=1,00.104)
[H3O+] = 0,120 + [A]
Gi thit rng [A] << 0,120, khi [H3O+] = 0,120 v pH = 0,92. kim tra ng
n ca gi thit trn ta tnh nng [A]:
A
1,00.104
= Ka
=
= 8,33.104
0,120
[HA ] H3O+

209

V:
0,080 = CA = [HA] + [A]
nn:
A
0,080 = + A
8,33.104

T :

[A] = 6,66.105 mol/l

R rng l [A] << 0,120, ngha l gi thit nu trn l ng.

Nh vy l, c th dng nhng gi thit tng t cho ti khi chun ht phn ln axit
mnh. T ta thy r, phn u ca ng chun hn hp axit mnh v axit yu khng
khc ng chun ring dung dch axit mnh. Tt nhin s c mt ca axit yu HA cn
phi c k n trong trng hp nng axit mnh thp.
V d: Tnh pH ca dung dch to thnh khi thm 29,00 ml dung dch NaOH 0,100 M vo
25,00 ml dung dch c [HCl] = 0,120 M v [HA] = 0,080 M (Ka = 1,00.104).
Tnh nng HCl v HA sau khi thm dung dch NaOH:
25,00 0,120 29,00 0,100
= 1,85.103 M
54,00
25,00 0,080
=
= 3,70.102 M
54,00

CHCl =
CHA

nn:
[H3O+] = CHCl + [A] = 1,85.103 + [A]

(11.1)

Ngoi ra ta c th vit:
CHA = [HA] + [A] = 3,70.102 M

(11.2)

Bin i phng trnh hng s phn li axit c th tm c [HA]:

H3 O+ A

[HA ] =
1,00.104

Gii ng thi hai phng trnh cui ta c:

H3 O+ A

+ A = 3,70.102

1,00.104

(11.3)

210

T ta tm c:
3,70.106
A =
H O+ + 1,00.104
3

Thay [A] v CHCl vo phng trnh (11.1) ta c:

3,70.106
H O+ = 1,85.103 +
3

H3O+ + 1,00.104

hoc:

[H3O+]2 1,85.103[H3O+] 3,88.106 = 0

[H3O+] = 3,03.103 mol/l; pH = 2,52

Nh vy l, trong tng s nng H3O+ ca dung dch (3,03.103 M), phn ng gp ca
axit mnh l 1,85.103, phn ng gp ca axit yu l 1,18.103 M, hon ton c th snh vi
s ng gp ca axit mnh.
Nu lng baz thm vo tng ng vi lng axit clohiric ban u th dung dch thu
c v mi mt ng nht vi dung dch c pha ch bng cch ho tan mt lng axit yu
v natri clorua tng ng vo mt lng nc thch hp. Natri clorua khng nh hng n
pH ca dung dch v c th b qua nh hng ca lc ion ti nng ion hiro xy dng
phn tip theo ca ng chun c tnh ton tng t nh khi xy dng ng chun
axit yu long HA.
Do , dng ca ng chun hn hp axit mnh v axit yu ch yu ph thuc vo
hng s phn li (cng ) ca axit yu. Trn hnh 11.1 dn ra nhngng chun hn hp
axit mnh v axit yu khc nhau v hng s phn li. Ta nhn thy rng, nu hng s phn li
ca axit yu tng i ln (ng cong s 1), trn ng chun thc t khng c bc
nhy im tng ng th nht. i vi nhng hn hp nh vy, trn c s kt qu chun
ch c th xc nh tng nng axit (ngha l [HCl] + [HA]). Trong trng hp hng s
phn li ca axit yu qu nh th trn ng cong chun hn hp axit mnh v axit yu
cng ch c mt bc nhy. Nhng trong trng hp ny ch chun c axit mnh. Khi
chun hn hp axit mnh v axit yu c gi tr hng s phn li trung gian th trn ng
chun xut hin hai bc nhy ring bit. ng chun ca php chun hn hp
baz mnh v baz yu iu kin ca hng s phn li ca baz yu < 104 nhng >108
cng c hai bc nhy ging nh trng hp chun hn hp axit mnh v axit yu m
t trn y.

211

Hnh 11.1
Cc ng chun hn hp axit mnh v axit yu c hng s phn li axit hc nhau bng dung dch NaOH 0,100 M

Mi ng chun tng ng vi php chun 25,00 ml dung dch

c [HCl] = 0,120 M v nng axit yu HA l 0,080 M.

11.2 Tnh ton nng cn bng ca cc h a axit - a baz

Nhiu axit yu c kh nng tch ra hai hoc mt s ln hn proton. Chng ta xt cn
bng ca axit photphoric trong dung dch nc:
H3PO4 + H2O

H2PO4

HPO24

+ H2O

+ H2O

H2PO4

H3O +

H3O + HPO4

H3O +

PO34

H3 O + H2 PO4

= 7,11.10 3
K1 =
[H3 PO4 ]

H3O+ HPO42

= 6,34.108
K2 =

H2PO4

H3O+ PO34

= 4,2.1013
K3 =
HPO24

i vi axit photphoric, cng nh i vi phn ln cc axit khc, mi hng s tip sau

lun nh hn hng s trc, ngha l K3 < K2 < K1.

212

Cng thng gp c cc a baz. Ion cacbonat l baz lin hp ca ion

bicacbonat tham gia vo cc cn bng tng nc sau:
CO32

HCO3

HCO3

+ H2O

+ OH ;

+ H2O

H2CO3 + OH

( K b )1

HCO3 OH

= 2,13.104
=
CO32

( K b )2 =

[H2CO3 ] OH
HCO3

= 2,25.108

C th thu c gi tr bng s ca nhng hng s phn li baz ca CO32 v HCO3

((Kb)1 v (Kb)2 tng ng) xut pht t nhng hng s phn li tng nc ca axit cacbonic
(chng 4):

( K b )1 =
( K b )2 =

K H2O

( K a )2

K H2O

( K a )1

y (Ka)1 v (Ka)2 l nhng hng s phn li th nht v th hai ca H2CO3.

C th tnh ton kh chnh xc pH ca cc dung dch a axit v cc dung dch m ca cc
a axit bng cch s dng bin php i vi cc h a cu t c m t trc y (chng
4). Nhim v i hi phi gii mt s phng trnh kh vt v. Nhng trong nhng trng
hp khi m t s nhng hng s phn li axit hoc baz tng nc khong 103 hoc ln hn th c
th thc hin mt s gi thit nhm n gin ha kh nhiu php tnh. Tip theo chng ta s
xem xt nhng v d trong nhng gi thit c ng dng thnh cng. Phng php tng
qut tnh pH ca cc dung dch c xem xt trng hp dung dch mui loi NaHA.

11.2.1 Dung dch mui loi NaHA

Trong dung dch mui loi NaHA c kh nng th hin c tnh axit c tnh baz.
Phngtrnh phn li axit i vi NaHA c vit nh sau:
HA + H2O

A2 + H3O+

V HA l baz lin hp ca axit H2A nn cn bng th hai c thit lp:

HA + H2O

H2A + OH

213

mt trong hai phn ng ny, ion hiro c to thnh, cn trong phn ng cn li ion
hiroxyl c sinh ra. Dung dch HA s l axit hoc baz ty thuc vo t s hng s cn
bng ca hai qu trnh :
H3 O+ A 2

K2 =
[HA ]

Kb =

K H2O
K1

[H2 A ] OH
HA

(11.4)

(11.5)

Nu Kb > K2, dung dch s kim, cn trong trng hp ngc li dung dch s axit. Cht
loi NaHA c kh nng th hin c tnh axit v tnh baz c gi l cht in li lng tnh.
i vi dung dch NaHA ta c phng trnh cn bng vt cht:
CNaHA = [H2A] + [HA] + [A2]

(11.6)

v iu kin trung ho in:

[Na+] + [H3O+] = [HA] + 2[A2] + [OH]
V nng ion natri bng nng chung ca mui nn c th chuyn phng trnh cui
cng thnh:
CNaHA = [HA] + 2[A2] + [OH] [H3O+]

(11.7)

Thng thng i vi cc dung dch cc cht loi NaHA, khng nn b qua nng ion
hiroxyl v nng ion hiro. Do tm c gi tr ca tt c cc n s ([H3O+], [HA],
[A2], [OH]) cn phi gii h 5 phng trnh. V vy cn c tch s ion nc:
K H2O = H3 O+ OH

Tm phng trnh chnh xc tnh [H3O+] suy ra t 5 phng trnh nu trn rt phc tp
nhng c th thc hin php gn ng chnh xc tnh pH ca cc dung dch ca phn
ln cc mui loi NaHA. Gii ng thi cc phng trnh (11.6) v (11.7) ta c:
[H2A] = [A2] + [OH] [H3O+]
Thay th cc gi tr [H2A] v [A2] bng cc phng trnh biu din qua [HA] nh cc
phng trnh (11.4) v (11.5) vo cc phng trnh trn ta s thu c:
K H2O HA K 2 HA

+ OH H O+

K1 OH
H O

214

v v
K H2O
OH =

H O+
3

nn
H3 O+ HA K 2 HA

+ K H2O H O+
3

+
K1
H3 O
H3 O+

Sau khi nhn 2 v ca phng trnh vi [H3O+] v bin i:

HA

2
+ 1 = K HA + K
H3 O+
2
H2O

K1

v t ta tm c gi tr cn tm:
H3 O+ =

K1K 2 HA + K1K H2O

HA + K1

(11.8)

Trong phn ln trng hp, c th chp nhn:

[HA] CNaHA

(11.9)

v do c th chuyn phng trnh (11.8) thnh dng:

H3 O+ =

K1K 2CNaHA + K1K H2O

CNaHA + K1

(11.10)

Phng trnh (11.9) c ngha trong iu kin hai hng s cn bng K1 v K2 nh v nng
NaHA khng qu nh.
Thng CNaHA >> K1 v K1K H2O << K1K2CNaHA nn phng trnh (11.10) c rt gn:
H3 O+ K1K 2

(11.11)

Rt ng ch l, c mt khong nng m pH ca dung dch mui loi NaHA

khng ph thuc vo nng .
V d 1: Tnh nng ion hiro trong dung dch NaHCO3 0,100 M.

215

Trc ht ta cn kim tra nhng iu kin cn thit s dng phng trnh (11.11).
H2CO3 c K1=4,45.107 v K2=4,7.1011. R rng l, K1 nh hn CNaHA rt nhiu; K1K H2O =
4,45.1021 v K1K2CNaHA=2.1018. Do chng ta c th s dng phng trnh n gin
ha:
H3 O+ 4,45.107 4,7.10 11 = 4,6.10 9 mol / l

V d 2: Tnh nng ion hiro trong dung dch Na2HPO4 0,001 M.

gii bi tp trong trng hp ny cn s dng hp l cc hng s phn li, K2 =
6,34.108 v K3 = 4,2.1013 ca H3PO4. Xem xt nhng iu kin s dng phng trnh
(11.11) ta thy rng, K1 = 6,34.108 nh hn rt nhiu nng Na2HPO4, do c th n
gin ha mu s. Mt khc, khng th b qua i lng K 2K H2O khi so snh vi
K2K3 CNa2HPO4 bi v thnh phn th nht l 6.1022 v thnh phn th hai l 3.1023. Nh vy
ta phi s dng phng trnh (10.11) dng n gin ha mu s:
8
13
1,0.103 + 6,34.10 22
H3 O+ = 6,34.10 4,2.10
= 8,1.1010 mol / l
3

1,0.10

Khi s dng phng trnh (11.11) ta thu c kt qu:

[H3O+] = 1,6.1010 mol/l.
V d 3: Tnh nng ion hiro trong dung dch NaH2PO4 0,0100 M.
Trong trng hp ny, K1 = 7,11.103 v K2 = 6,34.108 ca H3PO4 l nhng hng s cn
thit. K1 v CNaH2PO4 l nhng i lng khng khc nhau nhiu nn mu s ca phng
trnh (10.11) khng th n gin ha c, nhng v K1K2 CNaH2PO4 >> K1K H2O nn t s ca
phng trnh c n gin ha n K1K2 CNaH2PO4 v tm c gi tr ca n s l:
3
8
2
H3 O+ = 7,11.10 6,34.10 1,0.10 = 1,6.105 mol / l

1,0.102 + 7,11.103

11.2.2 Dung dch a axit

S phn li ca iaxit H2A xy ra theo hai giai on:
H2A + H2O

H3O+ + HA

HA + H2O

H3O+ + A2

c m t bng cc hng s cn bng tng ng:

216

H3 O+ HA

K1 =
[H2 A ]

(11.12)

H3 O+ A 2

K2 =

HA

(11.13)

i vi dung dch axit H2A bit nng , phng trnh cn bng vt cht c th vit
di dng:
CH2 A = [H2 A ] + HA + A 2

(11.14)

v iu kin trung ho in:

[H3O+] [HA] + 2[A2] + [OH]

(11.15)

V dung dch l axit nn c th b qua s hng cui cng trong phng trnh (11.15).
Bn phng trnh i s c lp trn cho php tnh ton tt c cc gi tr ca cc n s:
[H3O+], [HA], [H2A], [A2]. Nhng nu t s K1/K2 ln th cn c kh nng n gin ha
tip theo, ngha l gi thit rng nhng ion hiro to thnh giai on phn li th nht ngn
cn s phn li giai on th hai n mc l c th b qua s phn li ny. Theo gi thit ,
[A2] trong cc phng trnh (11.14) v (11.15) s nh thua nhiu so vi [HA] v [H2A]. Nu
gi thit c thc hin, phng trnh (11.14) s tr thnh:
CH2 A [H2 A ] + HA

(11.16)

v phng trnh (11.15) c n gin n:

[H3O+] [HA]

(11.17)

Gii ng thi cc phng trnh (11.16), (11.17) v (11.12) s thu c:

2

H3 O+

= K1
CH2 A H3 O+

(11.18)

Phng trnh cui cng tng t phng trnh dn ra trc y, tnh nng ion
hiro trong dung dch n axit yu (chng 4) v cng ging nh trng hp c m t
trc y c th gii hon ton hoc gii theo cch n gin ha nu H3O+ << CH2 A .
S thch ng ca gi thit cho rng, s phn li giai on th hai ca H2A l tht s c
th b qua c minh chng bng cch thay th phng trnh (11.17) vo phng trnh K2
(11.13). Kt qu thu c: [A2] K2 c s dng so snh [A2] vi cc kt qu tnh ton

217

c i vi mi trng hp c th ca [H3O+] hoc [HA]. Trong trng hp tng qut, s

b qua phn li giai on hai ca H2A khi tnh ton nng ion hiro c th dn ti sai lm
ng k ch trong trng hp nu t s K1/K2 nh hoc dung dch axit qu long. Trong nhng
trng hp nh vy cn phi gii h t bn phng trnh.
V d 1: Tnh pH ca dung dch axit maleic 0,100 M.
Ta k hiu axit maleic l H2M v vit cc phng trnh phn li:
+

H2M

HM

H3O + HM

H3O + M

H3 O+ HM

= K = 1,20.102
1
[H2 M]

H3 O+ M2

= K = 5,96.107
2
HM

B qua s phn li ca H2M giai on 2 v s dng phng trnh (11.18) tnh [H3O+]
ta c:
2

H O+
3
= K1 = 1,20.102
+

0,100 H3O

Hng s phn li th nht ca axit maleic ln n mc l phi gii hon ton phng trnh
bc 2 tm [H3O+].
[H3O+]2 + 1,20.102[H3O+] 1,20.103 = 0
[H3O+] = 2,92.102 = [HM]
pH = log2,92.102 = 1,54
chng minh rng, s phn li ca axit maleic giai on 2 trong nhng iu kin
cho tht s c th b qua ta thay [H3O+] = [HM] vo phng trnh K2:
H3 O+ M2

= 5,96.107 ; M2 = 5,9.107

HM

Nh vy l, [M2] tht s nh thua nhiu so vi [HM] v gi thit a ra khng c th

dn ti sai s ng k trong tnh ton nng ion hiro.
V d 2: Tnh nng ion hiro trong dung dch H2SO4 0,0400 M.
Axit sunfuric phn li hon ton giai on th nht v ch phn li mt phn giai on th
hai. Nu b qua s phn li giai on th hai th nng ion hiro l:

218

[H3O+] = [ HSO4 ] = 0,0400 mol/l

Nhng tnh [ SO24 ] t phng trnh K2 trn c s gi thit ch r rng:
H3 O+ SO24

1,20.102

HSO4

R rng l khng th b qua gi tr [ SO24 ] khi so snh vi gi tr [ HSO4 ] nn i hi

phi gii chnh xc hn.
Nng ion hiro ca dung dch l do s phn li ca H2SO4 nn:
[H3O+] = 0,0400 + [ SO24 ]
[ SO24 ] = [H3O+] 0,0400
Do iu kin cn bng vt cht nn:
CH2SO4 = 0,0400 = [HSO4 ] + [SO42 ]

Hp nht v bin i hai phng trnh cui cng ta c:

[ HSO4 ] = 0,0800 [H3O+]
Thay cc gi tr [ SO24 ] v [ HSO4 ] vo phng trnh K2 s c phng trnh:

H3 O+ H3 O+ 0,0400

= 1,20.102
+

0,0800 H3 O

Sau khi bin i phng trnh s thu c:

[H3O+]2 0,0280[H3O+] 9,60.104 = 0
[H3O+] = 0,0480 mol/l

11.2.3 Dung dch a baz

Tnh ton pH ca dung dch a baz c thc hin tng t nh m t i vi dung
dch a axit.
V d: Tnh pH ca dung dch natri cacbonat 0,100 M.

219

Cn thit phi xem xt cc cn bng sau:

CO32

HCO3

HCO3

+ H2O

+ OH

+ H2O

H2CO3 + OH

HCO3 OH

= 2,13.104
CO32

[H2CO3 ] OH
HCO3

= 2,25.108

Nu do kt qu ca phn ng th nht, lng OH to thnh ngn cn s phn li

theo phng trnh th hai th [H2CO3] << [ HCO3 ] v [H2CO3] << [ CO32 ]. Do :
[HCO3] = [OH]
CO32 = CNa CO [OH ] CNa CO
2
3
2
3

Thay th nhng gi tr [ HCO3 ] v [ CO32 ] vo phng trnh K1 ta c:

[OH]2 = 2,13.104.1.101 = 2,13.105
[OH] = 4,62.103 mol/l
Gi thit a ra khng dn n sai s ng k trong tnh ton pH:

[H2CO3 ] OH
HCO3

= 2,25.108

S tht l, [H2CO3] << [ HCO3 ] v [ CO32 ]. C th ni rng, gi thit a ra

( CO32 CNa2CO3 ) mang li sai s nh hn 5%.

11.2.4 Dung dch m ca cc h axit yu v baz lin hp vi n

T a axit yu v mui ca n c th iu ch hai loi dung dch m:
1. Dung dch m ca h axit yu t do H2A v baz lin hp vi n NaHA.
2. Dung dch m ca h axit NaHA v baz lin hp vi n Na2A.
V hng s phn li ca HA nh hn hng s phn li ca H2A nn pH ca dung dch m
h NaHA v Na2A lun ln hn pH ca dung dch m h H2A v HA.

220

xc nh chnh xc nng ion hiro ca mt h m bt k, cn thit lp

s phng trnh tng ng. Nhng tnh ton ch cn s dng nhng cn bng chim u
th, v vy cn n gin ha nhng cn bng khng chim u th. V d nh, trong dung dch
m H2A v NaHA ch cn ch ti s phn li ca H2A giai on th nht, b qua giai
on th hai. Trong trng hp ny c th tnh ton nng ion hiro tng t nh dung
dch m ca n axit yu v baz lin hp vi n (chng 10). Ging nh trc y,
kim tra ng ca gi thit a ra cn tnh nng A2 v so snh vi [H2A] v [HA].
V d: Tnh nng ion hiro trong dung dch m ca axit phtaleic 0,100 M (H2P) v
kali biphtalat 0,200 M (KHP).
Cn bng c bn c ngha quyt nh trong dung dch l:
H2P + H2O

H3O+ + HP

H3 O+ HP

= K = 1,12.103
1
[H2P ]

B qua s phn li ca H2P giai on th hai ngha l gi thit rng:

[P2] << [HP] v [P2] << [H2P]
nn
[H2P] CH2P = 0,100
[HP] CKHP = 0,200
v do :
3
H3 O+ = 1,12.10 0,100 = 5,60.104 mol / l

0,200

Tnh [P2] c thc hin bng cch thay th [H3O+] v [HP] vo phng trnh K2. Kt
qu tnh ton ch r rng gi thit a ra l hon ton ng n.
i vi dung dch m c iu ch t NaHA v Na2A th cn bng c bn l s phn li
ca H2A giai on hai v phng trnh:
HA + H2O

H2A + OH

c b qua. Nu c th gi thit rng, nng H2A nh n mc khng ng k so vi

nng HA v A2 th c th tnh ton nng ion hiro ging nh i vi nhng dung dch
m n gin, ngha l s dng hng s phn li th hai ca H2A. kim tra ng n ca
gi thit a ra cn so snh nng H2A vi nng HA v A2.
V d: Tnh nng ion hiro trong dung dch m kali biphtalat (KHP) 0,0500 M v kali
phtalat (K2P) 0,150 M.

221

Phng trnh phn li ca axit phtaleic giai on hai:

HP + H2O

H3O + P

H3 O+ P2

= 3,91.106
K2 =
HP

Gi thit rng, [H2P] << [HP] v [H2P] << [P2], ta c

[HP] CKHP = 0,0500
[P2] C K 2 P = 0,150

T :
6
2
H3 O+ = 3,91.10 5.10 = 1,30.106 mol / l

1,5.101

kim tra ng n ca gi thit th nht ta tnh gi tr gn ng ca [H2P] bng cch

thay vo phng trnh K1 nhng gi tr bng s ca [H3O+] v [HP]:
1,3.106 0,0500
= 1,12.103
[H2P ]

Do gi thit a ra l hon ton c th ng dng c. Nng H2P nh thua rt

nhiu so vi nng HP v P2, v c th b qua phn ng phn li ca baz HP.
Khng phi trong tt c mi trng hp u c th chp nhn trong mt dung dch ch
tn ti mt cn bng duy nht. iu dn n nhng sai lm rt ng k trong tnh ton pH
ca nhng dung dch m bao gm nhng a axit nu nng axit v baz lin hp qu nh
hoc l hng s phn li ca axit giai on 1 v giai on 2 gn nhau v gi tr. Trong nhng
trng hp nh vy cn thit phi lao ng nng nhc hn tnh ton chnh xc hn.

11.3 ng chun a axit

ng chun a axit c dng phc tp hn so vi tt c cc ng chun cp
trc y. Nu nhng hng s phn li khc nhau ln th c th quan st thy mt s bc
nhy trn ng chun . C th s dng cc bc nhy trong thc t nu pH trong vng
bc nhy bin i t ngt.
Nhng bin php c s dng xy dng ng chun c m t trc y
u thch ng i vi h a axit iu kin t s K1/K2 cao hn 103 mt cht. Nu t s K1/K2
thp hn gi tr , sai s, c bit l trong vng im tng ng th nht cao hn nhiu
gi tr c th chp nhn c, do nhng tnh ton khi gii nhng cn bng cn thit phi
chnh xc hn.

222

lm v d, chng ta xem xt cch tnh nng ion hiro nhng thi im

khc nhau trong php chun axit maleic - mt axit hu c, kp, yu - c cng thc H2C4H2O2.
Ta k hiu axit t do l H2M v vit cn bng phn li ca axit theo hai giai on:
H2M + H2O

H3O+ + HM

K1 = 1,20.102

HM + H2O

H3O+ + M2

K2 = 5,96.107

V t s K1/K2 c gi tr ln (2.104) nn giai on u ca php chun c th b qua

s phn li ca H2M giai on 2, ngha l:
[M2] << [HM] v [M2] << [H2M]
C th ni rng, gi thit a ra trn y khng dn ti nhng sai s ng k trong gii
hn mt vi phn mi mililit trong vng im tng ng th nht. Sau im tng ng
th nht, cn bng chim u th l cn bng phn li ca axit maleic giai on 2 v khi c
th gi nh rng, phn ng phn li ca baz HM:
HM + H2O

OH + H2M

khng th hin nh hng ng k n pH ca dung dch. Nh vy l, trong cc tnh ton

ta chp nhn [H2M] << [HM] v [M2].
V d: Xy dng ng chun 25,00 ml dung dch axit maleic 0,100 M bng dung
dch NaOH 0,100 M.

Gi tr pH ca dung dch axit maleic 0,100 M trc khi bt u php chun c

tnh trc y (xem v d 1, mc 11.2.2, dung dch a axit); pH =1,54.
Tnh pH ca dung dch sau khi thm 5,00 ml dung dch NaOH. Sau khi thm dung dch
kim, axit maleic cha b chun H2M v baz lin hp vi n HM to thnh dung dch m.
B qua s phn li ca HM v tnh pH ging nh trng hp ca dung dch m to thnh t
n axit yu. Ta tm c nng H2M ( CH2M ) cha b chun v nng ca baz lin hp
HM (CNaHM).
CH2M =
CNaHM

25,00 0,100 5,00 1,00

= 6,67.102 M
30,00
5,00 1,00
=
= 1,67.102 M
30,00

Nh cc phng trnh (11.9) v (11.10) ta tm c:

[H2M] 6,67.102 M
[HM] 1,67.102 M

223

Thay th cc gi tr tm c vo phng trnh K1 ta c [H3O+] = 4,8.102 mol/l. Do ,

gi thit [H3O+] << CH2M hoc CHM u khng ng nn cn thit phi s dng nhng
phng trnh (11.7) v (11.8) chnh xc hn:
[H2M] 6,67.102 + [H3O+] [OH]
[HM] 1,67.102 [H3O+] + [OH]
V dung dch l axit nn gi thit cho rng [OH]rt nh l hon ton ng n. Thay th
cc gi tr [HM] v [H2M] trn vo phng trnh K1:

H3 O+ 1,67.102 + H3 O+

K1 =
= 1,2.102
2
+
6,67.10 H3O

Sau khi bin i ta c:

[H3O+]2 + 2,87.102[H3O+] 8,00.104 = 0
v t
[H3O+] = 1,74.102 mol/l;
pH = 1,76
Bng cch tng t c th tnh pH tt c cc im ca vng m th nht.
im tng ng th nht: im tng ng th nht:
HM 25,00 0,100 = 5,00.102

50,00

R rng l, c th n gin ha t s phng trnh (11.10). Mt khc, nng HM

khng khc nhiu gi tr K1 nn
H3 O+

K1K 2CHM
K1 + CHM

1,20.102 5,96.107 5,00.102

5,00.10

+ 1,20.10

= 7,60.105 mol / l

pH = 4,12
Vng m th hai: Tip tc thm kim vo, mt dung dch m mi s hnh thnh, bao
gm axit HM cha chun ht v baz M2 lin hp vi n. Nu baz thm vo n lng
b qua phn ng ca HM vi nc to thnh OH (mt vi phn mi mililit), pH ca
dung dch c th tnh ton d dng t K2. Chng ta tnh pH ca hn hp khi thm 25,50 ml
dung dch kim lm v d:

224
CNa2M

( 25,50 25,00 ) 0,100

50,50

0,050
50,50

v nng chung ca NaHM s bng:

CNaHM

25,00 0,100 ( 25,50 25,00 ) 0,100

50,50

2,45
50,50

Thay nng NaHM v M2 bng cc gi tr bng s tm c trn y vo phng trnh

K2:
H3 O+ 0,050

50,50
2,45
50,50

= K 2 = 5,96.107

[H3O+] = 2,92.105 mol/l

im tng ng th hai: sau khi thm 50,00 ml dung dch NaOH 0,100 M vo 25,00
ml dung dch H2M 0,100 M ta thu c dung dch Na2M 0,0333 M. Trong h ny, phn ng
ca M2 vi nc l cn bng chim u th nn ch cn ch n cn bng m thi. Nh
vy l:

M2 + H2O
Kb =

K H2O
K2

OH + HM
=

1,00.1014
5,96.107

[OH] = 2,36.105 mol/l

pH = 14,00 (log2,26.105) = 9,37

225

Hnh11.2
ng chun 25,00 ml dung dch axit maleic (H2M) 0,100 M

Tnh pH sau im tng ng th hai: Tip tc thm kim vo, s phn li ca M2 s b

cn tr, do pH ca dung dch c tnh theo lng kim d thm vo.

Hnh 11.3
Cc ng chun 25,00 ml cc a axit bng dung dch NaOH 0,100 M

226
1. Dung dch axit photphoric 0,100 M

227
2. Dung dch axit oxalic 0,100 M
3. Dung dch axit sunfuric 0,100 M

ng chun dung dch axit maleic 0,100 M bng dung dch kim NaOH 0,100 M
c dn ra trn hnh 11.2. ng chun c xy dng trn c s nhng tnh ton
trong v d trn y. Nhng bc nhy tng ng vi php chun proton th nht v th hai
c phn chia rt r rng. V nguyn tc, nu chn ng ch th s xc nh c hoc mt
hoc c hai bc nhy khi chun axit maleic. Vi quan im thc t, s dng bc nhy
th 2 thun tin hn bi v s bin i pH trong vng im tng ng th hai c th
hin chnh xc hn.
Trn hnh 11.3 dn ra nhng ng chun 3 a axit khc. Nhng ng chun ny
ch r rng, bc nhy tng ng vi im tng ng th nht c th hin r trn hnh
v ch c quan st thy trong trng hp nu cc hng s phn li K1 v K2 ca a axit khc
nhau ln.
Trong trng hp ca axit oxalic (ng s 2) t s K1/K2 bng khong 1000, do trong
vng im tng ng th nht, im un ca ng cong c quan st thy nhng bc
nhy nh ti mc thc t khng th xc nh c bng ch th. Kt qu l, xc nh chnh
xc oxalic ch c th s dng im tng ng th hai.
ng cong 1 l ng chun l thuyt ca axit photphoric, mt axit phn li 3 nc.
Trong trng hp ny t s K1/K2 bng khong 105, ln hn gn 100 ln so vi t s ca
axit oxalic, do trn ng chun , hai bc nhy c xc nh chnh xc v mi bc
nhy u hon ton thch ng cho mc ch phn tch. Nu dng ch th chuyn mu trong
vng axit cho php chun th 1 mol axit tiu tn 1 mol kim. Nu ch th i mu trong vng
kim th s tiu tn 2 mol kim cho 1 mol axit. Khng nn chun proton th 3 ca axit
photphoric bi v hng s phn li giai on qu nh (K3 = 4,2.1013). Hiu ng m ca giai
on phn li th 3 ca axit photphoric khng ln nhng theo dng ng cong 1 trn hnh
11.3 ta thy, d sao i na hiu ng cng gy nn s gim pH r rt hn sau im tng
ng th hai so vi cc ng chun ca axit 2 nc (ng cong 2 v 3) trn hnh 11.3.
Nh vy l, nhng bc nhy tch bit trn ng chun a axit ch c quan st
thy khi t s 2 hng s phn li khng nh hn 104. Nu t s hng s phn li nh hn gi tr
nu trn th s bin i pH trong vng im tng ng th nht s rt nh v bc nhy
khng nn s dng xc nh chnh xc. Trong trng hp ny cn c nh ha im tng
ng th hai.

11.4 ng chun a baz

Xy dng ng chun a baz, ni chung, tng t cch xy dng ng chun
a axit. Chng ta xem xt cch xy dng ng chun dung dch natri cacbonat bng dung
dch axit clohiric. Trong dung dch natri caconat trong nc nhng cn bng sau y c
thit lp:

228
CO32 + H2O

HCO3 + OH ;

( K b )1 =

HCO3 + H2O

H2CO3 + OH ;

( K b )2 =

K H2O

= 2,13.104

K H2O

= 2,25.108

( K a )2
( K a )1

Phn ng din t tng tc ca ion cacbonat vi nc quyt nh pH ban u ca dung

dch. pH ca dung dch c tnh theo phng php m t mc 11.2.3. Sau khi thm
nhng phn axit u tin, dung dch m c to thnh t baz cha b chun CO32 v axit
lin hp HCO3 . Nng ion hiroxyl c tnh t phng trnh (Kb)1 hoc nng ion
hiro c tnh t phng trnh (Ka)2. im tng ng th nht, natri bicacbonat l hp
cht ch yu nn nng ion hiro trong dung dch c xc nh bng phng trnh (11.11).
Tip tc thm axit, dn ti s hnh thnh dung dch m mi t bicacbonat v axit cacbonic.
Nng ion hiroxyl tng ng c tm thy t phng trnh (Kb)2 hoc nng ion hiro
tng ng c tm thy t phng trnh (Ka)1. im tng ng th 2, dung dch bao
gm axit cacbonic v natri clorua. Nng ion hiro c tnh ton theo phng php thng
thng, ging nh trng hp cc n axit yu, s dng (Ka)1. Cui cng, nu thm d axit
clohiric, s phn li ca axit yu b cn tr ti mc, nng ion hiro thc t do nng axit
clohiric quyt nh. Trn hnh 11.4 dn ra ng chun dung dch natri cacbonat. Trn
ng cong xut hin 2 bc nhy, bc nhy th hai th hin chnh xc hn. iu c
ngha l, c th dng phng php chun axit - baz xc nh cacbonat v bicacbonat
khi chng cng tn ti. Php chun theo phenolphtalein cho php nh lng s mmol
cacbonat. Nu chun n i mu bromcrezol lc, lng axit tiu tn tng gp 2 ln (lng
milimol cacbonat cng vi s milimol ca bicacbonat trong dung dch b chun).

Hnh 11.4
ng chun 25,00 ml dung dch natri cacbonat 0,100 M bng dung dch axit clohiric 0,100 M

229

11.5 ng chun cht in li lng tnh

Nh ni trc y, trong cc dung mi thch hp, nhng cht in li lng tnh c kh
nng th hin c tnh cht axit yu v c tnh cht baz yu. Ty thuc vo iu kin c th
m tnh axit hoc tnh baz th hin mnh hn. C th chun dung dch cht in li lng
tnh bng baz mnh hoc axit mnh, v d nh trong dung dch ihirophotphat trong nc,
cc cn bng sau y c thit lp:
H2PO4 + H2O

H3O+ + HPO24

K2 = 6,34.108

H2PO4 + H2O

OH + H3PO4

Kb =

K H2O
K1

= 1,14.1012

Kb qu nh nn khng th chun bng axit, ngc li K2 ln v do c th chun

thnh cng H2PO4 bng dung dch kim chun. Trong dung dch natri hirophotphat, phn
ng xy ra:
HPO24 + H2O

H3O+ + PO34 ;

K3 = 4,2.1013

nn khng th chun bng kim, nhng mt khc:

HPO24 + H2O

OH + H2PO4 ;

Kb =

K H2O
K2

= 1,58.107

nn c th chun HPO24 bng dung dch axit clohiric chun.

Cc amino axit n gin nht thuc loi cc cht in li lng tnh quan trng. Tnh cht
axit - baz ca chng l do trong phn t c c nhm chc axit v nhm chc baz. Trong
dung dch nc ca aminoaxit in hnh, v d glyxerin, ba cn bng quan trng sau y c
thit lp.
H2NCH2COOH

H3+NCH2COO

(11.19)

H3+NCH2COO + H2O

H2NCH2COO + H3O+ ; Ka = 2.1010

(11.20)

H3+NCH2COO + H2O

H3+NCH2COOH + OH ; Kb = 2.1012

(11.21)

Phng trnh u tin l mt bin dng ca phn ng axit - baz - phn ng axit - baz ni
phn - v v thc cht tng t phn ng ca axit cacboxilic vi cc amin:
R1NH2 + R2COOH

R1NH3+ + R2COO

(11.22)

Hng s ion ha ca nhng amin bo in hnh c c trng bng nhng i lng trong
khong 104 105. Hng s phn li ca phn ln axit cacboxilic cng nm trong khong . Do
, nhng cn bng (11.19) v (11.22) thc t chuyn dch v bn phi.

230

Cc ht amino axit mang ng thi c in tch dng v in tch m

(phng trnh 11.19) c gi l cc ion lng cc. T gi tr cc hng s cn bng (11.20)
v (11.21) th tnh cht axit ca ion lng cc glixin th hin mnh hn tnh baz v do
dung dch glixin c phn ng axit yu.
Khc vi cc ion ch c in tch dng hoc m, ion lng cc amino axit mang ng
thi c in tch dng v in tch m nn khng in chuyn ti c catt v ant trong in
trng. pH ca dung mi c nng dng anion v cation bng nhau, s in chuyn ca
amino axit trong in trng khng quan st thy. Gi tr pH c gi l im ng in
v l c tnh quan trng ca amino axit. C th d dng tm c im ng in khi bit
hng s phn li. V d nh i vi glixin:
H3 O+ H2NCH2COO

=K ;
a
+

H3 NCH2COO

OH H3+ NCH2COOH

=K
b
+

H3 NCH2COO

im ng in:
[H2NCH2COO] = [H3+NCH2COOH]
Chia Ka cho Kb ta thu c:
H3 O+

= Ka
OH K b

Sau khi thay [OH] bng

H3 O+ =

K H2O
H3 O+

v bin i:

K a K H2O
Kb

i vi glixin, im ng in nm pH = 6,0:
10
H3 O+ = 2.10
1.1014 = 1.106
12

2.10

Nhng gi tr Ka v Kb ca nhng amino axit n gin thng nh ti mc khng th xc

nh trc tip bng phng php chun axit - baz. Khi thm focmalehit vo h s xy ra
phn ng phong to nhm chc baz do c th chun sn phm bng dung dch baz
chun. V d nh, trong trng hp glixin:

231

H3+NCH2COO + CH2O

CH2=NCH2COOH + H2O

ng chun sn phm phn ng c dng c trng cho cc axit cacboxilic in hnh.

11.6 Thnh phn ca dung dch a axit l hm s ca pH

c th hnh dung mt cch r rng hn v s bin i thnh phn ca dung dch xy ra
trong qu trnh chun a axit, cch biu din lng tng i ca phn t axit t do v tt
c cc dng anion ca n di dng hm s ca pH l rt c ch. lm vic cn nh
ngha i lng i vi mi ht trng thi cn bng xut pht t nng chung ban u
ca a axit. V d, nng chung ban u ca axit maleic l CH2M . Khi , cn bng vt cht
s l:

CH2M = [H2M] + [HM ] + [M ]

v theo nh ngha:
o

[H M ]
= 2 ;
CH2M

HM
M2

=
; 2 =
CH2M
CH2M

R rng l, tng ca tt c cc gi tr i vi mt h bt k cn phi bng n v:

o + 1 + 2 = 1

Chng ta c th din t o, 1 v 2 qua [H3O+], K1, K2. Bin i cc phng trnh hng
s phn li ta c:
K H M
K K H M
HM = 1 [ 2 ] ; M2 = 1 2 [ 2 ]
2

[H3 O+ ]
H3 O+

Sau khi thay th cc gi tr [HM] v [M2] tm c trn y, phng trnh cn bng

vt cht c dng:
CH2M = [H2 M] +

K1 [H2 M]
+

K1K 2 [H2 M]

[H3 O ]

H3 O+

v sau khi bin i:

[H2 M] =

CH2M H3 O+

H3 O+ + K1 H3 O+ + K1K 2

232

Thay gi tr [H2M] va tm c vo phng trnh o ta c :

o =

H3O+

H3 O+ + K1 H3 O+ + K1K 2

(11.23)

Bng cch tng t, c th tm c nhng gi tr khc :

1 =

2 =

K1 H3 O+

H3 O+ + K1 H3 O+ + K1K 2

K 1K 2
+ 2

H3 O
+ K1 H3O+ + K1K 2

(11.24)

(11.25)

Chng ta nhn thy rng, mu s trong tt c cc phng trnh l ng nht v nh vy

l, s tnh ton gi tr gi tr pH xc nh khng phi l cng vic phc tp. Ngoi ra, t
phng trnh (11.23) n (11.25) cn thy r, lng tng i ca mi dng bt k gi tr
pH c nh no cng khng ph thuc vo nng chung ca axit ( CH2M ).

Hnh 11.5
Thnh phn ca dung dch axit maleic (H2M) bin i theo pH

233

Ba ng cong biu din trn hnh 11.5 minh ha s bin i cc gi tr ca tt c cc

ht trng thi cn bng xut pht t axit maleic ph thuc vo pH. i chiu cc ng
cong vi ng chun axit maleic (hnh 11.2) ta s c hnh nh trc quan v s bin i
nng ca tt c cc dng ca H2M trong qu trnh chun . V d, t hnh 11.2, pH ca
dung dch axit maleic trc khi bt u chun phi bng 1,5. Theo hnh 11.5, gi tr pH
o khong 0,7, cn 1 ca HM bng khong 0,3. Do 2 thc t bng khng. Nh vy
l, pH 1,5 khong 70% axit maleic tn ti dng khng phn li cn 30% tn ti dng
HM. Theo mc thm kim vo, pH ca dung dch tng ln, im tng ng th nht
(pH = 4,12) ton b axit maleic tn ti dng HM (11). Khi thm tip tc kim vo, hp
phn HM gim xung v hp phn M2 tng ln. Hon ton r rng l, im t ti im
tng ng th hai (pH = 9,37) thc t ton b lng axit maleic chuyn thnh baz M2.

234

Chng 12
Chun Axit Baz trong mi trng khng nc

chng 10 chng ta bit khng th chun c nhng axit hoc baz c hng s
phn li nh hn 1.108 bi v phn ng xy ra khng hon ton v rt kh xc nh im cui.
Nhng c th chun nhiu hp cht trong s nhng hp cht k trn trong dung mi khng
nc, bi v cc dung mi ny c kh nng lm tng tnh axit hoc tnh baz ca cc hp cht
. Nhng dung mi khng nc c s dng thnh cng chun nhiu cht kh tan
trong nc.
ng tic l nhng d kin nh lng cn thit xy dng ng chun trong dung
mi khng nc thng khng c hoc khng , do ch c th nh gi chun mt
cch nh tnh.

12.1 Dung mi chun khng nc

C th chia dung mi theo tnh cht ca chng thnh 3 loi:
Dung mi lng tnh: dung mi lng tnh l nhng dung mi c c tnh axit v tnh
baz, t ion ha hoc proton phn. Mc d nc l dung mi lng tnh in hnh nht, nhiu
hp cht khc cng th hin tnh cht tng t thng qua cc phn ng.

2H2O

H3O+ + OH

2C2H5OH

C2H5 OH2+ + C2H5O

2HOAx
2NH3

H2OAx+ + OAx
NH4+ + NH2

hoc l di dng tng qut:

2SH

SH2+ + S

y SH l phn t dung mi lng tnh, SH2+ l proton solvat ha; S l baz.

235

Trong bng 12.1 dn ra nhng gi tr hng s proton phn ca mt s dung mi ph bin

nht.
o

Bng 12.1 Hng s proton phn ca mt s dung mi thng dng nht 25 C

Dung mi

KS

Hng s in mi

Nc

1,01.1014

78,5

Metanol

2.1017

32,6

Etanol

8.1020

24,3

Axit focmic

6.107

58,5

Axit sunfuric

1,4.104

>84

Axit axetic

3,6.1015

6,2

Amoniac (50oC)

1.1033

22

Etileniamin

5.1016

14,2

Khc vi nc v ru, mt s dung mi lng tnh nh axit axetic, sunfuric, focmic th

hin tnh cht axit r rng hn tnh baz nhiu v ngc li, nhng dung mi nh amoniac
hoc ietyliamin li c tnh baz mnh hn tnh axit.
Dung mi aproton hoc dung mi tr: Nhng dung mi ny khng th hin tnh axit
hoc tnh baz v khng proton phn mc ng k. Benzen, tetraclorua cacbon, pentan
thuc loi dung mi ny.
Cui cng cn c mt dy dung mi nh xeton, ete, este v nhng dn xut ca pyriin.
Nhng dung mi ny c tnh baz v khng biu l tnh axit, chng khng c xu hng
proton phn.

12.1.1 Phn ng axit - baz trong dung mi lng tnh

Thay th dung mi thng c nh hng su sc n hon ton ca phn ng axit baz. Trong mc ny, chng ta s xem xt nh hng ca dung mi lng tnh n hon
ton ca phn ng axit - baz.
hon ton ca phn ng axit - baz: c th hnh dung phn ng xy ra khi chun
baz yu B bng dung dch chun axit mnh trong nc dng:

B + H3O+

BH+ + H2O

(12.1)

236

v hon ton ca phn ng xy ra c th c c trng bng gi tr ca

hng s cn bng:
K cb

BH+
= Kb
=
[B] H3O+ K H2O

(12.2)

R rng l, hng s cn bng ca phn ng trn bng t s hng s phn li baz B v tch
s ion ca nc.
Mt cch tng t, hon ton ca phn ng gia axit yu HA v baz mnh c th
c biu din bng hng s cn bng:
K cb

A
Ka

=
=

[HA ] OH K H2O

(12.3)

C th dn ra nhng t s tng t cho nhng phn ng trong dung mi khng nc. V

d, nu chun baz yu B bng axit mnh trong axit focmic khng nc, chng ta c th
vit:
B + HCOOH2+

BH+ + HCOOH

(12.4)

y HCOOH2+ l proton solvat ha, tng t nh H3O+ trong dung dch nc. Hng s
cn bng ca phn ng :
K cb =

BH+

[B] HCOOH2+

K 'b
KS

(12.5)

y K 'b l hng s phn li baz B trong axit focmic, ngha l:

B + HCOOH

BH+ HCOO

K 'b =
[B ]

BH+ + HCOO;

(12.6)

Cn KS l hng s proton phn ca axit focmic:

2HCOOH

HCOOH2+ + HCOO ;

KS = [ HCOOH2+ ][HCOO]

(12.7)

V nng ca dung mi HCOOH thc t khng bin i nn i lng , ging nh

trong trng hp tch s ion nc, c bao hm trong KS.
Chun axit yu HA bng natri etilat trong etanol, c th d dng hnh dung dng:
HA + C2H5O

A + C2H5OH

(12.8)

237

y dung dch natri etilat C2H5ONa trong etanol c dng lm dung dch chun baz
mnh. Ging nh trong cc v d trn y, hon ton ca phn ng c th c c trng
bng hng s cn bng:
K cb

A
K'

=
= a
[HA ] C2H5O+ K S

(12.9)

y K 'a l hng s phn li ca axit HA trong etanol:

C2H5OH2+

HA + C2H5OH

A C2H5 OH2+

=
[HA ]

(12.10)

KS = [ C2H5OH2+ ][C2H5O]

(12.11)

K 'a

+A ;

v KS l hng s proton phn ca etanol:

2C2H5OH

C2H5 OH2+ + C2H5O ;

Nhng v d ch r rng, hon ton ca phn ng ph thuc c vo hng s phn li

ca cht b chun, c vo hng s proton phn ca dung mi. S c mt ca c hai hng s
phn li trong phng trnh chc chn s lm d hiu hn nu xem mi phn ng axit - baz
nh cuc chy ua ginh proton. V d nh, chiu su ca s xy ra phn ng (12.4) ph
thuc vo vic, nhng phn t dung mi HCOOH chy ua vi nhng phn t baz B
ginh ly nhng ion hiro H+ thnh cng n mc no m chng ta bit rng s ion li b
hn ch do s hp thc ca phn ng. Hng s phn li KS v K 'b quyt nh hiu qu ca mi
hp phn trong cuc cnh tranh . Mt cch tng t, c th hnh dung phn ng (12.8) nh
cuc chy ua ginh ion H+ gia cc anion A v C2H5O m ginh thng li thuc v ion no
trong chng l do cc i lng K 'a v KS quyt nh.
T nhng bn lun trn y, r rng l nhng php chun axit - baz trong cc dung
mi c hng s proton phn thp chim u th. Ngoi ra, nhng phn ng axit - baz s xy
ra hon ton hn trong cc dung mi c gi tr K 'a v K 'b ln. Hai iu kin gii trn y
khng phi l hon ton c lp vi nhau v cng khng th c on quyt nh s la
chn dung mi lng tnh cho php chun khng nc.
nh hng ca cng axit hoc cng baz ca dung mi ln tnh cht ca cht
tan: Hng lot nhng dung mi lng tnh nh axit focmic, axetic, sunfuric d dng cho
proton hn l lin kt proton v do c xem nh nhng dung mi axit. Trong nhng
dung mi nh th, tnh baz ca cht tan c tng ln ng thi tnh axit gim xung. V
d nh, khng nn chun anilin C6H5NH2 trong dung dch nc bi v hng s baz ca
n khong 1010 nhng trong axit axetic bng, alinin l baz mnh hn nhiu bi v kh
nng tng tc vi dung mi ca n c tng cng. V d: hng s cn bng Kb ca
phn ng:

C6H5NH2 + HOAx

C6 H5 NH3+ + OAx

238

cao hn kh nhiu so vi Kb ca phn ng tng t trong nc.

C6H5NH2 + H2O

C6H5NH3+ + OH

Trong khi , nhng dung mi axit li c kh nng lm tng cng baz, cn i vi

axit chng biu l tc dng ngc li, ngha l lm gim cng ca chng. Axit clohiric
l axit mnh trong nc nhng ch phn li mt phn trong axit axetic bng. Nhng axit l yu
trong nc, trong dung mi axit cn tr thnh yu hn.
Nhng dung mi nh etileniamin, amoniac lng c i lc mnh vi proton v do l
nhng dung mi baz. Trong mi trng ca chng, nhng tnh cht axit ca cht tan c
tng cng. V d, phenol c hng s phn li trong nc khong 1010 tr thnh axit
mnh trong etileniamin v c th chun c bng dung dch kim chun. Cng
baz trong cc dung mi loi th ngc li, b gim xung.
Nc v ru no mch thng nh metanol v etanol c dng lm v d cho nhng dung
mi lng tnh trung tnh. Nhng dung mi ny c kh nng cho v nhn proton km nht so vi
nhng dung mi cng loi xt trn. Nhng iu quan trng cn nh l, iu khng c
ngha l tnh axit v tnh baz ca chng chnh xc bng nhau.
nh hng ca hng s in mi ln tnh cht ca cht tan: Hng s in mi c trng
cho kh nng tch cc ht mang in tch tri du. Trong dung mi c hng s in mi cao,
v d trong nc ( DH2O = 78,5 ), ch i hi cng ti thiu tch cc ion mang in tch

dng v m, cn i vi cc dung mi c hng s in mi thp, v d axit axetic (DHOAx =

6,2), mun thc hin qu trnh tch cn tiu ph nng lng ln. Metanol v etanol c hng s
in mi tng ng l 33 v 24, theo tnh cht ca mnh chng chim v tr trung gian. Gi tr
hng s in mi ca mt s dung mi c dn ra bng 12.1.
Hng s in mi ca dung mi c th hin nh hng ln n cng axit hoc
baz ha tan, bi v do kt qu ca qu trnh phn li, nhng ion tch in tri du c to
thnh. V d nh, nu axit yu khng tch in HA ha tan trong dung mi lng tnh SH, qu
trnh phn li i hi sinh ra nhng ht tch in.
HA + SH

SH2+ + A

Mt qu trnh tng t cng c quan st thy khi ha tan baz khng tch in B:
B + SH

BH+ + S

Do , c th hy vng rng, trong cc dung mi nh vy, ging nh trong nc, nhng

phn ng tng t s chuyn dch v bn phi mc ln hn so vi trong cc dung mi
nh metanol v etanol, bi v xy ra phn ng phn li ch i hi mt cng nh. Hiu ng
c th rt d nhn thy; v d nh, hng s phn li ca axit axetic trong nc khong 105,
cn trong etanol nh hn, khong 1010. Cng ca nhng axit tng t khc cng gim
xung nh vy.

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Nu phn ng phn li khng bao hm giai on sinh ra in tch th cng axit hoc
baz t ph thuc vo hng s in mi ca dung mi. V d, s bin i hng s in mi
ca dung mi SH s khng nh hng n cn bng:
BH+ + SH

SH2+ + B

A + SH

HA + S

La chn dung mi lng tnh chun axit - baz: hon ton ca phn ng axit baz t l thun vi gi tr hng s phn li ca axit hoc baz ha tan v t l ngc vi hng
s proton phn ca dung mi. Ngoi ra, hng s phn li ph thuc vo tnh axit hoc tnh baz
v hng s in mi ca dung mi. Nh vy l, la chn thnh cng dung mi cho mt
php chun cn ch 3 yu t c lp.

1. Hng s proton phn ca dung mi. Sao cho i lng ny cng nh cng tt.
2. Tnh cht axit - baz ca dung mi. chun baz yu, dung mi c tnh cht cho
proton (ngha l dung mi axit) l thch hp. chun axit yu cn chn dung mi c tnh
cht nhn proton tt.
3. Hng s in mi ca dung mi. Tt nht l s dng dung mi c hng s in mi
cao.
Ngoi ra, dung mi la chn phi ha tan tt cht cn phn tch.
chun baz rt yu, nn chn axit axetic bng lm dung mi, bi v axit ny c kh
nng cho proton v lm tng cng baz ha tan. Hng s proton phn ca axit cng cn
thch hp (3,6.1015), thp hn ca nc mt cht. Nhng c lp vi nhng u th trn, axit
axetic li c hng s in mi thp. Hai u im quan trng hn mt nhc im nn axit
axetic l dung mi tt nht chun baz yu; nhng khi chun axit yu, axit axetic li
thua nc bi v c tnh cht nhn proton yu hn.
Xem xt kh nng s dng axit focmic lm dung mi axit. Tng t nh dung mi axit
axetic, nhng axit focmic c kh nng cho proton mnh hn nc. Ngoi ra, khc vi axit
axetic, axit focmic c hng s in mi gn vi nc. Phn xt theo hai tnh cht th axit
focmic dng nh s l dung mi l tng cho chun baz yu. Nhng ng tic l, hng
s proton phn ca axit focmic li ln hn nhiu so vi nc hoc axit axetic. Do , mc d
c hai phm cht rt tt, axit focmic ch c u th cc tiu so vi nc.
Metanol v etanol c s dng rng ri lm dung mi chun axit - baz. C hai
thuc loi dung mi trung tnh bi v theo tnh cht cho nhn proton, chng rt gn vi nc.
u th ca chng so vi nc l tnh cht, chng u c hng s proton phn thp hn.
Nhng hng s in mi thp ca c hai dung mi ny lm mt i u th ni trn ca
chng. V d, hng s phn li ca phn ln nhng axit khng mang in tch, nh axit
benzoic, trong etanol gim xung hu nh 106 ln so vi trong nc, nhng hng s proton
phn li hu nh bng s ln nh vy (8.106) thp hn so vi nc. Do t s K 'a /KS i vi
etanol ch cao ln khng ng k so vi nc nn u th trong xc nh im cui khi s dng

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dung mi rt khim tn. Ngc li, php chun axit tch in, nh ion amoni,
trong etanol li mang li ch ln. Trong trng hp ny, trong qu trnh phn li khng xy ra
giai on phn chia in tch.
NH4+ + C2H5OH

NH3 + C2H5OH2+

Khc vi s phn li ca axit benzoic, s phn li ca NH4+ trong etanol gim xung khng
ng k. Phn ng ca NH4+ vi baz mnh trong etanol xy ra hon ton hn so vi trong
nc bi v hng s proton phn ca etanol thp hn so vi nc. Do , php chun NH4+
trong etanol c ngha.
V d sau y s minh ha iu : Tnh phn trm NH4+ khng b chun im
tng ng khi chun dung dch NH4+ 0,20 M.
1. Bng dung dch NaOH 0,20 M trong nc.
2. Bng dung dch C2H5ONa trong etanol tuyt i.
Hng s proton phn ca nc bng 1.1014, ca etanol tuyt i l 8.1020; hng s phn
li ca NH4+ bng 6.1010 trong nc v 1.1010 trong etanol tuyt i.
Khi chun trong nc xy ra phn ng:
NH4+ + OH

NH3 + H2O

c c trng bng hng s cn bng:

K cb =

[NH3 ]
NH4+ OH

Ka
6.1010
=
= 6.104
K H2O 1.1014

Mt cch tng t, khi chun trong etanol:

NH4+ + C2H5O

K cb =

NH3 + C2H5OH

[NH3 ]
NH4+ C2H5 O

K a'
1.1010
=
= 1,2.109
K S 8.1020

Trong c hai trng hp, im tng ng, nng chung ca NH3 s l 0,10 M. Khi
chun trong nc:
[ NH4+ ] = [OH]

; [NH3] =0,10 [ NH4+ ]

Khi chun trong etanol:

241

[ NH4+ ] = [C2H5O] ; [NH3] = 0,10 [ NH4+ ]

Nu gi thit rng, im tng ng, trong c hai trng hp [ NH4+ ] << [NH3] ta c:
1.

2.

0,10

OH

6.104 ; OH = NH4+ = 1.103 mol / l

1,2.109 ; OH = NH4+ = 9.106 mol / l

0,10
OH

Nh vy l, khi chun trong dung dch nc, im tng ng cn li khong 1%

cha phn ng, cn trong etanol tuyt i, ch cn khong 0,01% NH4+ cha phn ng.

NH4+

chun nhng axit rt yu, mt s dung mi lng tnh c

Etileniamin, H2NCH2CH2NH2, c nhng tnh cht c bn, biu l r nt nht
coi l dung mi lng tnh tt nht lm tng cng axit ca cht tan. Hng
phn ca etileniamin khong 5.1016. imetylfocmamit HCON(CH3)2 l mt
hn etileniamin, c hng s in mi bng 27 cng c s dng thnh cng.

s dng.
nn c
s proton
baz yu

12.1.2 Phn ng axit - baz trong dung mi aproton v dung mi hn hp

Nhng dung mi khng lng tnh c u th l khng chy ua ginh proton vi cc cht
tham gia chun ; ni cch khc l, hng s proton phn ca nhng dung mi ny tin dn
ti khng. Do , khi chun trong nhng dung mi ny c th t ti hon ton ca
phn ng ln.
Nhng cht v c c tan gii hn trong cc dung mi aproton, do ngi ta
nghin cu s dng nhiu hn hp gia dung mi aproton vi cc dung mi phn cc hn. C
th dn ra hn hp benzen-metanol v etilenglicol-hirocacbon lm v d. Nhng ng tic l
nhng kin thc c bn v tnh cht v v tng tc ca axit v baz trong cc h nh vy
cn thiu v ngho nn. Do , vn s dng cc dung mi hn hp trong cc trng hp
c th c gii quyt ch bng thc nghim.

12.1.3 Pht hin im cui khi chun trong dung mi hn hp

Phng php ph bin nht pht hin im cui khi chun trong dung mi khng
nc l o th ca in cc thy tinh nh hm s ca nng proton solvat ha. in cc
thy tinh s c bn chi tit trong gio trnh phng php phn tch cng c. Nhiu ch th
c ng dng khi chun trong cc dung mi nc cng thch hp trong dung mi khng
nc. Tt nhin l khng th s dng tnh cht ca ch th trong mi trng nc d on
tnh cht ca n trong dung mi khng nc. S hn ch trong thng bo v tnh cht ca ch

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th trong dung mi khng nc dn ti vic la chn ch th, trong a s trng

hp, c thc hin mt cch thc nghim.

12.2 ng dng phng php chun trong dung mi khng nc

Chun axit - baz trong dung mi khng nc c ng dng gii quyt nhiu vn .
Trong cc mc tip theo ca chng ny s bn lun ti nhng kh nng .

12.2.1 Chun trong axit axetic bng

Nhiu baz qu yu, khng th chun trong nc nhng c th chun d dng
trong axit axetic bng. Trong dung mi ny, dung dch axit pecloric chun l axit mnh hn
axit clohiric v axit sunfuric c dng lm cht chun. Trong axit axetic bng, natri axetat
l baz mnh gn nh bng natri hiroxit trong nc. Do , khi cn thit c th dng dung
dch natri axetat chun chun ngc.
H s dn n ca cc dung dch trong axit axetic bng: Ging nh phn ln cc dung
mi hu c, axit axetic c h s dn n cao hn ng k so vi nc (0,11% trn 1oC so vi
0,025% trn 1oC ca nc). Do , cn c bit ch loi b sai s do s tng nhit khi
o th tch. Trong thc t, ngi ta thng phi ghi nh nhit dung dch axit pecloric trong
thi gian chun ha, ghi chp nhit trong thi gian chun bng thuc th nu trn v
thc hin php o th tch nhit chun ha tng ng vi phng trnh:

Vhc =V[1 + 0,0011(Tch T)]

(12.12)

y Tch l nhit ca thuc th trong thi gian chun ha, T l nhit trong thi
gian hon thnh php phn tch, V l th tch thuc th, Vhc l th tch thuc th c hiu
chun.
nh hng ca nc: Trong axit axetic, nc x s nh l baz yu v tham gia cuc
cnh tranh dnh proton vi dung mi. Do , s c mt ca nc lm cho s bin i pH
gn im tng ng km t ngt, gy kh khn cho vic xc nh im cui trong chun
axit - baz. Lng nc cho php ph thuc vo dng chun . Khi chun axit rt yu
i hi phi thc t hon ton khng c nc. Ngc li, khi chun baz tng i mnh
trong dung mi ang bn, hm lng nc c mt thm ch ln ti 3% (theo th tch) cng
khng gy cn tr.

Trong thc t, c th iu ch axit axetic bng cch s dng anhirit axetic. Nc c

trong dung mi phn ng vi anhirit axetic to thnh axit axetic. Lng d anhirit axetic
phi c tch ra bi v n c th cn tr php chun .
Pht hin im cui khi chun trong axit axetic: Tm tinh th v metyl tm l hai ch
th axit - baz thch hp cho php chun trong axit axetic. C hai ch th ny c s chuyn
mu phc tp. V d nh mu ca metyl tm, theo mc axit ha, mu ca dung dch bin
i t tm qua lc n vng. S mt mu tm ch r rng, t ti im tng ng. Mu

243

ca metyl tm bin i khng tht r rng nh mong mun, nhng khi chun baz
mnh, sai s c h thp. Khi chun nhng baz rt yu, xc nh im cui bng mt
khng chnh xc, cn xc nh bng phng php in th vi in cc thy tinh (xem
phng php phn tch cng c).
Tiu chun ha dung dch axit pecloric: tiu chun ha dung dch axit pecloric trong
axit axetic, kalibiphtalat thng c dng lm cht chun gc. Cn ch l,
kalihirobiphtalat trong axit axetic l mt baz mnh, do c th s dng n tiu
chun ha dung dch axit. Phn ng xy ra to thnh axit t phn li.
ng dng php chun trong axit axetic: S dng axit axetic khng nc lm dung
mi cho php chun nhiu hp cht v c v hu c khng th chun c trong dung
mi nc. V d, bng cch chun trong axit axetic bng c th xc nh nhng mui natri
nh clorua, bromua, ioua, nitrat, peclorat v sunfat. Dung dch axit pecloric chun trong axit
axetic bng hoc trong ioxan khng nc c dng lm cht chun. Trong dung mi ny
cng c th xc nh cc mui amoni v cc mui kim loi kim ca phn ln cc axit
cacboxilic, v d nh amoni benzoat, natri salixilat, natri axetat, kali tactrat, natri xitrat.
ng 1 trn hnh 12.1 l ng cong in hnh tng ng vi php chun dung dch natri
axetat trong axit axetic khng nc bng dung dch axit pecloric cng trong dung mi .
so snh, ng chun l thuyt (ng 2) dung dch natri axetat bng dung dch axit
pecloric cng nng vi ng 1 nhng trong nc cng c dn ra trn hnh 12.1.

Hnh 12.1
Hai ng chun dung dch natri axetat 0,075 M bng dung dch HClO4 0,100 M

1. ng chun thc nghim (cht b chun v cht chun u trong axit axetic khng
nc).
2. ng chun l thuyt ca dung dch natri axetat bng dung dch HClO4 u trong
nc.

244

Axit axetic khng nc l dung mi c bit thch hp cho chun cc cht

hu c c nhm chc amino hoc amid. Khc vi nc, dung mi ny thch hp cho chun
trc tip phn ln cc amino axit bng cc dung dch axit chun. Nh nhn xt trong
chng 11, cc amino axit tn ti ch yu dng ion lng cc l axit hoc baz khng
mnh c th chun . Nhng trong axit axetic bng, s phn li ca nhm cacboxilic thc
t hon ton b cn tr nn c th chun nhm amino bng axit pecloric.
Trong nhiu v d dn ra trn y, dung dch natri axetat trong axit axetic c s
dng lm dung dch chun trong chun ngc.

12.2.2 Chun trong dung mi baz

xc nh cc baz qu yu i vi php chun trong nc, ngi ta s dng mt
s dung mi baz. Etileniamin, pyriin, imetylfocmamit, axeton, metylisobutylxeton,
axetonitryl v hn hp etilenglycol v ru isopropilic (1 : 1) c dng lm cc dung mi
loi . Mt s baz mnh ha tan trong cc dung mi c dng lm dung dch chun.
Dung dch natri metilat trong hn hp benzen-metanol c chn lm dung dch chun
chun axit yu. C th xc nh mt s phenol v c nhng axit cacboxilic yu nht bng
dung dch natri aminoetilat trong etileniamin. C th dng cc dung dch baz mnh nh
hiroxit tetrabutylamoni (C4H9)4NOH trong hn hp benzen-metanol, isopropanol, hoc
etanol lm dung dch baz chun thch hp cho chun khng nc.
Trong cc dung mi baz c th d dng xc nh phn ln cc axit cacboxilic cng nh
nhiu phenol. Khi chun mt s mui ca cc baz yu, v d nh, mui amoni, mui ca
cc amin bo v thm trong etileniamin hoc imetylfocmamit, bc nhy c quan st
thy rt r rng. Trong cc dung mi c tnh baz mnh hn, c th chun c mt s ru
v imid.

245
Hnh 12.2
Chun hn hp axit trong metylisobutylxeton

Trn hnh 12.2 dn ra ng chun thc nghim hn hp axit trong

metylisobutylxeton bng dung dch chun hiroxit ca tetrabutylamoni trong ru isopropilic
0,2 M. Trn trc tung l th ca in cc thy tinh bin i tuyn tnh theo s bin i ca
pH. R rn l, trong dung mi ny, axit pecloric mnh hn axit hirocloric rt nhiu, do
im cui ca mi php chun c xc nh ring bit. Ta cng nhn thy rng, phenol l
mt axit qu yu i vi php chun trong nc nhng trn ng chun trong mi trng
khng nc, bc nhy c th hin r rt.

12.2.3 Chun trong dung mi aproton hoc trung tnh

Nhng dung mi aproton rt t c s dng chun bi v thuc th v cht b
chun t tan trong cc dung mi ny. Nhng chng thng c s dng trong hn hp vi
cc dung mi trung tnh khc. V d, hn hp (1 : 1) ca etylenglycol hoc propilenglycol vi
hirocacbon hocc dn xut halogen ca hirocacbon l nhng dung mi tuyt vi i vi
mui kim loi kim ca cc axit hu c. chun cc mui , ngi ta s dng dung dch
axit pecloric cng trong cc dung mi trn lm dung dch chun . Cng c th chun cc
axit yu trong metanol v etanol.

246

Chng 13
Chun to phc
Ion ca nhiu kim loi phn ng vi cp in t cho t mt cht khc to thnh hp cht
phi tr hoc ion phc. Cht c kh nng cho i in t c gi l phi t (ligan), cn phi
c t nht mt i in t khng phn chia to lin kt. Cc phn t nc, amoniac v cc
ion halogenua l nhng phi t thng gp.
Mc d cn c nhng ngoi l, cc cation thng to thnh s lin kt phi tr cc i l
2, 4 hoc 6 v s cc i c chp nhn l s phi tr. Hp cht phi tr c to thnh c
th mang in tch dng, in tch m hoc trung tnh. V d nh, ng (II) vi s phi tr 4
c th to thnh phc amoniac cation Cu ( NH3 )24+ , phc glixin trung tnh Cu(H2NCH2COO)2
hoc phc anion vi ion clorua CuCl24 .
Cc phng php chun da trn cc phn ng to phc c s dng c th k
qua. Nhng ch khi mt loi hp cht phi tr c bit c gi l cc phi t vng cng c
pht hin, phng php chun to phc mi thc s bc vo giai on pht trin diu k.
Chelat l phc vng cng c to thnh gia ion kim loi vi phi t c hai (hoc nhiu
hn) nhm cho in t. Trong phc ca ng vi glixin nu trn, ng lin kt c vi oxi ca
nhm cacboxilic v c vi nguyn t nit ca nhm amino. Phi t to phc vng cng c 2
nhm cho in t tham gia to lin kt phi tr c gi l phi t hai rng. Ngi ta bit
cc phi t 3 rng, 4 rng, 5 rng v 6 rng.
Trong phn tch chun , cc thuc th to phc vng cng c u th hn cc thuc th
to phc khng vng cng bi v s to phc vng cng thc t xy ra trong mt giai on,
trong khi s to phc n gin thng phi tri qua mt hoc mt s ln hn cc hp cht
trung gian.
Chng ta xt cn bng gia ion kim loi M c s phi tr bng 4 v phi t 4 rng D, in
tch ca M v D quyt nh in tch ca sn phm phn ng nhng i vi cc bn lun tip
theo, iu khng c ngha nn in tch c b qua.
M+D

MD

Khi cn bng ca qu trnh c thit lp:

K=

[ MD]
[ M][D]

247

K l hng s cn bng.
Mt cch tng t, cn bng gia M v hng s bn tng ng l kt qu ca qu trnh 2
giai on, bao hm s to thnh mt hp cht trung gian MB:
M +B

MB

MB + B

MB2

Hai cn bng c th hin bng hai hng s bn:

K1 =

[ MB] v
[ M][B]

K2 =

[ MB2 ]
[ MB][B]

Tch s K1 v K2 cho ta phng trnh hng s cn bng ca qu trnh tng hp:

2 = K1K 2 =

[ MB] [ MB2 ] = [ MB2 ]

[ M][B] [ MB][B] [ M][B]2

Mt cch tng t, phn ng gia M v phi t mt rng A c th vit di dng cn

bng tng cng:
M + 4A

MA4

v hng s cn bng 4 tng ng vi s to thnh MA4 t M v A, bng tch s hng s

cn bng ca 4 giai on ring bit.

248
Hnh 13.1
ng chun complexon

1. Chun 60,0 ml dung dch kim loi M 0,020 M bng dung dch phi t D 4 rng vi
s to thnh hp cht MD.
2. Chun bng dung dch phi t 2 rng B 0,040 M vi s to thnh hp cht MB2.
3. Chun bng dung dch phi t 1 rng A 0,080 M vi s to thnh hp cht MA4.
Hng s bn chung ca tt c cc hp cht nu l 1,0.1020.
Mi ng chun c dn ra trn hnh 13.1 tng ng vi mt phn ng c hng s
cn bng chung bng 1020. ng s 1 c xy dng cho qu trnh mt giai on, to thnh
hp cht MD, ng s 2 phn nh qu trnh 2 giai on to thnh MB2 vi cc hng s
cn bng tng ng K1 =1012 v K2 =108. ng s 3 i din cho qu trnh to thnh
MA4; cc hng s cn bng ca 4 giai on tng ng l 108, 106, 104, 102. Cc ng
cong minh ha u th rt r rng ca cc phi t phn ng vi ion kim loi theo t l 1 :
1, bi v i vi nhng h nh vy, s bin i pM vng im tng ng l cc i.
Nh vy l, i vi php phn tch chun , nhng phi t a rng l thch hp nht bi
v, thng thng phn ng tng tc ca chng vi cc ion kim loi c c trng bng
h s hp thc n gin nht.
Khng ph thuc vo loi phn ng c s dng chun , sai s chun gim khi
hon ton ca phn ng tng ln. Vi quan im , khng cn nghi ng g na, nhng
phi t a rng c u th r rt so vi nhng phi t n rng bi v chng to vi ion kim
loi nhng phc bn hn.

13.1 Chun bng cc thuc th v c

Chun to phc l mt trong nhng phng php chun lu i nht. Php chun
ion ioua bng dung dch thy ngn (II) theo phn ng:
Hg2+ + 4I

HgI24

ln u tin c cng b vo nm 1834, phng php xc nh ion xianua da trn

phn ng to thnh ion phc Ag(CN) cng c cng b vo nm 1851. Trong bng
13.1 di y dn ra nhng cht chun in hnh khng to phc vng cng.
Bng 13.1 Nhng v d in hnh v php chun bng cc cht to phc v c

Cht chun

Cht cn nh lng

Ghi ch

Hg(NO3)2

Br, Cl, SCN, CN, tior

To phc trung ha in ca Hg(II), s

dng nhiu ch th

249

Sn phm ca phn ng l Ag(CN)2 ,

ch th l I, chun n xut hin c
dung dch do AgI

AgNO3

CN

Sn phm ca phn ng l Cu(CN)24 ,

Cu2+, Hg2+, Ni2+

KCN

Hg(CN)24 , Ni(CN)24 , s dng nhiu

ch th

13.2 Chun bng cc axit aminopolicacboxilic

13.2.1 Thuc th
Phng php chun da trn phn ng to phc ca cc ion kim loi vi nhm cc
axit aminopolicacboxilic c gi l phng php chun complexon. Cc complexon l
nhng dn xut ca cc axit aminopolicacboxilic:
Nitrilotriaxetic axit hay complexon I:

CH2

COOH

CH2

COOH

CH2

COOH

vit tt l H3Y

Etileniamin tetraaxetic axit (EDTA) hay complexon II:

H2C

HOOC

N
HOOC

CH2

CH2

H2C

CH2

COO

CH2

COO

vit tt l H4Y

V axit ny t tan trong nc nn trong thc t ngi ta thng dng dng mui inatri
(Na2H2Y hay comlexon III, trilon B).
trans-1,2-iaminoxiclohexan tetraaxetic axit, comlplexon IV:
CH2
H2C

H2C

CH

CH
CH2

CH2

COOH

CH2

COOH

CH2

COOH

CH2

COOH

250

Cc complexon to phc bn vi nhiu ion kim loi. Cc phn ng to phc

ny tha mn tt c cc iu kin ca phn tch th tch; do , ngy nay phng php chun
complexon tr thnh mt trong nhng phng php phn tch th tch ph bin nht.
EDTA l thuc th c s dng nhiu nht. l mt axit yu c 4 nc phn li: pK1 =
2,0; pK2 = 2,67; pK3 = 6,16; pK4 = 10,26. Nh vy l, hai proton u tch ra kh d dng, hai
proton sau tch ra kh khn hn nhiu. Ngoi 4 ion hiro ca cc nhm cacboxilic axit, phn
t EDTA cn c hai nguyn t nit, mi nguyn t u c i in t khng phn chia (t
do), do c tim nng to 6 lin kt vi ion kim loi (phi t 6 rng).
4

Y .

EDTA c k hiu l H4Y v c th tn ti 5 dng sau: H4Y, H3Y, H2Y2, HY3 v

H4Y v Na2H2Y.2H2O c th iu ch c dng tinh khit dng lm dung dch gc.

Mun vy phi sy 130 150oC lm mt nc.
Thnh phn ca dung dch EDTA nh l mt hm s ca pH. Trong dung dch nc
EDTA tn ti 5 dng. Lng tng i ca mi dng trong dung dch ny ph thuc vo
pH. Nhng t s c din t bng th qua s ph thuc ca gi tr i vi cc dng
khc nhau nh l hm s ca pH.
o

[H Y ]
= 4 ;
C

H3 Y

=
C

y C l tng s nng cn bng ca tt c cc dng. Nh vy l t s mol ca mi

dng.
R rng l vng axit va phi (pH = 3 6) dng H2Y2 l dng chim u th, pH = 6
10 dng HY3 chim u th v ch pH > 10 th dng Y4 mi bt u chim u th.
Nhng t s nh hng ln n cn bng trong dung dch cha EDTA v cc cation
khc.

251

Hnh 13.2
Thnh phn ca dung dch EDTA bin i theo pH

13.2.2 Phc ca EDTA vi cc cation kim loi

Tnh cht qu gi nht ca cht chun EDTA l kh nng phn ng ca n vi cc ion
kim loi theo t l 1 : 1 khng ph thuc vo in tch cation. Trong cc dung dch axit va
phi, c th vit cc phn ng di dng:
Me2+ + H2Y2

MeY2 + 2H+

Me3+ + H2Y2

MeY + 2H+

Me4+ + H2Y2

MeY + 2H+

T th phn b trn, r rng rng nhng phn ng xy ra trong dung dch trung tnh v
kim va phi vit di dng sau:
Men+ + HY3

MeY + 2H+

EDTA c tnh cht cc k qu gi l to phc bn v tan trong nc vi nhiu ion kim

loi. Tt c cc cation phn ng vi EDTA, tr cc kim loi kim u to thnh cc phc
bn, l c s cho cc phng php chun . bn cao ca cc phc to thnh l do s
c mt trong phn t EDTA mt s nhm cho: nhng nhm ny c th to cu trc i xng

252

t sc cng. Mt trong cc dng ca phc c din t trn hnh 13.3. Cn ch l,

su nhm cho ca phn t EDTA tham gia to lin kt vi ion kim loi ha tr 2.

Hnh 13.3
Cu trc phc ca kim loi vi EDTA

Cn phi c bit nhn mnh rng, tt c cc hng s cn bng u m t tng tc ca

ion kim loi vi Y4:
Men+ + Y4

K MeY

MeY(n4)+

MeY (n 4)+

=
+

n
4
Me Y

(13.1)
o

Bng 13.2 Hng s bn ca phc kim loi vi EDTA ( 20 C v lc ion bng 0,1)

Cation

KMY

lgKMY

Cation

KMY

lgKMY

Ag+

2,1.107

7,32

Cu2+

6,3.1018

18,80

Mg2+

4,9.108

8,69

Zn2+

3,2.1016

16,50

Ca2+

5,0.1010

10,70

Cd2+

2,9.1016

16,46

Sr2+

4,3.108

8,63

Hg2+

6,3.1021

21,80

Ba2+

5,8.107

7,76

Pb2+

1,1.1018

18,04

Mn2+

6,2.1013

13,79

Al3+

1,3.1016

16,13

Fe2+

2,1.1014

14,33

Fe3+

1,3.1025

25,1

253

Co2+

2,0.1016

16,31

V3+

7,9.1025

25,9

Ni2+

4,2.1018

18,62

Th4+

1,6.1023

23,2

13.2.3 Xy dng ng chun

Xy dng ng chun cho phn ng gia ion kim loi v EDTA v c bn khng
khc vic xy dng ng chun trong phng php chun axit baz, nhng trong
trng hp ny phc tp hn v trng hp chun axit baz thng ch cn nghin cu
mt cn bng, cn trong trng hp chun complexon cn nghin cu mt s cn bng ln
hn.
13.2.3.1 nh hng ca pH

S nghin cu cn bng trong dung dch cha ion kim loi v EDTA ch r rng, mc
to phc ph thuc vo pH ca dung dch. chun nhng cation to phc km bn (v
d: Mg2+, Ca2+) ngi ta phi chun trong mi trng kim. Ngc li, chun nhng
cation to phc bn hn (v d: Zn2+, Ni2+) c th thc hin thnh cng ngay c trong mi
trng axit va phi.
c bit ch ti s to phc ph thuc vo pH, nn php chun bng dung dch
EDTA thng c thc hin trong cc dung dch m vi cc gi tr pH thch hp, c nh.
Gi pH khng i, cho php n gin kh nhiu cch tnh ton xy dng ng chun.
xy dng ng chun ion kim loi bng EDTA trong dung dch m c th s
dng gi tr 4 mt cch rt tin li:
Y 4

4 =
C

(13.2)

trong C l nng chung ca EDTA khng to phc.

Nh vy:
C = [Y4] + [HY3] + [H2Y2] + [H3Y] + [H4Y]
v 4 l phn thuc th khng to phc, tn ti dng Y4, 4 ch ph thuc vo pH v
nhng hng s phn li ca EDTA K1, K2, K3, K4.
4 =

K 1K 2 K 3 K 4
4

H + + K 1 H + + K 1K 2 H + + K1 K 2 K 3 H + + K 1 K 2 K 3 K 4

(13.3)

254

Bng 13.3 Cc gi tr 4 ca EDTA cc gi tr pH

pH

pH

2,0

3,7.1014

7,0

4,8.104

3,0

2,5.1011

8,0

5,4.103

4,0

3,6.109

9,0

5,2.102

5,0

3,5.107

10,0

3,5.101

6,0

2,2.105

11,0

8,5.101

12,0

9,8.101

Thay [Y4] bng 4C (phng trnh (13.2)) vo phng trnh hng s bn ca phc (13.1)
ta c:
K 'MeY

= K MeY

MeY (n 4)+

=
n
+
Me C

(13.4)

trong K'MeY l hng s bn iu kin hay biu kin m t cn bng ch gi tr pH

dng tnh gi tr 4. Hng s bn iu kin cho php tnh ton d dng nng cn bng
ca ion kim loi v phc bt k im no ca ng chun . D dng nhn thy rng,
phng trnh hng s bn iu kin khc vi phng trnh hng s bn c s dng trc
y ch mt iu duy nht l nng cn bng tuyt i (ton phn) ca anion phn li [Y4]
c thay th bng gi tr C - nng chung ca EDTA. Nhng iu cc k quan trng
bi v C d dng xc nh t phn ng hp thc hn l [Y4].
V d: V ng chun 50,0 ml dung dch Ca2+ 0,0100 M bng dung dch EDTA
0,0100 M trong dung dch m c pH = 10.
Tnh hng s bn iu kin pH=10: K'CaY = 4KCaY = 0,35.5.1010 = 1,75.1010.
Tnh pCa trc im tng ng: Cho n trc im tng ng, nng chung
ca Ca2+ bng tng s nng ion Ca2+ cha b chun v nng Ca2+ do phc phn li ra.
Thng thng, hon ton hp l khi chng ta chp nhn rng nng ion Ca2+ do phc phn
li ra nh thua nng ion Ca2+ cha b chun nn c th b qua nng ny (Ta c chp
nhn gi thit ny bi v [Ca2+] do phc phn li ra im tng ng cn nh thua [Ca2+]
do phc phn li ra trc im tng ng v nng [Ca2+] cha b chun cn ln,
ngn cn s phn li ca phc CaY2. Khi ta tnh ton [Ca2+] im tng ng di y ta
s thy r hn iu ta gi thit trn y l hon ton ng n).
V d: Sau khi thm 25,0 ml cht chun th:

255
Ca2+ = 50,0 0,0100 25,0 0,0100 + C 3,33.103 mol / l

75,0

pCa=2,48.

Tnh pCa im tng ng: thi im ny [CaY2] = 0,00500 M v s phn li ca

phc l ngun duy nht cung cp Ca2+. R rng l [Ca2+] bng nng chung ca EDTA
cha to phc:

[Ca2+] = CEDTA
[CaY2] = 0,00500 [Ca2+] 0,00500 mol/l
K'CaY pH = 10 l 1,75.1010
(xem mc trn)
Vy:
0,00500
0,00500
=
= 1,75.1010
2
2
+
Ca CEDTA 2+
Ca

[Ca2+] = 5,35.107 M;
do :
pCa = 6,27.
Kt qu ny khng nh gi thit ca chng ta mc trn l ng.
Tnh pCa sau im tng ng: Tnh nng chung ca CaY2 v EDTA sau im
tng ng rt d dng. V d, sau khi thm 60,0 ml cht chun.
50,0 0,0100
= 4,55.103 M
110
10,0 0,0100
=
= 9,1.104 M
110

CCaY =
CEDTA

Mt cch gn ng c th vit:
[CaY2] = 4,55.103 M [Ca2+] 4,55.103
CEDTA = 9,1.104 M + [Ca2+] 9,1.104
4,55.103
= 1,75.1010 = K 'CaY
2
+

4
Ca 9,1.10

256
2+

10

[Ca ] = 2,86.10

do :
pCa = 9,54.
T nhng tnh ton nh trn ta c th v ng chun ion Ca2+ trong nhng dung dch
m c pH khc nhau. T hnh 13.4, r rng l, s bin i pCa ch r rt im tng
ng khi pH 8 (Nhng ti sao ta khng chun pH=12 c bc nhy pCa ln nht? Cu
hi ny s c tr li mc sau ni v im cui khi chun ).
i vi nhng cation to phc bn hn, c th xc nh im cui rt r, ngay c trong
dung dch axit.

Hnh 13.4
nh hng ca pH ln ng chun dung dch Ca2+ 0,0100 M bng dung dch EDTA 0,0100
M

257

Hnh 13.5
Nhng ng chun 50 ml dung dch cc cation 0,0100 M pH=6

13.2.3.2 nh hng ca cc thuc th to phc l n php chun bng EDTA

Thng qu trnh chun bng EDTA tr thnh phc tp do hin tng kt ta mt

phn ion cn xc nh di dng oxit baz hay hiroxit pH cn thit cho qu trnh chun .
gi ion kim loi trong dung dch, c bit l giai on u ca php chun , cn thit
phi thm cht to phc ph vo dung dch cht cn nh phn. V d, khi chun Zn(II)
thng phi dng mt lng ln amoniac v amoni clorua. Cp axit baz lin hp ny to
thnh dung dch m c gi tr pH cn thit. Ngoi ra, amoniac cn ngn cn s kt ta
hiroxit km nh s to thnh cc phc amoniacat. Nh vy l, phn ng chun km bng
dung dch EDTA c din t nh sau:
Zn(NH3 )42+ + HY

ZnY2 + 3NH3 + NH4+

258

Hnh 13.6
Gi tr pH nh nht, cn thit chun cc dung dch cation bng dung dch EDTA

Trong nhng h tng t nh vy, hon ton ca phn ng v do cht lng xc

nh im cui khng ch ph thuc vo pH m cn ph thuc vo nng amoniac trong
dung dch.
nh hng ca ca thuc th to phc ph n qu trnh chun c th tnh ton c
ging nh tnh ton nh hng pH n nng cc dng khc nhau ca EDTA.
Ta k hiu:

259
Men +

=
CMe

(13.5)

vi CMe l nng chung ca tt c cc dng cha ion kim loi cn chun , tr loi
phc ca EDTA vi kim loi cn chun . i vi dung dch cha Zn(II) v amoniac ta c
th m t nh sau:
CMe = [Zn2+] + [Zn(NH3)2+] + [ Zn(NH3 )22+ ] + [ Zn(NH3 )32+ ] + [ Zn(NH3 )42+ ]

(13.6)

D dng tm c gi tr bng s ca t nng ca amoniac v hng s bn ca phc

to thnh. V d:
Zn(NH3 )2+

K1 =
2
+
Zn [NH3 ]

v t :
[Zn(NH3)2+] = K1[Zn2+][NH3]
Mt cch tng t:
[Zn(NH3)22+] = K1K2[Zn2+][NH3]2
Thay th nhng gi tr tm c vo phng trnh (13.6) ta c:
CM = [Zn2+](1 + K1 [NH3] + K1K2 [NH3]2 + K1K2K3 [NH3]3 + K1K2K3K4 [NH3]4)
Gii phng trnh ny cng vi phng trnh (13.5) v cho [Men+] = [Zn2+] ta tm c:
=

1
1 + K1 [NH3 ] + K1K 2 [NH3 ] + K1K 2K 3 [NH3 ] + K1K 2K 3 K 4 [NH3 ]
2

(13.7)

Cui cng gii ng thi cc phng trnh (13.4) v (13.5) ta tm c hng s cn bng
iu kin ca phn ng EDTA vi Zn2+ trong dung dch m cha amoniac v amoni clorua:
K "ZnY = 4K ZnY

ZnY 2

=
CMe .CEDTA

(13.8)

y K"ZnY l hng s bn iu kin mi ch c s dng khi gi tr pH l duy nht v

nng amoniac cng l duy nht. V d c xem xt di y s ch r cch dng hng s
iu kin xy dng ng chun .
V d: Tnh pZn trong cc dung dch khi trn ln 40,0; 50,0; 60,0 ml dung dch EDTA
0,0010 M vi 50,0 ml dung dch Zn2+ 0,0010 M. Gi thit rng dung dch Zn2+ v dung dch

260

EDTA u cha 0,100 M NH3 v 0,176 M NH4Cl to nn gi tr pH khng i

bng 9,0. Nhng hng s bn ca cc phc amiacat Zn(II) l nh sau: K1 = 1,9.102; K2 =
2,2.102; K3 = 2,5.102; K4 = 1,1.102; KZnY = 3,2.106.
1. Tnh hng s bn iu kin: tnh c ta ly [NH3] = CNH3 v thay vo phng
trnh (13.7) gi tr CNH3 v cc gi tr hng s bn tng nc K1, K2, K3, K4 ca phc amiacat
km:
=

1
4

1 + 19 + 420 + 1,04.10 + 1,14.10

= 8,0.106

Thay vo phng trnh (13.8) gi tr KZnY = 3,2.1016; 4 = 5,2.102 v gi tr

8,0.106 ta c:

K"ZnY = 5,2.102.8,0.106.3,2.1016 = 1,33.1010

2. Tnh pZn sau khi thm vo 40,0 ml EDTA. Nng Zn2+ cha phn ng vi EDTA
thi im ny vi s gn ng kh tt l:
CMe =

50,0 0,00100 40,0 0,00100

= 1,11.104 mol / l
90,0

Chng ta gi thit rng c th b qua s phn li ca cc dng phc ca Zn2+ v thay th

vo phng trnh (13.5), nng chung ca ion kim loi CMe l tng nng cn bng ca tt
c cc phc ca Zn2+ khng cha EDTA v tnh nng cn bng ca ion km:
[Zn2+] = CMe(1,11.104)(8x106) = 8,9.1010 mol/l;
do :

pZn = 9,05.

3. Tnh pZn sau khi thm 50,0 ml EDTA: im tng ng [ZnY2] = 5,00.104. Tng
nng cn bng ca cc dng phc km khng cha EDTA bng tng nng cn bng ca
cc dng khng to phc vi EDTA:
CMe = CEDTA.
v:
[ZnY2] = 5,00.104 CMe 5,00.104 mol/l
a kt qu ny vo (13.8) ta c:
K"ZnY =1,33.1010 =

5.10.104

CMe = 1,94.107 mol/l

C2Me

261

T (13.5) ta c:
[Zn2+] = CMe = (1,94.107)(8.106) = 1,55.1012 mol/l;
do :

pZn = 11,81

4. Tnh pZn sau khi thm 60,0 ml EDTA: trong trng hp ny dung dch c d EDTA:
60,0 0,0010 50,0 0,0010
= 9,1.105 M
110
50,0

0,0010

ZnY =
= 4,55.104 M

110

CEDTA =

Thay cc kt qu thu c vo (13.8) ta c:

1,33.1010 =

4,55.104
9,51.105.CMe

10

CMe = 3,76.10

mol/l

[Zn2+] = CMe = (3,76.1010)(8.106) = 3,01.1015 mol/l;

do :

pZn = 14,52.

T cc tnh ton nh trn ngi ta xy dng c cc ng chun l thuyt Zn2+

bng EDTA (pH = 9) cc nng (cn bng) amoniac khc nhau.
Trn hnh 13.7 dn ra hai ng chun l thuyt Zn2+ bng dung dch EDTA pH =
9. Nng cn bng ca amoniac trong trng hp th nht l 0,100 M v trong trng hp
th hai l 0,0100 M. Hnh v ch r, amoniac lm gim bc nhy trn ng chun . V
vy, nng cht to phc ph khng c vt qu nng ti thiu, ngn nga to
hiroxit. (Chng ta nhn thy rng, gi tr khng nh hng n pZn sau im tng ng
nhng gi tr 4 v do pH ng vai tr quan trng trong s to thnh vng ny ca ng
chun ).

262

Hnh 13.7
nh hng ca nng amoniac n php chun dung dch Zn2+ 0,0010 M bng dung dch EDTA
0,0010 M. C hai php chun u c thc hin dung dch m c pH = 9.

13.2.3.3 im cui trong chun complexon

Ch th kim loi: Trong chun bng EDTA hoc l bng nhng thuc th to phc
khc, ngi ta thng dng mt s cht ch th kim loi xc nh im cui. Nhng ch th
ny l nhng cht mu hu c to phc vng cng (chelat) vi cc cation kim loi nhng
vng pH xc nh, ty thuc vo tnh cht ca cation kim loi v ch th. Nhng phc ny c
mu kh m, c th pht hin ion kim loi trong khong nng 106 107 M. Phn ln
ch th kim loi c kh nng lin kt proton v to thnh nhng hp cht mu gn nh ging
mu phc kim loi. V vy, chng ng thi cng l ch th axit baz nn chng ch ng vai
tr ch th kim loi mt cch thun li vng pH m khng c phn ng cnh tranh ca
proton. Ericrom T l ch th c tnh cht nh nu trn v c s dng rng ri nht trong
chun complexon. Trong dung dch axit v kim va phi, cn bng sau y chim u th:

263

OH

O
Ka = 5.107

+ H+

N
OH

O2N

OH
O2N

SO3

H2In

SO3
Xanh bin

H2In

+ H+

Xanh bin

Hnh 13.8
S i mu ca ET- OO v ca MgIn ph thuc vo pH v pMg

gi tr pH rt cao HIn2 phn li tip to thnh In3 c mu da cam. Sau y l bc tranh

ton cnh v mu sc ca Ericrom T en v phc ca n vi Mg ph thuc vo pH. Hnh 13.8
gii thch v sao khng chun Mg2+, Ca2+ pH = 12 (v pH ny ch th c mu da cam).
Ch th chun complexon cn to phc vi ion kim loi c hng s bn 10 ln nh
thua hng s bn ca phc kim loi vi EDTA. Nu nh thua qu 10 ln, php chun s
kt thc sm (sai s m) hoc ngc li, hai hng s bn khc nhau qu nh, nh trng hp
ca Ca2+, im cui s c xc nh qu mun (sai s dng). im yu ca Ericrom T en

264

l dung dch ca n km bn. khc phc, ngi ta dng dng rn (hn hp 1 :

100 vi NaCl) hoc dng canmagit c tnh cht tng t v c cng thc nh bn.

13.2.3.4 Nhng phng php chun complexon

Trong chun complexon, ngi ta s dng nhiu bin php khc nhau. Sau y l
nhng cch ph bin nht:
Chun trc tip: Theo Welcher, ngi ta c th chun trc tip 25 ion kim loi. Chun
trc tip ch c th thc hin vi nhng ion kim loi phn ng nhanh vi EDTA v c ch th
thch hp xc nh im cui. Trong trng hp ngc li, ngi ta c th s dng phng
php chun ngc hay chun thay th.
Chun ngc: Chun ngc c s dng chun nhng cation to phc rt bn
vi EDTA nhng phn ng chm hoc khng tm c ch th thch hp. Trong trng hp
ny, lng d EDTA c xc nh bng php chun ngc bng dung dch magie chun
vi ch th Ericrom T en hoc canmagit. Phc ca ion kim loi cn xc nh vi EDTA phi
bn hn phc ca Mg2+ vi EDTA, nu khng ion kim loi s b y ra t phc.
Chun thay th: Trong chun thay th, ngi ta a vo dung dch phn tch mt
lng d phc ca EDTA vi Mg2+ hoc Zn2+. Nu cation kim loi cn xc nh to vi
EDTA phc bn hn phc tng ng ca Zn2+ hoc Mg2+ th phn ng s din ra nh sau:

MgY2 + Me2+

MeY + Mg2+

Sau ngi ta chun Mg2+ b y ra khi phc bng dung dch chun EDTA.
Chun axit baz: Trong phng php chun axit baz, ngi ta thm vo dung
dch trung tnh ca ion kim loi mt lng d EDTA. Phn ng xy ra nh sau:

Me2+ + H2Y2

MeY2 + 2H+

Chun lng ion hiro c gii phng ra bng dung dch kim suy ra lng ion
kim loi cn xc nh.

265

Chng 14
Chun Oxi ha kh
14.1 Nhng khi nim c bn
14.1.1 nh ngha
Cht oxi ha l cht c kh nng nhn electron.
Cht kh l cht c kh nng cho electron.
Cht oxi ha (Ox) sau khi nhn electron tr thnh cht kh (Kh) gi l cht kh lin hp
vi n. Mi cp oxi ha kh lin hp c th biu din bng phng trnh:
Ox + ne

Kh

Mt vi v d v cp oxi ha kh lin hp:

Dng oxi ha

Dng kh

Cp oxi ha kh lin hp

Zn2+ + 2e

Zn0

Zn2+/Zn

Fe3+ + e

Fe2+

Fe3+/Fe2+

2H+ + 2e

H2

2H+/H2

2Cl

Cl2/2Cl

MnO4 + 5e + 8H

Mn2+ + 4H2O

MnO4 /Mn

Fe(CN)36 + e

Fe(CN)64

Fe(CN)36 / Fe(CN)64

AgCl + e

Ag0 + Cl

Ag+/Ag0

Cl2 + e
+

2+

Electron khng tn ti trng thi t do trong dung dch, do mt cht ch th hin tnh
oxi ha khi c cht kh cho electron ca n hay ngc li.
Phn ng trao i electron gia cc cht oxi ha v cht kh gi l phn ng oxi ha kh.

266

aOx1 + bKh2

cKh1 + dOx2

V d, khi nhng mt thanh kim loi hot ng hn ng, v d km vo dung dch ng

sunfat th s xy ra phn ng oxi ha kh.
Trong phn ng oxi ha kh c tnh cht ha hc di y, ion Cu2+ nhn 2e ca nguyn
t km, b kh thnh nguyn t ng, cn nguyn t km b oxi ha thnh ion Zn2+.
Chng ta c th lm mt th nghim in ha nu r rng trong phn ng trn c s
chuyn electron t cht kh l km kim loi sang cht oxi ha l ion Cu2+ cch xa nhau,
hay ni mt cch khc l c mt dng in i t cht oxi ha l ion ng sang cht kh l
km.
Chiu quay ca kim in k ch r rng c dng in i t cc ng sang cc km. iu
c ngha l th bn cc ng ln hn th bn cc km v electron chuyn t cc km sang
cc ng.
Sau mt thi gian, kim in k tr v v tr khng, trong h khng cn dng in. em
cc dung dch ra phn tch th thy nng dung dch km tng ln v nng dung dch
ng gim i, cc km sng ra, cc ng c ph mt lp ng kim loi. Chiu ca dng
in trong th nghim trn chng t rng Cu2+ ca cp oxi ha kh lin hp Cu2+/Cu0 c th
cao hn nn oxi ha km kim loi ca cp Zn2+/Zn0 c th thp hn. Th oxi ha kh ca
cp oxi ha kh lin hp quyt nh chiu ca phn ng:
Zn0 + Cu2+

Hnh 14.1

Zn2+ + Cu0

267
H oxi ha kh ng km

14.1.2 Phng trnh Nerst

Th oxi ha kh ca mt cp oxi ha kh lin hp c tnh bng phng trnh Nerst.
i vi h n gin:
Ox + ne

Kh

E = Eo +

RT aOx
ln
nF aKh

trong : E l th oxi ha (Von), R l hng s kh (8,331 Jun), T l nhit tuyt i, F l

s Faraday (96500 c), n l s electron trao i, Eo l th oxi ha kh tiu chun, th khi biu
thc sau logarit bng 1, ln l logarit c s e (logarit t nhin) aOx, aKh l hot ca dng oxi
ha v dng kh. Eo ch ph thuc vo bn cht ca h oxi ha kh lin hp.
Trong thc t, ngi ta khng th xc nh c gi tr tuyt i th ca mt cp oxi ha
kh lin hp m ch xc nh c gi tr tng i ca n (xem th nghim trn).
so snh th ca cc cp oxi ha kh lin hp vi nhau cn phi xc nh gi tr tng
i th ca mt cp oxi ha kh lin hp c quy c bng khng. Ngi ta quy c th oxi
ha kh tiu chun ca cp 2H+/H2 bng khng.

14.2 Nhng yu t nh hng n th oxi ha kh

Th oxi ha kh tiu chun quyt nh chiu ca phn ng oxi ha kh, nhng trong thc
t c nhng yu t nh hng rt mnh n th oxi ha kh ca cc cp oxi ha kh lin hp
v do nh hng n chiu ca phn ng. Sau y ta xt tng trng hp c th.

14.2.1 nh hng ca axit

Tnh th oxi ha kh iu kin ca cp AsO34 / AsO33 trong mi trng natri hiro
cacbonat - ngha l pH = 8; bit Eo ca cp ny pH = 0 l +0,57 V.
Vi cp ny c th xy ra phn ng:
AsO34 + 2H + 2e
+

Th oxi ha kh ca cp ny:

AsO33 + H2O

268
E = Eo +

a AsO3
0,059
0,059
4
log a2 + +
log
H
2
2
a AsO3
3

Th chun iu kin Eo khi pH = 8 ngha l th khi:

[ AsO34 ] = [ AsO33 ] v [H+] =108
E' = Eo +

2
0,059
0,059
( 8 ) 2 = +0,10(0,098)
log 108 = 0,57 +

2
2

Nh vy, pH cng tng th th chun iu kin cng gim ngha l kh nng oxi ha ca
AsO34 gim khi pH tng, cn kh nng kh ca AsO33 li tng cng vi pH. Chnh v vy
m th oxi ha chun ca cp AsO34 / AsO33 = 0,57 V khi pH = 0 nn AsO34 c th oxi ha
c I v th chun ca cp I2/2I = 0,54 V.
AsO34 + 2I + 2H

AsO33 + I2 + H2O

Nhng trong dung dch NaHCO3 (pH 8) th I2 li oxi ha c AsO33 v nh trn

tnh l th chun ca cp AsO34 / AsO33 ch cn l +0,10 V. Phn ng xy ra theo chiu
ngc li:
AsO33 + I2 + H2O

AsO34 + 2I + 2H

14.2.2 nh hng ca phn ng to phc

Khi cht oxi ha hoc cht kh ca mt cp oxi ha kh lin hp tham gia vo phn ng
to phc th th oxi ha kh cng bin i. Chng ta xt mt v d c th.
V d 1: Tnh th oxi ha kh tiu chun iu kin ca cp Fe3+/Fe2+ trong dung dch c
d florua to phc. Phc FeF63 c hng s bn = 1016; Eo 3 + 2+ = 0,77 V .
Fe

/ Fe

Vi h ny xy ra hai phn ng:

Fe2+ e

Fe3+

(1)

Fe3+ + 6F

FeF63

(2)

Cng li: Fe2+ + 6F e

FeF63

269

Lc ny: E = Eo + 0,059 log

FeF63

Fe2+ F

o'

E =E = th oxi ha kh tiu chun iu kin khi

Theo phng trnh to phc (2):

FeF63

3+

Fe

FeF63

Fe2+ F

= 1016

(3)

=1

(4)

Fe3 +
= 1
Chia (3) cho (4) ta c:
Fe2+ 1016

Fe3 +
= 0,77 + 0,059 log 1 = 0,17 V
Eo ' = Eo + 0,059 log
2
+
Fe
1016

Nh vy, trong mi trng c d F kh nng oxi ha ca Fe3+ gim i v kh nng kh

ca Fe2+ li tng ln.

14.2.3 nh hng ca phn ng kt ta

Phn ng kt ta cng lm thay i th oxi ha kh ca cc cp oxi ha kh lin hp v
do lm thay i chiu ca phn ng.
V d: Tnh th oxi ha kh tiu chun iu kin ca cp Cu2+/Cu+ khi c d I to thnh
kt ta CuI, cho bit TCuI = 1012, Eo 2+ + = +0,17 V , Eo = 0,54 V .
Cu

/ Cu

I2 / 2I

Th oxi ha kh tiu chun ca cp I2/2I cao hn cp Cu2+/Cu+ nn I2 s oxi ha Cu+

tr thnh I v Cu2+ ngha l phn ng cn xy ra theo chiu:
2CuI + I2

2Cu2+ + 2I

Nhng trong thc t phn ng li khng xy ra nh vy v th oxi ha kh tiu chun

iu kin ca cp Cu2+/Cu+ khi c d I thay i rt nhiu. Ta tnh th . Khi khng c
ion I th th oxi ha kh ca cp Cu2+/Cu+ ng vi phng trnh:
Cu2+ + e

Cu+

c xc nh bng cng thc:

270
Cu2+
;
E = E + 0,059 log
Cu+

trong Eo = 0,17 V
Khi c ioua lm kt ta CuI theo phn ng:
Cu2+ + I + e

CuI

th
E = Eo + 0,059log[Cu2+][I]
E =Eo': th oxi ha kh tiu chun iu kin khi [Cu2+][I] =1
Chia v vi v ca biu thc ny vi biu thc tnh tch s tan ca CuI:
[Cu+][I] = TCuI = 1012
ta c:
Cu2+

= 1
+
Cu 1012

E' = E + 0,059 log

1
10

12

= 0,17 + 0,059 log1012

= 0,17 + 0,050 12 = +0,86 V

Nh vy l khi c I d, Eo '

Cu2 + / Cu+

= 0,88 V > Eo

I2 / 2I

= 0,54 V v phn ng thc t xy ra

theo chiu sau y:

2Cu2+ + 4I

2CuI + I2

14.5 Hng s cn bng ca phn ng oxi ha kh

Gi s c phn ng:
aOx1 + bKh2

aKh1 + bOx2

trong :
aOx1 + ne

aKh1

271

bOx2 + ne

bKh2

[Ox1 ]
0,059
+
log
n
[Kh ]a
a

E1 = E1o

[Ox2 ]
0,059
+
log
n
[Kh ]b
b

E2 = E2o

Khi phn ng t cn bng, E1= E2 nn:

[Ox1 ] = Eo + 0,059 log [Ox2 ]

0,059
log
2
n
n
[Kh ]a
[Kh ]b
a

E1o +

[Kh1 ] [Ox2 ]
0,059
log
n
[Ox1 ]a [Kh2 ]b
a

E1o E2o =

[Kh1 ]a [Ox2 ]b
[Ox1 ]a [Kh2 ]b
log K =

=K

n E1o E2o

0,059

V d: Tnh hng s cn bng ca phn ng:

Ce4+ + Fe2+ = Ce3+ + Fe3+

Cho bit: Eo

Ce4 + / Ce3 +

= 1,55 V;Eo

Fe3 + / Fe2 +

= 0,77 V

p dng cng thc trn:

log K =

1,55 0,77
= 13,4 K = 1013,4
0,059

thy mc hon ton ca phn ng ny ta hy tnh cc t s nng [Fe3+]/[Fe2+] v

[Ce4+]/[Ce3+] khi nng ban u bng nhau.
Khi cn bng th [Ce3+] = [Fe3+] v [Ce4+] = [Fe2+], do :
2

13,4

10

Fe3+ Ce3 + Fe3+

Ce3+

;
=K =
=
=
2
2
2
4
+
+
Fe Ce 2+
Ce4 +

Fe

272
Fe3 + Ce3 +

=
= 1013,4 = 106,7
Fe2+ Ce4 +

Nh vy l khi phn ng t cn bng lng Fe2+ v lng Ce4+ ch cn di mt phn

triu lng ban u.

14.5 ng chun oxi ha kh

V d: Tnh th ca dung dch khi chun 50 ml FeSO4 0,100 M bng dung dch
KMnO4 0,020 M [H+] lun bng 1 M. Cho bit Eo 3+ 2+ = 0,77 V; Eo
2 + = 1,51 V .
Fe

/ Fe

MnO4 / Mn

Trc im tng ng tnh th theo cp Fe3+/Fe2+ theo bn phn ng:

Fe2+ e

Fe3+

Fe3+

0,059
E = 0,77 +
log
1
Fe2+

(14.1)

Sau khi qua im tng tng ng, lc ny cp MnO4 /Mn2+ d nn tnh th theo cp
ny da vo bn phn ng:
MnO4 + 8H+ + 5e

Mn2+

8
MnO H+
0,059
4
(m [H+] = 1)

E = 1,51 +
log
5
Mn2+

(14.2)

im tng ng th ca 2 cp bng nhau, nn th l th chung cho 2 cp v phn

ng t cn bng:
Fe3+

0,059
E = 0,77 +
log
1
Fe2+

MnO H+
4
5E = 5.1,51 + 0,059log
Mn2+

Fe3+ MnO4 H+

6E = 0,77 + 5.1,51 + 0,059log
2
+
Fe Mn2+

(14.3)

273

V im tng ng, lng ion MnO4 c ua vo dung dch tng ng chnh xc

vi phn ng:
5Fe2+ + MnO4 + 8H+

5Fe3+ + Mn2+ + 4H2O

V vy, [Fe2+] = 5[ MnO4 ] v [Fe3+] = 5[Mn2+] nn:

Fe3+ 5 Mn2+

Fe2+ 5 MnO4

v do :
Fe3 + MnO4

= 1 v [H+] =1 theo gi thit.

+
+
2
2
Fe Mn

Thay cc gi tr trn vo (14.3) ta c:

6E = 0,77 + 5.1,51

E=

0,77 + 5.1,51
= 1,39
6

Cc kt qu chun c dn ra bng 14.1 v c din t bng th trn hnh 14.2.

Bng 14.1

Lng d (ml)
Lng
KMnO4
thm vo
KMnO
(ml)
FeSO4

Fe3+

Fe2+

MnO4

Cng thc tnh

E (V)

25,0

25,0

25:25=1

E=0,77+0,059log1

0,77

45,0

45:5=9

E=0,77+0,059log9

0,83

49,5

0,5

49,5:0,5=99

E=0,77+0,059log99

0,89

49,9

0,1

49,9:0,1=49
9

E=0,77+0,059log49
9

0,93

50,0

0,1:50,1
=2.103

E=

Mn2+

0,77 + 5.1,51
5 +1

1,39

274

(im T)
50,1

0,1

51,0

1,0

E = 1,51 +

0, 059

log 2.10

E = 1,51 +

0,059
5

log 2.10

1,49

1,50

Hnh 14.2
ng chun 50,00 ml dung dch Fe2+ 0,100 M bng dung dch KMnO4 0,020 M

14.5 Cc yu t nh hng ln ng chun oxi ha kh

Trong cc chng trc y chng ta ni v hiu ng nng cht phn ng v
hon ton ca phn ng ln ng chun . Trong chng ny chng ta s bn lun v hiu
ng ca cc thng s ln ng chun oxi ha kh.

275

14.2.1 Nng cht phn ng

Trn y chng ta thy rt r rng, E ca h chun oxi ho kh thng thng
khng ph thuc vo s pha long. V vy, ng chun ca nhng phn ng oxi ha kh
thng khng ph thuc vo nng cht cn phn tch v cht phn ng. iu hon ton
tri ngc vi nhng iu thy v cc ng chun loi khc m chng ta gp.

14.2.2 hon ton ca phn ng

Phn ng ca mt php chun oxi ha kh ch xy ra cng hon ton khi s bin i
th ca h vng im tng ng cng ln. Hiu ng v th in cc nh nu trn y
c minh ho rt y trn hnh 14.3. Hnh 14.3 dn ra nhng ng chun mt cht
kh gi nh c th in cc l 0,20 V bng mt s cht oxi ha gi nh c th in cc
chun t 0,40 n 1,20 V v hng s cn bng tng ng nm trong khong 2.103 n 8.1016.
R rng l s bin i th ln nht ca h gn lin vi phn ng xy ra hon ton nht. V
phng din , ng chun oxi ha kh tng t ng chun ca nhng phn ng
loi khc.

Hnh 14.3
Hiu ng th in cc ca cht chun ln hon ton ca phn ng

276
Eh (V)

EOxoEKho

Kcb

1,0

A 1,20 V

0,8
0,6

8.1016

13

B 1,00 V

3.10

C 0,80 V

1.1010

D 0,60 V

6.106

E 0,40 V

2.103

C
D

0,4

E
0,2

10

20

30

Th tch dung dch cht chun 0,100 M, ml

14.2.3 Tc phn ng v th in cc
Th in cc ca cc cp ng vai tr cht oxi ha v cht kh cho bit phn ng xy ra
c hon ton hay khng c th s dng v c bit l cho mc ch phn tch, nhng th
in cc khng cho mt thng tin no v tc t ti trng thi cn bng. Kt qu l, mt
phn ng xt v mt th in cc c th xy ra hon ton thun li nhng kt cuc li khng
c chp nhn theo quan im ng hc. S oxi ha asen (III) bng xeri (IV) trong dung
dch axit sunfuric long l mt v d in hnh. Phn ng xy ra nh sau:
H3AsO3 + 2Ce4+ + H2O

H3AsO4 + 2Ce3+ + 2H+

Th hnh thc Eo' i vi hai h ny:

Ce4+ + e

Ce3+

H3AsO4 + H+ + 2e

; Eo' = +1,3 V
H3AsO3 + H2O

; Eo' = +0,56 V

v c th suy ra hng s cn bng khong 1028 t cc s liu trn. Thm ch c th ngh

rng, theo quan im cn bng, phn ng s xy ra rt thun li nhng khng th chun
As(III) bng Ce(IV) nu khng dng xc tc, bi v sau vi gi mi t ti cn bng. Rt may
mn l, c mt s cht xc tc cho phn ng v do php chun c thc hin d dng.

277

14.7 Chun hn hp
Cc dung dch c hai cht oxi ha hoc hai cht kh sinh ra cc ng chun c hai
im un nu th chun ca hai cht cn phn tch khc nhau ln. Nu s khc nhau ln
hn 0,2 V th hai im un thng c phn bit r rng xc nh ring tng hp
phn. Tnh hung hon ton ging php chun hai axit c hng s phn li khc nhau
ln hoc php chun hai ion to kt ta c tan khc nhau ln.
Thm vo , tnh cht ca mt s t h oxi ha kh tng t nh tnh cht ca a axit.
V d nh, xt hai na phn ng:
VO2+ + 2H+ + e

V3+ + H2O ; Eo = + 0,369 V

V(OH)4+ + 2H+ + e

VO2+ + 3H2O

; Eo = + 1,00 V

ng chun V3+ bng cht oxi ha mnh, v d nh pemanganat, c hai im un,

im un tng ng vi s oxi ha V3+ n VO2+ v im th hai tng ng vi s oxi ha
VO2+ n V(OH)4+ . S oxi ha tng bc ca molipen (III), bc u n trng thi oxi ha
+5 v bc tip theo n trng thi oxi ha +6, l mt v d thng dng khc. y, mt ln
na, im un xut hin r rng trn ng chun bi v s khc v th chun ca na
phn ng tng ng l 0,4 V.
Phn tch chi tit ngun gc ca ng chun cho tng cht ring bit trong hn hp
ca nhng cht phn ng loi ny khng c g kh khn nu s khc bit v th chun ln.
Chng ta ly php chun dung dch cha ion st (II) v titan (III) bng kali pemanganat lm v
d. Th chun ca hai cp ng vai tr cht kh trn l:
TiO2+ + 2H+ + e

Ti3+ + H2O

Fe3+ + e

Fe2+

; Eo = +0,099 V
; Eo = +0,77 V

Nhng phn thm pemanganat u tin c dng cho ion titan (III) v d dng b oxi
ha hn. Cho n khi nng ca cht ny cn ln trong dung dch, th ca h khng th
cao lm bin i nng ion st (II). Nh vy l, c th thu c nhng im to nn
phn th nht ca ng chun bng cch thay th nhng nng hp thc ca ion titan
(III) v titan (IV) vo phng trnh:
E = +0,099 0,059 log

Ti3 +

TiO2+ H+

on u ca ng chun titan (III) bng kali pemanganat l ng nht. Sau im

tng ng th nht, nng c hai ion st (II) v st (III) u ln nn c th c cc im
trn ng chun mt cch thun li nht theo h thc:

278
Fe2+

E = E 0,059 log
Fe3 +

Khp c vng v vng sau im tng ng th hai, ng chun thc cht l

ng nht vi ng chun ion st(II) ring bit. Nhng php tnh nh vy khng tnh
c th im tng ng th nht. C mt cch thun tin tnh gi tr l cng cc
phng trnh Nerst biu din th ca st(II) v titan(III). V th in cc ca hai h bng nhau
im cn bng nn ta c th vit:
2E = +0,099 + 0,77 0,059 log

Ti3+ Fe2+

TiO2+ Fe3 + H+

Cc ion st (III) v titan (III) tn ti lng nh v bng nhau do kt qu ca cn bng:

2H+ + TiO42+ + Fe2+

Fe3+ + Ti3+ + H2O

[Fe3+] = [Ti3+]

nn

Thay kt qu ny vo phng trnh th trn y ta c:

0,87 0,059
E=+
log

2
2

Hnh 14.4

Fe2+

[TiO2 ] H+

279
ng chun 50,0 ml dung dch hn hp Ti3+ 0,050 M v Fe2+ 0,200 M bng dung dch KMnO4
0,050 M. Nng H+ ca dung dch lun bng 1,0 M

Cui cng, nu [ TiO22+ ] v [Fe2+] c gi nh l c nng phn tch ng nht ta c

th tnh th tng ng.
ng chun hn hp st (II) v titan (III) bng dung dch pemanganat c dn ra
trn hnh 14.4.

14.7 Cht ch th oxi ha kh

C hai loi ch th ha hc c s dng pht hin im cui ca nhng php chun
oxi ha kh: nhng cht ch th oxi ha kh thng thng v nhng ch th oxi ha kh
c bit.

14.7.1 Nhng ch th oxi ha kh thng thng

Nhng ch th oxi ha kh thng thng l nhng cht chuyn mu khi b oxi ha hoc
kh. Khc vi cc cht ch th c bit c mu bin i ph thuc nhiu vo bn cht ha hc
ca cht cn phn tch v cht chun, s chuyn mu ca cc cht ch th tht s oxi ha kh
ph thuc vo s bin i th in cc ca h xut hin do s tin trin ca php chun .
C th vit na phn ng tng ng vi s chuyn mu ca mt cht ch th oxi ha kh
thng thng nh sau:
Inox + ne

Inkh

Nu phn ng ch th thun nghch, c th vit:

E = Eo

[ InKh ]
0,059
log
n
[InOx ]

(14.4)

Mt ngi ch c kh nng nhn bit s bin i mu khi

[InKh ] 1 chuyn thnh [InKh ] 10

[InOx ] 10
[InOx ]
C th tm thy s bin i th cn thit to nn s chuyn mu hon ton ca cht ch
th thng thng in hnh bng cch thay th hai gi tr trn y vo phng trnh (14.4).
E = EoIn

0,059
n

280

Phng trnh trn ch r rng, mt cht ch th thng thng ch c th biu l

kh nng pht hin s chuyn th ca mnh khi cht chun gy nn s chuyn dch th ca
h t EoIn + 0,059/n n EoIn 0,059/n hoc khong (0,118/n) V. i vi nhiu ch th n = 2
v s chuyn dch 0,059 V l .
Bng 14.2 di y lit k th dch chuyn ca mt s cht ch th oxi ha kh. Cu trc
v phn ng ca mt s ch th c lit k trong bng nu trn s c bn lun mc
di y.
Bng 14.2 Cc cht ch th oxi ha kh la chn

Mu
Cht ch th

Dng
ha

ox

Dng kh

Th chuyn
iu kin
dch

Phc Fe(II)-5-nitroXanh nht

1,10-phenantrolin

tm

+1,25

H2SO4 1 M

Axit iphenylamin
Xanh tm
icacboxilic

Khng mu

+1,12

H2SO4 7 10 M

Phc
Fe(II)-1,10Xanh nht
phenantrolin

+1,11

H2SO4 1 M

Phc
Fe(III)-5Xanh nht
metyl,1,10phenantrolin

+1,02

H2SO4 1 M

Erioglancin A

Xanh

Vng lc

+0,98

H2SO4 0,5 M

iphenylamin
sunfomic axit

tm

Khng mu

+0,85

Axit long

iphenylamin

Tm vng

Khng mu

+0,76

Axit long

p-Etoxicrisidin

Vng

+0,76

Axit long

Metylen xanh

Xanh

Khng mu

+0,53

Axit 1 M

Indigo tetrasunfonat

Xanh

Khng mu

+0,36

Axit 1 M

Phenosafranin

Khng mu

+0,28

Axit 1 M

Phc ca st (II) vi o-phenantrolin

281

Mt lp cc hp cht hu c c bit nh 1,10-phenantrolin (hoc o-phenantrolin)

to phc bn vi st (II) v mt vi ion khc. Hp cht ny c hai nguyn t nit c phn
b v tr c th to lin kt cng ha tr vi ion st (II). Ba phn t o-phenantrolin lin kt
vi mt ion st (II) to thnh phc c cu trc:

Phc ny i khi c gi l "feroin" c cng thc ha dng (phen)3Fe2+.

Phc st feroin tham gia phn ng oxi ha kh thun nghch:
(phen)3Fe3+ + e

(phen)3Fe2+

Xanh nht

; Eo = +1,06 V

Trong thc t mu ca dng oxi ha rt nht, kh pht hin nn s chuyn mu lin hp

vi dng kh l t dng gn nh khng mu n mu . V s khc nhau v cng mu
nh vy nn im cui thng l lc ch 10% ch th dng phc vi st (II). Th dch
chuyn khong +1,11 V trong axit sunfuric 1 M.
Trong tt c cc ch th oxi ha kh, feroin l cht gn nht vi ch th oxi ha kh l
tng. Ch th ny phn ng nhanh v thun nghch, chuyn mu r rng, dung dch ch th
bn v c iu ch sn. Khc vi nhiu ch th oxi ha kh khc, dng oxi ha ca feroin
c bit tr i vi cc cht oxi ha mnh. nhit khong 60oC feroin b phn hy.
Nhng tnh cht ch th ca mt s dn xut ca phenantrolin cng c nghin cu v
mt s trong chng chng t rng, cng hu dng nh hp cht gc. Trong s , ng
ch l cc dn xut 5-nitro v 5-metyl:

O 2N

N
N

H3C

N
N

Th dch chuyn tng ng ca chng l +1,25 V v +1,02 V.

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iphenylamin v cc dn xut ca n

iphenylamin, C12H11N, l mt trong nhng cht ch th oxi ha kh c pht hin

u tin v c Knop s dng nm 1924 chun st (II) bng kali icromat. Khi c mt
cht oxi ha mnh, chc chn l iphenylamin s tri qua nhng phn ng:

iphenylamin
(khng mu)

+ 2H+ + 2e

iphenylbenziin
(khng mu)

N
+ 2H+ + 2e

iphenylbenziin
(khng mu)

iphenylbenziin tm
(mu tm)

Phn ng th nht khng thun nghch, nhng phn ng th hai l thun nghch v to
nn phn ng ch th tht s.
Th kh ca phn ng th hai vo khong 0,76 V. Do ion hiro xut hin trong phng
trnh, s dao ng v axit c nh hng nh n gi tr th, c l do sn phm mu l cht
proton ha.
iphenylamin khng phi l cht tan nhiu trong nc, nn phi iu ch dung dch ch
th trong axit sunfuric. Cn ch l, khng c dng ch th cho cc dung dch c cha ion
wonfram v s to thnh kt ta mu tm. Ion Hg(II) cng gy cn tr v km hm phn ng
ch th.
Dn xut sunfonic ha iphenylamin c cu trc:
H
HO3S

khng gp phi nhng tr ngi nu trn. Dung dch ch th trong nc c iu ch t

mui kali hoc natri ca axit ny c nhng tnh cht c bn ging nh iphenylamin. Tuy
vy, s chuyn mu hi khc mt cht: chuyn t khng mu qua lc sang tm thm. Th dch
chuyn khong +0,8 V v ph thuc vo nng axit. Ngy nay, dn xut sunfonic c s
dng rng ri trong chun oxi ha kh.
iphenylbenziin, sn phm trung gian ca phn ng oxi ha iphenylamin, c tnh cht
ging nh iphenylamin trong cc phn ng oxi ha kh nhng tiu th t cht oxi ha hn.
ng tic l, do tan thp trong nc v trong axit sunfuric nn iphenylbenziin khng
c s dng rng ri. C th hy vng rng, dn xut sunfonic ha ca iphenylbenzidin s l
cht ch th thch hp.

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Dung dch iot-h tinh bt

H tinh bt to thnh mt phc mu xanh tri vi triioua, nn c s dng rng ri

lm cht ch th c bit trong cc phn ng oxi ha kh sinh ra io do mt cht oxi ha hoc
sinh ra ioua do mt cht kh. V vy, mt dung dch h tinh bt cha mt lng nh ion
triioua hoc ioua cng c th lm chc nng ca mt cht ch th oxi ha kh thc s. Khi
d cht oxi ha, t s nng iot trn ioua cao lm cho dung dch c mu xanh. Khi d cht
kh, nng ion ioua chim u th nn mu xanh bin mt. Nh vy l, h ch th bin i
t khng mu n xanh trong php chun nhiu cht kh bng cc cht oxi ha. S chuyn
mu ny hon ton c lp vi thnh phn ha hc ca cc cht phn ng, ch ph thuc vo
th ca h ti im tng ng.
La chn cht ch th oxi ha kh

T hnh 14.3, r rng l tt c ch th bng 14.2, tr ch th u tin v cui cng, u c

th s dng vi thuc th A. Ngc li, vi thuc th D ch c th s dng indio
tetrasunfonat. Th chuyn i (dch chuyn) vi thuc th E qu nh nn pht hin c
ch c mt ch th.

14.7.2 Ch th c bit
Mt ch th c bit c bit n nhiu nht l h tinh bt. Ch th ny to phc xanh
thm vi triioua. Phc ny cho tn hiu v im cui ca php chun nh phn ng lm
xut hin hoc bin mt iot.
Mt ch th c bit khc l kali tioxianat. C th s dng tioxianat, v d nh, chun
st (III) bng titan (III) sunfat. im cui c pht hin theo s bin mt phc mu st
(III)-tioxianat do nng st (III) b gim ti im tng ng.

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Chng 15
Phn hy v ha tan mu

Hu ht cc php o phn tch u c thc hin trong cc dung dch (thng l dung
dch nc) ca cht cn phn tch. Trong khi mt s mu c th tan tt trong nc hoc trong
cc dung dch nc ca axit hoc baz thng thng th mt s mu li i hi cc thuc th
c tc dng mnh v cch x l chnh xc, nghim ngt. V d nh, khi cn xc nh lu
hunh hoc halogen trong mt hp cht hu c, cn phi x l mu nhit cao v bng
ha cht c tc dng mnh ph v nhng lin kt bn vng gia cc nguyn t ny vi
cacbon. Mt cch tng t, nhng iu kin m bo c tc dng mnh, c hiu qu cao cng
thng c s dng ph v cu trc silicat ca cc khong liu silic a cc cation ca
mu v trng thi t do, to iu kin thun li cho php phn tch.
S la chn thuc th v k thut thch hp phn hy v ha tan mu phn tch c
ngha quyt nh, m bo thnh cng cho php phn tch, c bit l khi phi s dng vt
liu chu nhit v chu s tn cng bng cc ho cht c tc dng mnh hoc khi cht cn
phn tch tn ti lng vt. Trong chng ny, u tin, chng ta bn lun v cc loi sai s
xut hin trong qu trnh phn hy v ha tan mu phn tch, sau s trnh by 4 phng
php phn hy cc mu rn v lng thu c cc cht cn phn tch trong dung dch nc.
Cc phng php khc nhau nhit phn hy mu v cng ca ha cht c s
dng. Chng bao gm:
1. un dung dch cc axit mnh (hoc i khi l cc baz) trong cc m.
2. un bng vi sng dung dch cc axit trong bnh nt kn.
3. t chy nhit cao trong khng kh hoc trong oxi.
4. Nung chy trong mi trng mui nng chy.

15.1 Ngun sai s trong phn hy v ha tan mu

Mt vi ngun sai s thng gp trong phn hy mu. Ngun sai s ny lm gii hn
chnh xc ca php phn tch c thc hin. Nhng ngun sai s nh th c dn ra di
y:

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15.1.1 S ha tan khng hon ton cc cht cn phn tch

Php x l mu l tng l php x l ha tan hon ton mu, bi v mi c gng tch
nh lng cht cn phn tch t b khng tan thng khng thnh cng, do mt phn cht
cn phn tch cn li bn trong phn khng tan ca mu.

15.1.2 S mt i mt phn cht cn phn tch do bay hi

Mt iu quan trng cn ch khi ha tan mu l mt phn cht cn phn tch c kh
nng b bay hi. V d nh CO2, SO2, H2S, H2Se, H2Te thng b bay hi khi ha tan mu
trong axit mnh, nhng ngc li amoniac li thng mt khi s dng thuc th baz. Mt
cch tng t, axit fluoric phn ng vi silicat v cc hp cht cha bo to thnh hp cht
bay hi florua. Cc dung mi oxi ha thng gy ra s bay hi clo, brom, iot. Cc dung mi
kh c th dn ti s bay hi cc hp cht nh asin, photphin, stibin.
Mt s nguyn t to thnh cc clorua bay hi nn b mt mt phn hay hon ton t cc
dung dch axit clohiric nng. Nhng hp cht l: thic (IV), gecmani (IV), antimon (III),
asen (III), thy ngn (II) clorua. Nhng oxiclorua ca selen v telua cng b bay hi n mt
mc no t dung dch axit clohiric nng. S c mt ca ion clorua trong dung dch
axit sunfuric hoc pecloric m c v nng c th lm mt do bay hi bismut, mangan, tali,
molypen, vanai v crom.
Axit boric, axit nitric v cc axit halogen u b mt t cc dung dch nc un si. Cc
oxit bay hi nh tetraoxit osmi, ruteni, heptaoxit ruteni cng c th b mt t cc dung dch
axit nng.

15.1.3 a cht bn dung mi vo cht cn phn tch

Thng thng khi lng ca dung mi cn thit ha tan mt mu phi d hn khi
lng mu hng chc hoc hng trm ln. Kt qu l, cht cn phn tch tn ti trong dung
mi ngay c khi ch c nng thp cng c th gy sai s ng k, c bit l khi cht cn
phn tch ch c hm lng vt trong mu.

15.1.4 a cht bn t phn ng ca dung mi vi thnh bnh vo mu

Ngun sai s thng gp khi phn hy mu, v d nh nung chy nhit cao. Hn
na, ngun sai s li tr thnh mi quan tm c bit trong phn tch lng vt.

15.2 Phn hy mu bng axit v c trong bnh m

Hu ht cc thuc th dng phn hy cc mu phn tch v c trong bnh m l cc
axit v c (amoniac v cc dung dch nc ca hiroxit kim loi kim t c s dng hn).
Thng thng, huyn ph ca mu trong axit c un nng bng ngn la hoc bng mt

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bn kim loi nng cho n khi s ho tan mu c thc hin hon ton c biu
th bng s bin mt ca pha rn. Nhit phn hy l im si (hoc phn hy) ca thuc
th axit.

15.2.1 Axit clohiric

Axit clohiric m c l mt dung mi tt nht cho cc mu v c nhng ch c ng
dng hn ch phn hy cc vt liu hu c. Axit ny c s dng rng ri ha tan
nhiu oxit kim loi cng nh cc kim loi d b oxi ha hn hiro v thng l dung mi cho
cc oxit tt hn cc axit oxi ha. Nng ca axit clohiric c khong 12 M, nhng khi b
un nng, hiro clorua b mt i cho ti khi cn li mt dung dch 6 M si hng nh (im
si khong 110oC).

15.2.2 Axit nitric

Axit nitric c v nng l mt cht oxi ha mnh, ha tan tt c cc kim loi thng
thng, tr nhm v crom tr thnh th ng vi thuc th do s to thnh oxit trn b mt.
Khi nhng hp kim cha thic wonfram hoc antimon c x l bng thuc th nng,
nhng oxit hirat ha t tan, v d nh SnO2.4H2O c to thnh. Sau khi lm ng t, c th
tch cc hp cht keo ny khi cc hp cht ca cc kim loi khc bng cch lc.
Axit nitric nng ring mt mnh, hoc vi hn hp cc axit khc v cc cht oxi ha khc
nh hiro peoxit v brom c s dng rng ri phn hy cc mu hu c trc khi xc
nh hm lng vt kim loi. Qu trnh phn hy c gi l s tro ha t, lm bin i
mu hu c thnh cacbon ioxit v nc. Nu khng thc hin trong bnh ng kn, cc
nguyn t phi kim nh halogen, lu hunh v nit s b mt i hon ton hay mt phn do
bay hi.

15.2.3 Axit sunfuric

Nhiu vt liu b phn hy v ha tan bng axit sunfuric c nng nh tnh hiu qu ca
n nh mt dung mi im si cao (khong 340oC). Hu ht cc hp cht hu c b
ehirat ha v oxi ha nhit v sau li b loi tr khi mu dng cacbon ioxit
v nc nh php x l tro ha t . Hu ht cc kim loi v nhiu hp kim b ha tan
bng axit nng ny.

15.2.4 Axit pecloric

Axit pecloric c nng, mt cht oxi ha c hiu qu mnh, ha tan c mt s hp kim
st v thp khng g l nhng cht khng ha tan c trong nhng axit v c khc. Cn c
bit ch khi s dng ha cht ny v tnh gy n tim tng ca n. Axit c lnh khng gy
n, axit long nng cng khng gy n. N mnh xy ra khi axit pecloric c nng tip xc

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vi cc vt liu hu c d b oxi ha. V tnh cht nn axit pecloric ch c un nng

trong nhng ci chp c bit.
Trn nhn chai axit pecloric thng ghi hm lng t 60% n 72%. hn hp si hng
nh (72,4% HClO4) thu c 203oC.

15.2.5 Cc hn hp oxi ha
i khi c th tro ha t nhanh hn bng cch s dng hn hp axit hoc c th thm
cc cht oxi ha vo mt axit v c. Cng thy l mt hn hp gm 3 th tch axit clohiric
c trn vi mt th tch axit nitric c. Thm brom hoc hiro peoxit vo axit v c thng
nng cao c hot tnh ca dung mi v thc y s oxi ha cc vt liu hu c trong mu.
Hn hp ca axit nitric v pecloric cng c li cho mc ch nhng t nguy him hn so
vi axit pecloric c dng ring bit. Tuy vy, vi hn hp ny cng cn ch trnh s bay
hi ca ton b axit nitric trc khi s oxi ha cc vt liu hu c xy ra hon ton. S gii
thch mt cch r rng l cn thit v nhng thit hi s l tt yu do nhng thiu st trong
tun th bin php phng.

15.2.6 Axit fluoric

ng dng ch yu ca axit fluoric l phn hy qung silicat v cc khong liu dng
phn tch cc cht khc ngoi silic ioxit. Trong php x l , silic c tch ra dng
tetrafluorua. Sau khi php phn hy hon thnh, lng axit fluoric d c tch ra bng
cch lm bay hi nh axit sunfuric hoc axit pecloric. Tch hon ton axit fluoric l rt cn
thit, m bo cho php phn tch thnh cng bi v ion florua phn ng vi mt s cation
to thnh phc bn gy cn tr cho vic xc nh cc ion ny. V d, kt ta nhm (di dng
Al2O3.xH2O) bng amoniac rt khng hon ton nu ion florua c mt d ch lng nh.
Thng thng, s loi b nhng lng vt cui cng ca ion florua khi mu l rt kh khn
nn thi gian tiu ph cho ng tc ni trn chnh l li ph nhn c tnh v cng hp dn
ca axit fluoric trong chc nng lm dung mi cho silicat.
Axit fluoric c dng cng vi cc axit khc ha tan nhng thp kh tan trong cc
dung mi khc.
V axit fluoric rt c nn cn ha tan mu v lm bay hi loi b thuc th trong mt ci
chp c thng hi tt. Axit fluoric gy ra nhng tn tht nghim trng, to ra vt thng au
n khi tip xc vi da. Tc dng ca n c th khng r rng ti hng gi sau khi trn. Nu
axit tip xc vi da cn ra ngay vng b tc dng bng lng nc ln. X l bng dung dch
canxi long kt ta ion florua cng c tc dng tt.

15.3 Phn hy bng vi sng

S dng l vi sng phn hy c mu v c v hu c c ngh ln u tin
gia nhng nm 70 v n nay n tr thnh mt phng php quan trng phn hy

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mu. S dng vi sng c th dng bnh ng v dng bnh m, nhng dng bnh
ng c a chung hn v p sut cao hn v do nhit cng cao hn. Nhng bn lun
ca chng ta ch yu tp trung vo vn phn hy mu bng vi sng trong bnh ng.
Mt trong nhng tin b ch yu ca phn hy vi sng so vi cc phng php thng
thng khc nh s dng ngn la hoc bn kim loi c nung nng l tc . V d nh,
phn hy vi sng thm ch nhng mu kh phn hy c th c hon tt trong 5 n 10 pht.
Ngc li, c c nhng kt qu nh trn phi cn nhiu gi khi thc hin bng cch t
trn ngn la hoc trn bn kim loi c nung nng. S khc nhau v tc phn hy mu
ca 2 phng php nu trn l do c ch v dng nng lng c chuyn ti mu ca chng
khc nhau. Trong phng php thng thng, nhit c chuyn ti nh tnh dn nhit. Bnh
c s dng trong phng php ny thng c dn nhit km nn cn thi gian nung
nng bnh v sau mi chuyn nhit ti dung dch cng bng dn nhit. Hn na, do s
i lu trong dung dch nn ch mt phn nh ca dung dch c c nhit ca bnh v
tnh hnh cng nh vy ti im si ca dung dch. Ngc li, nng lng vi sng c
chuyn trc tip ti ton b cc phn t ca dung dch gn nh cng mt lc, khng c giai
on t nng bnh. Nh vy l, ton b dung dch t ti im si rt nhanh.
Nh nhn xt trc y, thun li ca vic s dng bnh ng kn phn hy vi sng
l c c nhit cao hn do p sut tng ln. Thm vo , v trnh c mt mt do bay
hi nn lng thuc th cn thit t hn v do gim c tc dng cn tr do tp cht ca
thuc th gy nn. Mt thun tin na ca vic phn hy loi ny l, cc hp phn bay hi
ca mu hu nh khng b mt. Cui cng, phn hy vi sng trong bnh ng kn thng d
dng t ng ha nn gim c thi gian cho vic chun b mu phn tch.

Hnh 15.1
Bnh iu chnh p sut phn hy mu bng vi sng

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15.4.3 Bnh phn hy mu c iu chnh p sut

Bnh un mu bng vi sng c ch to bng vt liu bn, vi sng d truyn qua. Nhng
vt liu ny cng cn phi bn nhit v chu c tc dng ca cc axit thng dng phn
hy mu. Teflon l vt liu gn nh l tng i vi nhiu axit thng dng ha tan mu.
Teflon c im nng chy khong 300oC, khng b mt axit thng thng no tc dng, cho
vi sng chuyn qua rt d dng. Nhng axit sunfuric v axit photphoric u c im si cao
hn im chy ca teflon nn cn phi kim tra nhit rt cn thn trong qu trnh phn hy.
i vi cc axit ny, bnh thch anh hoc bnh thy tinh bosilicat i khi c s dng
thay th cho bnh teflon. Nhng bnh silicat c bt li l b axit fluoric tc dng - mt axit
thng dng phn hy silicat v cc hp kim chu nhit.
Trn hnh 15.1 l s bnh phn hy mu ng kn, tin li c bn th trng, c
thit k dng trong l vi sng.

15.4.3 Bnh vi sng p sut cao

Trn hnh 15.2 dn ra s bom vi sng c bn th trng, c thit k dng 80
atm hoc 10 ln p sut c th chu ng c ca bnh c iu chnh p sut c m t
trn y. Nhit ti a c khuyn co vi thit b ny l 250oC. Thnh ca thn bom
c ch to bng vt liu cao phn t nn vi sng truyn qua d dng. S phn hy c
thc hin trong mt ci chn teflon t trong thn bom. Bom vi sng lin kt mt vng teflon
trong rnh ca np nm i din vi mt khe hp thng ra bn ngoi v np c mang v
chng ta nhit c xoy cht vo v tr t. Khi p sut qu ln, vng teflon b bin dng v
p sut d, sau s nn ln a m, cho php kh thot ra mi trng xung quanh. Khi iu
xy ra, mu c th b nguy him. C th xt on phng chng p sut bn trong bom bng
khong cch ca c p sut nh ln khi np. Bom vi sng rt hay c s dng ha tan
cc vt liu chu nhit cao bi v cc vt liu ny b ha tan mt phn trong bnh p sut c
iu chnh c trnh by trn y.

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Hnh 15.2
Bom phn hy vi sng p sut cao

15.4.3 L vi sng

Hnh 15.3
L vi sng c thit k s dng cho 12 bnh

Trn hnh 15.3 gii thiu s l vi sng c thit k un cng mt lc 12 bnh p

sut c iu chnh c trnh by mc 15.3.1. Cc bnh c t trong gi quay, quay
lin tc 360o sao cho nng lng trung bnh cp cho mi bnh l ng nht.

15.4.3 L thiu vi sng

Gn y l thiu vi sng c pht trin thc hin nung chy v tro ha kh mu
cha mt lng ln vt liu hu c. L thiu vi sng bao gm mt bung nh c xy dng
bng cacbua silic v c bao ph bng thch anh cch in. Khi vi sng c tp trung cho
bung , nhit t ti 1000oC trong 2 pht. S thun li ca l loi ny so vi l muf
truyn thng l t ti nhit cao nhanh chng. Ngc li, khi dng l muf thng thng
phi thao tc lin tc nn cn c thi gian l mi t ti nhit cn c. Hn na, l thiu
vi sng khng c tt dn, khng c nung nng cun dy hoc thanh nung nh trong cc l
muf thng thng. Cui cng l, ngi iu chnh l khng cn phi iu chnh nhit khi

291

a mu vo v khi ly mu ra khi l. im bt li ca l thiu vi sng l th tch c nung

nng nh, ch thch hp vi chn nung c kch thc thng thng.

15.4.3 S dng phn hy vi sng trong bnh ng kn

Trong 20 nm cui ca th k XX xut hin hng trm cng trnh s dng bnh ng
kn phn hy mu trong l vi sng vi cc thuc th c dn ra mc 15.2. Nhng
ng dng ny c chia lm 2 loi:
1. Phn hy oxi ha cc mu hu c v sinh vt (tro ha t).
2. Phn hy cc cht v c chu nhit thng gp trong cng ngh.
Trong c 2 trng hp, k thut mi ny thay th cc phng php truyn thng c
bi v tit kim c thi gian, cng sc v c hiu qu kinh t cao.

15.4 Phng php t chy phn hy cc mu hu c

15.4.1 t chy trn ngn la m (tro ha kh)
Phng php n gin nht phn hy mt mu hu c trc khi xc nh cc cation c
trong mu l t mu trong mt ci a hoc chn nung m cho ti khi ton b vt liu cha
cacbon b oxi ha hon ton n cacbon ioxit. t n nng thng l iu kin oxi
ha hon ton. Phn tch cc hp cht khng bay hi c thc hin bng cch ha tan cn
cn li. Nhng thng vn xy ra mt s tht, khng chc chn thu c hon ton nhng
nguyn t khng bay hi t cc mu tro ha kh. Kt qu cng c th b mt i mt phn nh
do b cun i nhng ht mu rt mn trong vng i lu vng quanh chn nung. Thm vo ,
nhng hp cht kim loi bay hi c th b mt trong qu trnh t chy. V d nh, ng, st,
vanai c th b bay hi khi mu cha cc hp cht porphyrin b tro ha.
Mc d tro ha kh l phng php n gin nht phn hy cc hp cht hu c
nhng li thng l phng php t tin cy nht. Phng php ny s khng c ng dng
nu nh khng c nhng th nghim chng t kh nng ng dng ca phng php cho loi
mu cn c phn tch.

15.4.2 Phng php t trong ng

Nhng hp phn c s quan trng v thng thng ca cc hp cht hu c c chuyn
thnh cc sn phm kh khi nhit phn mu iu kin c oxi. Vi nhng thit b thch
hp c th thu nh lng cc hp cht bay hi v chuyn chng thnh dng thch hp
phn tch nhng nguyn t c quan tm. Phn hy nhit thng c thc hin trong ng
nhit phn bng thy tinh hoc thch anh c dng kh mang i qua. Dng kh chuyn cc
sn phm bay hi n nhng phn ca thit b m cc sn phm ny c tch ra v gi

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li o. C th s dng kh mang nh l thuc th oxi ha. Cc nguyn t c

chp nhn cho loi x l ny l cacbon, hiro, nit, halogen, lu hunh v oxi.
Ngy nay, my phn tch ng thiu nhit t ng rt tin dng xc nh hoc l
cacbon, hiro v nit hoc l hirocacbon v oxi trong mt mu n gin. Thit b khng i
hi s ch ca ngi thao tc v php phn tch c hon thnh trong thi gian t hn 15
pht. Trong my phn tch loi ny, mu c thiu chy trong dng heli v oxi chuyn qua
trn xc tc oxi ha l hn hp bc vanaat v bc tungstat. Halogen v lu hunh c
chuyn ti cng vi gi mui bc. Mt gi ng c nung nng c t cui b phn
thiu nhit chuyn ng kh oxi v chuyn nit oxit thnh nit. Kh ra l mt hn hp gm
nc, cacbon ioxit, nit v heli c thu thp li trong mt bnh cu thy tinh. Phn tch hn
hp ny c hon thnh nh 3 php o dn nhit. Php o th nht c thc hin trn
hn hp cn nguyn vn, php o th hai c thc hin trn hn hp sau khi tch nc
bng cch cho hn hp kh i qua thuc th ehirat ha v php o th ba c thc hin
trn hn hp sau khi cacbon ioxit c loi tr bng mt cht hp th. Mi quan h gia
dn nhit v nng l tuyn tnh v dc ca ng biu din i vi mi hp phn c
xc nh bng cch chun ha nh mt hp cht tinh khit, v d nh axetanlinid.

15.4.3 Thiu nhit vi oxi trong bnh cha ng kn

Phng php phn hy nhiu hp cht hu c nh s thiu nhit vi oxi trong bnh ng
l phng php kh tin cy. Cc sn phm phn ng c hp th trong mt dung mi thch
hp trc khi bnh phn ng c m ra. Sau , cc sn phm c phn tch bng cc
phng php thng thng.
Mt thit b n gin rt ng ch thc hin s oxi ha nh vy c Schniger
ngh (hnh 15.4). Thit b l mt bnh thnh dy c th tch t
300 1000 ml,
ming kht vi mt nt thy tinh trn. Gn vo nt l mt ci r bng li platin rt mn dng
gi t hai n 200 mg mu. Nu cht cn phn tch l cht rn, s c gi trong mt mu
giy lc t tn ct theo hnh c dn ra trn hnh 15.4. Nu mu l cht lng, s c cn
trong chn gelatin v sau gi li theo cch tng t. ui ca t giy c dng lm im
t chy.

293

Hnh 15.4
Thit b thiu nhit Schniger

Mt th tch nh dung dch cht hp th (thng l natri cacbonat) c cho vo bnh v

khng kh trong bnh c thay bng oxi. Sau khi t chy ui mu giy lc, nhanh chng
ng kn bnh v ln ngc bnh ngn cn sn phm oxi ha bay hi thot ra ngoi. Thng
thng phn ng xy ra nhanh v c xc tc bi li platin bao quanh mu. Trong bc
t chy, bnh phi c che y cn thn gim n cc tiu nguy c b n.
Sau khi lm lnh, lc bnh cn thn ri tho my, ra mt bn trong ca bnh n sch.
Php phn tch c thc hin trn dung dch thu c. Quy trnh s c p dng phn
tch halogen, lu hunh, photpho, flo, asen, bo, cacbon v nhng kim loi khc trong hp cht
hu c.

15.5 Phn hy cc vt liu v c bng cht nung chy

Mt s cht thng thng nh silicat, oxit v c v mt s t hp kim st, ch b ha tan
mt cch chm chp bng tt c cc phng php bn lun trn y. Trong trng hp nh
vy phi cu cu ti mi trng mui nng chy. Trong phng php ny, mu c trn vi
mui kim loi kim (c gi l cht nung chy) v sau cho hn hp nung chy c
lm ngui tc dng vi nc to thnh cc sn phm tan trong nc. Cc cht nung chy
phn hy hu ht cc cht nhit cao, t 300 n 1000oC, v tip xc vi mu nng
cao.
Khi c kh nng nn trnh dng cht chy do c nguy c gy bt li khi s dng chng.
V d nh, gy nhim bn mu do c tp cht trong cht chy. S nhim bn tr nn trm
trng hn do lng tng i ln ca cht chy (t nht 10 ln ln hn trng lng mu) cn
phi c mi m bo nung chy thnh cng. Hn na, dung dch nc thu c khi ha tan
mu nng chy c hm lng mui cao c th gy nhng kh khn trong nhng bc tip

294

theo ca php phn tch. Thm vo , nhit cao cn thit cho nung chy s lm
tng nguy c mt do bay hi. Cui cng, chn nung thc hin nung chy gn nh chc
chn b tn cng n mt mc no do nung chy v mt ln na nhim bn mu l kt qu.

15.5.1 Thc hnh nung chy

Trn mu dng bt rt mn vi khong 10 ln d cht chy. Trn mu v cht chy
thng c thc hin trong chn nung sau nung chy. Thi gian cn thit cho qu
trnh nung chy t vi pht n vi gi. Khi thu c khi nng chy trong sut l du hiu
chng t s phn hy hon thnh mc d iu kin thng khng phi lun r rng.
Khi s nng chy hon thnh, lm lnh chm sn phm thu c. Ngay trc khi m
np cn phi xoay trn chn phn b cht rn nng chy trn thnh chn mt lp mng d
ly ra.

15.5.2 Cc loi cht nung chy

Loi tr mt t ngoi l, cc cht nung chy thng c s dng trong phn tch l cc
hp cht ca kim loi kim, cacbonat, hiroxit, peoxit v borat. Kim loi kim l cht nung
chy baz, chng ha tan cc vt liu axit. Cc cht nung chy axit l pyrosunfat, florua v
oxit bo. Nu cn cht nung chy oxi ha, c th dng natri peoxit. Cng c th dng lng
nh nitrat hoc clorat kim loi kim trn vi natri cacbonat lm cht nung chy. Tnh cht ca
cc cht nung chy ph bin c tm tt trong bng 15.1.
Natri cacbonat: C th phn hy silicat v cc vt liu chu nhit khc bng cch nung
n nhit t 1000 n 1200oC vi natri cacbonat. Php x l ni chung c th lm bin i
cc hp phn cation ca mu thnh cacbonat axit tan hoc oxit; cc hp phn phi kim c
chuyn thnh mui natri tan. Nung chy cacbonat c thc hin bnh thng trong chn
platin.
Kali pyrosunfat: Kali pyrosunfat l cht nung chy axit mnh, c s dng mt cch c
bit ha tan nhng kim loi rt kh tan. Cc php nung chy vi thuc th ny c thc
hin khong 400oC; nhit ny s bin chuyn chm ca kali pyrosunfat xy ra nh sau:

K2S2O7

K2SO4 + SO3(kh)

C th iu ch kali pyrosunfat bng cch nung kalihiro sunfat:

2KHSO4

K2S2O7 + H2O

Liti metaborat: Liti metaborat LiBO2 c dng ring hoc hn hp vi liti tetraborat
c s dng nhiu ha tan silicat chu nhit, cc khong liu nhm, c bit l cho phn
tch hp th AAS v pht x tia X. Thng thng, php nung chy c thc hin trong chn
graphit hoc platin khong 900oC. Khi thy tinh sinh ra do lm lnh hn hp nng chy c
th c s dng trc tip o hunh quang tia X. Cng c th ha tan hn hp nng chy

295

sau khi lm lnh bng cc axit v c. Sau khi dung dch ca hn hp nng chy c lm bay
hi n kh vi metyl ancol v metyl borat B(OCH3) c ct loi b.
Bng 15 Cc cht nung chy ph bin

Cht nung chy

im
chy,
(oC)

Loi chn
dng
Loi cht phn hy cc cht
nung chy

Na2CO3

851

Pt

Silicat v cc mu cha silic, cc mu

cha nhm, cc photphat v sunfat t tan

Na2CO3 + mt thuc
th oxi ha nh

KNO3, KClO3 hoc

Na2O2

Pt (khng Cc mu i hi mi trng oxi ha.

dng vi V d nh, cc mu cha S, Ag, Sb, Cr
Na2O2) Ni ...

LiBO2

849

Pt,
than
tinh

NaOH hoc

318

KOH

380

Au,
Cht nung chy baz mnh cho silicat,
thy
hu ht cc khong liu, g st, gm.

Au, Ag, Ni

Cht nung chy baz mnh cho silicat,

cacbua silic v mt s khong liu (hn
ch ch yu l tinh khit ca thuc
th).

Na2O2

B
phn
hy

Fe, Ni

Cc cht chy oxi ha baz mnh cho

cc sunfua, cc hp kim ca Fe, Ni, Cr,
Mo, W v Li khng tan trong axit, cc
hp kim platin, cc khong liu ca Cr,
Sn, Zn.

K2S2O7

30

Pt, s

Cht chy cho axit cho oxit t tan v

cc cht mu cha oxit

B2O3

577

Pt

Cht chy axit cho silicat v oxit

xc nh cc kim loi kim.

Ni

Cht chy nung hn hp l CaO v

CaCl2 c s dng phn hy silicat
cho mc ch phn tch kim loi kim.

CaCO3 + NH4Cl

296

Chng 16
Loi b cc tc dng cn tr
Mi tc dng cn tr no trong ha phn tch cng lm ny sinh mt hp cht trong nn
mu, hoc l sinh ra tn hiu khng th phn bit c vi tn hiu ca cht cn phn tch
hoc l lm gim tn hiu phn tch. Ch trong mt s rt t trng hp, tn hiu phn tch c
trng n mc khng b nh hng ca tc dng cn tr. Cn hu ht cc phng php phn
tch u i hi mt hoc mt s bc ban u loi b cc hiu ng cn tr.
C hai phng php tng qut rt c ch cho vic x l cc tc dng cn tr. u tin l
s dng thuc th cn tr v hiu ha cht cn tr hoc lin kt vi cht cn to thnh hp
cht mi t ng gp vo hoc t lm gim tn hiu ca cht cn phn tch. R rng l, thuc
th cn phi khng nh hng n tnh cht ca cht cn phn tch nhiu. V d nh, dng
ion florua ngn cn st (III) cn tr php o iot xc nh ng (II). y tc dng cn tr
ca ion florua l do xu hng to phc rt mnh ca n vi st (III) nhng khng to phc
vi Cu(II) gy ra. Kt qu l th in cc ca cp Fe(III)/Fe(II) gim xung, to ra iu kin
ch c cc ion Cu(II) trong mu oxi ha ioua thnh iot.
Cch x l tc dng cn tr th hai l, chuyn ha hoc cht cn phn tch hoc cht gy
cn tr vo pha tch tch ring ra. Trong chng ny chng ta ch cp ti cc phng
php tch c in, c s dng trc khi dng phng php sc k.

Bn cht ca qu trnh tch

Tt c mi qu trnh tch u c mt c s chung l s phn b cc cu t trong mt
hn hp gia hai pha v sau c th tch bit mt cch my mc. Nu t s v lng ca
mt cu t ring bit trong cc pha (t s phn b) khc nhau ln vi t s ca mt cu t
khc th phng php tch hai cu t c th thc hin c. Chc chn rng, phc tp ca
phng php tch ph thuc vo ln ca s khc nhau gia cc t s phn b. Khi s
khc nhau ln, m bo cho mt qu trnh n giai on xy ra. V d nh, kt ta bng
ion bc l hon ton thch hp tch clorua khi nhiu anion khc bi v khi d ion bc, t
s lng ion clorua trong pha rn v trong pha nc l rt ln so vi cc t s khc, v d
nh i vi ion nitrat, peclorat l rt gn vi s khng.
Mt tnh hung phc tp hn thng xy ra khi t s phn b i vi mt cu t gn vi
s khng nh trong v d dn ra trn y nhng t s i vi mt cu t khc li khng
ln. Trong trng hp ny cn mt qu trnh a giai on. V d nh uran (VI) c th b

297

chit vo ete t mt dung dch axit nitric trong nc. Mc d rng, t s phn b hp thc
duy nht vi php chit n, tuy nhin uran (VI) vn c th b tch nh lng bng php
chit lp, hoc mt cch trit hn, chit dung dch nc bng mt phn ete mi.
Khi cc t s phn b ca hai cht cn tch bit u cng ln hn s khng v gn nhau
v gi tr, cn phi s dng nhng quy trnh phc tp nht, ngha l k thut phn on nhiu
giai on nh sc k. K thut phn on da trn s khc nhau v h s phn b ca cht
tan. C hai yu t c gi tr tng cng hiu sut tch phn on. Th nht l, s ln phn
on xut hin gia hai pha c tng ln nhiu. Th hai l, s phn b xut hin gia cc
phn mi ca hai pha. Chit trit khc phn on ch l nhng phn mi ca ch mt
pha xut hin pha ch c.

Tch bng kt ta
Mun tch bng kt ta, s khc nhau v tan ca cht cn phn tch v cht gy cn
tr phi ln. C s l thuyt ca phng php tch loi ny l nhng tnh ton tan,
c dn ra chng 5. ng tic l c mt s yu t cn tr s dng thnh cng phng
php kt ta tch. V d nh, hin tng cng kt c cp ti mc 7.2.4 c th
gy nhim bn mnh kt ta do mt hp phn bt thng no ngay c khi tan ca sn
phm nhim bn khng ln. Hn na, tc to thnh kt ta ca mt kt ta khc cng c
kh nng nhng li qu chm s c li cho s tch bit. Cui cng, khi kt ta to thnh
dng keo huyn ph, s keo t c th kh khn v chm, c bit l khi c nh tch lng
nh ca pha rn. Nhiu thuc th to kt ta c ng dng tch nh lng cc cht
v c. Mt s thuc th ph bin v c s dng thnh cng nht s c trnh by cc
mc di y.

16.2.1 Tch da trn s kim tra axit

C s cch bit rt ln v tan ca hiroxit, hirat oxit v cc nguyn t trong axit.
Hn na, nng ca ion hiro hoc ion hiroxyl c th dao ng vi h s 10 hoc ln hn
v c th gi c n nh bng cch s dng cc dung dch m. H qu l, nhiu cch tch
da trn s kim tra pH t ra c hiu qu. C th phn chia chng thnh 3 loi:
1. Cc cch tch c thc hin trong dung dch axit mnh c nng tng i cao.
2. Cc cch tch c thc hin trong cc dung dch m cc gi tr pH trung bnh.
3. Cc cch tch c thc hin trong cc dung dch natri hoc kali hiroxit m c.

Bng 16.1 Cc cch tch da trn kim tra axit

298

Thuc th

Cc hp cht to thnh
kt ta

Cc cht khng b kt ta

HNO3 c, nng

Oxit ca W(VI), Ta(V),

Nb(V), Si(IV), Sn(IV),
Sb(V)

Hu ht cc ion kim loi

khc

Fe(III), Cr(III), Al(III)

Kim v kim th Mn(II),

Cu(II), Zn(II), Ni(II),
Co(II)

Dung
dch
m
CH3COOH/NH4CH3CO
O

Fe(III), Cr(III), Al(III)

Cc ion mang in tch 2+

ph bin

NaOH/Na2O2

Fe(III), hu ht cc ion
kim loi mang in tch
2+, t him

Zn(II), Al(III),
V(V), U(VI)

Dung
dch
NH3/NH4Cl

Cr(VI),

16.2.2 Tch bng sunfua

Ngoi cc ion kim loi kim v kim th, hu ht cc cation u to thnh cc sunfua t
tan; tan ca cc sunfua li khc nhau rt ln. C th kim tra nng ion sunfua trong
dung dch nc kh d dng thng qua vic iu chnh pH (xem mc 5.2.2) nn tch da
trn s to thnh cc sunfua c s dng rng ri trong thc t. C th kt ta sunfua mt
cch thun tin t dung dch ng th khi c cung cp anion S2 nh s thy phn
tioaxetamit (bng 7.2). X l l thuyt cn bng ion nh hng n tan ca kt ta sunfua
c bn lun mc 5.6. Nhng mt cch x l nh vy cng c th tht bi trn ng
i ti mt kt lun hin thc v kh nng tch do cng kt v do to thnh mt s sunfua vi
tc chm gy ra. Kt qu l, cch gii quyt phi da vo kh nng quan st thc t. Bng
16.2 dn ra mt s cch tch thng gp c thc hin bng H2S thng qua kim tra pH.
Bng 16.2 Kt ta sunfua

Nguyn t

iu kin kt ta (1)

Hg(II), Cu(II), Ag(I)

1, 2, 3, 4

As(V),
Sb(III)

(1)

As(III),

Sb(V),

1, 2, 3

iu kin khng kt
ta

1 = HCl 3 M; 2 = HCl 0,3 M; 3 = m pH = 6 bng CH3COOH/CH3COONa; 4 = m pH = 9 bng

NH3/(NH4)2S

299

Bi(III), Cd(II), Pb(II), Sn(II)

2, 3, 4

Sn(IV)

2, 3

1, 4

Zn(II), Co(II), Ni(II)

3, 4

1, 2

Fe(II), Mn(II)

1, 2, 3

16.2.3 Tch bng cc cht kt ta v c khc

Ni chung khng c ion v c khc c dng tch nh hiroxit v ion sunfua. Cc
ion photphat, cacbonat v oxalat thng c dng kt ta cc cation nhng tnh cht ca
chng khng la chn nn cn xem xt trc kh nng ng dng phng php tch loi ny.
Clorua v sunfat u c tnh cht la chn cao nn thng c s dng trong thc t.
Clorua thng c dng tch bc ra khi hu ht cc kim loi khc v sunfat thng
c dng tch ring nhm cc kim loi ch, bari, stronti.

16.2.4 Tch bng cc cht kt ta hu c

Cc thuc th hu c la chn tch cc ion v c c bn lun mc 7.4.3. Mt
s cc cht kt ta hu c ny, v d nh, imetylglyoxim c la chn rt cao khi to
thnh cc kt ta vi mt s t kim loi nn thng c s dng. Mt thuc th khc l 8hiroxiquinolin to thnh hp cht t tan vi s ln cc cation. la chn ca loi hp cht
ny ca thuc th l do tan ca sn phm phn ng ca n dao ng trong mt gii hn
rng v ng thi cng l do thuc th kt ta - mt anion - l baz lin hp ca mt axit
yu. V th cho nn nhng cch tch da trn s kim tra pH c th c thc hin hon
ton ging nh trng hp H2S.

16.2.5 Tch cc cht tn ti dng lng vt bng kt ta

Mt vn chung ca phn tch lng vt l tch bit lng microgam ca cht c
quan tm ra khi cc hp phn lng ln ca mu. Mc d rng bin php tch nh th i
khi c thc hin da trn mt phn ng kt ta nhng k thut i hi phi khc vi k
thut c dng khi phn tch lng ln.
C mt s vn cn c quan tm khi tch nh lng vt nguyn t bng cch kt
ta ngay c khi s mt mt do tan khng quan trng. Hin tng qu bo ha thng lm
chm qu trnh to thnh kt ta v s ng t nhng lng keo ca cht khuych tn
thng gy kh khn. Thm vo , mt phn cht rn b mt trong qu trnh chuyn v lc.
gim n ti a nhng kh khn , mt lng ca mt s ion khc cng to kt ta vi
thuc th thng thm vo dung dch. Kt ta c to thnh vi ion c thm vo c
gi l cht gp, n ko theo cht c hm lng nh thua ra khi dung dch. V d nh, khi
mun tch mangan dng ioxit mangan t tan, mt lng nh ion st (III) thng c

300

thm vo dung dch phn tch trc khi thm thuc th kt ta amoniac. Oxit baz
st (III) ko vo kt ta c lng nh nht ca oxit mangan. Cc v d khc: oxit baz nhm
l cht gp lng vt titan v ng sunfua c dng lm cht gp lng vt km v ch.
Nhiu cht gp khc c Sandell (1) v Onishi gii thiu.
Cht gp c th li cun theo hp phn vt nh s tng t v tan ca chng. Cc
cht gp khc to ra s cng kt, trong hp phn lng nh b hp ph trn b mt hoc
b hp nht vo kt ta gp nh s to thnh tinh th hn hp. R rng l, cht gp khng
c gy cn tr cho phng php c la chn xc nh hp phn vt.

Tch bng chit

Trong mc ny chng ta s cp ti vn ng dng hin tng phn b tch.

L thuyt
Hai thut ng c s dng din t s phn b mt cht tan gia hai dung mi
khng trn ln vo nhau l: h s phn b v t s phn b. iu quan trng l hiu r s
khc nhau gia hai i lng y :
H s phn b: H s phn b l hng s cn bng din t s phn b ca mt cht tan
gia hai dung mi khng trn ln. V d nh, khi lc mt dung dch nc cha mt cht hu
c tan A vi mt dung mi hu c, v d nh hexan, mt cn bng s c thit lp nhanh
chng v c din t bng cn bng sau :

A(n)

A(hc)

(16.1)

y (n) v (hc) l k hiu ch tng nc v tng hu c. Mt cch l tng, t s

hot ca cht A trong c hai tng l hng s v c lp vi tng lng ca A, bt k
nhit no hng s cng l :
Kd =

[ A ]hc
[ A ]n

(16.2)

y hng s cn bng Kd l h s phn b; A nm trong du ngoc vung, mt cch

cht ch, phi l hot ca cht A trong hai dung mi nhng nng phn t vn thng
c th thay th m khng phm sai lm nghim trng. Thng Kd xp x bng t s tan
ca A trong hai dung mi.
Khi cht tan tn ti cc dng lin hp khc nhau trong hai dung mi th cn bng tr
thnh:

(1)

E. B. Sandell v H. Onishi, Colorimetric Determination of Traces Metals, 4 th ed., pp 709-721. New York:
Interscience, 1978.

301

xAy(n)

yAx(hc)

v h s phn b c dng
Kd =

y
[ Ax ]hc
[ Ay ]nx

T s phn b: T s phn b D ca cht cn phn tch c nh ngha l t s nng

phn tch ca n trong hai dung mi khng trn ln. i vi trng hp n gin nh
c din t bng phng trnh 16.1 th t s phn b ng nht vi h s phn b. V vy,
i vi trng hp phc tp hn th hai i lng ny c th khc nhau hon ton. V d, s
phn b ca mt axit bo HA gia nc v ietylete chng ta c th vit:
D=

Chc
Cn

(16.3)

y Chc v Cn l nng phn t phn tch ca HA trong hai pha. Trong mi trng
nc, nng phn tch ca axit bng tng nng cn bng ca axit yu v baz lin hp
ca n:
Cn = [HA]n + [A]n
Ngc li, khng c s phn li ng k ca axit xut hin trong lp hu c khng phn
cc nn nng phn tch v nng cn bng ca HA l ng nht v chng ta c th vit:
Chc = [HA]hc
Thay th hai gi tr Chc v Cn trong phng trnh (16.3) bng cc gi tr tng ng trn
y, ta c:
D=

[HA ]hc
[HA ]n + A n

(16.4)

thit lp mi lin h gia D v Ka cho hp cht HA chng ta din t s phn li axit

ca HA bng phng trnh:
H3O+ A

n n
Ka =
[HA ]n

hoc l

[HA ]n K a
A =
n
H3O+

302

Thay gi tr mi thu c ca [A ]n vo phng trnh (16.4) ta c:

D=

[HA ]hc
[HA ]n + [HA ]n

Ka

H3 O+

[HA ]hc

[HA ]n 1 +

1
Ka

= Kd

H3 O+

1+

1
Ka

H3 O+

S sp xp li ch r mi quan h gia D v Kd i vi HA
H3 O+
Chc

n
D=
= Kd
+
Cn
H3O + K a

(16.5)

C th s dng phng trnh (16.5) tnh ton mc chit HA t cc dung dch m

trong nc. Cn thy r s khc nhau gia h s phn b Kd v t s phn b D.
V d: H s phn b ca axit yu gia ietylete v nc l 800 v hng s phn li axit
ca n trong nc l 1,5.105. Hy tnh nng phn tch ca HA (CHA) cn li trong dung
dch nc sau khi chit 50,0 ml dung dch HA 0,050 M bng 25,0 ml ete, gi thit dung dch
nc c m pH bng: a) 2,00; b) 8,00.

a) Thay [H3O+] = 1,00.102 v hai hng s cn bng vo phng trnh (16.5) ta c:

D=

Chc
800.1,00.102
=
= 799
Cn 1,00.102 + 1,50.105

(16.6)

Tng s milimol axit c trong hai dung mi bng s molimol ban u trong dung dch
nc.
Tng s s milimol HA = 50,00.0,050 = 2,50
Sau khi chit, 2,50 milimol HA c phn b gia hai dung mi nn:
50,0Cn + 25,0Chc = 2,50
Trong phng trnh trn Cn v Chc l nng phn tch trong hai dung mi. Phng
trnh (16.6) ch r rng: Chc = 799Cn nn c th vit:
50,0Cn + (25,0)(799Cn) = 2,50;
Cn =1,25.104 M.
b) Khi [H3O+] = 1,00.108
D=

Chc
800.1,00.108
=
= 0,533
Cn 1,00.108 + 1,50.105

303

Tng t nh trong phn a, c th vit:

50,0Cn + (25,0)(0,533Cn) = 2,50;
Cn =3,95.102 M.
hon ton ca cch chit nhiu ln: H s phn b v t s phn b thng c s
dng bi v chng dn ti con ng hiu qu nht hon thin cch tch bng chit.
lm v d, chng ta s dng phng trnh (16.3) bn lun mt ln na qu trnh chit hp
cht HA t dung dch nc pH = 2,00. Gi thit rng, trong Vn mililit nc c ao milimol
HA b chit bng Vhc mililit ietylete, ti thi im cn bng, a1 milimol HA cn li trong
lp nc v ao a1 milimol c chuyn vo lp hu c. Nng phn tch ca HA trong
mi lp s l:
C1n =

a1 1
a a1
;Chc = o
Vn
Vhc

Thay th nhng i lng ny vo phng trnh (16.3) v sp xp li ta c:

Vn
a1 =
Vhc D + Vn

ao

(16.7)

S milimol a2 cn li trong lp nc sau ln chit th hai bng mt th tch dung mi

ng nht theo cng mt cch lp lun:

Vn
a2 =
a1
Vhc D + Vn

Khi thay th a1 ca phng trnh trn y bng phng trnh (16.7) chng ta thu c:
2

Vn
a2 =
ao
Vhc D + Vn

Bng cng mt cch lp lun, sau n ln chit, s milimol HA cn li trong lp nc l:

n

Vn
an =
ao
Vhc D + Vn

(16.8)

C th vit li phng trnh (16.8) di dng thut ng nng phn tch ban u v
cui cng ca HA trong nc bng cch thay th:
an = (Cn)nVn v ao =(Cn)oVn vo phng trnh :

(Cn )n

Vn
=

Vhc D + Vn

(Cn )o

(16.9)

304

(Cn)o v (Cn)n l nng ban u v cui cng (sau n ln chit) ca HA trong

pha nc.
Nh c ch r trn y, php chit nhiu ln vi nhng th tch nh dung mi t
hiu sut cao hn so vi php chit n vi th tch ln dung mi.
V d: H s phn b ca iot gia CCl4 v H2O l 85. Hy tnh nng I2 cn li trong
lp nc sau khi chit 50,0 ml dung dch I2 1,00.103 M bng cc lng CCl4 nh sau: a)
50,0 ml, 1 ln; b) 2 ln, mi ln 25,0 ml; c) 5 ln, mi ln 10,0 ml.

Thay s liu vo phng trnh (16.9) ta c:

50,0

3
5
.1,00.10 = 1,16.10 M
+
50,0.85
50,0

a)

(Cn )1 =

b)

(Cn )2 =

c)

50,0

3
7
.1,00.10 = 5,28.10 M
25,0.85 + 50,0

(Cn )5

50,0

.1,00.103 = 5,29.1010 M
=

10,0.85 + 50,0

Cc loi quy trnh chit

C ba loi quy trnh chit da trn cn bng phn b gia hai dung mi khng trn ln
vo nhau:
Chit n.
Chit ly ht cht ra khi mu.
Chit ngc dng.
Chit n: Khi t s phn b i vi mt cht trong hn hp l thun li (t 5 n 10
hoc ln hn) cn i vi cc cht khc th khng thun li (< 0,001) ta c th chit tch
n, nhanh v nh lng. C th chit thnh cng cht cn phn tch t dung dch nc
bng mt vi n 6 phn dung mi mi. Dng mt phu chit thng thng hoc l vi dung
dch u hoc l vi dch cn li hon thnh php chit n.

305

Hnh 16.1
B chit Soxlet

Chit ly ht cht ra khi mu: Cch chit n cn kit, cho php tch cc hp phn c
cc t s phn b tng i khng thun li (< 1) ca mt hn hp khi cc hp phn c cc
t s gn khng. Trong thit b thng dng, dung mi hu c c chuyn lin tc qua lp
nc (xem hnh 16.2). Nh vy l, vi vi trm ln chit bng dung mi mi c thc hin
trong mt gi hoc t hn trong mt thit b khng cn phi theo di thng xuyn, c th
chit ly ht cht cn quan tm ra khi mu.
Phn on ngc dng: Nhng thit b t ng cho php thc hin thnh cng hng
trm ln chit t ng. Vi nhng thit b ny s phn on din ra nh s ngc dng
trong s phn b gia nhng phn mi ca hai pha c thc hin trong hng lot cc
bc giai on. Php chit n cn kit khc vi k thut ngc ch l, nhng phn mi
ca ch mt pha c sinh ra trong pha c.

Phng php ngc dng cho php tch nhng hp phn c h s phn chia kh ng
nht. V d nh Craig ch r rng, c th tch 10 aminoaxit bng chit ngc dng ngay
c khi h s phn b ca chng ch khc nhau t hn 0,1.

306

16.4 ng dng cc quy trnh chit

tch cc cht v c, chit thng hp dn hn so vi kt ta c in bi v cn bng
v tch pha trong phu chit t t nht, t tn thi gian hn so vi kt ta, lc v ra. Thm
vo , chit trnh c cng kt v kt ta sau. Cui cng, chit thch hp mt cch l
tng tch lng vt mt cht.

16.4.1 Chit tch cc ion kim loi dng chelat

Nhiu thuc th to ni phc (chelat) l nhng axit yu phn ng vi cc ion kim loi
to thnh cc phc khng tch in, tan tt trong cc dung mi hu c nh ete, hirocacbon,
xeton v cc hp cht clo ha (bao gm clorofom, tetraclorua cacbon). Mt khc, cc hp
cht ni phc kim loi thng gn nh khng tan trong nc, cn cc thuc th to phc
thng tan kh tt trong dung mi hu c nhng ch tan hn ch trong nc.
Hiu ng pH v nng thuc th ln t s phn b

Cc thuc th vng cng c th nghim rt thnh cng tch da trn quy trnh
chit la chn cc ion kim loi t mt dung dch m trong nc vo mt dung mi hu c
c sn cc thuc th . Nh ch r trn hnh 16.3, mi qu trnh nh th, bao gm mt
vi cn bng v mt vi cht. Cc cht l phi t HQ khng phn li, baz lin hp ca n
Q, phc kim loi - phi t MQn, ion kim loi v H+. Nhng cn bng quan trng xy ra l:
HQn

HQn + H2O

Mm
+ mQ(n)
n

MQm(n)

HQhc

H3O +

MQm(n) ;

MQm(hc)

Q(n)

K d1 =

[HQ]hc
[HQ]n

H3 O+ Q

n
Ka =
HQ
[ ]n

Kf =

(16.10)

[ MQm ]n
m

Mn + Q

n n
K d2 =

[ MQm ]hc
[ MQm ]n

(16.11)

(16.12)

(16.13)

Cc thuc th vng cng hu c cng nh cc hp cht ni phc kim loi trung ha

in thng tan tt trong cc cht lng hu c nn h s phn b K d1 v K d2 ni chung l
nhng s ln. Hn na, nng Mm+ trong lp hu c khng phn cc thng tin ti
khng trong hu ht cc trng hp. la chn ca thuc th c xc nh bng hng s
to phc kh ln Kf i vi cc cation kim loi. Nh ch r trong phng trnh (16.11),
nng dng hot ng ca thuc th Q ph thuc vo pH. Nh vy, bng cch kim tra

307

pH c th kim tra nng Q v do c th bit nhng cation no b chit v nhng

cation no khng b chit.
tm c mt biu thc din t mi quan h gia lng cation b chit vi pH v
nng thuc th chng ta s dng h s phn b ca h c dn ra trn hnh (16.3)
di dng:
D=

[ MQm ]hc
[ MQm ]hc
Chc
=

Cn
Mm + + [ MQm ]
Mm +
n

(16.14)

Chc v Cn l nng mol phn tch ca Mm+ trong pha hu c v pha nc. Thng
thng, gi thit cho rng, [MQm]n << [Mm+]n l hp l bi v:
Thuc th vng cng ni chung rt t tan trong nc.

Hnh 16.2
Nhng cn bng trong qu trnh chit cation M2+ trong nc vo mt dung mi
hu c khng trn ln vi nc, c ha tan sn 8-oxiquinolin

Phn trong nc b phn li rt mnh.

iu bt ngun t ngun gc sau: D khng ph thuc vo tng lng ion kim loi
trong 2 tng nhng ph thuc vo c nng HQ trong lp hu c v nng H+ trong
dung dch nc. Nu CQ l nng phn t ban u ca HQ trong tng hu c, cn bng
khi lng i hi nh sau:
CQ = [HQ]hc + [HQ]n + [Q]n + m[MQm]n + m[MQm]hc
Thng thng nhng quy trnh chit c thc hin vi lng d cht to phc, v d
nh nng HQ trong lp hu c phi d nhiu so vi nng ca tt c cc cht khc c
cha Q. Nh vy l, biu thc cn bng khi lng trn y c n gin n:
CQ [HQ]hc

(16.15)

308

dng li mt biu thc din t mi quan h gia D ca h ny vi nng

u ca phi t to phc trong dung dch hu c v pH ca dung dch nc, chng ta
nhn phng trnh (16.12) vi phng trnh (16.13) v sp xp li s c :
[MQm]hc = Kf K d2 [Mn+]n[Q]nm
Thay th kt qu thu c trn y vo phng trnh (16.14) ta c :
D=

Chc
m
= K f K d2 [Q ]n
Cn

(16.6)

Chia phng trnh (16.11) cho phng trnh (16.10) ta c th din t [Q]n qua [H3O+]n
v [HQ]hc:

[HQ]hc
Q = K a
n K d
H3 O+
1

(16.17)

Thay th phng trnh ny v phng trnh (16.15) vo phng trnh (16.16) s i ti

kt qu:
D=

m
m
CQ
Chc K f K d2 K a
=

m
Cn
Km
H3O+
d1

(16.18)

Lin hp 4 hng s cn bng thnh mt hng s chung Kex ta thu c:

D=

m
CQ
Chc
= K ex
m
Cn
H3 O+

V d: Ch to mt phc trung ha in PbQ2 vi phi t Q. Hng s Kex l s phn b

phc ny gia nc v CCl4 c xc nh bng thc nghim l 2,0.104. Chit 15,0 ml
dung dch nc c nng Pb2+ 5,00.104 M v nng HClO4 0,025 M bng hai phn 10,0
ml CCl4 c nng HQ 0,0250 M. Tnh phn trm Pb2+ cn li trong dung dch.

Thay cc gi tr tng ng vo phng trnh (16.18) :

D=

(2,0.104 ).(0,0250)2
(0,500)2

= 50,0

Thay cc gi tr tng ng vo phng trnh (16.9) cho 2 ln chit :

25,0

4
= 1,13.106
. 5,00.10
10,0.50,0
25,0
+

(Cn )2 =

309

% Pb2+ khng b chit =

1,13.106
5,00.104

.100% = 0,23

Mt s quy trnh tch da trn phng php chit cc hp cht ni phc

Chit bng iphenyltiocacbazon

iphenyltiocacbazon hoc ithizon l thuc th thng dng tch lng nh ca c

chc hoc hn na ion kim loi. ithizon phn ng vi cation ha tr 2, v d nh Pb2+ theo
phn ng:
H
H5C6

N
N N

C6H5
H

2+

+ Pb

H5C6

N N
N N

C6H5
Pb + 2H+

C
S
2

C ithizon v phc kim loi ca n u khng tan trong nc, nhng tan tt trong dung
mi hu c nh CCl4 v CHCl3. Dung dch thuc th c mu lc thm nhng dung dch
phc kim loi li c mu , tm, da cam hoc vng m nn xut hin nhiu phng php
o mu nhy xc nh cc ion b tch. T s phn b ca cc ithizonat kim loi c din
t bng cc phng trnh (16.18) v (16.14). Nh vy, i vi ch:
C2D
Chc PbDz2
Z
=
= K ex
D=
2
Cn
Pb2+
+
H3 O

Hnh 16.3
Hiu ng pH ln phn trm chit cc cation bng dung dch ithizon trong CCl4

Hnh 16.4 ch r phn trm ch v mt s ion kim loi khc b chit vo dung dch
ithizon trong CCl4 bin i nh th no theo pH ca mi trng nc. Nhng s liu thu

310

c cho nhng ng cong ny thu c bng con ng tng t nh nhng

tnh ton c dn ra trong v d 16.3. R rng l t nhng ng cong ny tch c rt
p ng, ch v cadimi bng cch kim tra pH. Ty thuc vo ph hp th ca n, thic (II)
c th gy cn tr nh cho php xc nh ng v ch.
Bng 16.3 Chit phc clorua kim loi bng ietylete t dung dch HCl 6 M

Phn trm
b chit

Cc nguyn t v trng thi oxi ha

90 100

Fe(III) 99%; Sb(V) 99% *; Ga(III) 97%; Ti(III) 95% *; Au(III) 95%

50 90

Mo(IV) 80 90%; As(III) 80% **; Ge(IV) 40-60%

1 50

Te(IV) 34%; Sn(II) 15 30%; Sn(IV) 17%; Ir(IV) 5%; Sb(III) 2,5% *

< 1, > 0

As(V) *; Cu(II); In(III); Hg(II), Pt(IV); Se(IV); V(V); V(IV); Zn(II)

Al(III); Bi(III); Cd(II); Cr(III); Co(II); Be(II); Fe(II); Pb(II); Mn(II)

Ni(II); Os(VIII); Pd(II); Rh(III); Ag(I), Th(IV); Ti(IV), W(VI);
Zr(IV)

Isopropyl ete c s dng nhiu hn ietylete;

**

8 M HCl c dng nhiu hn 6 M.

Chit bng 8-hiroxiquinolin

Nhiu phc kim loi ca 8-hiroxiquinolin (mc 7.4.3) c chit rt thun li vo

dung mi hu c. C th din t qu trnh chit bng phng trnh:
2HQ(hc) + M(n)2+

MQ2 (hc) + 2H+(n)

R rng l cn bng chit ph thuc vo pH, do c th tch cc ion kim loi thng
qua s iu chnh pH ca pha nc. Nhng th nghim trong thc t chng t rng, phng
php ny rt tin dng tch lng vt cc kim loi.

16.4.2 Chit cc phc clorua kim loi

Cc s liu trong bng 16.3 ch r rng, mt s rt ng k cc phc clorua kim loi b
chit vo ietylete t dung dch axit clohiric 6 M. Mt thng tin khc khng km phn quan
trng l, mt s rt ln cc ion kim loi khc hoc khng b chit hoc ch b chit mt phn
rt nh nhng iu kin nu trn. Nh vy l, c th thc hin nhiu quy trnh chit rt c
ch. Mt trong nhng quy trnh quan trng l tch st (III) (c 99%) khi s ln cc
kim loi khc. V d nh, phn rt ln st trong cc mu thp hoc qung st c th c
tch ra bng cch chit trc khi phn tch vt cc nguyn t nh crom, nhm, titan v

311

niken. Hp cht b chit dng lin hp ion H3O+ FeCl4 . Phn trm st c chuyn vo
tng hu c ph thuc vo hm lng axit clohiric trong tng nc (mt phn nh c
chuyn li tng nc khi nng HCl thp hn 3 M v cao hn 9 M) v mt mc no
ph thuc vo hm lng st.
Metylizobutyl xeton cng chit c st t cc dung dch st clorua. Trong trng hp
ny, h s phn b tt hn mt cht so vi ietylete v cn c mt thun li khc l khng b
bt la.
16.4.3 Chit cc mui nitrat

Cc mui nitrat b chit la chn bng ietylete cng nh bng cc dung mi hu c

khc. V d nh, c th chit uran (VI) rt thun li khi cc nguyn t khc nh ch v thori
bng ete t dung dch nc bo ha amoni nitrat, v c nng axit nitric khong 1,5 M.
Bismut (III) v st (III) nitrat cng b chit n mt mc nht nh nhng iu kin nh
th.

16.5 Tch bng trao i ion

Nha trao i ion c nhiu ng dng trong ha phn tch. ng dng quan trng nht l
sc k lng hiu qu cao, s c cp n trong gio trnh cc phng php phn tch
cng c. Trong mc ny ch trnh by mt cch tm tt nhng ng dng khc trong ha phn
tch ca nha trao i ion.

16.5.1 Tch nhng ion cn tr c in tch tri du vi ion cn phn tch

Nha trao i ion c s dng loi b cc ion cn tr, c bit l nhng ion ny c
in tch tri du i vi ion cn phn tch. V d nh, st (II), nhm (III) v mt s nhng
cation khc cn tr php xc nh ion sunfat bng phng php khi lng do khuynh
hng cng kt vi bari sunfat ca chng. Cho dung dch cn phn tch chy chm qua ct
nha trao i cation, tt c cc cation b gi li v mt lng proton tng ng c gii
phng. Ion sunfat i qua ct nh vy mt cch t do v php phn tch c thc hin trn
dung dch chy ra khi ct. Bng cch tng t, ion sunfat cn tr php xc nh cc ion bari
v canxi c th b loi b bng cch cho mu chy chm qua ct nha anionit.

16.5.2 Lm giu vt ca cht in li

Cc cht trao i ion thng c dng lm giu lng vt ion t mt dung dch rt
long. V d, nha trao i cation c s dng tch gp cc nguyn t kim loi t th
tch ln nc t nhin. Sau , x l nha bng axit cc ion c gii phng, ta s thu c
dung dch m c hn nhiu phn tch.

312

16.5.3 Chuyn ha mui thnh axit hoc baz

Hm lng mui tng s ca mt mu c th c xc nh bng cch chun ion hiro
thu c khi mt phn ca mu c dng ra nha trao i cation dng axit. Mt cch
tng t, c th iu ch dung dch axit clohiric chun bng cch cho chy chm dung dch
cha mt lng bit natri clorua qua nha trao i cation dng axit. Dung dch chy ra
v dung dch ra c thu vo mt bnh nh mc v thm nc n vch nh mc. Theo
con ng nh trn c th iu ch dung dch natri hiroxit chun bng cch x l nha trao
i anion vi mt lng bit dung dch natri clorua.

16.6 Tch cc hp cht v c bng chng ct

Chng ct cho php tch cc hp phn khi t s phn b dung dch/tng hi ca chng
khc nhau ln. Nu mt hp phn c t s phn b ln so vi ch s ca cc cu t
khc ca mt hn hp th c th tch mt cch n gin. Bng 16.4 thng k mt s cc hp
cht v c c th b tch mt cch thun li bng cch chng ct n gin.
Bng 16.4 Tch mt s hp cht v c bng chng ct
Cht cn
phn tch

X l mu

Cht
hi

CO32

Axit ha

CO2

Ba(OH)2
H2O

SO32

Axit ha

SO2

SO2 (kh) + H2O2 (n) H2SO4 (n)

S2

Axit ha

H2S

Cd2+(n) + H2S (kh) CdS (rn) + 2H+

Thm SiO2 v axit

ha

H2SiF6

Dung dch baz

Si

Thm HF

SiF4

Dung dch baz

H3BO3

Thm H2SO4
metanol

B(OCH3)3

Dung dch baz

Cr2O7

Thm HCl c

CrO2Cl2

Dung dch baz

NH4+

Thm NaOH

NH3

Dung dch axit

As, Sb

Thm HCl c v
H2SO4

AsCl3,
SbCl3

Nc

Sn

Thm HBr

SnBr4

Nc

bay

Phng php thu

(n)

+ CO2

(kh)

BaCO3

(rn)

313

Ph lc
Ph lc I
CC TP CH PHN TCH LN C LU HNH RNG RI TRN TH GII
American Laboratory

The Analyst
Analitical Biochemistry
Analytical Chemistry
Analytica Chimica Acta
Analytical Instrumentation
Analytical Tetters
Applied Spectroscopy
Clinical Chemistry
Fresenins Journal of Analytical Chemistry
Journal of the Association of Official Analytical Chemists
Journal of Chromatography Science
Journal of Chromatography
Journal of Electroanalytical Chemistry and Interfacial Electrochemistry
Microchemical Journal
Microchimica Acta
Saparation Science
Spectrochimica Acta
Talanta
Zeitschrift fr Analytische Chemie

Ph lc II
NGUYN T KHI QUC T

Nguyn t

K hiu

Nguyn t s

Nguyn t khi

Actinnium
Aluminum
Americium
Antimony

Ac
Al
Am
Sb

89
13
95
51

227
26,981539
243
121,757

314

Nguyn t

K hiu

Nguyn t s

Nguyn t khi

Argon
Arsenic
Astatine
Barium
Berkelium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Califormium
Carbon
Cerium
Cesium
Chlorine
Chromiun
Cobalt
Copper
Curium
Dysprosium
Einsteinium
Erbium

Ar
As
At
Ba
Bk
Be
Bi
B
Br
Cd
Ca
Cf
C
Ce
Cs
Cl
Cr
Co
Cu
Cm
Dy
Es
Er

18
33
85
86
97
4
83
5
35
48
20
98
6
58
55
17
24
27
29
96
66
99
68

39,984
74,92159
210
137,327
247
9,012182
208,98037
10,811
79,904
112,411
40,078
251
12,011
140,115
132,90543
35,4527
51,9961
58,93320
63,546
247
162,50
252
167,26

Europium
Ferium
Fluorine
Francium
Gadolinium
Gallium
Germanium
Gold
Hafnium
Helium
Holmium

Eu
Fm
F
Fr
Gd
Ga
Ge
Au
Hf
He
Ho

63
100
9
87
64
31
32
79
72
2
67

151,965
257
18,9984032
223
157,25
69,723
72,61
196,96654
178,49
4,002602
164, 93032

315

Nguyn t

K hiu

Nguyn t s

Nguyn t khi

Hydrogen
Indium
Ioine
Iridium
Iron
Krypton
Lanthanum
Lawrencium
Lead
Lithium
Lutentium
Magnesium
Manganese
Mendelevium
Mercury
Molybdenum
Neodymium
Neon
Neptunium
Nickel
Niobium
Nitrogen

H
In
I
Ir
Fe
Kr
La
Lr
Pb
Li
Lu
Mg
Mn
Md
Hg
Mo
Nd
Ne
Np
Ni
Nb
N

1
49
53
77
26
36
57
103
82
3
71
12
25
101
80
42
60
10
93
28
41
7

1,00794
114,82
126,90447
192,22
55,847
83,80
138,9055
262
207,2
6,941
174,967
24,305
54,93805
258
200,59
95,94
144,24
20,1797
237
58,6934
92,90638
14,00674

Nobelium
Osmium
Oxygen
Palladium
Phosphorus
Platium
Plutonium
Polonium
Potassium
Praseodymium
Promethium
Protatinium

No
Os
O
Pd
P
Pt
Pu
Po
K
Pr
Pm
Pa

102
76
8
46
15
78
94
84
19
59
61
91

259
190,2
15,9994
106,42
30,973762
195,08
244
210
39,0983
140,90765
145
231,03588

316

Nguyn t

K hiu

Nguyn t s

Nguyn t khi

Radium
Radon
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Technetium
Tellurium
Terbium
Thallium
Thorium
Thulium

Ra
Rn
Re
Rh
Rb
Ru
Sm
Sc
Se
Si
Ag
Na
Sr
S
Ta
Tc
Te
Tb
Tl
Th
Tm

88
86
75
45
37
44
62
21
34
14
47
11
38
16
73
43
52
65
81
90
69

226
221
186,207
102,90550
85,4678
101,07
150,36
44,955910
78,96
28,0855
107,8682
22,989768
87,62
32,066
180,9479
98
127,60
158,92534
204,3833
232,0381
168,93421

Tin
Titanium
Tungsten
Uranium
Vanadium
Xenon
Ytterbium
Yttrium
Zinc
Zirconium

Sn
Ti
W
U
V
Xe
Yb
Y
Zn
Zr

50
22
74
92
23
54
70
39
30
40

118,710
47,88
183,85
238,0289
50,9415
131,29
173,04
88,90585
65,39
91,224

317

Ph lc III
PHN T LNG CA MT S HP CHT THNG DNG

Hp cht

Phn t lng

Hp cht

Phn t lng

AgBr
AgCl
Ag2CrO4
AgI
AgNO3
AgSCN
Al3O3
Al2(SO4)3
As2O3
B2O3
BaCO3
BaCl2.2H2O
BaCrO4
Ba(IO3)2
Ba(OH)2
BaSO4
Bi2O3
CO2
CaCO3
CaC2O4
CaF2
CaO
CaSO4
Ce(HSO4)4
CeO2
Ce(SO4)2
(NH4)2Ce(NO3)6

187,772
143,321
331,730
234,773
169,873
165,952
101,961
342,154
197,841
69,620
197,336
244,263
253,321
487,132
171,342
233,391
465,959
44,010
100,087
128,098
78,075
56,077
136,142
528,401
172,114
332,242
548,222

Hg2Cl2
HgCl2
KBr
KBrO3
KCl
KClO3
KCN
K2CrO4
K2Cr2O7
K3Fe(CN)6
K4Fe(CN)6
KHC8H4O4
KH(IO3)2
K2HPO4
KH2PO4
KHSO4
KI
KIO3
KIO4
KMnO4
KNO3
KOH
KSCN
K2SO4
La(IO3)3
Mg(C9H6NO)2
MgCO3

472,09
271,50
119,002
167,001
74,551
122,519
65,116
194,190
294,185
329,248
368,347
204,224
389,912
174,176
136,086
136,170
166,003
214,001
230,000
158,034
101,103
56,106
97,182
174,260
663,614
312,611
84,314

(NH4)4Ce(SO4)4.2H2O
Cr2O3
CuO
Cu2O

632,554
151,990
79,545
143,091

MgNH4PO4
MgO
Mg2P2O3
MgSO4

137,315
40,304
222,553
120,369

318

Hp cht

Phn t lng

CuSO4
159,610
Fe(NH4)2(SO4)2.6H2O 392,143
FeO
71,846
Fe2O3
159,692
Fe3O4
231,539
HBr
80,912
HC2H3O2
60,053
HC7H5O2
122,123
(HOCH2)3CNH2(Tris) 121,136
HCL
36,461
HCLO4
100,458
H2C2O4.2H2O
126,066
H5IO6
227,941
HNO3
63,013
H2O
18,015
H2O2
34,015
H3PO4
97,995
H2S
34,082
H2SO3
82,080
H2SO4
98,079
HgO
216,59
(NH4)S2O8
228,204
NH4VO3
116,978
Ni(C4H7O2N2)2
228,917
PbCrO4
323,2
PbO
223,2
PbO2
239,2
PbSO4
303,3

Hp cht

Phn t lng

MnO2
Mn2O3
Mn3O4
Na2B4O7.10H2O
NaBr
NaC2H3O2
Na2C2O4
NaCl
NaCN
Na2CO3
NaHCO3
Na2H2EDTA.2H2O
Na2O2
NaOH
NaSCN
Na2SO4
Na2S2O3.5H2O
NH4Cl
(NH4)2C2O4.H2O
NH4NO3
(NH4)2SO4
P2O5
Sb2S3
SiO2
SnCl2
SnO2
SO2
SO3
Zn2P2O7

86,939
157,874
228,812
381,372
102,894
82,034
133,999
58,442
49,008
105,989
84,007
372,240
77,978
39,997
31,074
142,043
248,186
58,491
142,112
80,043
132,141
141,945
339,712
60,084
189,615
130,709
64,065
80,064
304,72

319

Ph lc IV
TCH S TAN 25OC
Hp cht

Cng thc

Ghi
ch

Nhm hiroxit

Al(OH)3

Bari cacbonat

BaCO3

Bari cromat

10

10

BaCrO4

Bari hiroxit

Ba(OH)2.8H2O

Bari ioat

Ba(IO4 )2
BaC2O4

Bari sunfat

BaSO4

Cadimi cacbonat
Cadimi hiroxit

CdC2O4

Cadimi sunfua

CdS

Canxi cacbonat

CaCO3

10
10

14

10

15

Canxi florua

27

10

10

10

11

Canxi hiroxit

10

Canxi oxalat

10

Canxi sunfat

CaF2
Ca(OH)2
CaC2O4.H2O
CaSO4

1,57

1,1.
1,8.
4,5.
9.10

CaCO3

2,1.

1.10

10

Cd(OH)2

Cadimi oxalat

CdCO3

5,0.

3.10

.10
Bari oxalat

3.10

34

1.10
4,5.

Kh
ong canxit

6,0.

Kh
ong
aragonit

3,9.
6,5.
1,7.
2,4.

320
Hp cht

Cng thc

Ghi
ch

10

10

10

10

15

CoCO3

Coban(II) cacbonat

Co(OH)2

Coban(II) hiroxit
Coban(II) sunfua

CoS

22

CoS
ng(I) bromua

26

CuBr

ng(I) clorua

10

10

10

CuCl
Cu2O

ng(I) oxit

Cu2O + H2O

2 Cu +

15

1,0.
1,3.
5.10

3.10

1,0.
1,9.
2.10

2OH
ng(I) ioua

CuI

ng(I) tioxianat

CuSCN

ng(II) hiroxit

CuS

St(II) cacbonat

FeCO3

14

10

20

37

10

11

10

15

Fe(OH)2

St(II) sunfua

FeS

St(III) hiroxit

Fe(OH)3

Lantan ioat

La(IO3) 3

Ch cacbonat

10
Cu(OH)2

ng(II) sunfua

St(II) hiroxit

12

19

39

10

11

10

14

PbCO3

1.10
4,0.
4,8.
8.10
2,1.
4,1.
8.10
2.10
1,0.
7,4.

321
Hp cht

Cng thc

Ghi
ch

PbCl2

Ch clorua

10
Ch cromat

PbCrO4

Ch oxit

PbO

13

+
PbO(r)

H2O

Pb

2+

Pb

2+

10

14

1,7.
3.10
7,4.

V
ng

2OH

PbO

+
PbO(r)

H2O

16

5.10

7,9.

2OH
Ch ioua
Ch oxalat
Ch sunfat

PbI2

Magie amoni photphat

MgNH4PO4

Magie cacbonat

MgCO3

Mangan hiroxit
Mangan sunfua

Thu ngn(I) cacbonat

10

28

28

10

10

12

10

10

10

12

Mg(OH)2
MnCO3
Mn(OH)2
MnS
MnS

Thu ngn(I) bromua

PbSO4
PbS

Mangan cacbonat

10

PbC2O4

Ch sunfit

Magie hiroxit

10

11

14

Hg2Br2
10

23

10

17

Hg2CO3

ng

8,5.
0,05
1,6.
3.10
3.10
3,5.
7,1.
5,0.
7,1.
3.10

H
ng

3.10

L
c

5,6.
8,9.

322
Hp cht

Cng thc

Ghi
ch

Hg2Cl2

Thu ngn(I) clorua

10

18

10

29

10

20

10

26

Hg2I2

Thu ngn(I) ioat

Hg2(SCN)2

Thu ngn(I) tioxianat

**

HgO

Thu ngn(II) oxit

HgO(r)+ H2O

Hg

2+

1,2.
4,7.
3,0.
3,6.

2OH
Thu ngn(II) sunfua

HgS
HgS

Niken cacbonat

10
Ni(OH)2

Niken sunfua

NiS

Ag2AsO4

Bc bromua

AgBr

Bc cacbonat
Bc clorua

25

10

13

10

12

AgCl
.10

Bc cromat
Bc xianua
Bc ioat
Bc ioua

Ag2CrO4

12

10

16

10

AgIO3
AgI

10

10
AgCN

1,3.

4.10

1,3.

6.10

23

Ag2CO3

6.10

20

10
Bc asenat

5.10

16

NiS

e
n

54

NiCO3

Niken hiroxit

2.10

53

5,0.
8,1.
1,82
1,2.
2,2.
3,1.
8,3.

323
Hp cht

Cng thc

Ghi
ch

Bc oxalat

Ag2S

Bc tioxianat

AgSCN

SrC2O4

Stronti sunfat

SrSO4

10

12

10

10

Tl2S

Km cacbonat

ZnCO3

10

10

22

10

10

10

16

Zn(OH)2

Km oxalat

ZnC2O4

Km sunfua

ZnS
ZnS

3,5.
8.10
1,1.
9,3.
5.10

TlCl

Tali(I) sunfua

Km hiroxit

51

SrCO3

Stronti oxalat

Tali(I) clorua

10

11

Ag2C2O4

Bc sunfua

Stronti cacbonat

10

17

25

23

3,2.
1,8.
6.10
1,0.
3,0.

V
nh hnh

8.10
2.10

3.10

324

Ph lc V
CC HNG S PHN LI AXIT 25OC

Axit

Cng thc

K1

Axit axetic
Ion amoni
Ion anilin
Axit asenic
Axit asen
Axit benzoic
Axit boric
Axit butanoic
Axit cacbonic
Axit cloaxetic
Axit xitric
Ion dimetyl amoni
Ion etanol amoni
Ion etyl amoni
Ion etylen diamoni
Axit foocmic
Axit fumaric
Axit glicolic
Ion hirazini
Axit hirazoic
Axit xianic
Axit hirofloric
Hiro peroxit
Hiro sunfua
Ion hiroxyl amoni
Axit hipoclor
Axit ioic
Axit lactic
Axit maleic
Axit malic
Axit malonic

CH3COOH
NH4+
C6H5NH3+
H3AsO4
H3AsO3
C6H5COOH
H3BO3
CH3(CH2)2COOH
H2CO3
ClCH2COOH
HOOC(OH)C(CH2 COOH)2
(CH3)2NH2+
HOC2H4NH3+
C2H5NH3+
+
H3NC2H4NH3+
HCOOH
trans-HOOCCH=CHCOOH
HOCH2COOH
H2NNH3+
HN3
HCN
HF
H2O2
H2S
HONH3+
HOCl
HIO3
CH3CHOHCOOH
cis-HOOCCH=CHCOOH
HOOCCHOHCH2COOH
HOOCCH2COOH

1,75.105
5,70.1010
2,51.105
5,80.103
5,10.1010
6,28.105
5,81.1010
5,10.1010
4,45.107
1,36.105
7,45.104
1,68.1011
3,18.1010
2,31.1011
1,42.107
1,80.104
8,85.104
1,47.104
1,05.108
2,2.105
6,20.1010
6,.104
2,2.1012
9,6.108
1,10.106
3,0.108
1,7.101
1,38.104
1,3.102
3,48.104
1,42.103

K2

K3

1,1.107

3,2.1012

4,69.1011
1,73.105 4,02.107

3,21.105

1,3.1014

5,9.107
8,00.106
2,01.106

325

Axit mandelic
Ion metyl amoni
Axit nitr
Axit oxalic
Axit peioic
Phenol
Axit photphoric
Axit photphor
Axit phtalic
Axit picric
Ion piperidini
Axit propanoic
Ion piridini
Axit piruvic
Axit salixinic
Axit sunfamic
Axit sucxinic
Axit sunfuric
Axit sunfur
Axit tactric
Axit tioxianic
Axit tiosunfuric
Axit tricloaxetic
Ion trimetyl amoni

C6H5CHOHCOOH
CH3NH3+
HNO2
HOOCCOOH
H5IO6
C6H3OH
H3PO4
H3PO3
C6H4(COOH)2
(NO2)3C6H2OH
C5H11NH+
CH3CH2COOH
C5H5NH+
CH3COCOOH
C6H4(OH)COOH
H2NSO3H
HOOCCH2CH2COOH
H2SO4
H2SO3
HOOC(CHOH)2COOH
HSCN
H2S2O3
Cl3SCCOOH
(CH3)3NH+

4,0.104
2,3.1011
7,1.104
5,60.102
2.102
1,00.1010
7,11.103
3.102
1,12.103
4,3.101
7,50.1012
1,34.105
5,90.106
3,2.103
1,06.103
1,03.101
6,21.105

1,23.102
9,20.104
0,13
0,3
3
1,58.1010

5,42.105

6,32.108
1,62.107
3,91.106

4,5.1013

2,31.106
1,02.102
6,6.108
4,31.105
2,5.102

Hu ht cc s liu lc ion bng khng. (Ngun: A.E. Martell and R. M. Smith.

Crittical Stability Constants. Vol. 1-6. New York: Plenum Press, 1989)

326

Ph lc VI
CC HNG S TO PHC 25OC

Phi t

Cation log K1

log K2

Ag+
Axetat
2+
CH3COO Ca

Cd2+

0,73
1,18
1,93

0,9

2+

2,21

1,42

Cu

3+

Fe

Hg2+
2+

Mg

0,0

3,38

3,1

1,8

0,1

log K1K2 = 8,45

0,0

1,27

0,0

2,68

1,40

0,0

3.31
2,55
1,99*

3,91
2,01
1,51

0,0
0,0
0,0

log K5 = 0,06
Cu2+
2+

Hg

2+

2+

Zn

Clorua
(Cl)

0,0
0,0
0,0

1,22

Lc ion

Ag
Amoniac
Cd2+
NH3
Co2+

Bromua
(Br)

log K4

2+

Pb

Ni

log K3

Ag+

1,48

0,0

8,8

8,6

1,0

0,7

0,5

2,72

2,17

1,66

1,12

0,0

log K5 = 0,67

log K6 = 0,03

2,21
2,29
+

Ag +2Br
AgBr2

2,36

1,77
Ag++2Cl
AgCl2
AgCl2+ Cl
AgCl3

Fe

2+

Hg

0,0

2,80

Pb2+

3+

log K6 = 0,74

3,43

9,00

Cu2+

0,84
0,64

4,04

Hg2+

Ag+

1,34
0,93

2,3

Pb +3Cl
PbCl3

Sn2+

1,51

1,6

0,0
0,0

0,0
0,0

logK1K2=5,25
log K3 = 0,37

0,0
0,0

log K = 5,5

0,65

7,30

Pb2+

0,0

0,0

Cu2++2Cl CuCl2

2+

2,03

logK1K2=7,5

8,1

1,48

0,0

6,70

1,0

0,6

0,0

logK1K2K3 =1,8
0,74

0,3

0,0
0,5

0,0

327

Xianua
(CN)

Ag+
Cd2+
Hg2+

Ag++2CN
AgCN2
6,01

5,11

4,53

17,00

15,75

3,56

Ni2+

Ni2++4CNNi(CN)4

logK1
K2K3
K4=30
,22

Zn2+

logK1K2 = 11,07

4,98

EDTA

Xem hnh 13.3

Florua
(F)

Al3+
Fe 3+

7,0
5,18

Hiroxit
(OH)

Al3+
Cd2+

Al3++4OHAl(OH)4
3,9

2,27

0,0
0,0

2,66

0,0

logK1K2=20,48

5,6
3,89

0,0
3,57

0,0

4,1
3,03

2,4

logK1K2K3K4=33,4

Fe

11,5

0,0

10,60

11,2

0,0

4,1

4,9

2+

Pb
Zn2+
Cd2+
2+

Hg

logK1K2K3=13,9

2+

logK1K2K3K4=15,5

Pb +3OH Pb(OH)3

Zn +4OH Zn(OH)4
2,28
12,87

1,0

Cu+ 2I = CuI2

logK1K2 = 8,9

10,95

3,8

Pb2+ + 3I = PbI3

logK1K2K3 =
3,9

0,0

Pb2+ + 4I = PbI32

logK1K2K3K4
= 4,5

0,0

4,96

5,04

0,1

5,97

Ca2+

3,19

Cd2+

2,73

1,4

7,58

6,23

2+

Mg

1,0

0,0
0,0
0,0

1,64

Al3

Fe

0,0

Pb2+

2+

Cu+

Oxalat
(C2O42)

0,0

11,81

2+

Iot (I )

4,6

2+

Hg

0,0

Fe3
Ni

0,0
0,0

3,8

Cu2+
2+

0,0
0,0

0,0
2,2

0,5

0,0

3,42 (18 C)

1,0

1,0

4,8

1,0
1,0

328

Sunfat
(SO42)

Pb2+

4,20

Al3+

3,89

0,0

Ca2+

2,13

0,0

2+

2,34

0,0

3+

4,04

Cu
Fe

2+

Tioxianat
(SCN)

Mg

2,23

Cd2+

1,89

2,11

1,34

0,89

0,1

3SCN
Cu+
Cu(SCN)32

Fe3+

3,02

Hg

1,76

Ag+

8,82

= logK1K2K3 =
11,60
2,7

1,8

4,7

0,7

0,0

logK1K2 = 6,3

2+

Hg

0,0

logK1K2 = 29,23

1,4

0,0

Ph lc VII
MT S TH IN CC CHUN V HNH THC
o

E ,V

Na phn ng

Th hnh thc, V

Nhm
3+

+ 3e = Al(r)

1,662

Antimon
+

Sb2O5(r) + 6H 4e = 2SbO + 3H2O

+0,581

Asen
H3AsO4 + 2H + 2e = H3AsO3 + H2O

+0,559

Bari
Ba

2+

+ 2e = Ba(r)

2,906

Bismut
+

0,0
0,0

Cu2+

Al

0,0
0,0

logK1K2 = 17,26

2+

0,0

0,62

2+

Tiosunfat
(S2O32)

0,0
0,0

Cu+

Ni

0,0

BiO + 2H 3e = Bi(s) + H2O

+0,320

0,577 trong HCl.HClO4

329
o

E ,V

Na phn ng

BiCl4 + 3e = Bi(s) + 4 Cl

Th hnh thc, V

+0,16

Brom

Br2(l) + 2e = 2Br

+1,065

Br2(n) + 2e = 2Br

+1,087

BrO3 + 6 H + 5 e = Br2(l) + 3H2O

1,05 trong HCl 4 M

BrO3 + 6H + 6e = Br + 3H2O

+1,52
+1,44

Cadimi
Cd

2+

+ 2e = Cd(s)

0,403

Canxi
Ca

2+

+ 2e = Ca(s)

2,866

Cacbon
+

C6H4O2 (quinon) + 2H 2e = C6H4(OH)2

+

2CO2(g) + 2H + 2e = H2C2O4

+0,699

+0,696 trong HCl, HClO4, H2SO4 1

M

0,49

Xeri
Ce

4+

+ e = Ce

+1,70 trong HClO4 1 M, +1,61 trong

HNO3 1 M, +1,44 trong H2SO4

3+

Clo

Cl2(k) + 2e = 2Cl

+1,359

HCl + H e = 1/2Cl2(k) + H2O

ClO3 + 6H 5e = 1/2Cl2(k) + 3H2O

+1,63
+1,47

Crom
3

+ e = Cr

Cr
Cr

0,408

+ 3e = Cr(r)
2

Cr2O7

0,744

3+

+ 14H + 6e = 2Cr

+ 7H2O

+1,33

Coban
Co

2+
3

+ 2e = Co(r)

0,277

2+

Co + e = Co

+1,808

ng
Cu

2+

Cu

2+
+

+ 2e = Cu(r)

+ e = Cu

+0,337

+0,153

Cu + e = Cu(r)
Cu

2+

+0,521

+ I + e = CuI(r)

CuI(r) + e = Cu(r) + I

+0,86
1,85

330
o

E ,V

Na phn ng

Th hnh thc, V

Flo
+

F2(k) + 2H + 2e = 2HF(n)

+3,06

Hiro
+

2H + 2e = H2(k)

0,000

0,005 trong HCl, HClO4

Io

I2(s) + 2e = 2I

+0,5355

I2(n) + 2e = 2I

+0,615

I3 + 2e = 3I

+0,536

ICl2 + e = 1/2I2(s) + 2Cl

+1,056

IO3 + 6H + 5e = 1/2I2(r) + H2O

IO3 + 6H + 5e = 1/2I2(n) + 3H2O

IO3 + 2Cl + 6H + 4e = ICl2 + H2O

H5IO6 + H + 2e = IO3 + 3H2O

+1,196
+1,178
+1,24
+1,601

St
Fe

2+

+ 2e = Fe(r)

Fe

3+

+ e = Fe

Fe(CN)

0,440

2+

+ e = Fe(CN)6

+0,771

0,700 trong HCl 1 M; 0,732 trong

HClO4 1 M, 0,68 trong H2SO4 1 M

+0,36

0,71 trong HCl 1 M; 0,72 trong

HClO4 1 M, H2SO4

0,126

0,14 trong HClO4 1 M; 0,29 trong

H2SO4 1 M

Ch
Pb

2+

+ 2e = Pb(r)
+

PbO2(r) + 4H + 2e = Pb

2+

+ 2H2O
2

PbSO4(r) + 2e = Pb(r) + SO3

+1,455
0,350

Liti
+

Li + e = Li(r)

3,045

Magie
Mg

2+

+ 2e = Mg(r)

2,363

Mangan
Mn

2+

Mn

3+

+ 2e = Mn(r)

+ e = Mn

1,180

2+

1,51 trong H2SO4 7,5 M

2+

MnO2(s) + 4H + 2e = Mn

MnO4 + 8H + 5e = Mn

2+

+ 2H2O

+ 4H2O

MnO4 + 4H + 3e = MnO2(r) + H2O

MnO4 + e = MnO4

+1,23
+1,51
+1,695
+0,564

331
o

Na phn ng

E ,V

Th hnh thc, V

+0,788

0,274 trong HCl; 0,776 trong HClO4;

0,67 trong H2SO4

+0,920

0,907 trong HClO4

Thy ngn
2+

+ 2e = 2Hg(l)

2+

+ 2e = Hg2

Hg2

2Hg
Hg

2+

2+

+ 2e = Hg(l)

+0,854

Hg2Cl2(r) +2e =2Hg(l) + 2Cl

+0,268
2

Hg2SO4(r) +2e =2Hg(l) + SO4

0,244 trong KCl bo ha; 0,282 trong

KCl; 0,334 trong KCl

+0,165

Nicken
Ni

2+

+ 2e = Ni(s)

0,250

Nit
+

N2(k) + 5H + 4e = N2H5
+

0,23

HNO2 + H + e = NO(k) + H2O

NO3 + 3H + 2e = HNO2 + H2O

+1,00
+0,94

0,92 trong HNO3

Oxi
H2O2 + 2H + 2e = 2H2O

+1,776

HO2 + H2O + 2e = 3OH

+

+0,88

O2(k) + 4H + 4e = 2H2O

+1,229

O2(k) + 2H + 2e = H2O2

+0,682

O3(k) + 2H + 2e = O2(k) + H2O

+2,07

Paladi
Pd

2+

+ 2e = Pd(r)

+0,987

Ptatin
2+

PtCl3

PtCl6

+ 2e = Pt(r) + 4 Cl

+ 2e =

2
PtCl3

+ 2Cl

+0,73

+0,68

Kali
+

K + e = K(r)

2,925

Selen
+

H2SeO3 + 4H + 4e = Se(k) +3H2O

2

SeO3

+ 4H + 2e = H2SeO3 + H2O

+0,740
+1,15

Bc
+

Ag + e = Ag(r)

+0,799

AgBr(r) + e = Ag(r) + Br
AgCl(r) + e = Ag(r) + Cl

0,228 trong HCl; 0,792 trong HClO4;

0,77 trong H2SO4

+0,073
+0,222

0,228 trong KCl

332
o

E ,V

Na phn ng

AgCl(r) + e = Ag(r) + 2CN

Th hnh thc, V

0,31
2

Ag2CrO4(r) + 2e = 2Ag(r) + CrO4

AgI(r) +e = Ag(r) + I

+0,446
0,151

AgI(r) + e = Ag(r) + 2S2O3

+0,017

Natri
+

Na + e = Na(r)

2,714

Sulfua
+

S(r) + 2H 2e = H2S(k)

+0,141

H2SO3 + 4H + 4e = S(r) + 3H2O

2

SO4

+ 4H + 2e = H2SO3 + H3O

S4O6

S2O8

+ 2e = 2S2O3

+0,450
+0,172
+0,08

+ 2e = 2SO

+2,01

Tali

Tl + e = Tl(r)
Tl

3+

+ 2e = Tl

0,336

0,551 trong HCl;

HVlO4, H2SO4

+1,25

0,77 trong HCl

0,136

0,16 trong HClO4

+0,154

0,14 trong HCl

0,33

trong

Thic
Sn

Sn

4+

+ 2e = Sn(r)

+ 2e = Sn

2+

Titan
Ti

2+

+ e = Ti

2+

TiO

0,369

3+

+ 2H + e = Ti

+ H2O

+0,099

0,04 trong H2SO4

Uran
2+

UO3

4+

+ 4H + 2e = U

+ 2H2O

+0,334

Vanadium
3

2+

+e =V

2+

VO

0,256

+ 2H + e = V + H2O
+

2+

V(OH)4 + 2H + e = VO

0,21 trong HClO4

+0,359
+ 3H2O

+1,00

1,02 trong HCl, HClO4

Km
Zn

2+

+ 2e = Zn(r)

0,763

Nhng th ny l gi nh bi v chng tng ng vi dung dch Br2 hoc I2 bng

1,00 M. tan tng ng ca hai hp cht ny 25oC l 0,18 M v 0,0020 M. Trong cc
dung dch bo ha cha lng d Br2 lng hoc I2 rn th chun ca na phn ng:

333

Br2(lng) + 2e = 2Br
I2(rn) + 2e = 2I
vn c s dng. Ngc li nng Br2 v I2 thp hn nng bo ha, nhng th in
cc gi nh cng c s dng.
* Th hnh thc l th in cc ca mt cp c nng phn tch ca tt c cc cht
tham gia bng n v v nng cc cht khc trong dung dch c nh r.
G. Milazzo, S. Caroli, K. Sharma, Tables of Standard Electrode Potentials, London:
Willey, 1978.
E. H. Swift and E. A. Butler, Quantitive Measurement and Chemical Equilibria, New
York: Freeman, 1972.

Ph lc VIII
CC CHT C KHUYN DNG IU CH CC DUNG DCH
CHUN CHO NHNG NGUYN T THNG DNG

Nguyn t

Cht

Khi lng

Nhm

Al kim loi

26,98

Antimon
Asen
Bari
Bismut
Bo
Brom
Cadimi
Canxi
Xeri
Crom
Coban
ng
Flo
Io

KSbOC2H4O6.1/2H2)
As2O3
BaCO3
Bi2O3
H2BO3
KBr
CdO
CaCO3
(NH4)2Ce(NO3)6
K2Cr2O7
Co kim loi
Cu kim loi
NaF
KIO3

333,93
197,84
197,35
465,96
61,83
119,01
128,40
100,09
548,23
294,19
58,93
63,55
41,99
214,00

Dung mi
HCl
nng,
long
H2O
HCl long
HCl long
HNO3
H2O
H2O
NHO3
HCl long
H2SO4
H2O
HNO3
HNO3 long
H2O
H2O

Ghi ch
a
c
i, b, d

d, e
a
i
i, d
a
a
b
i

334

Nguyn t

Cht

Khi lng

Dung mi

Ghi ch

St
Lantan
Ch
Liti
Magie
Mangan
Thy ngn
Molipen
Niken
Photpho
Kali

Fe kim loi
La2O3
Pb(NO3)2
Li2CO3
MgO
MnSO4.H2O
HgCl2
MoO3
Ni kim loi
KH2PO4
KCl
KHC8H4O4
K2Cr2O7
Si kim loi
SiO2
AgNO3
NaCl
Na2C2O4
SrCO3
K2SO4
Sn kim loi
Ti kim loi
Na2WO4.2H2O
U3O8
V2O5
ZnO

55,85
325,82
331,20
73,89
40,31
169,01
271,50
143,94
58,70
136,09
74,56
204,23
294,19
28,09
60,08
169,87
58,44
134,00
147,63
174,27
118,69
47,90
329,86
842,09
181,88
81,37

HCl nng
HCl nng
H2O
HCl
HCl
H2O
H2O
NaOH 1 M
HNO3 nng
H2O
H2O
H2O
H2O
NaOH c
HF
H2O
H2O
H2O
HCl
H2O
HCL
H2SO4 1 : 1
H2O
HNO3
HCl nng
HCl

a
f
a
a

Silic
Bc
Natri
Stronti
Lu hunh
Thic
Titan
Wolfram
Uran
Vanadi
Km

g
b
a
a
i, d
i, d
j
a
i
i, d
a

a
h
d
a
*

Nu khng c ghi ch g c bit khc, cc cht s c lm kh n khi lng khng i

110oC.
* Nu khng c ghi ch g c bit khc, cc axit u l axit c tinh khit phn tch.
a. Ph hp vi cc tiu chun c lit k mc 7.2 v t cht lng chun
b. c tnh cao
c. Mt 1/2H2O 110oC. Sau khi lm kh khi lng phn t = 324,92 g. Hp cht
kh c cn li nhanh sau khi ly khi bnh phng m.

335

d. C hiu lc nh mt tiu chun c bn ca vin Quc gia v tiu chun v cng

ngh.
e. H3BO3 c cn trc tip trong mt cc cn, mt 1 mol H2O 100oC, kh lm kh
n khi lng khng i.
f. Hp th CO2 v H2O. Nung ngay trc khi s dng
g. C th lm kh 110oC m khng mt nc
h. Mt c hai phn t nc. Khi lng phn t = 293,82. Gi trong bnh
i. Tiu chun c bn
j. HF c c tnh cao v ha tan thy tinh

Ph lc IX
H M pH
HN HP M TRONG VNG pH = 2,2 8,0

Dung
dch
Dung dch axit
pH Na2HPO4 0,2 M,
pH
limonic 0,1 M, ml
ml

Dung
dch
Dung dch axit
Na2HPO4 0,2 M,
limonic 0,1 M, ml
ml

2,2
2,4
2,6
2,8
3,0
3,2
3,4
3,6
3,8
4,0
4,2
4,4
4,6
4,8
5,0

10,72
11,15
11,60
12,09
12,63
13,22
13,85
14,55
15,45
16,47
17,39
18,17
18,73
19,15
19,45

0,40
1,24
2,18
3,17
4,11
4,94
5,70
6,44
7,10
7,71
8,28
8,82
9,35
9,86
10,30

19,60
18,76
17,82
16,83
15,89
15,06
14,30
13,56
12,90
12,29
11,72
11,18
10,65
10,14
9,70

5,2
5,4
5,6
5,8
6,0
6,2
6,4
6,6
6,8
7,0
7,2
7,4
7,6
7,8
8,0

9,28
8,85
8,40
7,91
7,37
6,78
6,15
5,45
4,55
3,53
2,61
1,83
1,27
0,85
0,55

336

HN HP M VN NNG TRONG VNG pH = 1,81 11,98 ( 18oC)

Thm vo 100 ml dung dch hn hp H3PO4 0,04 M; CH3COOH 0,04 M v

H3BO3 0,04 M nhng th tch V ml dung dch NaOH 0,2 M.
V (ml)

pH

V (ml)

pH

V (ml)

pH

V (ml)

pH

0
2,5
5,0
7,5
10,0
12,5
15,0
17,5
20,0
22,5
25,0

1,81
1,89
1,98
2,09
2,21
2,36
2,56
2,87
3,29
3,78
4,10

27,5
30,0
32,5
35,0
37,5
40,0
42,5
45,0
47,5
50,0

4,35
4,56
4,78
5,02
5,33
5,72
6,09
6,37
6,59
6,80

52,5
55,0
57,5
60,0
62,5
65,0
67,5
70,0
72,5
75,0

7,00
7,24
7,54
7,96
8,36
8,69
8,95
9,15
9,37
9,62

77,5
80,0
82,5
85,0
87,5
90,0
92,5
95,0
97,5
100,0

9,91
10,38
10,88
11,20
11,40
11,58
11,70
11,82
11,92
11,98

337

Ti liu tham kho

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Nguyn Thc Ct, T Vng Nghi, o Hu Vinh, C s l thuyt Ha hc Phn tch,

xut bn ln th 2, H Ni, 1985.
Herbert A. Laitinen, Chemical Analysis, London, 1960.
Von Einem, Autorenkollektiv Anlytikum, Leipzig, 1971.
W. F. Pickering, Modern Analytical Chemistry, New York, 1976.
Donald J. Pietrzyk, Clyde W. Frank, Analytical Chemistry, New York, 1979.
James S. Fritz, George H. Schenk, Quantitative Analytical Chemistry, Fifth Edition,
New York, 1988.
Douglas A. Skoog, Analytical Chemistry, New York, 1990.
Kennendy J. H., Analytical Chemistry Principles, New York, 1990.
Douglas A. Skoog, Donald M. West, F. James Holler., Analytical Chemistry,
New York, 1996.
W. Franklin Smyth, Analytical Chemistry of Complex Matrices, New York,1996.