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vn
i hc quc gia H ni
Trng i hc khoa hc t nhin
------------------------------




Nguyn Xun Trung








ha Phn tch




















H ni 2004
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M u
1. VI TR V TM QUAN TRONG CUA HO HOC PHN TCH
Ho hc phn tch l mt mn hc v cc phng php xc nh thnh phn
nh tnh v thnh phn nh lng cc cht v hn hp ca chng.
Phn tch nh tnh nhm tr li cu hi cc hp cht c to ra t
nguyn t no hay ni cch khc cc cht no (nguyn t no) tham gia vo
thnh phn. Thng thng trc khi phn tch nh lng ngi ta phi tin hnh
phn tch nh tnh. Kt qu phn tch nh tnh gip cho vic ra qui trnh
phn tch nh lng thch hp. Ni dung ch yu ca ho hc phn tch l phn
tch nh lng. Phn tch nh lng ng vai tr quan trng trong s pht trin
ca khoa hc cng ngh v sn xut.
Nhiu ngnh khoa hc cng ngh khc nhau: ho hc, khoa hc v tri t,
sinh vt hc, l hc, th nhng, y hc, kho c hc u rt cn n phn tch nh
lng. Chng ti xin n c mt vi th d:
Trong lnh vc y hc vic xc nh hm lng glucose trong mu gip cho
bc s chn on bnh tiu ng ca bnh nhn.
Trong lnh vc thc phm, xc nh hm lng protein, cacbonhirat, hm
lng vitamin, mui khong gip cho vic nh gi gi tr dinh dng ca thc phm.
Trong nh my sn xut thp, phn tch thnh phn nguyn liu u vo v
sn phm sau cng gip cho cc nh sn xut iu chnh thnh phn nguyn liu
u vo sn xut c loi thp c cng, do, mi mn ph hp.
Ngy nay trong lnh vc mi trng, ho hc phn tch chim mt v tr v
cng quan trng. Mc nhim mi trng ch c nh gi c th qua s liu
kt qu phn tch. V nhn r tm quan trng ca ho hc phn tch i vi cc
ngnh khoa hc cng ngh, sn xut v i sng, cng nh ng dng rng ri
chng vo cc lnh vc m nhiu chuyn ngnh khoa hc phn tch mi ra i
nh: Ho hc phn tch mi trng, phn tch dc phm, ho phn tch lm sng,
ho phn tch thc phm Ho hc phn tch c xem l trung tm ca nhiu
ngnh khoa hc k thut.

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Cng ngh ho hc
Cng ngh xy dng
C khi
in t
Y hc
Ho hc lm sng
Ho y sinh
Ho dc
c hc
Khoa hc vt liu
Luyn kim
Vt liu mi
Khoa hc x hi
Php y
Kho c hc
Nhn chng hc
Nng nghip:
Khoa hc ng vt
Khoa hc sau thu hoch
Khoa hc thc phm
Khoa hc t
Khoa hc mi trng
i dng
Kh tng
Sinh thi hc
a cht
a vt l
a ho
C sinh vt hoc
C thc vt
Sinh hc:
Thc vt hc
Vi trng hc
Sinh hc phn t
ng vt hc
Vt l
Vt l thin vn
L sinh
Ho hc:
Ho sinh
Ho V c
Ho Hu c
Ho l
Ho hc phn tch













2. PHN LOAI CC PHONG PHP PHN TCH
thu nhn y cc thng tin v thnh phn ho hc ca i tng phn
tch ngi ta phi tc ng n i tng mt dng nng lng no , lm cho
cc nguyn t cc phn t chu s bin i trng thi nng lng th hin qua thay
i tnh cht ca chng (xut hin mu, hnh thnh kt ta, thay i dn in,
thay i tnh cht t tnh). Nu ta ghi o c cc tn hiu ny c th c c cc
thng tin thnh phn nh tnh v nh lng ca i tng nghin cu. Da trn
dng nng lng tc ng m ngi ta phn loi cc phng php phn tch thnh
cc nhm sau:
Nhm u tin l cc phng php phn tch ho hc. Trong qu trnh phn
ng ho hc xy ra ngi ta quan st c cc thng tin lin quan n lng cht
ban u b tiu tn hay lng sn phm to thnh. Nu da vo xc nh khi lng
sn phm to thnh th thuc phng php phn tch khi lng. Nu ta o th tch
lng thuc th tiu tn (dung dch chun) th thuc phng php phn tch th tch
(phng php chun ). Phng php phn tch th tch da trn cc loi phn ng:
phn ng axit baz; phn ng to phc; phn ng kt ta; phn ng oxi ho - kh.
Nhm th 2 trong lnh vc ho hc phn tch l phng php phn tch
cng c bao gm:
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+) Phng php phn tch in ho ch yu da trn cc thng tin ca phn
ng in ho. Cc tn hiu (th, cng dng, dn in) ghi o c xem nh
hm s t l thun vi nng cc cht phn ng.
+) Phng php phn tch quang hc lin quan n tng tc tia bc x in
t vi vt cht. Vt cht hp th mt phn nng lng hay b kch thch di tc
dng ca dng nng lng . Dng v cng tia bc x pht ra ph thuc vo
bn cht ca cht phn tch v nng cc cu t c trong .
S ra i v pht trin cc phng php phn tch cng c hin i gn lin
vi s pht trin c s l thuyt cc phng php phn tch hin i kt hp vi cc
thnh tu ca vt l hc hin i, cng ngh thng tin - in t cng nh cc thnh
tu ca cc lnh vc ho hc khc. Cc phng php phn tch cng c hin i c
u im ni bt l c th xc nh bn t ng, t ng lng vt, siu vt cc cht
v c v hu c c trong cc i tng khc nhau.
Bng 1. Phn loi cc phng php phn tch theo dng nng lng tng tc.
Dng nng lng
kch thch
Tnh cht o c Phng php phn tch
Nng lng phn ng
ho hc
Khi lng sn phm
Th tch thuc th
Tc phn ng
Phng php phn tch khi lng
Phng php phn tch th tch
Phng php phn tch ng hc
Dng electron (phn
ng in ho trong
dung dch v trn in
cc).
Hiu in th, th dng
phn cc, cng ,
lng in.
Khi lng sn phm
ca phn ng in ho.
Phng php phn tch in th
Phng php Von - ampe
Phng php cc ph
Phng php in khi lng
(in phn)
Tia bc x in t.
Nng lng quay v
dao ng phn t, s
kch thch cc electron
ho tr (=10
_3
10
8
m)

di sng v cng
vch quang ph
Quang ph (hng ngoi, kh
kin, t ngoi). Quang ph cng
hng t ht nhn. Quang ph
cng hng t electron.
Tia bc x Rnghen
electron, ion v ntron
( = 10
8
10
11
m)


di sng (tn s).
Cng vch quang
ph,hot phng x.
Quang ph Rnghen; quang ph
electron; quang ph Owe; quang
ph Messbaier; phn tch kch
hot phng x.
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Mi phng php phn tch nu ra trn thng c tin hnh xc nh
trong khong nng nht nh, sai s mc phi cng tu thuc vo phng php
phn tch. Bng 2 ch r khong nng v sai s mc phi ca mi phng php.
Bng 2. Khong nng v sai s mc phi ca mi phng php.
Phng php Khong nng
xc nh (mol/l)
Sai s tng i
(%)
Phng php phn tch khi lng
10
1
10
2
0,1
Phng php phn tch th tch
10
1
10
4
0,1 1
Phng php chun in th
10
1
10
6
2
Phng php phn tch in khi lng
10
1
10
4
0,01 2
Phng php Von - ampe
10
3
10
9
2 5
Phng php trc quang
10
3
10
6
2
Phng php hunh quang
10
6
10
9
2 5
Phng php quang ph nguyn t
10
3
10
9
2 10
Phng php sc k
10
3
10
9
2 5
Phng php phn tch ng hc
10
2
10
10
2 10
3. CC GIAI OAN CUA QU TRNH PHN TCH.
Qu trnh phn tch c tin hnh qua 4 giai on ch yu sau:
1. Chn mu
Kt qu phn tch ch ng khi chn ng mu i din, c ngha l mu
c chn phn nh trung thnh i din cho i tng cn phn tch. Nu nh qu
trnh phn tch c tin hnh rt cn thn, phng php phn tch rt chun, nhng
ly mu khng i din th kt qu phn tch khng c ngha. Vic ly mu khng
i din s dn n sai lm nghim trng nh hng rt ln n s pht trin kinh t
x hi, nht l trong lnh vc iu tra nh gi ti nguyn khong sn ca t nc.
V vy, chn mu l mt trong nhng giai on quan trng nht ca qu trnh phn
tch. Vic chn mu bao gm ly mu ban u t khi lng mu ln bng cc cch
khc nhau, ly mu nh dn n mu phng th nghim l mu tin hnh phn tch.
Mu phn tch c th cc trng thi khc nhau: rn, lng, kh.
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2. Chun b mu
Giai on ho tan, ngi ta tin hnh ho tan bng cc dung mi thch hp
(nc, axit, kim, dung mi hu c) hay nung chy vi cht chy ph hp sau
chuyn cht nng chy sang trng thi dung dch. Loi tr cc cht cn tr bng cc
phng php khc nhau: chit lng lng, sc k, dng cht che, v.v
3. Giai on o
Tin hnh ghi o xc nh nng cc cht c trong mu phn tch.
4. nh gi kt qu phn tch
Giai on cui cng ca qu trnh phn tch l nh gi sai s php xc nh,
khong bin gii tin cy, gii hn pht hin ca phng php, gii hn nh lng,
ng, lp li

Nh trn trnh by ho hc phn tch gm hai ni dung ch yu: Phng
php phn tch bng phng php ho hc v phng php phn tch bng phng
php phn tch cng c. Trong gio trnh ny chng ti trnh by ni dung ch yu
cc phng php phn tch bng phng php ho hc. Chc chn trong qu trnh
bin son khng trch khi nhng thiu st, chng ti mong nhn c s ng gp
kin ca cc ng nghip v bn c. Chng ti xin chn thnh cm n.












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Chng 1
Phn ng phn tch cn bng ho hc hot
1.1. PHN LOAI CC PHAN NG PHN TCH
Phn ng phn tch l phn ng ho hc c ng dng tch nhn bit v
xc nh nh lng. nhn bit ngi ta ng dng cc phn ng km theo xut
hin cc du hiu c th quan st c (bin i mu sc, to kt ta, tch kh).
xc nh nh lng, ngi ta ng dng cc phn ng m cc cht ban u hay sn
phm phn ng c cc tnh cht c th ghi o c. Cc gi tr o c t l vi
nng cc cht c trong mu phn tch. Cc phn ng phn tch xy ra nhanh,
hon ton v theo t l xc nh. Theo c tnh tng tc ngi ta chia thnh 4 loi
phn ng:
1. Phn ng axit baz
2. Phn ng to phc
3. Phn ng kt ta
4. Phn ng oxi ho - kh
Cc phn ng phn tch thng c vit di dng phn t, ion hay ion
electron. Hai nh lut c bn c ng dng trong ho hc phn tch khi tin hnh
tnh ton l: nh lut bo ton khi lng (nh lut bo ton nng ban u)
v nh lut bo ton in tch (phng trnh trung ho in tch).
Theo nh lut bo ton khi lng, nng ban u ca mt cu t bng
tng nng cn bng ca cc dng tn ti ca cu t c mt trong dung dch .
Nu mt nguyn t no tham gia thnh phn vi dng khc nhau th cn phi tnh
hm lng ca n trong cc dng. Th d trong dung dch ion kim loi M tham gia
phn ng to phc vi phi t L hnh thnh cc phc: ML, ML
2
, ML
3
ML
n
. Theo
nh lut bo ton khi lng chng ta c th vit:
C
M
= [M] + [ML] + [ML
2
] + + [ML
n
] (1.1)
O y: C
M
: tng nng cc dng ca M
[ML
i
]: nng cn bng cc dng phc.
C
M
=

[ML
n
0
i
] (1.2)
Th d 1.1. Vit phng trnh bo ton khi lng vi dung dch H
2
CO
3
:
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Axit cacbonic phn li trong dung dch theo cc phn ng sau:
H
2
CO
3
+ H
2
O + H

3
HCO
3
O
+
+ H

3
HCO
2
O H
3
O
+
+
2
3
CO
Trong dung dch c mt cc ion: , H

3
HCO
3
O
+
, , H
2
3
CO
2
CO
3

Nng tng cng ca axit cacbonic:
= [ ] + [ ] + [H
3 2
CO H
C
2
3
CO

3
HCO
2
CO
3
]
= [H
+
O H
C
3
3
O
+
] + [ ] + 2 [H

3
HCO
2
CO
3
]

Theo nh lut trung ho in tch: trong mt n v th tch tng s in tch
dng bng tng in tch m.
C
i
Z
i
= 0 (1.3)
O y: C
i
: Nng cn bng cc dng trong dung dch
Z
i
: in tch ca cc dng
.
V d 1.2. Vit phng trnh trung ho in tch ca dung dch NaCl
Trong dung dch NaCl c mt cc ion Na
+
, Cl

, H
3
O
+
v OH

.
Phng trnh trung ho in tch:
[Na
+
] + [H
3
O
+
] = [Cl

] + [OH

]

1.2. IU KIN XAY RA CC PHAN NG
1.2.1. nh hng ca nhit
Anh hng ca nhit n cc phn ng khng ging nhau. Chng ta c th
xem xt da trn s ph thuc nhit ca hm s nhit ng. i vi cc qu trnh
xy ra p sut khng i, ngi ta ng dng entrpi H v nng lng t do Gibbs
G (th ng p, ng nhit). Chng lin quan vi nhau theo biu thc sau:
G = H TS (1.4)
O y: T nhit tuyt i
S entrpi
Hng s cn bng nhit ng ca phn ng ho hc ph thuc vo nhit .
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dT
K ln d
o
=
2
RT
H
(1.5)
T s
dT
K ln d
o
cng ln, gi tr tuyt i hiu ng nhit phn ng cng ln.
Ngi ta cng c th nh gi nh tnh nh hng ca nhit , nu bit hiu ng
nhit ca phn ng. Theo nguyn l Le Chatelier khi un nng cn bng chuyn dch
theo hng km theo hp th nhit, c ngha khi tng nhit s lm tng hng s
cn bng ca qu trnh thu nhit,cn gim nhit to iu kin thun li cho qu
trnh to nhit. Chiu hng chuyn dch cn bng khi bin i nhit c xc
nh bi du ca hiu ng nhit phn ng, cn mc chuyn dch cn bng c
xc nh bi gi tr H (H cng ln nh hng ca nhit cng mnh).
Nhit cng nh hng n tc phn ng. Tt c cc phn ng ho hc
xy ra vi tc xc nh, thng c c trng bi bin i nng mt trong cc
cu t ca h trong mt n v thi gian ():
v =
d
dC
(1.6)
Nu dC < 0 th c ly du m
dC > 0 th c ly du dng
Khi un nng, tc phn ng tng. Theo qui tc Van Hoff khi nhit
tng 10
o
C th tc phn ng tng 2 4 ln.
1.2.2. Anh hng ca mi trng phn ng
Anh hng ln nht n iu kin xy ra phn ng l gi tr pH - axit ca
mi trng phn ng. Trng thi ion tn ti trong dung dch c xc nh bi gi
tr pH. Th d ion Cr(VI) trong mi trng axit tn ti dng , trong mi
trng kim tn ti dng . Ion biu th kh nng oxi ho ln nht
trong mi trng axit mnh, nh nht trong mi trng kim. iu ny c th gii
thch ion H
2
7 2
O Cr
2
4
CrO

4
MnO
3
O
+
tc ng n anion lm yu lin kt Mn O lm cho tnh kh
yu i, cn ion OH

4
MnO

lm cho lin kt Mn O bn hn. Mt s nguyn t tn ti
dng ion phc trong mi trng axit mnh ( , ), mt s nguyn t khc
(Cr, Al, Zn, Pb) tn ti dng phc hiroxo trong mi trng kim.
2
4
CdCl

4
FeCl
Bng thc nghim ngi ta nhn thy trng thi cn bng ca nhiu phn
ng ho hc trong dung dch s thay i khi thm vo cht in li. Anh hng ca
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cht in li n cn bng ho hc khng ch ph thuc vo bn cht ho hc ca cht
in li, m cn ph thuc vo tnh cht ca dung dch c nh gi qua lc ion .
=
2
1
([A] + [B] + [C] + . . . ) (1.7)
2
A
Z
2
B
Z
2
C
Z
O y: [A], [B], [C], [] l nng cn bng cc dng A, B, C, .. trong dung dch .
Z
A
, Z
B
, Z
C
, l in tch ca cc ion A, B, C
Do tng tc ca ion qua lc ion m nng c biu th qua gi tr hot a.
a
A
= f
A
[A] (1.8)
O y: a
A
: hot

ca ion A
[A]: nng cn bng ca A
f
A
: h s hot
Dng tng qut: =
2
1

C
=
i
i 1
2
i
Z
i
(1.9)
Nu gn bng khng, dung dch rt long, khng c tng tc tnh in
gia cc ion, th f = 1 v hot bng nng .
Trong dung dch long lc ion < 0,02 th h s hot c tnh theo
phng trnh gn ng ca bai Hucken (Debye Hckel ):
lg f
j
= 0,5
2
i
Z (1.10)
Cn lc ion trong gii hn: 0,02 < < 0,20 th lc ion tnh theo biu thc:
lg f
j
=
+

1
5 0
2
i
Z ,
(1.11)
Cn > 0,2 th lg f
j
=
+

1
5 0
2
i
Z ,
+ h (1.12)
Th d 1.3. Tnh h s hot ca ion K
+
v trong dung dch K
2
4
SO
2
SO
4
0,0020 M
K
2
SO
4
2K
+
+
2
4
SO
= 0,5 (2 . 0,0020 . 1
2
+ 0,0020 . 2
2
) = 6,0.10
3

lg f
K
+

=
3
3
10 0 6 1
10 0 6 5 0

+ . ,
. , 1 . ,
2
= 0,037
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lg

=
2
4
SO
f
3
3
10 0 6 1
10 0 6 5 0

+ . ,
. , 2 . ,
2
= 0,147
f
K
+ = 10
0,037
= 10
1
. 10
0,963
= 0,918

= 10
2
4
SO
f
0,147
= 10
1
. 10
0,853
= 0,713

1.2.3. nh hng nng cht phn ng
nh lut c bn thit lp ph thuc gia nng cc cht tham gia phn
ng v sn phm phn ng iu kin cn bng l nh lut tc dng khi lng do
Gildberg v Waage ngh vo nm 1867: Tc phn ng xy ra trong mi trng
ng th nhit khng i t l thun tch nng cc cht phn ng.
Th d phn ng:
mA + nB cC + dD (1.13)
Nng A v B gim dn, nng C v D tng dn trong qu trnh phn
ng. Tc phn ng thun:
v
t
= k
t
[A]
m
[B]
n
(1.14)
Tc phn ng nghch:
v
n
= k
n
[C]
c
[D]
d
(1.15)
Khi h t cn bng v
t
= v
n
:
k
t
[A]
m
[B]
n
= k
n
[C]
c
[D]
d
(1.16)
K =
n
t
k
k
=
n m
d c
] B [ ] A [
] D [ ] C [
(1.17)
O y K c gi hng s cn bng nng c gi tr khng i khi nhit
v p sut khng i.
Trng hp k n tng tc cc ion trong dung dch th nng c thay bng
hot .
K
o
=
n
B
m
A
d
D
c
C
a a
a a
(1.18)
K
o
: c gi l hng s cn bng nhit ng ph thuc vo nhit v p sut
K
o
=
n m
d c
] B [ ] A [
] D [ ] C [
.
n
B
m
A
d
D
c
C
f f
f f
= K
n
B
m
A
d
D
c
C
f f
f f
(1.19)
1.3. INH LUT TC DUNG KHI LONG NG DUNG I VI CC
PHAN NG PHN TCH
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Bng 1.1. ng dng nh lut tc dng khi lng i vi mt s dng cn bng
Cc kiu
cn bng
K hiu
tn gi
Th d Hng s cn bng
S phn li ca
H
2
O
Tch s ion ca
H
2
O
2H
2
O H
3
O
+
+ OH

O H
K
2
= [H
3
O
+
] [OH

]

Cn bng d th Tch s tan T
BaSO
4
Ba
2+
+
2
4
SO
4
BaSO
T =[Ba
2+
] [ ]
2
4
SO
Cn bng axit
hay baz
K
a
(hng s
phn li axit)
K
a
(hng s
phn li baz)
CH
3
COOH + H
2
O
CH
3
COO

+ H
3
O
+

CH
3
COO

+ H
2
O
CH
3
COOH + OH


K
a
=
] COOH CH [
] O H [ ] COO CH [
3
3 3
+

K
b
=
] COO CH [
] OH [ ] COOH CH [

3
3

Cn bng
to phc
Hng s bn
phc cht

Ni
2+
+ 4 CN



2
4
) CN ( Ni

2
4
) CN ( Ni
=
4 2
2
4
] CN [ ] Ni [
] ) CN ( Ni [
+



Cn bng phn
ng oxi ho -
kh
Hng s cn
bng phn ng
oxi ho - kh

4
MnO + 5 Fe
2+
+ 8H
+

Mn
2+
+ 5Fe
3+
+ 4 H
2
O
K
cb
=
8 5 2
4
5 3 2
] H [ ] Fe [ ] MnO [
] Fe [ ] Mn [
+
+ +


Cn bng
phn b
H phn b I
2
(nc) I
2
(hc)
K
d
=
nc
hc
] I [
] I [
2
2



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Chng 2
i cng v phng php phn tch th tch
2.1. Nguyn tc chung phng php phn tch th tch
Phng php phn tch th tch ch yu da trn o th tch thuc th (dung
dch chun) bit chnh xc nng tiu tn khi phn ng vi cht phn tch. Qu
trnh thm dung dch chun t buret vo dung dch phn tch gi l qu trnh chun
. Phn ng gia dung dch chun vi cht phn tch s xy ra sau mi ln thm
dung dch chun :
nA + mB An Bm (2.1)
y: A: cht phn tch
B: dung dch chun
n, m: h s t l cc cht tham gia phn ng.
Trong qu trnh chun nng cht phn tch v dung dch chun gim
dn, nng sn phm phn ng tng dn. Khi lng dung dch chun tiu tn
tng ng cht phn tch th qu trnh chun kt thc. Thi im ny c gi
im tng ng. Trong thc t khng th xc nh chnh xc im tng ng,
ch xc nh c im kt thc chun gn vi im tng ng. im kt thc
chun quan st c nh s bin i mu sc ca dung dch . Cht to ra tn hiu
c th quan st c bng mt gi l cht ch th.
Phng php phn tch th tch thng c tin hnh theo cc cch sau:
Chun trc tip: Xc nh trc tip cht A da vo phn ng gia cht
A v dung dch chun B.
Chun ngc (nghch): Trong mt s trng hp khng th xc nh
trc tip do phn ng xy ra chm hoc khng tm c cht ch th thch hp, ngi
ta dng phng php chun ngc. Thm mt lng d chnh xc dung dch
chun vo cht cn xc nh, sau chun lng dung dch chun d bng dung
dch chun th 2.
Chun thay th: Cho cht D tc dng vi cht A, to ra mt lng
tng ng cht C, chun lng cht C bng mt dung dch chun thch hp.
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Chun gin tip: Cch ny c s dng khi khng th xc nh
trc tip hay bng phng php chun ngc hoc chun thay th. Thng
c s dng xc nh cc anion, th d xc nh cc anion , . Ngi ta
chuyn cht cn xc nh vo mt hp cht trong c cha t nht mt nguyn
t c th xc nh trc tip.
2
4
SO
3
4
PO
Trong phng php phn tch th tch nng dung dch chun c ngha
quan trng, quyt nh chnh xc ca cc php xc nh tip theo. Dung dch
chun (dung dch gc) thng c chun b t mt lng cn chnh xc mt loi
ho cht c gi l cht gc v phi tho mn cc yu cu sau:
Cht phi c tinh khit cao, lng tp cht trong phi nh hn
0,05%.
Thnh phn phi tng ng ng cng thc k c nc kt tinh.
Phi bn trng thi rn v trng thi dung dch khi bo qun.
Khi lng mol cng ln cng tt.
Trong trng hp khng c cht tho mn cc yu cu nu trn, ngi ta
ch chun b c dung dch c nng gn ng, sau xc nh li bng
dung dch cht gc thch hp. Th d, ngi ta ch chun b c dung dch
NaOH c nng gn ng, sau phi dng dung dch H
2
C
2
O
4
c nng
chnh xc xc nh li nng NaOH.
2.2. Phn loi cc phng php chun
Cc phng php chun c phn theo loi phn ng. Bng 2.1 ch r
phn loi cc phng php chun theo loi phn ng.
u im c bn ca phng php phn tch th tch nhanh, n gian,
thun li khi phn tch hng lot, sai s php xc nh 0,1 1%, gii hn nh lng
10
1
10
4
M.





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Bng 2.1. Phn loi cc phng php chun
Cc cht c xc nh Loi phn
ng
Tn gi
phng php
Dung dch
chun
Trc tip Ngc Gin tip
Tng tc
axit vi
baz
Phng php
chun axit
baz
H
2
C
2
O
4
, HCl,
H
2
SO
4
, NaOH,
KOH
Baz, mui ca baz
mnh v axit yu;
axit, mui ca baz
yu v axit mnh
Mui baz yu
v axit mnh,
cc hp cht
hu c

Oxi ho -
kh
Phng php
chun oxi
ho - kh
KMnO
4
;
K
2
Cr
2
O
7
;
I
2
; Na
2
S
2
O
3
.5H
2
O
Cht kh
Cht kh
Cht kh
Cht oxi ho
Cht oxi ho
Cht kh

Phn ng
to phc
Phng php
chun
Complexon
EDTA Cc cation to phc
bn vi EDTA
Cc cation phn
ng chm vi
EDTA hoc
khng tm thy
ch th thch hp
Cc cation
kim loi to
phc bn vi
EDTA so
vi Mg
2+
Phn ng
kt ta
Phng php
chun kt
ta
AgNO
3
Cc anion to kt ta
vi AgNO
3
Cc cation to
hp cht t tan
vi Cl

, Br

,
SCN

, S
2
,
,
2
4
CrO
3
4
PO


2.3. Nng dung dch
Nng dung dch l i lng dng ch hm lng mt cht (ion hay phn
t) trong dung dch .
Nng mol ca dung dch: Nng mol ca mt cht l s mol cht
c trong 1 lt dung dch. Nu ta gi n
A
l s mol cht A c ho tan trong V lt
dung dch , nng mol ca cht A:
C
A
=
V
n
A
=
dch dung tch th
A cht mol s
(2.2)
Th d 2.1. Tnh nng mol ca ru etylic C
2
H
5
OH khi ho tan 2,30 g C
2
H
5
OH
(46,07 g/mol) trong 3,5 lt H
2
O
= 2,30 g.
OH H C
C
5 2
3,5 . 46,07g
H C mol 1
5 2
OH
= 0,04992 M
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Nng mol ban u (nng mol tng cng) (nng mol phn tch):
Nng mol ban u l nng mol tng cng cc dng tn ti ca mt cht c
trong dung dch .
Nng mol cn bng trong dung dch: Nng mol cn bng l
nng mol ca cc dng (ion hay phn t) tn ti trong dung dch thi im cn
bng.
Th d 2.2. Tnh nng mol ban u v nng mol cn bng ca axit tri-
cloaxetic (163,4 g/mol) khi ho tan 285 mg axit trong 10,0 ml H
2
O. Bit phn li
ca axit tricloaxetic l 73%.
K hiu axit tricloaxetic l HA:
C
HA
=
g/mol 163,4 . 10,0
mg 1000
HA g 1
. mg 285
.
lt 1
ml 1000
= 0,174 M
phn li ca axit tricloaxetic 73%, vy nng axit cha phn li:
C
HA
=
100
73 100
. 0,174 = 0,047 M
Nng axit phn li:
C
A
=
HA mol 100,0
A mol 73,0

. 0,174 mol/lt = 0,127 M


Th d 2.3. Tnh nng K
+
ra g/lt khi trn ln 100,0 ml dung dch KCl 0,250 M
vi 200,00 ml dung dch K
2
SO
4
0,1000 M.
S mmol K
+
c trong dung dch sau khi trn ln:
= 100 . 0,250 + 2 . 200,00 . 0,1000 = 65,00 mmol
Nng K
+
qui ra g/l
=
ml 300,0
ml 1000 . g/mg 0,001 . mg/mmol 39,0 . mol 65,00
= 8,47 g/l
Nng mol ng lng: Nng mol ng lng ca mt cht l s
mol ng lng ca cht c trong 1 lt dung dch hoc s milimol ng lng
c trong 1 ml dung dch .
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ng lng mol ca mt cht thay i theo phn ng n tham gia.
Th d trong phn ng trung ho H
3
PO
4
bng NaOH nu thay th mt ion H
+

th ng lng mol ca H
3
PO
4
bng khi lng mol. Trong phn ng oxi ho - kh
ng lng mol ca mt cht bng khi lng mol cht chia cho s electron cho
hay nhn.
Th d phn ng gia Fe
2+
vi K
2
Cr
2
O
7
+ 6Fe
2
7 2
O Cr
2+
+ 14 H
+
6 Fe
3+
+ 2Cr
3+
+ 7H
2
O
ng lng mol ca Fe
2+
bng khi lng mol ca n. ng lng mol
ca bng
2
7 2
O Cr
6
1
khi lng mol. Cng cn phn bit ng lng mol cht oxi
ho v cht kh vi ng lng mol ca cc cht trong phn ng trao i. Th d,
ng lng mol ca FeSO
4
trong phn ng vi KMnO
4
bng khi lng mol ca
n, nhng trong phn ng:
FeSO
4
+ 2NaOH Fe(OH)
2
+ Na
2
SO
4
ng lng mol ca FeSO
4
=
2
1
khi lng mol.
2.4. iu ch dung dch c nng xc nh
iu ch dung dch c nng chnh xc t cht gc l vic lm quan
trng u tin trong phng php chun , bi v t nng cht gc chng ta
xc nh nng cc cht khc. chun b dung dch c nng chnh xc t
cht gc ngi ta cn mt lng cht gc thch hp trn cn phn tch c
chnh xc 0,1 hoc 0,2 mg em ho tan vo th tch nc xc nh.
Th d 2.4: Cn cn bao nhiu gam BaCl
2
.2H
2
O chun b 2 lt dung dch
BaCl
2
0,108 M. Bit khi lng mol BaCl
2
.2H
2
O: 244g/mol.
S mol BaCl
2
:
2 lt . 0,108 mol/l BaCl
2
.2H
2
O = 0,216 mol BaCl
2
.2H
2
O
Khi lng BaCl
2
:
0,216 mol BaCl
2
.2H
2
O .
O H . BaCl mol
g ,
2 2
2
0 244
= 52,70 g BaCl
2
.2H
2
O
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Cn 52,7 g BaCl
2
.2H
2
O em ho tan vo nc ri chuyn vo bnh nh mc
2 lt, a nc n vch mc, lc u, ta c dung dch BaCl
2
0,108 mol/l
Trng hp phi chun b dung dch c nng xc nh t dung dch c
nng phn trm th phi bit khi lng ring ca dung dch .
Th d 2.5. Tnh nng mol ca axit nitric c 70% c khi lng ring d= 1,42
g/ml .
S gam HNO
3
c trong 1 lt dung dch HNO
3
70%:
1,42 g/ml .
lt 1
1000 ml
.
dch dung 0 1
70
0
HNO
3
=
dch dung lt
994
3
HNO

=
3
HNO
C
dch dung lt
994
3
HNO
.
3
3
HNO g ,
HNO mol
0 63
1
= 15,8 M
Th d 2.6. Cn ly bao nhiu ml dung dch HCl c 37% c khi lng ring 1,18
g/ml chun b 100,0 ml dung dch HCl 6M. Khi lng mol ca HCl l 36.5
g/mol.
C
HCl
=
ml
18 1 g ,
.
lt
10
3
ml
.
dch dung g 100
37 HCl g
.
HCl g 36,5
1 HCl mol
= 12,0 M
S mol HCl cn phi ly:
100,0 ml .
ml 1000
lt 1
.
lt 1
0 6 mol ,
= 0,600 mol
Th tch HCl phi ly:
V
HCl
=
mol 12,0
mol 600 0 ,
= 0,0500 lt
V
HCl
= 50 ml
Ly 50,0 ml HCl c 37% cho vo bnh nh mc 100 ml , thm nc n
vch mc, lc u ,ta c dung dch HCl 6M .
2.5. Cch tnh kt qu trong phn tch th tch
tnh kt qu trong phng php phn tch th tch, ngi ta da vo nng
v th tch dung dch chun tiu tn trong qu trnh chun .
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Th d 2.7. Tnh khi lng NaCl c trong mu phn tch ?Bit rng em chun
bng dung dch AgNO
3
O,100M ht 25,0ml.
S mol AgNO
3
tham gia phn ng:
25,0 ml . 0,100 mmol/ml = 2,5 mmol AgNO
3
Phn ng gia Cl

v AgNO
3
theo t l 1 : 1. Vy khi lng NaCl c trong
mu phn tch:
2,50 mmol .
mmol
NaCl mg ,44 58
= 146 mg = 0,146 g
Th d 2.8. Cn 0,4671 gam NaHCO
3
k thut ho tan vo nc, ri em chun
bng dung dch HCl 0,106 M ht 40,72 ml. Tnh % NaHCO
3
c trong mu phn
tch.
Phn ng chun :
+ H

3
HCO
+
H
2
O + CO
2
S mmol HCl tham gia phn ng:
40,72 ml . 0,106 mml/ml = 4,3448 mmol
v cng chnh l s mmol NaHCO
3
c trong mu phn tch.
% NaHCO
3
=
mg ,
mmol ,
1 467
3448 4
.
mmol
g ,1 84
. 100 % = 78,14 %
Nu cc cht phn tham gia phn ng khng theo t l 1 : 1 chng ta cn
ch n h s t l khi tnh kt qu. Th d phn ng gia hai cht A v T theo
t l (a/t).
a A + t T P
A: cht phn tch; T: Dung dch chun; a, t: h s t l
% Cht A =
(mg) mu lng Khi
mmol
mg
A mol lng Khi .
T) (mmol t
A) (mmol a
). ml ( V .
ml
mmol
C
T T

. 100%
C
T
: nng dung dch chun mmol/ml
V
T
: th tch dung dch chun tiu tn trong qu trnh chun (ml)
a, t: h s t l cc cht phn ng
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Th d 2.9. Cn 0,2638g Na
2
CO
3
k thut ho tan vo nc, ri em chun bng
HCl 0,128M ht 38,27 ml. Tnh phn trm Na
2
CO
3
c trong mu phn tch.
Phn ng chun :
+ 2H
2
3
CO
+
H
2
O + CO
2
S mmol HCl tham gia phn ng:
0,128 mmol/ml . 38,27 ml = 4,8985 mmol
S mmol Na
2
CO
3
c trong mu phn tch:
4,8985 mmol .
2
1
= 2,4492 mmol
% Na
2
CO
3
=
mg 263,8
4492 2 (mg/mmol) 105,99 . mmol ,
. 100% = 98,40 %
Thng thng kt qu phn tch c biu th theo n v phn trm khi
lng. Nhng i vi cc mu hm lng cht xc nh lng vt hay siu vt
ngi ta ca chng theo n v ppm hay ppb.
ppm =
(g) mu lng Khi
(g) tch phan cht lng Khi
. 10
6
ppm
ppb =
(g) mu lng Khi
(g) tch phan cht lng Khi
. 10
9
ppb
i vi mu lng kt qu phn tch biu th theo khi lng cht phn tch
(g) trong n v th tch (ml).
ppm =
(ml) mu tch Th
(g) tch phan cht lng Khi
. 10
6
ppm
ppb =
(ml) mu tch Th
(g) tch phan cht lng Khi
. 10
9
ppb
Th d 2.10. 25,0 l mu cha 26,7 g glucose. Tnh nng glucose ra n v
ppm.
25,0 l .
l
ml
1000
1
= 2,50.10
2
ml
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26,7 g .
g
g

6
10
1
= 2,67.10
5
g
Hm lng glucose : ppm =
) ml ( 2,5.
) g ( . ,
2
5
10
10 67 2

. 10
6
= 1,07.10
3
g/ml
Th d 2.11. Tnh ra nng mol dung dch Li
+
v Pb
2+
1,00 ppm.
Nng Li
+
= 1,00 ppm = 1,00 (mg/l) Li
Nng Pb
2+
= 1,00 ppm = 1,00 (mg/l) Pb
2+
C
Li
+ =
g/mol 6,94
) mg / g ( (mg/l). ,
3
10 00 1

= 1,44.10
4
M


C
Pb
2+ =
g/mol 207
) mg / g ( (mg/l). ,
3
10 00 1

= 4,89.10
6
M


Th d 2.12. Tnh s gam Pb(NO
3
)
2
c trong 1 lt dung dch Pb(NO
3
)
2
cha
100 ppm Pb
2+
.
100 ppm Pb
2+
=
lt
100 mg
Pb
2+
= 0,100 g/lt


S mol Pb
2+
:
lt
100 0 g ,
.
g 207
1
+ 2
Pb mol
= 4,83.10
4
mol
Khi lng Pb(NO
3
)
2
c trong 1 lt dung dch :
4,83.10
3
mol . 283,2 g/mol = 0,137 g Pb(NO
3
)
2
.


2.6. Sai s trong phn tch nh lng
2.6.1. Cc loi sai s trong phn tch nh lng
D vic tin hnh phn tch c th c thc hin ht sc cn thn, kt qu
phn tch cng khc vi gi tr thc mt i lng, ngha l c sai s. Ph thuc vo
tnh cht m sai s c chia ra lm 3 loi:
1) Sai s h thng.
Sai s h thng do nguyn nhn c nh, c du khng i (dng hay m) ph
thuc vo s sai lch theo chiu hng no. N xut hin do cc nguyn nhn sau:
21
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Do phn ng dng chun xy ra khng hon ton , hoc trong
phng php khi lng dng kt ta hay dng cn khng bn d dng b
phn hu.
Do s dng cc dng c khng chun, ho cht khng tinh khit, dung
dch chun c nng khng dng.
Do ngi phn tch thiu kinh nghim, ra kt ta khng sch, mt kt ta
trong qu trnh lc ra
Ngoi ra cn do ngi phn tch khng c kh nng quan st chnh xc
chuyn mu ca ch th khi chun chng hn. Sai s do nh kin ca ngi phn
tch, da vo kt qu chun ln 1, ly gn ng kt qu ln 2, thm ch ly kt
qu ca ngi khc.
2) Sai s ngu nhin
Sai s ngu nhin l sai s khng xc nh, s xut hin khng tun theo qui
lut no. N xut hin trong bt k php o no d c tin hnh ht sc cn thn.
Ngi ta khng th loi b c sai s ngu nhin m ch lm gim bng cch tng
s ln th nghim, sau x l cc s liu bng phng php ton hc thng k.
3) Sai s th bo
Sai s th bo l sai s qu ln, lm sai lch hn kt qu phn tch. Th d
c sai th tch burt khi chun , lm mt mt phn kt ta. Thng thng, trong
dy s liu thc nghim khi xc nh hm lng mt nguyn t no c th c
mt, hai kt qu mc phi sai s th bo , chng ta phi tm ra s liu no trong dy
kt qu mc phi sai s th bo, loi ra khi khi tnh kt qu trung bnh.
Cc sai s trong phn tch nh lng cng nh trong cc php o khc c th
biu th hai loi sai s tuyt i v sai s tng i.
Sai s tuyt i ca php xc nh l hiu gia kt qu thu c v gi tr
thc (hoc gi tr ng tin cy nht) ca thnh phn cn tm.
S
t
= x (2.3)
: gi tr thc
Th d t cng thc ho hc ca BaCl
2
.2H
2
O ta tnh c 14,75 % nc kt
tinh, nhng nu tin hnh phn tch tm thy 14,70 %
Sai s tuyt i : S
t
= x = 14,70 14,75 = 0,05 %
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Sai s tng i l t s gia i lng tuyt i vi i lng thc sai s
tng i thng biu th dng phn trm.
S
t/i
=
75 14
05 0
,
,
x 100 = 0,34 %
Nu ta khng bit c gi tr thc, c th dng i lng trung bnh.
2.6.2. Mt s i lng c trng thng c s dng x l s liu thc
nghim theo phng php ton hc thng k.
Trung bnh s hc: Nu ta tin hnh n ln phn tch mt nguyn t no
trong iu kin ng nht c cc gi tr x
1
, x
2
, x
3
x
n
.
Gi tr trung bnh s hc ca x:
x =
n
x ... x x x
n
+ + + +
3 2 1
(2.4)
Trung bnh bnh phng:
x
bp
=
n
x ... x x x
n
2 2
3
2
2
2
1
+ + + +
(2.5)
lch trung bnh:
d =
n
x x
i

(2.6)
Phng sai: Phng sai trung bnh cng cc bnh phng hiu gia cc gi
tr ring r v gi tr trung bnh:
S
2
=
1
2
1

=
n
) x x (
i
n
i
(2.7)
y n 1 gi l bc t do, nu n ln hn 10 th c th b qua 1 cnh n

2
=
n
) x (
i
n
i
2
1

=
(2.8)
lch chun hay sai s bnh phng trung bnh:
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S =
1
2

n
) x x (
i
(2.9)
=
n
) x (
i
2

(2.10)
y l cc i lng c trng cho phn tn c dng ch mc sai
s ngu nhin.
S =
1
2
1
2
1


= =
n
x x
i
n
i
i
n
i
(2.11)
Th d 2.13. Kt qu xc nh hm lng Pb trong mu mu nh sau: 0,752; 0,756;
0,752; 0,751; 0,760 ppm. Tnh lch chun ca dy kt qu ny.
p dng cng thc (2.11), ta c:
Mu x
i

2
i
x
1 0,752 0,565504
2 0,756 0,571536
3 0,752 0,565504
4 0,751 0,564001
5 0,760 0,577600
x
i
= 3,771 = 2,844145
2
i
x
x =
n
x
i
=
5
771 3,
= 0,7542 0,754 ppm Pb

( )
n
x
i
2

=
5
771 3
2
) , (
=
5
220441 14,
= 2,8440882
S =
1 5
8440882 2 844145 2

, ,
=
4
0000568 0,
= 0,00377
0,004 ppm Pb
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Bin gii tin cy: Nu sai s ngu nhin tun theo phn b chun c th
xc nh c bin gii tin cy, tc l khong trong cha gi tr thc:
= x
n
z
(2.12)
Tuy nhin trong thc t s th nghim c thc hin khng ln (2 10), khi
s phn b sai s ngu nhin khng tun theo nh lut Gauss, m theo phn b
khc c dng ng cong Gauss tiu chun t (h s Student v Fiso) ph thuc vo
xc xut tin cy p v s th nghim (p = n 1) (bc t do).
= x
n
S t
(2.13)
= x
=
n
S t
bin giii tin cy
Gi tr thc nm trong khong x < < x +
Nu biu th theo n v tng i, ta c:
= x
n x
. S t 100
(2.14)
2.6.3. nh gi kt qu phn tch
Th d 2.14. Khi tin hnh xc nh hm lng phtpho trong axit phtphoric k
thut, thu c cc s liu sau: 35,30; 35,40; 35,20; 35,00; 35,40; 35,30 %. Hy
kim tra kt qu phn tch theo phng php thng k ton hc vi sc xut p = 0,95
Gi tr trung bnh:
x =
6
30 35 35,30 35,40 35,00 35,20 35,40 , + + + + +
= 35,30 %
Kim tra gi tr 35,50 mc sai s th bo khng theo tiu chun:
Q =
x x
x x
min max
n m

+1

Q =
35,20 35,50
35,40 ,
+
50 35
= 0,33
25
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Tra bng vi p = 0,95; Q
bng
= 0,56
Q
tn
< Q
lt
gi tr 35,50% khng gp sai s th bo.
S =
1
2

n
) x x (
i

S =
5
05 0 05 0 15 0 15 0 05 0 05 0
2 2 2 2 2 2
) , ( ) , ( ) , ( ) , ( ) , ( ) , ( + + + + +
= 0,104
Tra bng vi p = 0,95, n = 6 (bc t do), t
lt
= 2,57
Bin gii tin cy: =
n
S t
=
6
104 0 57 2 , x ,
= 0,109 0,11
Hm lng phtphot nm trong khong: (35,30 0,11) %
chnh xc ca php phn tch:
=

100 x
p
% hoc =
x
100 x
p

%
chnh xc ca php phn tch phtpho:
=
30 35
11 0
,
100 x ,
= 0,31 %
Th d 2.15. Tin hnh phn tch hm lng ru trong mu thu c kt qu sau:
% C
2
H
5
OH: 0,084; 0,089; 0,079. Tm khong bin gii tin cy khi xc nh hm
lng ru vi sc xut tin cy 0,95.
x =
3
0 084 0 0,079 ,089 , + +
= 0,084 %
S =
1
3
2
2

n
) x (
x
i
i

x
i
= 0,252; = 0,021218
2
i
x
( x
i
)
2
= 0,063504
S =
1 3
3
063504 0
021218 0

,
,
= 0,0050% C
2
H
5
OH
26
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Tra bng k = n 1 = 2, p = 0,95, t = 4,30
=
n
S t
=
3
0050 0 30 4 , x ,
= 0,012
Hm lng ru: (0,084 0,012)% C
2
H
5
OH
27
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Chng 3
Cn bng axit baz
3.1. nh ngha axit baz
nh ngha axit baz ln u tin c ngh vo nm 1894 bi Svant
Areniut (nh ho hc Thu in). Theo Areniut axit l cht khi ho tan vo nc cho
phn li thnh cation H
+
v gc axit.
Baz l cht khi ho tan vo nc cho ion hiroxyl OH

. Nh vy, trong phn
t axit cha hiro, cn trong phn t baz cha nhm hiroxyl.
Ion H
+
lin kt vi phn t nc (H
2
O) to thnh ion hironi H
3
O
+
.
Th d: Axit HNO
3
H
+
+

3
NO

H
+
+ H
2
O H
3
O
+
Baz KOH K
+
+ OH

B + H
2
O BH
+
+ OH

Theo Areniut cc cht ch th hin tnh cht axit hoc baz khi ho tan vo nc.
Nm 1923 nh ho hc an Mch Bronsted v nha ho hc ngi c Lauri
c lp nghin cu nhng cng a ra mt nh ngha axit baz. Theo hai ng:
Axit l nhng cht c kh nng cho proton, Baz l nhng cht c kh nng
nhn proton.
Mt axit sau khi cho proton bin thnh mt baz lin hp vi axit . Ngc
li mt baz sau khi nhn proton bin thnh axit lin hp vi baz .
Axit + H
2
O baz lin hp + H
3
O
+
(3.1)
Proton khng tn ti trng thi t do trong dung dch nn mt cht ch th hin
tnh cht axit hoc tnh cht baz trong dung mi c kh nng cho hoc nhn proton.
chuyn proton chuyn proton
AH + B A

+ HB
+
axit baz baz lin axit lin hp
hp ca AH ca B
chuyn proton chuyn proton
HCl + NH
3
+ Cl
+
4
NH

axit
1
baz
2
axit lin hp
2
baz lin hp
1
28
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nh ngha axit, baz ca Bronsted Lauri nu bt c vai tr ca dung
mi, m Areniut khng cp n. HCl, HBr l axit mnh trong dung mi H
2
O,
nhng n tr thnh axit yu trong dung mi axit axetic bng.
HCl + HC
2
H
3
O
2
H
2
C
2
H
3
+
2 3
O H + Cl

axit 1 + baz 2 axit 2 + baz 1
Mt quan im tng qut hn v bn cht axit baz do Gilbert Levis a ra.
Theo Levis axit l nhng cht c kh nng tip nhn cp electron, baz l cht c
kh nng cho cp electron. Da vo nh ngha axit baz ca Levis ngi ta gii
thch tnh cht axit, baz ca cc cht trng thi khc nhau: lng, rn, kh.
Th d botriflorua th hin tnh cht axit trng thi kh khi cho phn ng vi
NH
3
.
B
F F
F
+
F
B
F F
N H
H
H
N H
H
H


axit baz hp cht mi
y nguyn t B trong phn t BF
3
c kh nng tip nhn cp electron ca
nguyn t N trong NH
3
hnh thnh mt hp cht mi vi lin kt cng ho tr.
Da vo nh ngha axit, baz ca Levis ngi ta gii thch c ti sao AlCl
3

li ho tan c vo dung mi dietylete (dung mi khng phn cc).
CH
3
CH
2
O
CH
2
CH
3
+
Cl
Al
Cl Cl
Cl
CH
2
CH
3
CH
3
CH
2
O Al Cl
Cl


AlCl
3
c tnh cht axit nn ngi ta hay dng lm xc tc trong cc phn ng
tng hp hu c. Th d phn ng tng hp toluen.
CH
3
Cl + AlCl
3
[ ] [Cl AlCl
+
3
CH
3
]

C
6
H
6
+ [ ] [Cl AlCl
+
3
CH
3
]

C
6
H
5
CH
3
+ AlCl
3
+ HCl
Mt s oxit kim loi th hin tnh cht baz. Th d khi cho CaO tc dng vi kh
CO
2
Ca
2+
O
2-
O C O
2+
Ca
+ C
O O
O
2



Cc ion kim loi th hin tnh cht axit trong dung dch nc do chng c kh
nng nhn cp electron.
M
2+
+ 4(H
2
O)
+ 2
4 2
) O H ( M
29
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Chng ta nhn thy quan im axit baz ca Levis i xa hn, khi qut hn
nu bt c vai tr cp electron ho tr trong lin kt ca cc hp cht. Theo quan
im ca Levis ngi ta d dng gii thch c ch phn ng ho hc hu c v cc
phn ng to phc. Tuy nhin trong ho hc phn tch thuyt Bronsted Lauri c
xem y c s gii quyt trn vn vn axit baz. V vy trong cc phn
tip theo chng ta ch xt tnh cht axit baz theo nh ngha ca Bronsted Lauri.
3.2. Tnh cht axit baz ca dung mi nc
Nc c xem l dung mi va c tnh cht axit va c tnh cht baz, lun
lun tn ti cn bng:
H
2
O + H
2
O + OH
+
O H
3

(3.2)
axit
1
+ baz
2
axit
2
+ baz
1
K
cb
=
2
2
3
] O H [
] [OH ] O H [
+
(3.3.)
25
o
C mt lit nc c 1,0.10
7
mol OH

hoc :
+
O H
3
[ ] = [OH
+
O H
3

] = 1,0.10
7
mol
Mt lt nc c 55,35 mol H
2
O. Nu ta em so snh t s nng [ ]
hoc [OH
+
O H
3

] vi nng phn t H
2
O th ch c khong 2 phn t phn t nc phn
li. Nh vy, c th xem s phn li ca H
2
O v cng nh.
K
cb
[H
2
O] = =
O H
K
2

[ ] [OH
+
O H
3

] (3.4)

O H
K
2
c gi tch s ion ca nc. 25
o
C = 1,0.10
O H
K
2
14
. Khi thm axit
vo dung mi nc s lm tng nng , ng thi lm gim nng OH
+
O H
3

.

7
1,0.10
7 7 7 7
[OH ] mol/l
Dung dch axit [H
3
O
+
] > [OH ]
[H
3
O
+
] mol/l
Dung dch trung tnh [H
3
O
+
] = [OH ]
Dung dch baz [OH ] > [H
3
O
+
]
2,0.10 4,0.10 6,0.10 8,0.10
7
7
7
7
7
8,0.10 -
6,0.10 -
4,0.10 -
2,0.10 -
1,0.10 -









Hnh 3.1. S bin i nng [ ] v [OH
+
O H
3

]

trong dung mi H
2
O 25
o
C
30
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thun li cho vic tnh ton lin quan nng H
+
nm 1909 Sorenson (nh
ho sinh an Mch) ngh s dng logarit c s 10 ch hot ion H
+
.
K hiu pH = log [ ]
+
O H
3
v pOH = log [OH

]
3.3. Hng s cn bng axit v baz trong dung dch nc
Khi ho tan mt axit hoc mt baz vo nc, phn t nc b ion ho nhn
proton ca axit hoc nhng poton cho phn t baz. Mc ion ho (cho hoc
nhn proton) ph thuc vo cng ca axit hoc ca baz. Th d, khi ta thm
HCl l mt cht in li mnh c khong 99,996 % phn t HCl b phn li, ch cn
0,004 % phn t HCl cha phn li. i vi axit axetic l mt cht in li yu, ch c
khong 1,3% phn t CH
3
COOH b phn li. iu ny ni ln axit hoc baz ph
thuc rt nhiu vo kh nng phn li ca chnh axit hoc ca chnh baz.
Chng ta xt trng hp tng qut, khi ho tan axit AH vo dung mi nc.
AH + H
2
O + A
+
O H
3

(3.5)
K =
] O [H ] AH [
] [A ] O H [
2
+
3
(3.6)
K [H
2
O] =
] AH [
] [A ] O H [
+
3
(3.7)
[H
2
O] =
ml
O H g ,
1
9971 0
2

lit
ml
1
1000

O H g ,
O H mol
2
2
055 18
1
= 55,35 M
Vy K [H
2
O] = const = Ka
Ka =
] AH [
] [A ] O H [
+
3
(3.8)
y Ka c gi l hng s axit, ch r cng axit, Ka cng ln, axit cng
mnh. Ngi ta hay dng pKa = log Ka.
Trng hp baz B:
B + H
2
O BH
+
+ OH

(3.9)
K =
] O [H ] B [
] [OH ] BH [
2
+
(3.10)
31
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K [H
2
O] = K
b
=
] B [
] [OH ] BH [
+
(3.11)
K
b
: hng s baz, ch r mc baz
Mi quan h gia hng s phn li axit K
a
v hng s phn li baz K
b
.
Theo (3.8) ta c: Ka =
] AH [
] [A ] O H [
+
3

em nhn mu s v t s vi [OH

]
Ka =
] AH [
] [A ] O H [
+
3
.
] OH [
] OH [


Ka =
] [OH ] AH [
] [A

. [H
3
O
+
[OH

]
K
a
=
K
b
1
. (3.12)
O H
K
2
K
a
. K
b
= (3.13)
O H
K
2
Tch s hng s axit v hng s baz ca mt cp axit baz lin hp bng
tch s ion ca nc, l mt gi tr khng i mt nhit nht nh nn K
a
cng
ln th K
b
cng b, khi bit mt trong hai gi tr ta tm c gi tr kia.
3.4. pH ca dung dch n axit trong nc
3.4.1. pH ca dung dch axit mnh
Cc axit mnh HCl, HClO
4
, HBr thng c gi tr K
a
v cng ln. Chng
phn li hon ton trong dung mi nc. Th d ta ho tan HX nng C
HX
vo
nc:
HX + H
2
O H
3
O
+
+ X

(3.14)
2 H
2
O H
3
O
+
+ OH

(3.15)
Theo nh lut bo ton khi lng:
C
HX
= [HX] + [X

] [X

] (3.16)
Phng trnh trung ho in tch:
[H
3
O
+
] = [X

] + [OH

] (3.17)
32
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Phng trnh (3.17) c th xem l phng trnh bo ton proton (s mol proton
axit cho lun bng s mol proton baz nhn). Trong mt s trng hp phng trnh
trung ho in tch trng vi phng trnh bo ton proton.
Dung dch axit mnh nn c th xem: C
X
= [H
3
O
+
] = [X

]
pH = log [H
3
O
+
] = log C
X
(3.18)
Trng hp nng axit b tng ng nng OH

khng b [OH

] cnh C
X
:
[H
3
O
+
] = [X

] + [OH

]
[H
3
O
+
] = C
X
+
] O H [
K
O H
+
3
2

[H
3
O
+
]
2
C
X
[H
3
O
+
] = 0 (3.19)
O H
K
2
[H
3
O
+
] =
2
2
2
O H X X
K . 4 C C + +
(3.20)
Th d 3.1. Tnh pH ca dung dch HCl 10
7
M
HCl + H
2
O H
3
O
+
+ Cl

2 H
2
O H
3
O
+
+ OH

[H
3
O
+
] [OH

] 1,0.10
14
[H
3
O
+
]
2
10
7
[H
3
O
+
] 1,0.10
14
= 0
[H
3
O
+
] = [Cl

] +
] O H [
K
O H
+
3
2

[H
3
O
+
] =
2
10 10 10 0 1
14 2 7 7
+ + . 4 ) ( . ,
= 1,618.10
7

pH = log 1,618.10
7
= 6,78

Nu nng C
X
rt nh, b hn 10
8
M th c th b qua C
X
cnh OH

v coi
nng H
3
O
+
ca axit khng ng k so vi s phn li ca H
2
O, pH ca dung dch
l pH ca nc v bng 7.
3.4.2. pH ca dung dch n axit yu

Gi s ta c axit yu AH nng C
a
ho tan vo nc:
AH + H
2
O H
3
O
+
+ A

(3.21)
2 H
2
O H
3
O
+
+ OH

(3.22)
33
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Theo nh lut bo ton khi lng:
C
a
= [AH] + [A

]
Phng trnh trung ho in tch:

[H
3
O
+
] = [A

] + [OH

]
K
a
=
] AH [
] [A ] O H [
+
3
(3.23)
Dung dch axit nn c th xem [OH

] << [A

]
[H
3
O
+
] = [A

] (3.24)
T phng trnh bo ton khi lng ta suy ra:
[AH

] = C
a
[A

] = C
a
[H
3
O
+
] (3.25)
Thay (3.24) v (3.25) vo (3.23)
K
a
=
] O H [ C
] O H [
a
+
+

3
2
3

[H
3
O
+
]
2
+ K
a
[H
3
O
+
] K
a
C
a
= 0
[H
3
O
+
] =
2
2
a a a a
C K . 4 K K + +
(3.26)
Trng hp s phn li axit khng ng k:
[H
3
O
+
] << C
a
c th xem C
a
= [AH]
K
a
=
a
C
] O H [
2
3
+

[H
3
O
+
]
2
= K
a
C
a

[H
3
O
+
] =
a a
C K (3.27)
pH =
2
1
pK
a

2
1
log C
a
(3.28)
Th d 3.2. Tnh pH dung dch HNO
2
0,120 M, K
a
= 7,1.10
4
HNO
2
+ H
2
O H
3
O
+
+ (a)

2
NO
2 H
2
O H
3
O
+
+ OH

(b)
34
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K
a
=
] HNO [
] [NO ] O H [
2
2
3
+
(c)
[H
3
O
+
] = [ ]

2
NO
K
a
=
] O H [ C
] O H [
a
+
+

3
2
3
= 7,1.10
4

K
a
b nn c th xem [H
3
O
+
] << C
a
[H
3
O
+
] =
a a
C K . =
4
7,1.10 . 0,120

= 9,2.10
3
M
pH = 2,04
Th d 3.3. Tnh pH ca dung dch HF 2,0.10
4
M. K
a
= 6,7.10
4
.

HF + H
2
O H
3
O
+
+ F


2 H
2
O H
3
O
+
+ OH


K
a
=
] HF [
] [F ] O H [
+
3
= 6,7.10
4
.
[H
3
O
+
] = [F

]
[HF] = 2,0.10
4
[H
3
O
+
]
Nu [H
3
O
+
] << 2,0.10
4
M
[H
3
O
+
] =
a a
C K . =
4 4
2.10 . 6,7.10


= 3,66.10
4
M
pH = 3,44
Nu khng b qua [H
3
O
+
] cnh C
a
:
K
a
=
] O H [ C
] O H [
a
+
+

3
2
3
=
] O H [ . ,
] O H [
+
+

3
4
2
3
10 0 2

[H
3
O
+
]
2
+ 6,7.10
4
. [H
3
O
+
] 13,4.10
8
= 0

[H
3
O
+
] =
2
10 4 13 4 10 7 6 10 7 6
8 2 4 4
+ + . , . ) . , ( . ,

= 1,61.10
4
pH = 3,80
Gi tr pH 3,80 ph hp hn, c ngha l khng b [H
3
O
+
] cnh C
a
.
35
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3.5. pH ca dung dch baz trong dung mi nc
3.5.1. pH ca dung dch baz mnh
Cc baz mnh thng gp trong thc t l hiroxit cc kim loi kim, kim
th: LiOH, KOH, NaOH, Ca(OH)
2

Khi ho tan vo nc baz mnh MOH nng C
b
:
MOH M
+
+ OH

2H
2
O H
3
O
+
+ OH

Tng t nh cch tnh i vi n axit mnh:
C
b
= [MOH] + [M
+
]
[H
3
O
+
] + [M
+
] = [OH

]
Dung dch baz mnh nn b qua [H
3
O
+
] v ta c [M
+
] = [OH

] v C
b
= [M
+
]
[OH

] = C
b
pOH = log C
b
pH = + log C
O H
pK
2
b
(3.29)
Th d 3.5. Tnh pH ca dung dch baz mnh KOH 1,0.10
4
M.
KOH K
+
+ OH


C
b
= 1,0.10
4
pH = + log C
O H
pK
2
b
= 14 + log1,0.10
4
= 10,0
3.5.2. pH ca dung dch baz yu
Ta c baz yu B nng C
b
em ho tan vo dung mi H
2
O.
B + H
2
O BH
+
+ OH

2H
2
O H
3
O
+
+ OH

K
b
=
] B [
] OH [ ] BH [
+
(3.30)
Theo nh lut bo ton khi lng:
C
b
= [BH
+
] + [B] (3.31)
Phng trnh ho in tch:
[H
3
O
+
] + [BH
+
] = [OH

] (3.32)
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Khi dung dch t cn bng c th xem [BH
+
] = [OH

]
T (3.31) suy ra: [B] = C
b
[BH
+
]
[B] = C
b
[OH

]
Thay cc gi tr ny vo phng trnh (3.30):
K
b
=
] OH [ C
] OH [
a

2

[OH]
2
+ K
b
[OH

] K
b
C
a
= 0
[OH

] =
2
2
b b b b
C K . 4 K K + +
(3.33)
Trng hp [OH

] << C
b


[OH

] =
b b
C K
pOH =
2
1
pK
b

2
1
log C
b
(3.34)
Th d 3.6. Tnh pH dung dch NH
3
1,0.10
3
M, K
b
= 1,75.10
5

NH
3
+ H
2
O + OH
+
4
NH

K
b
=
] NH [
] OH [ ] NH [
3
4
+

Khi cn bng: [ ] = [OH
+
4
NH

]
[ ] + [NH
+
4
NH
3
] = 1,0.10
3
M

[NH
3
] = 1,0.10
3
M [OH

]
K
b
=
] OH [ . ,
] OH [

3
2
10 0 1
= 1,75.10
5

p dng cng thc (3.33):
[OH

] =
2
2
B B b b
C K . 4 K K + +

=
2
10 10 75 1 10 75 1 10 75 1
3 5 5 5
+ + . . , . 4 ) . , ( . ,
2
= 4,09.10
4
M
pH = 14,0 log 4,09.10
4
= 10,60

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Nu gi thit [OH

] << 1,0.10
3


[OH

]
2
= 1,75.10
5
. 1,0.10
3
[OH

] = 1,32.10
4
M
pH = 10,12
Nu ta b qua nng [OH

] cnh nng C
B
c s sai khc gia hai gi tr. V
vy trong trng hp ny phi k n nng [OH ] trong phng trnh tnh ton.
B

Th d 3.7. Tnh nng [OH

] ca dung dch NaOCl 0,010 M. K


b
= 3,33.10
7
.
Cc qu trnh xy ra trong dung dch:
NaOCl Na
+
+ OCl

OCl

+ H
2
O HOCl + OH

2H
2
O H
3
O
+
+ OH

K
b
=
] OCl [
] OH [ ] HOCl [

= 3,33.10
7
[HOCl] + OCl

] = 1,0.10
2
Khi cn bng: [HOCl] = [OH

]
K
b
=
] OH [ . ,
] OH [

2
2
10 0 1

p dng cng thc (3.33):
[OH

] =
2
10 10 33 3 10 33 10 33 3
2 7 7 7
+ + . 1,0 . , . 4 ) . , (3 . ,
2
= 5,80.10
5
M
Nu b qua [OH

] cnh 1,0.10
2
[OH

]
2
= 1,0.10
2
. 3,33.10
7
= 3,33.10
9
[OH

] =
9
10 33 3

. , = 5,8.10
5
M
Do Kb tng i b nn c th b qua nng [OH

] cnh nng C
b
.

3.6. pH ca dung dch axit baz lin hp Dung dch m
Nu c hn hp gm c axit yu AH v mui ca n NaA, th d axit axetic v
mui natri axetat hay axit xianhiric HCN v mui natri xianua NaCN, th ngi ta
nhn thy pH ca dung dch hn hp ny rt t thay i khi thm vo mt t axit
mnh hay baz mnh.
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Loi dung dch ny thng c gi l dung dch m. Chng ta c th tnh
pH dung dch hn hp ny nh sau:
Gi s c hn hp axit AH nng Ca v mui NaA nng C
b
. Trong dung
dch c cc cn bng sau:
AH + H
2
O A

+ H
3
O
+

NaA Na
+
+ A


A

+ H
2
O AH + OH


2 H
2
O H
3
O
+
+ OH


K
a
=
] AH [
] A [ ] O H [
+
3
(1)
K
b
=
] A [
] OH [ ] AH [

+
(2)
C
a
+ C
b
= [AH] + [A

]
[Na
+
] + [H
3
O
+
] = [A

] + [OH

]
C
b
+ [H
3
O
+
] = [A
+
] + [OH

]
[A

] = C
b
+ [H
3
O
+
] [OH

] (3)
[AH] = C
a
+ C
b
[A

] = C
a
H
3
O
+
] + [OH

] (4)
T (1) suy ra: [H
3
O
+
] = K
a
] A [
] AH [

(3.35)
Thay (3) v (4) vo (3.35):
[H
3
O
+
] = K
a

] OH [ ] O H [ C
] OH [ ] O H [ C
b
a
+
+
+
+
3
3
(3.36)
Trong dung dch m thng [H
3
O
+
] v [OH

] << C
a
v C
b
nn phng trnh
(3.36) chuyn thnh: [H
3
O
+
] = K
a

b
a
C
C
(3.37)
pH = pK
a
+ log
a
b
C
C
(3.38)
Th d 3.8. Tnh pH dung dch gm c 10,0 ml CH
3
COOH 0,1 M v 20,0 ml
CH
3
COONa 0,1 M, bit pK
a
= 4,75.
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[CH
3
COOH] =
0 30
0 10
,
0,100 . ,
= 0,033 M
[CH
3
COO

] =
0 30
0 20
,
0,100 . ,
= 0,067 M
pH = pK
a
+ log
a
b
C
C
= 4,75 + log
033 0
067 0
,
,
= 5,06
biu th kh nng ca dung dch m chng li s thay i pH khi thm
axit mnh hoc baz mnh ngi ta a vo khi nim dung tch m cn gi l
m nng. m nng (dung tch m) l s mol axit mnh hoc baz mnh thm
vo mt lt dung dch m lm gim hoc tng pH mt n v.
=
dpH
db
=
dpH
da
(3.39)
y da v db k hiu s mol axit mnh hay baz mnh thm vo lm bin
i pH mt gi tr dpH.
Trong dung dch m C
a
+ C
b
= C (khng thay i). Nu thm db mol baz
mnh vo 1 lt dung dch m tng nng baz B ln mt lng dC
b
th nng
axit AH gim i mt lng dC
a
bng dC
b
.
=
dpH
db
=
dpH
dC
b
=
dpH
dC
a
(3.40)
pH = log [H
+
] nn:
=
dpH
db
= 2,3
] H [ ln d
db
+
= 2,3 [H
+
]
] H [ d
dC
b
+
(3.41)
Ta bit [H
+
] = K
a

b
a
C
C


db
] H [ d
+
=
b
dC
] H [ d
+
= K
a

2
b
b a
C
C C +
(3.42)
T hai phng trnh (3.41) v (3.42) suy ra:
= 2,3
b a
b a
C C
C C
+
= 2,3
C
C C
b a
(3.43)
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Th d 3.9. Dung dch m gm c CH
3
COOH 0,2 M v CH
3
COONa 0,2 M. Nu ta
thm 1,0 ml HCl 0,1 M vo 10,0 ml dung dch m ny th pH thay i nh th ?
Bit pK
a
= 4,75.
pH dung dch trc khi thm HCl:
C
a
= C
b
= 0,2 M
pH = pK
a
+ log
a
b
C
C
= 4,75
pH dung dch sau khi thm 1ml HCl 0,1 M:
Thm 0,1 M x 1 ml = 0,1 mmol HCl s lm gim tng ng 0,1 mmol
CH
3
COO

, ng thi cng lm tng 0,1 mmol CH


3
COOH. Vy nng CH
3
COOH
sau khi thm HCl.
C
a
= [CH
3
COO

] =
11
0 10 0,1 x 1,0 0,2 x , +
=
11
1 2 ,
M
C
b
= [CH
3
COO

] =
11
0 10 0,1 x 1,0 0,2 x ,
=
11
9 1 ,
M
pH = 4,75 + log
1 2
9 1
,
,
= 4,71
pH = pK
a
+ log
a
b
C
C
= 4,75 + lg
1 2
9 1
,
,
= 4,71
pH ca dung dch ch thay i 0,04 n v pH.
Th d 3.10. Tnh th tch NH
3
v trng lng NH
4
Cl cn phi ly chun b
100,0 ml dung dch m c pH = 10,0, nng ca mui NH
4
Cl 0,2 M.
S mmol NH
4
Cl c trong dung dch m:
100,0 ml x 0,2000 mmol/ml = 20,00 mmol.
S mg NH
4
Cl cn phi ly:
20,0 mmol x 53,5 mg/mmol = 1,07 10
3
mg.
Theo cng thc tnh pH dung dch m ta c th vit:
pH = pK
a
+ log
a
b
C
C
= 14,0 pK
b
+ log
a
b
C
C

10,0 = (14,0 4,75) + log
200 0
3
,
] NH [

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log
200 0
3
,
] NH [
= 0,76

200 0
3
,
] NH [
= 10
0,76
= 5,8
[NH
3
] = 5,8 x 0,200 = 1,16 mmol/l
Vy lng NH
3
cn phi ly:
100,0 ml x 1,16 mmol/ml = 14,8 mmol/ml x V
ml
(NH
3
)
(ml) = 7,8.
3
NH
V
c 100,00 ml dung dch m /NH
+
4
NH
3
c pH = 10 cn phi ly 1,07 g
NH
4
Cl v 7,8 ml NH
3
c sau thm nc c th tch 100,0 ml.
3.7. pH ca dung dch hn hp axit
3.7.1. pH ca dung dch hn hp axit mnh v axit yu
Gi s chng ta c hn hp hai axit: axit mnh A
1
H v axit yu A
2
H. Cc qu
trnh xy ra khi ho tan chng vo trong dung mi nc:
A
1
H + H
2
O + H

1
A
3
O
+
(3.42)
A
2
H + H
2
O H
3
O
+
+ (3.43)

2
A
A
1
H l axit mnh nn: C
1
= [A
1
H] = [ ] = H

1
A
3
O
+
] (3.44)
A
2
H l axit yu nn: C
2
= [A
2
H] + [ ] (3.45)

2
A
Dung dch axit nn c th b qua nng [OH

]
[H
3
O
+
] = [ ] + [ ] = C

1
A

2
A
1
+ [ ] (3.46)

2
A
[ ] = [H

2
A
3
O
+
] C
1
(3.47)
[A
2
H] = C
1
+ C
2
[H
3
O
+
] (3.48)
Hng s phn li axit ca A
2
H
=
H A
K
2
] H A [
] A [ ] O H [
2
2 3
+
(3.49)
Thay cc gi tr (3.47) v (3.48) vo (3.49)
=
H A
K
2
] O H [ C C
]) C [ ] O H [ ( ] O H [
+
+ +
+

3 2 1
1 3 3
(3.50)
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Bin i phng trnh (3.50):
[H
3
O
+
]
2
(C
1
) [H
H A
K
2
3
O
+
] (C
1
+ C
2
)
H A
K
2
[H
3
O
+
] =
2
4
2 2 2
2 1
2
1 1 H A H A H A
K ) C C ( ) K C ( ) K C ( + + +
(3.51)
Nu coi axit yu A
2
H phn li khng ng k, c ngha [A
2
H] = C
2
(ban u).
=
H A
K
2
2
1 3 3
C
]) C [ ] O H [ ( ] O H [
+ +

[H
3
O
+
] =
2
4
2
2
2
1 1 H A
K C C C ( + +
(3.52)
Th d 3.11. Tnh pH dung dch axit H
2
SO
4
0,5 M
Axit H
2
SO
4
hn hp hai axit: K

= v Ka
2
= 1,25.10
2
.

Trong dung dch xy ra cc qu trnh sau:
H
2
SO
4
+ H
2
O H
3
O
+
+

4
HSO
+ H

4
HSO
2
O H
3
O
+
+
2
4
SO
=
2
a
K
] SO [H
] SO [ ] O H [

+
4
2
4 3
= 1,25.10
2
Theo nh lut bo ton khi lng c th vit:
C = [ ] + [ ] = 0,5 M

4
HSO
2
4
SO
Phng trnh trung ho in tch:
[H
3
O
+
] = [OH

] + [ ] + 2[ ] = [ ] + 2[ ]

4
HSO
2
4
SO

4
HSO
2
4
SO
= [ ] + [ ] + [ ] = C + [ ]

4
HSO
2
4
SO
2
4
SO
2
4
SO
[ ] = [H
2
4
SO
3
O
+
] C
[ ] = 2C [H

4
HSO
3
O
+
]
Thay cc gi tr ny vo phng trnh phn li axit [ ]

4
HSO
=
2
a
K
] SO [H
] SO [ ] O H [

+
4
2
4 3
=
] O H [ 2C
) C ] O H [ ( ] O H [
+
+ +


3
3 3

43
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[H
3
O
+
]
2
(C )
2
a
K

[H
3
O
+
] 2C = 0
2
a
K
[H
3
O
+
] =
2
4
2 2 2
2
C . K . .2 ) K C ( ) K C (
a a a
+ +

Tm c

[H
3
O
+
] = 0,512 mol/l
pH = 0,29
[H
3
O
+
] = 0,512; [ ] =
2
4
SO

[H
3
O
+
] C = 0,012 M
[ ] = C [ ] = 0,488 M

4
HSO
2
4
SO
Nu xem H
2
SO
4
c = phn li hon ton, ngn cn qu trnh phn li nc
2, coi [ ] = C
1
a
K

4
HSO
=
2
a
K
] SO [H
] SO [ ] O H [

+
4
2
4 3
=
C
) C ] O H [ ( ] O H [
+ +
3 3



[H
3
O
+
]
2
C

[H
3
O
+
] C = 0
2
a
K
[H
3
O
+
] =
2
4
2
2
C . K C C
a
+ +

Thay s vo tm c: [H
3
O
+
] = 0,512 M
pH = 0,29
Chng ta c th xem H
2
SO
4
l axit mnh khng tnh n nc 2.
pH = logC
a
= log 0,5 = 0,3
S khc nhau khng nhiu gia hai cch tnh.
3.7.2. pH ca dung dch hn hp hai n axit yu
Gi s c hn hp hai axit yu A
1
H C
1
v A
2
H C
2
vi hng s phn li v
1
a
K
2
a
K
Theo nh lut bo ton khi lng c th vit:
C
1
= [ ] + [A

1
A
1
H] (1)
C
2
= [ ] + [A

2
A
2
H] (2)
Phng trnh ho in tch:
[H
3
O
+
] = [OH

] + [ ] + [ ]

1
A

2
A
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Dung dch axit nn c th b qua nng [OH

]
[H
3
O
+
] = [ ] + [ ] (3)

1
A

2
A
Hng s phn li axit A
1
H v A
2
H
=
1
a
K
] H [A
] O [H ] A [
1
3
+
1
v =
2
a
K
] H [A
] O [H ] A [
2
3
+
2

[ ] =

1
A
1
a
K
] O [H
] H [A
3
1
+
v [ ] =

2
A
2
a
K
] O [H
] H [A
3
2
+

Nu coi s phn li axit A
1
H v A
2
H khng ng k:
[A
1
H] = C
1
v [A
2
H] = C
2
[H
3
O
+
] =
1
a
K
] O [H
C
3
1
+
+
2
a
K
] O [H
] C
3
2
+

[H
3
O
+
]
2
= C
1
a
K
1
+ C
2
a
K
2
[H
3
O
+
] =
2 1
2 1
C K C K
a a
+ (3.53)
Th d 3.12. Tnh pH hn hp dung dch CH
3
COOH 0,1 M v HF 0,01 M.
= 3,55.10
HF a
K
1
4
, = 1,75.10
2
a
K
5
Cc cn bng xy ra trong dung dch :
HF + H
2
O H
3
O
+
+ F

CH
3
COOH + H
2
O CH
3
COO

+ H
3
O
+
C
HF
= [HF] + [F] = 0,01 M
= [CH
COOH CH
C
3
3
OOH] + [CH
3
COO

] = 0,1 M
[H
3
O
+
] = [F

] + [CH
3
COO

] + [OH

] = [F

] + [CH
3
COO

]
[F

] = K
HF
.
] O [H
[HF]
3
+
;
[CH
3
COO

] =
COOH CH
K
3
] O [H
] COOH CH [
3
3
+

[H
3
O
+
] = K
HF

] O [H
[HF]
3
+
+
COOH CH
K
3
] O [H
] COOH CH [
3
3
+

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C th xem [HF] = 0,01 M; CH
3
COOH] = 0,10 M
[H
3
O
+
]
2
= K
HF
[HF] + . [CH
COOH CH
K
3
3
COOH]
[H
3
O
+
] =
2 2 1 1
C Ka C Ka + = 2,31.10
3
pH = 2,64
3.8. pH ca dung dch hn hp hai baz
3.8.1. pH ca dung dch hn hp baz mnh v baz yu
Gi s hn hp gm c baz mnh B
1
nng C
1
v baz yu B
2
nng C
2
.
BB
1
+ H
2
O B
1
H + OH
+
BB
2
+ H
2
O B
2
H + OH
+
BB
1
l baz mnh nn C
1
= [B
1
] = [B
1
H ] =[OH ]
+ _
BB
2
l baz yu nn C
2
= [B
2
H ] + [B
+
2
]
[H
3
O
+
] + B
1
H
+
] + [B
2
H
+
] = [OH

]
C th b qua [H
3
O
+
]
[BB
1
H ] + [B
+
2
H ] = [OH ]
+
C
1
+ [B
2
H
+
] = [OH

] [B
2
H
+
] = [OH

] C
1
Mt khc ta c:
[B
2
] = C
1
+ C
2
[OH

]
Hng s phn li baz ca B
2
:
=
2
B
K
] [B
] [OH ] H [B
2
2
+
=
] [OH C C
) C ] ([OH ] [OH
2 1


+

1

[OH

]
2
(C
1


2
B
K ) [OH

] (C
1
+ C
2
) = 0
2
B
K
[OH

] =
2
4
2 2 2
B 2 1
2
B 1 B 1
K ) C C ( ) K C ( ) K C ( + + +
(3.54)
Th d 3.13. Tnh pH dung dch gm NaOH 0,01 M v Na
2
S 0,03 M.
NaOH Na
+
+ OH

Na
2
S Na
+
+ S
2
S
2
+ H
2
O

HS

+ OH

46
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1
b
K = ; =
2
b
K
2
14
10 0 1
a
K
. ,

=
14
14
10 3 1
10 0 1

. ,
. ,
= 0,769
[OH

]
t
= [OH

]
NaOH

+ [OH

]
S
2

= 0,01 + [HS

]
= [S
S Na
C
2
2
] + [HS

] + [H
2
S] = [S
2
] + [HS

] = 0,03
[S
2
] = 0,03 [HS

]
[HS

] = [OH]
t
0,01
[S
2
] = 0,03 [OH]
t
+ 0,01 = 0,04 [OH

]
t
= 0,769 =
2
b
K
] [S
] [OH ] [HS


2
=
] [OH 0,04
) , ] ([OH ] [OH

01 0

[OH

]
2
+ 0,759 [OH

] 0,0308 = 0
[OH

] =
2
4 759 0 0,0308 . 0,750) ( ,
2
+ +
= 3,86.10
2
pH = 12,59.
3.8.2. pH ca dung dch hn hp 2 n baz yu.
Gi s mt hn hp gm 2 baz yu F
1
nng C
1
v F
2
nng C
2
hng s
phn li baz

1
F
K v
2
F
K
F
1
+ H
2
O F
1
H
+
+ OH

H
2
O + F
2
F
2
H
+
+ OH

C
1
= [F
1
] + [F
1
H
+
]
C
2
= [F
2
] + [F
2
H
+
]
[H
3
O
+
] + F
1
H
+
] + [F
2
H
+
] = [OH

]
C th b qua [H
3
O
+
]
[F
1
H
+
] + [F
2
H
+
] = [OH

]
Gi thit s phn li ca baz khng ng k.
C
1
= [F
1
] v C
2
= [F
2
]
=
1
b
K
] [F
] [OH ] H [F
1
1
+
[F
1
H
+
] =
1
b
K
] [OH
] F [

1

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=
2
b
K
] [F
] [OH ] H [F
2
2
+
[F
2
H
+
] =
2
b
K
] [OH
] F [

2

Thay cc gi tr ny vo phng trnh trn:

2
b
K
] [OH
] F [

2
+
1
b
K
] [OH
] F [

1
= [OH

]
[OH

]
2
= C
1
b
K
1
+ C
2
b
K
2

[OH

] =
2 b 1 b
C K C K
2 1
+ (3.55)
Th d 3.14. Tnh pH ca hn hp dung dch NH
3
0,10 M v CH
3
COONa 0,10 M.
= 1,75.10
1
b
K
5
; = 5,7.10
2
b
K
10

Hng s phn li baz ca hai baz ny nh nn c th xem:
C
1
= [NH
3
] = 0,1 M
C
2
= [CH
3
COO

] = 0,1 M
p dng cng thc (3.55):
[OH

] = 0,1 . 5,7.10 0,1 . 1,75.10


10 2
+ = 1,32.10
3

pH = 11,12
3.9. pH dung dch a axit v mui ca chng
3.9.1. pH dung dch a axit
a axit l axit khi ho tan vo nc, chng ln lt cho proton, mi mt nc
cho mt proton, c hng s phn li ring cho tng nc.
Th d axit H
3
PO
4
c nng C
a

H
3
PO
4
+ H
2
O H
3
O
+
+

4 2
PO H
=
1
a
K
] PO [H
] PO [H ] O [H
4 3
4 2 3
+
= 1,1.10
2

+ H

4 2
PO H
2
O H
3
O
+
+
2
4
HPO
=
2
a
K
] PO [H
] PO [H ] O [H
4 2
4 2 3

+ 2
= 7,5.10
8

+ H
2
4
HPO
2
O H
3
O
+
+
3
4
PO
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=
3
a
K
] [HPO
] [PO ] O [H
4
4 3

+
2
3
= 4,8.10
13

nh lut bo ton khi lng:
C
a
= [H
3
PO
4
] + [ ] + [ ] + [ ]

4 2
PO H
2
4
HPO
3
4
PO
Phng trnh trung ho in:
[H
3
O
+
] = [OH

] + [ ] + 2 [ ] + 3 [ ]

4 2
PO H
2
4
HPO
3
4
PO
C th b qua nng [OH

] v >> >> nn [ ] >> [ ]


v [ ], v vy c th xem [H
1
a
K
2
a
K
3
a
K

4 2
PO H
2
4
HPO
3
4
PO
3
O
+
] = [ ] v C

4 2
PO H
a
= [H
3
PO
4
] + [ ]

4 2
PO H
[H
3
PO
4
] = C
a
[H
3
O
+
]
=
1
a
K
] PO [H
] PO [H ] O [H
4 3
4 2 3
= +
=
] O [H C
] O [H
3 a
2
+
+

3

[H
3
O
+
]
2
+ [H
1
a
K
3
O
+
] K
a
C
a
= 0
[H
3
O
+
] =
2
4
2
1
a a a a
C K K K
1 1
+ +
(3.56)
Nu C
a
= 0,1 M thay cc gi tr vo (3.56) ta tm c [H
3
O
+
] = 2,4.10
2
M
pH = 1,62.
Da vo gi tr hng s phn li

1
a
K , , v nng ban u C
2
a
K
3
a
K
a
ca
H
3
PO
4
chng ta c th tm c nng cc dng trong dung dch H
3
PO
4
.
T hng s phn li tng nc ta suy ra:
[ ] =
3
4
PO
3
a
K
] O H [
] HPO [
+

3
2
4
=
1
a
K
2
a
K
3
a
K
3
3
4 3
] O H [
] PO H [
+
(1)
[ ] =
2
4
HPO
2
a
K
] O [H
] PO [H
3
4 2
+
2
=
1
a
K
2
a
K
2
3
4 3
] O H [
] PO H [
+
(2)
[ ] = K

4 2
PO H
a1
] O H [
] PO H [
+
3
4 3
(3)
C
a
= [H
3
PO
4
] + [ ] + [ ] + [ ] (4)

4 2
PO H
2
4
HPO
3
4
PO
Thay (1), (2), (3) vo (4) ta c:
49
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C
a
= [H
3
PO
4
] +
1
a
K
2
a
K
3
a
K
3
3
4 3
] O H [
] PO H [
+
+
1
a
K
2
a
K
2
3
4 3
] O H [
] PO H [
+
+
1
a
K
] O H [
] PO H [
+
3
4 3

= [H
3
PO
4
]

+ + +
+ + +
] O H [
K
] O H [
K K
] O H [
K K K
a a a a a a
3
2
3
3
3
1 2 1 3 2 1
1
t
O

1
=
] O H [
K
] O H [
K K
] O H [
K K K
a a a a a a
+ + +
+ + +
3
2
3
3
3
1 2 1 3 2 1
1

o
=
1 2 1 2 1 1
3
2
3
3
3
3
3
a a a a a a
K K K ] O H [ K K ] O H [ K ] O H [
] O H [
+ + +
+ + +
+
(3.57)

o
=
a
C
] PO H [
4 3
;
1
=
a
4 2
C
] PO [H

;
2
=
a
4
C
] [HPO
2
;
3
=
a
4
C
] [PO
3
;

o
+
1
+
2
+
3
= 1

1
=
3 2 1 2 1 1
1
3
2
3
3
3
2
3
a a a a a a
a
K K K ] O H [ K K ] O H [ K ] O H [
] O H [ K
+ + +
+ + +
+
(3.58)

2
=
3 2 1 2 1 1
2 1
3
2
3
3
3
3
a a a a a a
a a
K K K ] O H [ K K ] O H [ K ] O H [
] O H [ K K
+ + +
+ + +
+
(3.59)

3
=
3 2 1 2 1 1
1 2 1
3
2
3
3
3 a a a a a a
a a a
K K K ] O H [ K K ] O H [ K ] O H [
K K K
+ + +
+ + +
(3.60)
Th d 3.15. Tnh nng cn bng cc dng ca H
3
PO
4
0,1 M pH = 3,0;
([H
+
] = 1,0.10
3
M)
Thay cc gi tr vo phng trnh (3.57):

o
=
) . , )( . , )( . , ( ) . , )( . , )( . , ( ) . , )( . , ( ) . , (
) . , (
13 8 2 3 8 2 2 3 2 3 3
3 3
10 8 4 10 5 7 10 0 1 10 0 1 10 5 7 10 1 1 10 0 1 10 1 1 10 0 1
10 0 1

+ + +
=
8
9
10 2 1
10 0 1
=
=
. ,
. ,
= 8,3.10
2
[H
3
PO
4
] = .
4 3
PO H
C
o
= 0,10 . 8,3.10
2
= 8,3.10
3
M
Tng t chng ta c th tnh:

1
= 0,92
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[ ] = .

4 2
PO H
4 3
PO H
C
1
= 0,10 . 0,92 = 9,2.10
2
M

2
= 6,9.10
5

[ ] = .
2
4
HPO
4 3
PO H
C
2
= 0,10 . 6,9.10
5
= 6,9.10
6
M

3
= 3,3.10
14

[ ] = .
3
4
PO
4 3
PO H
C
3
= 0,10 . 3,3.10
14
= 3,3.10
15
M
T cc kt qu tnh trn chng ta thy pH = 3 c 91 % lng axit tn ti
dng , 8,3 % tn ti dng H
2
4 2
PO H
3
PO
4
v c 3,3.10
12
% tn ti dng .
3
4
PO

H
3
PO
4

0
H
2
PO
4

1
:
2
:
HPO
4
2
3
PO
4

3
:
0
,
0
5
,
0 10
,
0
14
,
0








Hnh 3.3. Cc dng tn ti H
3
PO
4
ph thuc vo pH.
th hnh 3.3 biu din dng tn ti ca H
3
PO
4
ph thuc vo pH. Chng ta
d dng chn t l cc dng chun b dung dch m. Th d t hn hp H
3
PO
4

v c th chun b c dung dch m c pH khong 2,0 1; cn hn
hp v c pH khong 7,0 1, cn hn hp v c pH
khong 12,3.

4 2
PO H

4 2
PO H
2
4
HPO
2
4
HPO
3
4
PO
3.9.2. Dung dch mui a axit
1. Mui a axit thng c tnh lng tnh va c tnh axit v tnh baz. Th d mui
NaH
2
PO
4
, va c tnh axit v va c tnh baz.

4 2
PO H
+ H

4 2
PO H
2
O H
3
O
+
+
2
4
HPO

2
a
K
] PO [H
] [HPO ] O [H
4 2
4 3

+ 2
= 7,5.10
8
(3.61)
51
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+ H

4 2
PO H
2
O H
3
PO
4
+ OH


=
1
b
K
1
2
a
O H
K
K
=
] PO [H
] [OH ] PO [H
4 2
3

4
=
2
14

1,1.10
1,0.10
= 9,1.10
13
(3.62)
T gi tr v chng ta thy ln hn khong 10
2
a
K
1
b
K
2
a
K
1
b
K
5
ln, nn dung
dch c mi trng axit.
= [H
+
O H
C
3
3
O
+
]
t
= + (3.63)
O H 3
2
] O [H
+

+
4
PO H
3
2
] O [H

4
PO H
2
] [OH
Hay [H
3
O
+
]
t
= [OH

] + [ ] [H
2
4
HPO
3
PO
4
] (3.64)
T hng s phn li axit ca H
3
PO
4
chng ta tm c cc gi tr [ ],
[H
2
4
HPO
3
PO
4
] thay vo phng trnh (3.64) chng ta c:
[H
3
O
+
]
t
=
] O [H
K
3
O H
2
+
+
] O [H
] PO [H K
3
4 2 a
2
+


1
a
2
K
] [H ] PO [H
+
4
(3.65)
[H
3
O
+
]
2
=
2
2 2
a
2
2 a O H
K
] PO H [
1
] PO H [ K K

+
+
4
4
(3.66)
[H
3
O
+
] =
] PO [H K
] PO [H K K K K
4 2 a
4 2 a a O H a
1
2 1 2 1

+
+
(3.67)
T biu thc (3.67) ta c th suy ra dng chung mui HA

:
[H
3
O
+
] =
] [HA K
] [HA K K K K
1
2 1 2 1
a
a a O H a

+
+
(3.68)
Trong nhiu trng hp << . [HA] v < [HA], biu thc
(3.68) c n gin ho:
1
a
K
O H
K
2 1
a
K
2
a
K
1
a
K
[H
3
O
+
] =
2 1
a a
K K (3.69)
i vi trng hp HA
2
:

[H
3
O
+
] =
3 2
a a
K K (3.70)
T biu thc (3.69) v (3.70) cho chng ta thy gi tr pH khng ph thuc vo
nng . Gi tr pH ca mui NaH
2
PO
4
:
[H
3
O
+
] =
2 1
a a
K K = 7,5.10 . 1,1.10
8 2
= 2,9.10
5
M

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pH = 4,54
Tng t ta tm c gi tr pH ca dung dch mui Na
2
HPO
4
:


[H
3
O
+
] =
3 2
a a
K K =
13
4,8.10 . 7,5.10
8
= 1,9.10
10
M
pH = 9,72
Cc gi tr pH ca dung dch mui a axit khng ph thuc vo nng nn
thng c s dng chun b cc dung dch m chun ho my pH mt.
2. Mui Na
3
PO
4
cu axit H
3
PO
4
c tnh baz mnh.

+ H
3
4
PO
2
O + OH
2
4
PO H

K
b
=
3
2
a
O H
K
K
=
13
14

4,8.10
1,0.10
= 2,08.10
2
Th d 3.16. Tnh pH dung dch Na
3
PO
4
0,1 M
+ H
3
4
PO
2
O + OH
2
4
PO H

0,1-x x x

] PO [
] [OH ] PO [H


3
4
2
4
= K
b
=
3
2
a
O H
K
K
= 2,0.10
2


x 0,1
x

2
= 2,0.10
2

x
2
+ 2,0.10
2
x 2,0.10
3
= 0
x =
2
4 10 0 2 10 0 2
3
2.10 . ) . , ( . ,
2 2 2
+ +

= 0,036 M
[OH

] = 3,6.10
2
M
pH = 12,56
m photphat: m photphat l hn hp m khng ch c ng dng trong
chun ho my pH met m cn c ng dng trong sinh vt hc nghin cu
enzyme.
Th d 3.17. Cn ly bao nhiu gam NaH
2
PO
4
v Na
2
HPO
4
chun b 1 lt dung
dch c pH = 7,45; lc ion = 0,1, khi lng mol NaH
2
PO
4
120g/mol,khi lng
mol Na
2
HPO
4
142,0g/mol . Trong dung dch c cc cn bng:
53
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NaH
2
PO
4
Na
+
+ (1)

4
PO H
2
Na
2
HPO
4
Na
+
+ (2)
2
4
PO H
t [NaH
2
PO
4
] = y;
[Na
2
HPO
4
] = x
=
2
1
C
i
Z
i
2
0,1 =
2
1
([Na
+
] 1
2
+ [ ] (2)
2
4
PO H
2
+ [ ] 1

4
PO H
2
2
)
0,1 =
2
1
((2x + y) 1
2
+ x . 2
2
+ y . 1
2
) = 3x + y (3)
pH ca dung dch m
2
4 4
PO H PO H
2
:
pH = + log
2
a
pK
] PO [H
] PO [H
2

4
2
4

7,45 = 7,12 + log
] PO [H
] PO [H
2

4
2
4

log
] PO [H
] PO [H
2

4
2
4
= log
y
x
= 7,45 7,12 = 0,33

y
x
= 10
0,33
= 2,14 (4)
x = 2,14 y (5)
Thay (5) vo (3): 0,1 = 3 (2,14 y) + y
y = 0,0135 M
x = 2,14 . 0,0135 = 0,0289 M
[NaH
2
PO
4
] = 0,0135 M;
[Na
2
HPO
4
] = 0,0289 M
S gam NaH
2
PO
4
cn ly: 0,0135 mol/l . 120 g/mol = 1,62 g
S gam Na
2
HPO
4
cn ly: 0,0289 mol/l . 142 g/mol = 4,10 g
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m photphat c u im khng ph thuc vo nng , nhng c hn ch do
kh nng to phc ca ion vi mt s kim loi hoc to kt ta vi cc ion kim
loi a ho tr, nn m tris- c ng dng nhiu hn. m tris- l m c chun
b t tris (hidroxymethyl) aminomethane (HOCH
3
4
PO
2
)
3
CNH
2
(cn gi l THAM) v
axit lin hp vi chng. Hn hp m ny c tan tt, khng ht m, khng hp
th CO
2
, khng to kt ta vi canxi, khng km hm cc phn ng h enzym.
m sinh hc: pH ca mu chng ta thng c gi tr t 7,35 7,45 i vi
ngi kho mnh. Theo quan im sinh l hc khi pH ca mu thay i khong 0,3
n v cn ch . chng li s thay i pH, trong mu luon lun c h m
m bo t s nng cn bng [ ]/ [H

3
HCO
2
CO
3
] thay i khng ng k. T s
ny thay i gn lin vi p sut ca mu. Thng thng nng NaHCO
3
trong
mu 26,0 mmol/l v nng CO
2
1,3 mmol/l.
pH = 6,10 + log
30 1
0 26
,
,
= 7,40
Khi phi hot ng oxi t khng kh c chuyn vo c th kt hp vi
hemoglobin, CO
2
sinh ra trong qu trnh oxi ho thc phm duy tr hot ng ca
cc b phn trong c th c chuyn n phi v thi ra ngoi. Cc cn bng xy
ra trong mu.
H
2
CO
3
+ H
2
O H
3
O
+
+ K

3
HCO
1
(1)
CO
2
+ H
2
O H
2
CO
3
K
2
(2)
CO
2
(kh) CO
2
(ho tan) K
3
(3)
CO
2
(kh) + 2 H
2
O H
3
O
+
+ K

3
HCO
4
(4)
Theo phng trnh (4) nng [H
3
O
+
] hay pH ca mu ph thuc vo nng
. Khi c th hot ng (tp th dc) p sut ring phn CO

3
HCO
2
tng do sinh ra
nhiu CO
2
, cn bng (4) chuyn dch sang phi tng nng [H
3
O
+
] v [ ]
trong mu lc H

3
HCO
3
O
+
li kt hp vi to ra H

3
HCO
2
CO
3
, cn bng (4) thay i.
Ngc li nu tc trao i cht gim, lng CO
2
sinh ra trong cc b phn c th
gim, lng CO
2
thi ra ngoi t i, cn bng (4) chuyn dch sang tri m bo t
s [ ]/ [H

3
HCO
2
CO
3
]lun lun gi gi tr 20/1 c pH ca mu 7,40. Gi tr pH
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ny cao hn gi tr pH dung dch trung tnh ca H
2
O 25
o
C bi v pH mu ngi
37
o
C. 37
o
C = 2,5.10
O H
K
2
14
, = 13,60. pH = pOH = 6,80.
O H
pK
2
Th d 3.18. Tng s CO
2
( + CO

3
HCO
2
) trong mu mu c o bng dng c
monometric c gi tr 28,5 mmol/l. pH mu 37
o
C l 7,48. Tnh nng v
CO

3
HCO
2
trong mu.
Ta c cng thc tnh pH ca mu:
pH = 6,1 + log
] CO [
] HCO [
2
3


7,48 = 6,1 + log
] CO [
] HCO [
2
3


log
] CO [
] HCO [
2
3

= 1,38

] CO [
] HCO [
2
3

= 10
1,38
= 24
[ ] = 24 [CO

3
HCO
2
]
[ ] + [CO

3
HCO
2
] = 28,5 mmol/l
24 [CO
2
] + [CO
2
] = 28,5
[CO
2
] = 1,14 mmol/l
[ ] = 28,5 1,14 = 27,4 mmol/l

3
HCO

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Chng 4
Phng php chun axit baz
Phng php chun axit baz ch yu da trn phn ng:
H
3
O
+
+ OH

2H
2
O (4.1)
pH ca dung dch dch thay i trong qu trnh chun . xc nh im
kt thc chun ngi ta phi dng cht ch th. m mu sc ca chng thay i
theo gi tr pH ca dung dch . Ngi ta gi cc cht c mu sc thay i theo pH l
cht ch th axit baz hoc ch th pH.
ng biu din s ph thuc pH vo lng cht chun c thm vo mt th
tch xc nh dung dch cn chun gi l ng chun . Da vo ng chun
chn cht ch th,
Cc phn ng dng trong phng php chun phi tho mn cc yu cu
i vi phn ng dng trong phn tch th tch.
4.1. Cht ch th axit baz.
Cht ch th axit baz thng l cht mu hu c, l axt hu c yu hoc
baz hu c yu dng phn t v dng ion c mu khc nhau.
Th d k hiu cht ch th dng axit HInd v dng baz Ind

HInd + H
2
O H
3
O
+
+ Ind

(4.2)
Ind + H
2
O HInd + OH

(4.3)
Hng s cn bng dng axt : K
A
=
] HInd [
] Ind [ ] O H [
+
3
(4-4)
[H
3
O
+
] = K
A

] Ind [
] HInd [

(4.5)
pH = pK
A
+ log
] HInd [
] Ind [

(4.6)
T biu thc (4.6) chng ta nhn thy pH ca dung dch thay i ph thuc
vo t s nng
] HInd [
] Ind [

. Khi pH thay i km theo thay i dng tn ti ca ch th


trong dung dch , dn n mu sc thay i theo. Tuy nhin khng phi bt k thay
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i no t s nng
] HInd [
] Ind [

mt chng ta cng nhn bit c. Mt ca chng ta


ch nhn bit c khi nng ca dng ny hn km dng kia 10 ln.

] Ind [
] HInd [

= 10 v
] Ind [
] HInd [

=
10
1
(4.7)
pH = pK
A
+ 1 v pH = pK
A
1
Vy khong chuyn mu ca cht ch th:
pH = pK
A
1 (4.8)
Bng 4.1. Mt s cht ch th mu axit baz thng dng.
Cht ch th Khong pH
chuyn mu
pK
A
Mu dng
axit
Mu dng
baz
Thymol xanh 1,2 2,8
8,9 9,6
1,68
8,90

Vng
Vng
Xanh
Metyl dacam 3,1 5,4 3,46 Da cam
Bromocresol xanh 3,8 5,4 4,66 Vng Xanh
Metytl 4,2 6,3 5,00 Vng
Bromocresol ta 5,2 6,8 6,12 Vng ta
Bromothylmol xanh 6,2 7,6 7,10 Vng Xanh
Phenol 6,8 8,4 7,81 Vng
Cresol ta 7,6 9,2 Vng ta
Phenolphtalein 8,3 10,0 Khng mu Hng
Thymolphtalein 10 12 Khng mu Vng
Mu ca dung dch quyt nh bi dng no tn ti ch yu trong dung dch .
Nu chng ta kt thc chun vng pH, ti ch th tn ti dng phn t th
mu ca dung dch l mu ch th dng phn t. Ngc li nu chng ta kt thc
chun vng pH m ch th tn ti dng ion th mu ca dung dch l mu ca
dng ion.
Ngi ta cng nhn thy khi pH thay i s lm thay i cu trc ca nhm
mang mu trong phn t cht ch th dn n mu ca ch th cng thay i theo. Th
d phenolphtalein tn ti trong dung dch cc dng cu trc phn t sau:

58
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O
C
O
C
O
O
OH
C
OH
C
OH
O
O
2H
2
O
OH
C
OH
C
O
O
Dng lacton
Dng quinon
khng mu khng mu mu hng (4.9)
Ch th phenol (phenolsulfonphtalein)




(4.10)
Phenol dng da cam Phenol dng vng Phenol dng
Ch th mu azo.




(4.11)

S thay i mu ca ch th axit baz chu nh hng ca nhiu yu t: lc
ion ca dung dch, dung mi, nhit . nh hng ca cht in li trung tnh c
quyt nh bi hiu ng mui lm chuyn dch cn bng phn li ca cht ch th.
Th d i vi cn bng :
HInd
+
H
+
+ Ind (4.12)
HInd H
+
+ Ind

(4.13)
HInd

H
+
+ Ind
2
(4.14)
SO
3
N N (CH
3
)
2
NH
+
SO
3
N N (CH
3
)
2
N
H
+
H
+
OH
hng
SO
3
N N (CH
3
)
2
N
vng
H
3
O
+
+ +
OH
+
OH
SO
3
C
O OH
SO
3
O O
SO
3
C C H
OH
OH
2
O
-
H
+
H
+
-
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Theo cc cn bng (4.12), (4.13), (4.14) chng ta tnh c gi tr pK k n
lc ion:
= pK
/
A
pK
Ind
+ 0,5 (4.15)
= pK
//
A
pK
Ind
0,5 (4.16)
= pK
///
A
pK
Ind
1,5 (4.17)
Nu cht ch th l axit yu, khong chuyn mu chuyn vng axit, cn cht
mu ch th l baz yu th khong chuyn mu chuyn v vng pH cao hn. Th d
metyldacam c mu vng trong dung dch H
3
PO
4
, nhng li c mu trong dung
dch cha lng ln NaCl.
Dung mi c nh hng n thay i mu ca ch th. Th d phenolphtalein
trong dung dch kim c mu hng, trong dung mi ru c mu tm.
Mt s cht ch th c khong thay i mu thay i khi un nng. Th d,
metyldacam nhit phng c khong i mu t 3,1 4,4, nhng 100
o
C
khong i mu t 2,5 3,7. T cc iu trnh by trn, chng ta nhn thy s tng
tc ca cht ch th vi cc cu t c mt trong dung dch phn tch rt phc tp,
nn gi tr pH kt thc chun khng trng vi gi tr pT thay i mu ca ch th
nn php chun thng mc sai s h thng.
4.2. ng chun trong phng php chun n axit baz.
Nh trn trnh by ng chun l dng th biu din s ph thuc
nng cn bng ion H
3
O
+
vo lng cht chun tiu th khi chun . Thng xy
dng theo to pH V. y V (ml) l th tch dung dch chun c thm t
buret vo mt th tch xc nh dung dch cn chun . on pH ng vi thi
im cn 0,1 % lng cht cn chun n d 0,1 % lng dung dch chun so
vi lng cht cn chun c gi l khong bc nhy ca ng chun .
Da vo khong bc nhy m ngi ta d dng chn cht ch th thch hp. Khong
bc nhy di hay ngn ph thuc vo nng dung dch cn chun v gi tr
hng s phn li K
A
hoc K
B
ca cht cn chun .
4.2.1. Chun axit mnh bng baz mnh.
Gi s chun V
A
ml dung dch axit mnh HX c nng C
A
bng dung
dch baz mnh BOH c nng C
B
.
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Phn ng chun :
HX + BOH BX + H
2
O (4.18)
Chng ta ln lt thnh lp cng thc tnh gi tr pH khi tin hnh chun :
V
BOH
= 0,00 ml
[H
3
O
+
] = C
HX
pH = log C
HX
= log C
A
(4.19)
Gi s thm V ml dung dch BOH (V
BOH
0)
S mmol axit HX c trong dung dch : V
A
C
A
mmol
S mmol BOH thm vo: C
B
V
B
.
S mmol HX cn li: (V
A
C
A
V
B
C
B
) mmol
Nng HX cn li cha chun :
C
HX
= [H
3
O
+
] =

B A
B B A A
V V
C V C V
(4.20)
pH = log [H
3
O
+
] = log

B A
B B A A
V V
C V C V
(4.21)
Ti im tng ng: lng axit HX phn ng hon ton vi baz mnh
BOH, sn phm to thnh l mui trung tnh.
pH = pOH = 7 (4.22)
Sau im tng ng: pH c tnh theo nng kim d:
[OH

] = C
BOH d
=
A B
A A B B
V V
C V C V
+

2
2
(4.23)
y l lng kim thm vo thi im sau im tng ng.
pOH = log C
2
B
V
BOH d
= log
A B
A A B B
V V
C V C V
+

2
2
(4.24)
pH = 14,0 + log
2
2
B HX
A A B B
V V
C V C V
+

(4.25)
Th d 4.1. V ng chun 50,0 ml dung dch HCl 0,050 M bng dung dch
NaOH 0,100 M.
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pH ban u tnh theo cng thc (4.19)
pH = log C
HCl
= log 0,050 = 1,30
Sau khi thm 10,00 ml NaOH 0,100 M
p dng cng thc (4.20):
[H
3
O
+
] = C
HCl
=


ml 10,00 ml ,
M 0,1000 x ml 10,00 M 0,050 x ml ,
+

00 50
00 50

=
ml 0,00
mmol 1,00 mmol ,
6
50 2
= 2,5.10
2
M
pH = pOH 2,5.10
2
= 1,602

Ti im tng ng: nng [H
3
O
+
] = [OH

]
pH =
14
10 00 1

. , = 10
7
pH = pOH = 7,0
Sau im tng ng, thm 25,1 ml NaOH:
p dng cng thc (4.23)

[OH

] = C
BOH
=


10 75
1 25
,
M 0,05 x 50,00 0,1000 x ml ,
= 1,33.10
4

[OH

] = 1,33.10
4
M pOH = log 1,33.10
4
= 3,88
pH = 14,00 3,88 = 10,12
Dng ng chun thay i khi ta gim nng axit cn chun . Khong
bc nhy rt ngn khi gim nng axit. Chng ta s xt mt s th d c th trn
bng 4.1 v hnh 4.1.
Bng 4.1. Bin i gi tr pH trong qu trnh chun axit mnh bng bazo mnh.
Th tch NaOH
(ml)
50,00 ml HCl 0,050M
bng NaOH 0,100M
50,00ml HCl 0,005M
bng NaOH 0,010M
50,00ml HCl 0,0005M
bng NaOH 0,0010M
0,00 1,30 2,30 3,30
10,00 1,60 2,60 3,60
20,00 2,15 3,15 4,15
24,00 2,87 3,87 4,87
24,90 3,87 4,87 5,87
25,00 7,00 7,00 7,00
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26,00 11,12 10,12 9,12
30,00 11,80 10,80 9,80

14 -
12 -
10 -
8 -
6 -
4 -
2 -
0,00
0,00 5 10 15 20 25 30 35
-
pH
V(ml) NaOH
1
2
3
1
2
3










Hnh 4.1. Dng ng chun HCl bng NaOH
1. 50,00 ml HCl 0,050M bng NaOH 0,100M
2. 50,00ml HCl 0,005M bng NaOH 0,010M
3. 50,00ml HCl 0,0005M bng NaOH 0,0010M
T hnh 4.1 chng ta thy khong bc nhy khi chun HCl 0,05 M bng
NaOH 0,1 M ko di t 3,87 10,12 c 6,25 n v pH, cn khi chun HCl
0,0050 M bng NaOH 0,01 M, khong bc nhy cn 4,25 n v pH, i vi
trng hp HCl 0,00050 M bng NaOH 0,001 M ch cn 2,25 n v pH , d nhin
s ch th c chn cho php chun hn ch.
4.2.2. Chun baz mnh bng axit mnh.
ng chun baz mnh bng axit mnh c dng tng t nh trng hp
chun axit mnh bng baz mnh. Trong qu trnh chun pH gim dn. Ti
im tng ng gi tr pH = pOH = 7. Dng ng chun i xng hon ton
vi ng chun axit mnh bng baz mnh. V vy vic tnh pH trong qu trnh
chun cng tng t nh trng hp trn. Chng ta s xt mt s th d c th.
Th d 4.2. Tnh pH trong qu trnh chun 100,00 ml NaOH 0,100 M bng dung
dch HCl 0,100 M.
V
HCl
= 0,00 ml
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pOH = log C
B
= log 0,100 = 1,00
pH = 14,00 1,00 = 13,00
V
HCl
= 5,00 ml
S mmol OH

c trong dung dch ban u:
100,00 ml x 0,100 mmol/ml = 10,00 mmol
S mmol H
3
O
+
thm vo:
5,00 ml x 0,100 mmol/ml = 0,50 mmol
[OH

] =
105,00
0,5 , 00 10
= 9,04.10
2
M
pOH = log 9,04.10
2
= 1,05



pH = 14,00 1,05 = 12,95
V
HCl
= 90,00 ml
S mmol H
3
O
+
thm vo:
90,00 ml x 0,100 mmol/ml = 9,00 mmol
[OH

] =
190,00
9,00 , 00 10
= 5,26.10
3
M
pOH = log 5,26.10
3
= 2,28
pH = 14,00 2,28 = 11,72.
V
HCl
= 99,9 ml
S mmol H
3
O
+
thm vo:
99,9 ml x 0,1 mmol/ml = 9,99 mmol
[OH

] =
199,90
9,99 , 00 10
= 5,0.10
5
M
pOH = log 5,0.10
5
= 4,31
pH = 14,00 4,31 = 9,69
V
HCl
= 100,00 ml
pH = pOH = 7,0
V
HCl
= 100,10 ml. Sau im tng ng:
[H
3
O
+
] =
200,1
0,1 x ,1 0
= 4,90.10
5
M
pH = log 4,9.10
5
= 4,31
V
HCl
= 110,00 ml.
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[H
3
O
+
] =
210,00
0,10 x ,00 10
= 4,76.10
3
M
pH = log 4,76.10
3
= 2,33
V
HCl
= 120,00 ml.
[H
3
O
+
] =
220,00
0,10 x ,00 20
= 9,09.10
3
M
pH = log 9,09.10
3
= 2,05
Bng 4.2. S bin i pH trong qu trnh chun baz mnh bng axit
mnh.
Th tch HCl
(ml)
100,0 ml NaOH 0,10M
bng HCl 0,10M
100,00ml NaOH 0,01M
bng HCl 0,010M
100,00ml NaOH 0,001M
bng HCl 0,0010M
0,00 1,30 12,00 11,00
10,00 12,91 11,91 10,91
20,00 12,62 11,62 10,62
50,00 11,52 11,52 10,52
90,00 11,72 10,72 9,72
99,00 10,69 9,69 8,69
99,90 9,69 8,69 7,69
100,00 7,00 17,00 7,00
100,10 4,30 5,30 6,30
110,00 2,33 3,33 4,33
120,00 2,05 3,05 4,05
Tng t nh trng hp chun axit mnh bng baz mnh, bc nhy
trn ng chun gim xung khi gim nng dung dch cn chun . Th d
khi chun NaOH 0,10 M khong bc nhy ko di t 9,69 4,30 c 5,39 n v
pH, khi nng NaOH gim xung 10 ln khong bc nhy ch cn 3,39 n v
pH, nng NaOH gim xung 10 ln na, khong bc nhy ch cn 1,39 n v
pH. Nng dung dch cn chun cng b, bc nhy trn ng chun cng
ngn, vic chn ch th gp nhiu kh khn, nhiu khi khng tm thy ch th ph
hp, sai s php chun kh ln.
4.2.3. Chun axit yu bng baz mnh.
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Gi s tin hnh chun V
A
ml dung dch axit yu AH c nng C
A
(mol/l)
bng dung dch baz mnh MOH c nng C
B
(mol/l), Hng s phn li ca axit
yu K
a
.
Phn ng chun :
AH

+ MOH AM + H
2
O
Khi cha thm baz mnh, trong dung dch ch c axit yu AH, nng C
A
,
pH ca dung dch tnh theo cng thc (3.10).
[H
3
O
+
] =
A A
C K
pH =
2
1
pK
a

2
1
log C
A
(4.26)
Khi thm baz mnh MOH nhng cha phn ng ht vi axit AH, trong dung
dch c axit yu AH v baz yu A

to hn hp axit baz lin hp pH c tnh
theo cng thc (3.15).
pH = pK
A
+ log
AH
A
C
C

(4.27)
[A

] =

+
B A
B B
V V
C V
M (4.28)
[AH] =

B A
B B A A
V V
C V C V
M (4.29)
Thay (4.28) v (4.29) vo (4.27)
pH = pK
A
+ log

B B A A
B B
C V V V
C V
(4.30)
Ti thi im tng ng, khi thm va lng baz mnh phn ng ht
vi lng axit yu, trong dung dch ch c A

l baz yu. pH lc ny c tnh theo
cng thc (3.13).
[OH

] =
B B
C K
pOH =
2
1
pK
b

2
1
log C
B
pH = 14,00
2
1
pK
b
+
2
1
log C
B
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= 7 +
2
1
pK
a
+
2
1
log C
B
(4.31) B
C
B
=
B A
A A
V V
C V
+
(4.32)
Thay (4,32) vo (4.31):
pH = 7 +
2
1
pK
A
+
2
1
lg
B A
A A
V V
C V
+
(4.33)
Sau im tng ng, khi thm d baz mnh, trong dung dch c MOH d
v A

, nhng A

l baz yu bn cnh baz mnh MOH, pH c tnh theo nng


baz mnh (3.11).
pH = + log C
O H
pK
2
B
(4.34)
C
B
= [OH

]
d
=

B A
A A B B
V V
C V C V
(4.35)
Thay (4.35) v (4.29) vo (4.34)
pH = + log
O H
pK
2

B A
A A B B
V V
C V C V
(4.36)
Th d 4.3. V ng chun 50,00 ml dung dch axit yu HNO
2
0,1000M,
K
a
= 7,70.10
4
bng NaOH 0,1000 M.
p dng cc cng thc pH trn chng ta tnh gi tr pH trong qu trnh chun :
Bng 4.3. Gi tr pH trong qu trnh chun 50,00 ml dung dch HNO
2
0,1000 M,
K
a
= 7,10.10
4
bng dung dch NaOH 0,1000 M.
Th tch
NaOH (ml)
2
HNO
C
(mol)

2
NO
C (mol)
C
NaOH

(mol)
H [H
3
O
+
] [OH

] pH pOH
0,00 0,1000 0,000 0,0000 Axit yu 4,43.10
3
0,0000 2,07
5,00 8,18.10
2
9,09.10
3
0,0000 m 6,39.10
3
0,0000 2,19
15,00 3,38.10
2
2,30.10
2
0,0000 m 1,60.10
3
0,0000 2,82
25,00 3,33.10
2
3,33.10
2
0,0000 m 7,10.10
4
0,0000 3,17
40,00 1,11.10
2
4,44.10
2
0,0000 m 1,77.10
4
0,0000 3,76
45,00 5,26.10
3
4,73.10
2
0,0000 m 7,90.10
5
0,0000 4,11
49,00 1,00.10
3
4,95.10
2
0,0000 m 1,42.10
5
0,0000 4,85
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50,00 0,0000

5,00.10
2
0,0000 Baz yu

8,40.10
7
7,92 6.08
51,00 0,0000

4,95.10
3
9,90.10
4
Baz mnh

9,90.10
4
11,00 3.00
60,00 0,0000

4,54.10
3
9,09.10
3
Baz mnh

9,09.10
3
11,95 6.08
Da vo kt qu tnh ton trn bng 4.3 cho chng ta nhn thy khong bc
nhy trn ng chun axit yu bng baz mnh ngn hn bc nhy trn ng
chun axit mnh bng baz mnh.

Khong bc nhy ph thuc vo nng v cng ca axit. Hng s phn
li axit cng nh (axit cng yu) bc nhy trn ng chun cng ngn. iu ny
d nhn thy trn hnh 4.4. im tng ng khng trng vi im pH = 7, m n
lch v pha kim yu (pH > 7) ,ng chun khng cn c dng i xng.

10 20 30 40 50 60 70
12 -
10 -
8 -
6 -
4 -
2 -
0
pH
V(ml)











Hnh 4.3. ng chun 50,0ml dung dch HNO
2
0,100M bng NaOH 0,100 M.
12,0 -
10,0 -
8,0 -
6,0 -
4,0 -
2,0 -






68
10 20 30 40 50 60
pH
Phenolphtalein
Bromothymexanh
Bromocresolxanh
K =10
a
-10
-8
a
K =10
-6
a
K =10
-4
a
K =10
-2
a
K =10
axit mnh
V(ml) NaOH 0,1000M
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Hnh 4.4. nh hng cng axit n khong bc nhy trn ng chun
50,00 ml dung dch axit yu AH 0,1000M bng baz mnh MOH 0,100 M.
4.2.4. Chun baz yu bng axit mnh.
Gi s chun V
B
ml baz yu B c nng C
B
(mol/l) bng axit mnh HX
c nng C
A
(mol/l).
Phn ng chun :
B + HX BH
+
+ X

(4.37)
Khi cha thm axit mnh HX, trong dung dch ch c baz yu B, nng C
B
,
pH ca dung dch tnh theo cng thc (3.13).
[OH

] =
B B
C K ; K
B
=
A
K
. ,
14
10 00 1


pH = 14,00 pOH (4.38)
Khi bt u chun , trong dung dch cn baz yu B cha phn ng ht v
axit yu BH
+
to thnh hnh thnh mt h axit baz lin hp, pH ca dung dch
c tnh theo cng thc (3.15)
pH = pK
a
+ log
+
BH
B
C
C
(4.39)
C
BH
+ =
B A
A A
V V
C V
+
(4.40)
C
B
=
A B
A A B B
V V
C V C V
+

(4.41)
Thay (4.40) v (4.41) vo (4.39)
pH = pK
a
+ log


A A
A A B B
C V
C V C V
(4.42)
Ti im tng ng trong dung dch ch c axit yu BH
+
, pH tnh theo
cng thc (3.10).
[H
3
O
+
] =
A A
C K (4.43)
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C
A
=
B A
B B
V V
V C
+
(4.44)
Thay (4.44) vo (4.43)
[H
3
O
+
] =
B A
B B
A
V V
V C
K
+
(4.45)
Sau im tng ng, khi thm d axit mnh HX, trong dung dch gm c
axit mnh HX v axit yu BH
+
, tuy nhin c th b qua s phn li ca axit yu BH
+
,
pH tnh theo nng axit mnh HX d (cng thc (3.8).
[H
3
O
+
] = log C
A
C
A
=
B A
B B A A
V V
C V C V
+


pH = log

B A
B B A A
V V
C V C V
(4.46)
Th d 4.4. Tnh gi tr pH sau khi thm 0,00; 5,00; 15,00; 25,00; 40,00; 45,00;
49,00; 50,00; 51,00; 55,00 v 60,00 ml HCl 0,1000 M vo 50,00 ml dung dch
NH
3
0,1000 M.
Phn ng chun :
NH
3
+ H
3
O
+
+ H
+
4
NH
2
O
K
a
= 5,7.10
10
; K
b
=
10
14
10 7 5
10 00 1

. ,
. ,
= 1,75.10
5
V
A
= 0,00 ml HCl 0,1000 M
pH ca dung dch tnh theo cng thc (3.13).
[OH

] =
3
NH B
C K = 0,1000 x . ,
5
10 75 1

= 1,32.10
3
M
pH = 14,00 ( log 1,32.10
3
) = 11,12
V
A
= 5,00 ml HCl 0,1000 M
= +
4
NH
C
5,00 ,
0,1000 x ,
+ 00 50
00 5
= 9,09.10
3
M
=
3
NH
C
5,00
0,1000 x , 0,1000 x ,
5
00 5 00 50
= 8,18.10
2
M
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p dng cng thc tnh pH ca h axit baz lin hp:
[H
3
O
+
] = K
a

3
4
NH
NH
C
C
+
= 5,7.10
10
.
2
3
10 18 8
10 09 9

. ,
. ,
= 6,33.10
11

pH = log 6,33.10
11
= 10,20

V
A
= 15,00 ml HCl 0,1000 M
= C
+
4
NH
C
A
=
00 65
00 15
,
0,1000 x ,
= 2,30.10
2
M
=
3
NH
C
5,00
0,1000 x , 1 0,1000 x ,
6
00 5 00 50
= 5,38.10
2
M
[H
3
O
+
] = 5,7.10
10
.
2
2
10 38 5
10 3 2

. ,
. ,
= 2,44.10
10

pH = log 2,44.10
10
= 9,36
V
A
= 25,00 ml HCl 0,1000 M
= C
+
4
NH
C
A
=
00 75
00 25
,
0,1000 x ,
= 3,30.10
2
M
= C
3
NH
C
B
=
5,00
0,1000 x , 2 0,1000 x ,
7
00 5 00 50
= 3,33.10
2
M
[H
3
O
+
] = 5,7.10
10
.
2
2
10 33 3
10 3 3

. ,
. ,
= 5,70.10
10

pH = log 5,70.10
10
= 9,24
V
A
= 40,00 ml HCl 0,1000 M
= C
+
4
NH
C
A
=
00 90
00 40
,
0,1000 x ,
= 4,44.10
2
M
= C
3
NH
C
B
=

90,00
0,1000 x , 40 0,1000 x , 00 00 50
= 1,11.10
2
M
[H
3
O
+
] = 5,7.10
10
.
2
2
10 11 1
10 44 4

. ,
. ,
= 2,28.10
9
M


pH = log 2,28.10
9
= 8,65
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V
A
= 45,00 ml HCl 0,1000 M
= C
+
4
NH
C
A
=
00 95
00 45
,
0,1000 x ,
= 4,73.10
2
M
= C
3
NH
C
B
=

95,00
0,1000 x , 45 0,1000 x , 00 00 50
= 5,26.10
3
M
[H
3
O
+
] = 5,7.10
10
.
3
2
10 26 5
10 73 4

. ,
. ,
= 5,13.10
9
M


pH = log 5,13.10
9
= 8,29
V
A
= 50,00 ml HCl 0,1000 M
t im tng ng, trong dung dch tn ti ch yu l mt axit yu,
pH c tnh theo cng thc axit yu:
+
4
NH
[H
3
O
+
] =
A A
C K
C
A
= =
+
4
NH
C
00 100
00 50
,
0,1000 x ,
= 0,0500 M
[H
3
O
+
]

=

0,0500 x . ,
10
10 7 5

= 5,34.10
6
M
pH = log 5,34.10
6
= 5,27
V
A
= 51,00 ml HCl 0,1000 M
Sau im tng ng, d axit HCl:
C
HCl
= [H
3
O
+
] =
101,00
0,1000 x , 50 0,1000 x , 00 00 51

= 9,90.10
4
M
pH = log 9,90.10
4
= 3,00
V
A
= 55,00 ml HCl 0,1000 M
C
HCl
= [H
3
O
+
] =
105,00
0,1000 x , 50 0,1000 x , 00 00 55

= 4,76.10
3
M
pH = log 4,76.10
3
= 2,32
V
A
= 60,00 ml HCl 0,1000 M
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C
HCl
= [H
3
O
+
] =
110,00
0,1000 x , 50 0,1000 x , 00 00 60

= 9,09.10
3
M
pH = log 9,09.10
3
= 2,04

V(ml)
pH
0,00
14 -
12 -
10 -
8 -
6 -
4 -
2 -
10 20 30 40 50 60 70
HCl 0,100 M









Hnh 4.5. Dng ng chun 50,00 ml dung dch NH
3
0,1000M
bng HCl 0,1000 M
Cng tng t nh trng hp chun axit yu bng baz mnh. ng
chun baz yu bng axit mnh cng c bc nhy ngn hn, ph thuc vo
nng v hng s phn li ca baz. im tng ng khng trng vi im c
pH = pOH = 7 m lch v pha vng axit yu pH < 7.
b
b
b
b
b
0
Baz mnh
12,0 -
10,0 -
8,0 -
6,0 -
4,0 -
2,0 -
10 20 30 40 50 60
pH
Phenolphtalein
Bromothymexanh
Bromocresolxanh
k =10
-10
-8
k =10
-6
k =10
-4
k =10
-2
k =10
V(ml) HCl 0,1000M








Hnh 4.6. nh hng cng baz n bc nhy trn ng chun 50,00 ml
baz yu B 0,1000 M bng axit mnh HX 0,1000 M.
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4.3. ng chun a axit v a baz.
4.3.1. Chun a axit bng baz mnh.
a axit c th xem nh hn hp nhiu n axit, trong trng hp t s cc
hng s phn li axit cc nc k tip khc nhau trn 10
4
ln, th c th chun ring
tng nc, sai s mc phi b c th chp nhn c. Chng ta xt trng hp axit
H
3
PO
4
.
H
3
PO
4
+ H
2
O H
3
O
+
+ ; =

4 2
PO H
1
a
K
] PO H [
] PO H [ ] O H [
4 3
4 2 3
+
= 7,59.10
3
(4.47)
+ H

4 2
PO H
2
O H
3
O
+
+ ; =
2
4
HPO
2
a
K
] PO H [
] HPO [ ] O H [

+
4 2
2
4 3
= 6,32.10
8
(4.48)
+ H
2
4
HPO
2
O H
3
O
+
+ ; =
3
4
PO
3
a
K
] HPO [
] PO [ ] O H [

+
2
4
3
4 3
= 4,50.10
13
(4.49)
Th d 4.5. Tnh gi tr pH trong qu trnh chun 20,000 ml H
3
PO
4
0,1000 M
bng dung dch NaOH 1M.
Axit H
3
PO
4
l mt a axit c 3 nc phn li vi 3 hng s phn li khc nhau. V
vy, khi chun bng NaOH s c 3 im tng ng, nhng im tng ng th 3
khng c bc nhy v axit c hng s phn li rt nh (4,5.10
2
4
HPO
13
). Chng ta s
tnh gi tr pH trong qu trnh thm NaOH.
Khi cha thm NaOH (V
NaOH
= 0,00 ml)
Theo nh lut bo ton khi lng ta c:
= [H
4 3
PO H
C
3
PO
4
] + [ ] + [ ] + [ ] = 0,1000 M (1)

4 2
PO H
2
4
HPO
3
4
PO
Phng trnh trung ho in tch:
[H
3
O
+
] = [ ] + 2[ ] + 3[ ] (2)

4 2
PO H
2
4
HPO
3
4
PO
>> >> [ ] v [ ] << [ ]
1
a
K
2
a
K
3
a
K
2
4
HPO
3
4
PO

4 2
PO H
[H
3
O
+
] = [ ] (3)

4 2
PO H
= [H
4 3
PO H
C
3
PO
4
] + [ ] (4)

4 2
PO H
[H
3
PO
4
] = [ ] = [H
4 3
PO H
C

4 2
PO H
4 3
PO H
C
3
O
+
] (5)
=
1
a
K
] PO H [
] PO H [ ] O H [
4 3
4 2 3
+
(6)
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Thay (3) v (5) vo (6):
=
1
a
K
] O H [ C
] O H [
+
+

3
2
3

[H
3
O
+
]
2
+ [H
1
a
K
3
O
+
]

C = 0
1
a
K
[H
3
O
+
] =
2
C K K K
a a a
1 1 1
4
2
+ +

=
2
. . , . ) . , ( . ,
1 3 2 3 3
10 10 59 7 4 10 59 7 10 59 7

+ +
= 2,4.10
2
pH = log 2,40.10
2
= 1,62
Thm 1,00 ml NaOH 1M
C = [H
3
PO
4
] + [ ] + [ ] + [ ] (7)

4 2
PO H
2
4
HPO
3
4
PO
[H
3
O
+
] + [Na
+
] = [OH

] + [ ] + 2[ ] + 3[ ] (8)

4 2
PO H
2
4
HPO
3
4
PO
C = [H
3
PO
4
] + [ ] (9)

4 2
PO H
[Na
+
] =
2
C
(10)
[H
3
0
+
] +[ Na
+
] = [H
2
PO
4
_
] [H
3
O
+
] +
2
C
= [ ] (8

4 2
PO H
/
)
Thay (9) v (10) vo (8
/
) ta c:
[H
3
PO
4
] =
2
C
[H
3
O
+
] (11)
Thay(8

) v (11) vo (6):
=
1
a
K

+
+
+ +
] O H [
2
C
] O H [
2
C
] O H [
3
3 3
(12)
[H
3
O
+
]
2
+

+
2
1
C
K
a
[H
3
O
+
]
2
1
C
K
a
= 0
[H
3
O
+
] =
2
2
4
2 2
1 1 1
2
C
K
C
K
C
K
a a a
+

+ +

+
= 5,9.10
3
M (13)
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pH = log 5,9.10
3
= 2,23
Thm 2,00 ml NaOH 1M. t im tng ng 1.
Ton b lng H
3
PO
4
chuyn thnh [ ]

4 2
PO H
+ H

4 2
PO H
2
O H
3
PO
4
+ OH

(14)
+ H

4 2
PO H
2
O H
3
O
+

+ (15)
2
4
HPO
=
2
a
K
] PO H [
] HPO [ ] O H [

+
4 2
2
4 3
(16)

= [H
+
O H
C
3
3
O
+
]
t
= + (17)
O H
] O H [
2
3
+

+
4 2
3
PO H
] O H [

4 2
PO H
] OH [
= [OH

] + [ ] [H
2
4
HPO
3
PO
4
] (18)
[H
3
O
+
] =
] O H [
K
O H
+
3
2
+
] O H [
] PO H [ K
a
+

3
4 2
2

1
4 2 3
a
K
] PO H [ ] O H [
+
(19)
[H
3
O
+
]
2
=
1
2 2
4 2
4 2
a
a O H
K
] PO H [
1
] PO H [ K K

+
+
(20)
[H
3
O
+
] =
] PO H [ K
] PO H [ K K K K
a
a a O H a

+
+
4 2
4 2
1
1 2 2 1
(21)
Nu << [ ] v << [ ]
1
a
K
O H
K
2 1
a
K
2
a
K

4 2
PO H
1
a
K

4 2
PO H
[H
3
O
+
] =
2 1
a a
K K (22)
pH =
2
1
(p + p ) = 4,54 (23)
1
a
K
2
a
K
V
NaOH
= 3,00 ml NaOH 1M
S mmol H
3
PO
4
c trong dung dch 20,,00 x 0,1 = 2 mmol.
S mmol NaOH thm vo: 3,00 x 1 = 3,00 mmol.
Phn ng chun giai on ny:
[ ] + OH

4 2
PO H

+ H
2
4
HPO
2
O (24)
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Ti thi im ny c th xem [H
2
PO
4

_
] = [HPO
4
_
].
=
2
a
K
] PO H [
] HPO [ ] O H [

+
4 2
2
4 3
= 6,1.10
8
(25)
[H
3
O
+
] = 6,2.10
8
pH = p = 7,21
2
a
K
V
NaOH
= 4,00 ml
Ton b phn ng vi NaOH ht, trong dung dch tn ti cc
dng ch yu: , , .

4 2
PO H

4 2
PO H
2
4
HPO
3
4
PO
+ H
2
4
HPO
2
O = + OH

4 2
PO H

(26)
+ H
2
4
HPO
2
O = + H
3
4
PO
3
O
+
(27)
[H
3
O
+
]
t
= +
O H
] O H [
2
3
+

+
2
4
3
HPO
] O H [

2
4
HPO
] OH [
= [OH

] + [ ] (28)
3
4
PO

4 2
PO H
[H
3
O
+
] =
] O H [
K
O H
+
3
2
+
] O H [
] HPO [ K
a
+

3
2
4
3

2
2
4 3
a
K
] HPO [ ] O H [
+

[H
3
O
+
]
2
( + [ ]) = + [ ]
2
a
K
2
4
HPO
2
a
K
O H
K
2 3
a
K
2
a
K
2
4
HPO
[H
3
O
+
] =
] HPO [ K
] HPO [ K K K K
a
a a O H a

+
+
2
4
2
4
2
2 3 2 2
(29)
Nu << [ ]
2
a
K
O H
K
2 3
a
K
2
a
K
2
4
HPO
v << [ ] , chng ta c:
2
a
K
2
4
HPO
[H
3
O
+
] =
2 3
a a
K K (30)
pH =
2
1
( p + p ) = 9,76 (31)
2
a
K
3
a
K
V
NaOH
= 5,0 ml. Ti thi im ny ton b lng H
3
PO
4
chuyn thnh
, trong 1/2 lng phn ng vi NaOH chuyn thnh .
2
4
HPO
2
4
HPO
3
4
PO
Theo nh lut bo ton khi lng :
C = [H
3
PO
4
] + [ ] + [ ] + [ ] = 8,0.10

4 2
PO H
2
4
HPO
3
4
PO
2
M (32)

Theo phng trnh trung ha in tch:
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[H
3
O
+
] + [Na
+
] = [OH

] + [ ] + 2[ ] + 3[ ] (33)

4 2
PO H
2
4
HPO
3
4
PO
C th xem [H
3
PO
4
] v [ ] << [ ] v [ ]

4 2
PO H
2
4
HPO
3
4
PO
[Na
+
] =
2
5
C v gi thit [H
3
O
+
] << [Na
+
]
C = [ ] + [ ]
2
4
HPO
3
4
PO

(34)

2
5
C = [OH

] + 2 [ ] + 3[ ] (35)
2
4
HPO
3
4
PO

2
5
C = [OH

] + 2 C + [ ] (36)
3
4
PO
[ ] =
3
4
PO
2
C
[OH

] (37)
Thay (37) vo (34):
C = [ ] +
2
4
HPO
2
C
[OH

] (38)
[ ] =
2
4
HPO
2
C
+ [OH

] (39)
C = 8,0.10
2
[OH

] <<
2
C

[ ] = [ ] =
2
4
HPO
3
4
PO
2
C
= 4,0.10
2
M
=
3
a
K
] HPO [
] PO [ ] O H [

+
2
4
3
4 3
= 4,9.10
13

[H
3
O
+
] = 4,9.10
13
pH = 11,66
[OH

] = 4,6.10
3
M ,khng th chp nhn gi thit[OH
_
] << C/2
Chng ta cn tnh chnh xc hn:
=
3
a
K
] HPO [
] PO [ ] O H [

+
2
4
3
4 3
=
] OH [
2
C
] OH [
2
C
] O H [

+
+


3



3
a
K

+
+
] O H [
K
2
C

O H
3
2
= [H
3
O
+
]

+
] O H [
K
2
C

O H
3
2
(40)

2
C
[H
3
O
+
]
2

+
2
3 2
C
. K K
a O H
[H
3
O
+
] = 0
3
a
K
O H
K
2
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4.10
2
[H
3
O
+
]
2
2,96.10
14
[H
3
O
+
] 4,9.10
27
= 0 (41)
[H
3
O
+
] = 8,8.10
13
M
[OH

] = 1,13.10
2
M
pH = 12,06
V
NaOH
= 6,0 ml.

t im tng ng th 3.
C = [H
3
PO
4
] + [ ] + [ ] + [ ] = 7,7.10

4 2
PO H
2
4
HPO
3
4
PO
2
M

[H
3
O
+
] + [Na
+
] = [OH

] + [ ] + 2[ ] + 3[ ]

4 2
PO H
2
4
HPO
3
4
PO
[H
3
PO
4
] v [ ] << [ ] v [ ]

4 2
PO H
2
4
HPO
3
4
PO
[H
3
O
+
] << [Na
+
] = 3C
C = [ ] + [ ]
2
4
HPO
3
4
PO

(42)
3C = [OH

] + 2 [ ] + 3[ ] (43)
2
4
HPO
3
4
PO
Thay (42) vo (43) v bin i ta c:
= C [OH
3
4
PO

] v [ ] = [OH
2
4
HPO

]
=
3
a
K
] HPO [
] PO [ ] O H [

+
2
4
3
4 3
=
] OH [
]) OH [ (C ] O H [

3

[H
3
O
+
] = 3,25.10
13
; [OH

] = 3,07.10
2
M
pH = 12,49
V
NaOH
=10,0 ml. Ton b lng axit H
3
PO
4
chuyn thnh v cn d 4 mmol
NaOH.
3
4
PO
[OH

]
d
= O,133 M

[H
3
O
+
] =
] OH [
K
O H

2
= 7,5.10
14
M
pH = log 7,5.10
14
= 13,12
Chng ta c th tnh:

C = [ ] + [ ] = 6,6.10
2
4
HPO
3
4
PO
2
M (44)

[Na
+
] = 5C (45)
5C = [OH

] + 2[ ] + 3[ ] (46)
2
4
HPO
3
4
PO
79
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Thay (44) vo (46) v bin i:
[ ] = 3C [OH
3
4
PO

] (47)
[ ] = [OH
2
4
HPO

] 2C (48)
=
3
a
K
C ] OH [
]) OH [ (3C ] O H [
2
3

+

3C [H
3
O
+
]
2
( 2 ) [H
3
a
K
O H
K
2
3
O
+
] = 0
3
a
K
O H
K
2
[H
3
O
+
] = 7,0.10
14
M; [OH

] = 0,141 M
pH = 13,15 (49)
Gi tr pH biu thc (51) khng khc vi gi tr pH tnh trn.










NaOH 1 M
14 -
12 -
10 -
8 -
6 -
4 -
2 -
0,0
pH
V(ml) 2 4 6 8 10
Hnh 4.7. Dng ng chun 20,0 ml H
3
PO
4
0,1 M bng dung dch NaOH 1 M.
4.3.2. Chun a baz bng axit mnh.
Th d 4.6. Hy tnh pH trong qu trnh thm 0,00 ml; 12,50; 20,00; 24,00; 25,00;
26,00; 37,50; 45,00; 49,00; 50,00; 51,00; v 60,00 ml dung dch HCl 0,2000 M vo
50,00 ml dung dch Na
2
CO
3
0,100 M.
Ta bit axit H
2
CO
3
l a axit c hng s phn li v
1
a
K
2
a
K
=
1
a
K
] CO H [
] HCO [ ] O H [
3 2
3 3
+
= 4,45.10
7
(1)
80
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=
2
a
K
] HCO [
] HCO [ ] O H [

+
3
2
3 3
= 4,69.10
11
(2)
V
HCl
= 0,00 ml HCl 0,2 M.
Trong dung dch ch c mui Na
2
CO
3
+ H
2
3
CO
2
O + OH

3
HCO

(3)
K
b
=
] CO [
] [OH ] HCO [


2
3
3
=
11
14
10 69 4
10 00 1

. ,
. ,
= 2,13.10
4
C th xem [ ]

3
HCO

= [OH

]
[ ] = 0,100 [OH
2
3
CO

] 0,1000 M


1000 0,
] [OH
2
= 2,13.10
4
[OH

] =
4
2,13.10 x ,

1000 0 = 4,62.10
3
pH = 11,66.
V = 12,50 ml HCl 0,2000 M.
Phn ng chun :
+ H
2
3
CO
3
O
+
+ H

3
HCO
2
O
Trong dung dch gm c cha phn ng ht v va c to
thnh, c th xem nh hn hp axit baz lin hp.
2
3
CO

3
HCO
[ ] =

3
HCO
50 62
2000 0 50 12
,
, x ,
= 4,000.10
2
M
[ ] =
2
3
CO
50 62
2000 0 50 12 0 50
,
, x , 0,1000 x ,
= 4,00.10
2
M

Theo biu thc (2):
[H
3
O
+
] = 4,69.10
11

2
2
10 00 4
10 00 4

. ,
. ,
= 4,69.10
11
M
pH = 10,33
V = 20,000 ml HCl 0,2000 M
81
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Tnh tng t: pH = 9,73
V = 24,000 ml HCl 0,2000 M pH = 8,95
V = 25,000 ml HCl 0,2000 M (t im tng ng th 1).
Ti thi im ny ton b lng[ CO
3
2_
] ban u c chuyn [ HCO
3
_
]

Cc cn bng trong dung dch:
+ H

3
HCO
2
O H
3
O
+
+ (4)
2
3
CO
+ H

3
HCO
2
O H
2
CO
3
+ OH

(5)
C = [H
2
CO
3
] + [ ] + [ ] (6)

3
HCO
2
3
CO
[H
3
O
+
] + [Na
+
] = [ ] + 2[ ] + [OH

3
HCO
2
3
CO

] (7)
T (4) v (5) c th vit H
3
O
+
] = [ ] + [OH
2
3
CO

] [H
2
CO
3
] (8)
Theo phng trnh (1) ta c:
[H
2
CO
3
] =
1
a
K
] HCO [ ] O H [
+
3 3
(9)
Theo phng trnh (2) ta c:
[ ] =
2
3
CO
] O H [
] HCO [ K
2
a
+

3
3
(10)
Thay (10) v (11) vo (9):
[H
3
O
+
] =
] O H [
] HCO [ K
2
a
+

3
3
+
] O H [
K
O H
2
+
3

1
a
K
] HCO [ ] O H [
+
3 3
(11)
[H
3
O
+
]
2
= [ ] +
2
a
K

3
HCO
O H
2
K
1
a
K
] HCO [ ] O H [
+ 2
3
2
3
(12)
[H
3
O
+
]
2

1
2
3
1
a
K
] HCO [
= [ ] + (13)
2
a
K

3
HCO
O H
2
K
[H
3
O
+
] =
1
2 2
a
O H a
K
] HCO [
1
K ] HCO [ K

+
+
2
3
2
3
(14)
82
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C th gi thit 1 <<
1
a
K
] HCO [
2
3
v << [ ]
O H
2
K
2
a
K

3
HCO
Vy : [H
3
O
+
] =
2 1
a a
K K
(15)
[H
3
O
+
] =
11 7
4,69.10 x 0 . ,

1 45 4 = 4,57.10
9
pH = 8,34.
V = 26,00 ml HCl 0,2000 M.
+ H

3
HCO
3
O
+
H
2
CO
3
+ H
2
O (16)
Trong dung dch tn ti H
2
CO
3
v [ ]. y l mt hn hp axit baz
lin hp.

3
HCO
S mmol HCl thm vo: 26,00 x 0,2000 = 5,2000 mmol.
S mmol c trong dung dch trc khi thm HCl:

3
HCO
50,00 x 0,1000 = 5,0000 mmol.
S mmol H
2
CO
3
to thnh sau khi thm HCl:
5,2000 5,000 mmol = 0,2000 mmol.
S mmol cn li cha phn ng:

3
HCO
50,00 x 0,1000 0,2000 = 4,8000 mmol.
=
3 2
CO H
C
00 76
2000 0
,
,
= 2,63.10
3
M [H
2
CO
3
]
=
3
NaHCO
C
00 76
800 4
,
,
= 6,31.10
2
M [ ]

3
HCO
[H
3
O
+
] = 4,45
7
.

2
3

6,31.10
] 2,63.10
= 1,85.10
8
M
pH = 7,73
Tnh tng t nh trn ta tm c cc gi tr pH ti cc thi im V
HCl
=
37,500 ml; 45,00 ml v 49,00 ml. (pH = 6,35; 5,75; 4,97).
V = 50,00 ml HCl 0,2000 M.
83
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Ton b phn ng ht vi HCl
2
3
CO
Ka
1
=
] CO [H
] HCO [ ] O H [
2 3
3 3
+
= 4,45.10
7
M
[H
3
O
+
] = [ ]

3
HCO
[H
2
CO
3
] = 0,0500 [H
3
O
+
] 0,0500 M
[H
3
O
+
] =
3 2 1
CO H a
C K = 0,0500 x 0 . ,
7
1 45 4 = 1,49.10
4
M
pH = 3,83.
V = 51,00 ml HCl 0,2000 M (d 1mlHCL0,2000M).
C
HCl
= [H
3
O
+
] =
00 101
000 1
,
0,2000 x ,
= 1,98.10
3
M
pH = 2,70
V = 60,00 ml HCl 0,2000 M (d 10ml HCL0,2000M).
C
HCl
=
00 110
00 10
,
0,2000 x ,
= 1,81.10
2
M
pH = 1,75
Bng 4.6. Kt qu gi tr pH khi chun 50,00 ml Na
2
CO
3
0,1000 M
bng HCl 0,2000 M.
Th tch HCl (ml) pH Th tch HCl (ml) pH
0,00 11,66 37,50 6,35
12,50 10,33 45,00 5,75
20,00 9,73 49,00 4,97
24,00 8,95 50,00 3,83
25,00 8,34 51,00 2,70
26,00 7,73 60,00 1,74





84
14 -
12 -
10 -
8 -
pH
http://www.ebook.edu.vn










Hnh 4.8. ng chun 50,00 ml dung dch Na
2
CO
3
0,1 M
bng dung dch HCl 0,2 M.

4.3.3. Chun amino axit.
Amino axit ng vai tr quan trng trong lnh vc ho sinh v ho dc.
Chng l hp cht lng tnh cha c nhm chc axit v nhm chc baz :nhm
nhm chc axit cacboxylic (CO
2
H), nhm chc baz - nhm amin (NH
2
). Trong
dung dch nc thng xy ra khuynh hng chuyn proton t nhm cacboxylic n
nhm amino bi v nhm RNH
2
c tnh baz mnh hn R , kt qu hnh thnh
hp cht Zwitterion (va c tnh cht v va c tnh baz:

2
CO

CH R
NH
3
CO
2
+
c th c chun bng axit mnh hoc baz mnh . Axt lin hp ca hp cht
Zwitterion nh a axit vi hai hng s phn li v K .
1
a
K
a
2
Hp cht zwitterion
baz lin hp
ca zwitterion
axit lin hp
ca zwitterion
Ka
2
CH
NH
2
CO
2
R H
+
+
+
+
H
+
CH
NH
3
CO
2
R
Ka
1
+
CH
NH
3
CO
2
H R



Cn bng axit baz ca amino axit tng t nh mt a axit. Nng ion
hiro ca hp cht zwitterion c tnh tng t nh mui HCO

3
[H
+
] =
2 1
Ka Ka
85
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Khi chun hp cht zwitterion bng axit mnh vng m u tin bao gm
mui ca zwitterion v axit lin hp ca n. pH im tng ng c xc nh
bi axit lin hp K
a1
tng t nh H
2
CO
3
.
Khi chun bng baz mnh vng m gm baz lin hp v axit ca
zwitterion. pH im tng ng c xc nh bi baz lin hp K
b
tng t nh
K
b
ca CO
3
_
.
4.3.4. Phng php phn tch Kjeldahl.
Phng php phn tch Kjeldahl l phng php thng c ng dng xc
nh hm lng nit trong protein v trong cc hp cht cha nit khc.
Phng php ny c xem nh phng php tiu chun xc nh nit.
Phng php da trn nguyn tc sau:
Mu phn tch c phn hu bng axit H
2
SO
4
c chuyn nit thnh mui
amonisunfat.
C
a
H
b
N
c
a CO
2
+
2
1
b H
2
O + c NH
4
HSO
4
H
2
SO
4
x
qu trnh phn hu xy ra nhanh v hon ton, ngi ta thm mui K
2
SO
4

v mui selen hay ng lm xc tc.
Sau khi chuyn ton b nit thnh mui NH
4
HSO
4
, lm ngui hn hp phn
ng ri thm vo dung dch kim, ct ton b NH
3
vo bnh cha dung dch
axit bit trc nng (ly vi lng d), ngi ta tin hnh chun lng
axit d bng dung dch chun NaOH. T c th tnh c hm lng nit c
trong mu phn tch.
c NH
4
HSO
4
c NH

OH
3
+ c
2
4
SO
c NH
3
+ (c + d) HCl c NH
4
Cl + d HCl
d HCl + d NaOH d H
2
O + d NaCl
mmol N (c) = mmol HCl phn ng =
mmol HCl ly (c+d) mmol NaOH (d)
mmol C
a
H
b
N
c
= mmol N .
C
1

Th d 4.7. Cn 0,2000 g mu ur k thut v tin hnh phn tch theo
phng php Kjeldahl.
c tc
O
2
NH C NH
2
86
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Thu ton b NH
3
vo bnh cha 50,00 ml H
2
SO
4
0,050 M. Lng H
2
SO
4
d
c chun bng dung dch NaOH 0,0500 M v ht 3,40 ml. Tnh phn trm ur c
trong mu.
Phn ng thu NH
3
:
2 NH
3
+ H
2
SO
4
(NH
4
)
2
SO
4
Phn ng chun :
H
2
SO
4
+ 2 NaOH Na
2
SO
4
+ 2 H
2
O
% Ur =
% .
mg
mmolure
mg
CO )
2
(NH
M .
3
NH mmol
CO )
2
(NH mmol
2
1
.
SO
2
H mmol
3
NH mmol
.2
NaOH mmol
SO
2
H mmol
2
1
NaOH mmol SO
2
H mmol
100
mu
2
2
4
4
4


% Ur =


, x . 2 x x 3,40 x 0,0500 50,00 x ,
200
05 60
2
1
2
1
0500 0


x 100% = 72,50 %
Ngi ta cng c th dng axit H
3
BO
3
hp th NH
3
, lng amoni borat to
thnh tng ng amoniac.
NH
3
+ H
3
BO
3

+
4
NH +

3 2
BO H
Axit H
3
BO
3
l axit yu c th chun bng NaOH, nhng mui amoni borat
to thnh l baz tng i mnh c th chun bng axit, dng metyl lm ch
th. Axit H
3
BO
3
khng nh hng n php chun .
Th d 4.8. Cn 0,3000 g mu thc n xc nh hm lng protein bng phng
php phn tch Kjeldahl. Sau khi phn hu, ct ton b NH
3
vo bnh cha axit
H
3
BO
3
, ri tin hnh chun mui amoni borat bng dung dch axit HCl 0,100 M
ht 25,00 ml. Tnh % protein c trong mu phn tch.
y, chng ta thy phn ng chun xy ra theo t l 1 : 1. S mmol HCl
phn ng bng s mmol NH
3
. Mt khc ta thy c trong 1 mg nit tng ng
6,25 mg protein.
Vy ta c:
% protein =
87
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300
25 6 0 14 00 25 100 0
mgN
protein mg
, x
mmol
N mg
, x mlHCl , x HCl
ml
mmol
,
x 100% = 73,0%
88
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Chng 5
Cn bng to phc v phng php chun phc cht
5.1. Hng s cn bng phn ng to phc
Cc hp cht phc c thnh phn phc tp, bao gm ion trung tm lin kt vi
mt vi phi t v c hoc hu c (dng ion, phn t mang in tch hay trung tnh).
Trong dung dch cc ion kim loi thng b solvat ho, c ngha l n c bao bc
bi cc phn t dung mi nc to thnh phc aquo . (N: s phi t to
phc). Nu ta thm vo phi t L, s xy ra phn ng thay th dn cc phn t nc
trong lp v hirat ho.
+ n
N
) O H ( M
2
M(H
2
O)
N
+ L M(H
2
O)
N-1
L + H
2
O (5.1)
M(H
2
O)
N-1
+ L M(H
2
O)
N-2
L
2
+ H
2
O (5.2)
. . . . . . . . . . . .
M(H
2
O)
N-n+1
+ L
n-1
ML
n
+ N H
2
O (5.3)
Trong thc t ngi ta xem hot ca nc bng n v, nn khng tnh n
trong cn bng to phc, phn ng to phc xy ra trc tip gia ion kim loi v
phi t.
Chng ta cng nhn thy i b phn cc ion kim loi c kh nng to phc
vi cc cht khc nhau da trn lin kt phi tr. Theo quan im axit baz ca
Levis, ion kim loi l axit c kh nng nhn cp electron cn trong phn t phi t
cha cc nguyn t (O, N, S) c cp electron cha lin kt sn sng cho ion kim
loi cp electron ny hnh thnh lin kt phi tr .
Th d trong phn t NH
3
nguyn t nit c cp electron cha lin kt , to
lin kt phi tr vi ion Cu
2+
hnh thnh phc amoniacat ng mu xanh.
(5.4)
y: Cu
2+
c coi nh mt axit.
2+
Cu
2+
NH
3
NH
3
H
3
N Cu NH
3
NH
3
+ 4
NH
3
c coi nh mt baz
Phn ng tng t xy ra i vi cc ion Co
2+
, Ni
2+
vi

NH
3
.
Phn t NH
3
c kh nng to phc vi ion Ag
+
theo hai nc:
Ag
+
+ NH
3
Ag(NH
3
)
+
;
1
=
] NH ][ Ag [
)] NH ( Ag [
3
3
+
+
(5.5)
89
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Ag(NH
3
)
+
+ NH
3
+
2 3
) NH ( Ag

;
2
=
] NH ][ ) NH ( Ag [
] ) NH ( Ag [
3 3
2 3
+
+
(5.6)
T hp hai phng trnh (5.5) v (5.6):
Ag
+
+ 2 NH
3
+
2 3
) NH ( Ag

1,2
=
1
.
2
=
2
2
2 3
] NH ][ Ag [
] ) NH ( Ag [
+
+
(5.7)

1
v
2
c gi l hng s to thnh nc 1 v nc 2 hay hng s to phc
nc 1 v nc 2.

1,2
: hng s bn tng cng.
Chng ta c th vit hng s cn bng theo hng ngc lai hng s phn li.
Ag
+
2 3
) NH ( Ag
+
+ 2 NH
3

K
kb
=
] ) NH ( Ag [
] NH ][ Ag [

,
+
+
=

2 3
2
3
2 1
1
(5.8)
K
kb
: c gi hng s khng bn ca phc cht. Trong phc cht ch c mt
phi t to lin kt vi ion kim loi gi phc n, cn nu phc cht gm c nhiu
phi t lin kt vi cng mt ion kim loi gi phc cht a phi.
Th d phc hnh thanh gia ion Co
3+
vi 3 phn t etylendiamin:
Co
3+
+ 3NH
2
CH
2
CH
2
NH
2
Co (NH
2
CH
2
CH
2
NH
2
)
+ 3
3
NH
2
NH
2
CH
2
CH
2
NH
2
NH
2
CH
2
CH
2
Co
CH
2
H
2
N
H
2
N CH
2
3+




S phi t n =3.
Phc c nhiu ion trung tm gi l phc a nhn, th d phc [(CN)
5
-Co(CN)Fe(CN)
5
]
6
Vic gi tn phc cht thng theo th t sau:
Gi tn phi t sau gi tn ion trung tm. Nu phi t l gc axit cha oxi
th cn thm ui O vo sau. Th d: sunfato, nitrato. Nu phi t l nion
halogeanua th thm O vo tn halogen. Th d: F: floro; Cl: cloro; Br: bromo;
I: iodo.
90
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Mt s anion c tn: NO
2
: nitro; OH

: hiroxo; O
2
: oxo; S
2
: sunfo; : pesunfo.
2
2
S
S phi t c theo ch s rp.
1: mono 5: penta 9: nona
2: di 6: hexa 10: deca
3: tri 7: hepta 11: nodeca
4: tetra 8: octa 12: dodeca
Th d phc K
3
[Co(NO
2
)
6
]: Kali hexanitrocobanat
Co(SCN)(C
2
O
4
)(NH
3
): oxalatothioxianatotriamino coban III
5.2. Tnh nng cn bng cc phn t trong dung dch
phc cht
Khi tnh nng cn bng cc dng trong dung dch phc cht thng phi
gii bi ton phc tp do phn ng to phc thng xy ra theo tng giai on c
hng s bn khc nhau. Nhiu trng hp s khc nhau ny khng nhiu. Ngoi ra
trong dung dch thng xy ra cc phn ng ph, phn ng to thnh hp cht t
tan, phn ng oxi ho - kh, v vy tnh nng cn bng phn ng to phc
chng ta phi xt y cc yu t, c th b qua mt s qu trnh ph khng nh
hng n cn bng chnh.
Th d 5.1. Tnh nng cn bng ion Ag
+
trong dung dch khi trn 25,00 ml
AgNO
3
0,010 M vi 50,00 ml dung dch trietylentetramin (NH
2
(CH
2
)
2
NH(CH
2
)
2
-
NH(CH
2
)
2
NH
2
gi trien 0,015 M c hng s bn phc = 5,0.10
7
.
Phn ng to phc:
Ag
+
+ trien Ag(trien)
+
=
] trien ][ Ag [
)] trien ( Ag [
+
+

S mmol Ag
+
c trong dung dch:
25 ml x 0,010 mmol/ml = 0,25 mmol
S mmol trien: 50 ml x 0,015 mmol/ml = 0,75 mmol
Gi nng Ag
+
trong dung dch x mol/l ta c:
[trien] =
ml
mmol , mmol ,
75
25 0 75 0
+ x = 6,7.10
3
+ x = 6,7.10
3
mol/l

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[Ag(trien)]
+
=
ml ,
mmol ,
0 75
25 0
x = 3,3.10
3
x = 3,3.10
3
mol/l
= 5,0.10
7
=
) . , )( x (
. ,
3
3
10 7 6
10 3 3


x = [Ag
+
] = 9,8.10
9
M
Th d 5.2. Tnh nng cn bng ca cc cu t trong dung dch gm c Cu
2+

0,01 M v NH
3
1M.
Bit hng s bn phc
1
= 9,77.10
3
;
1,2
= 2,13.10
7
;
1,3
= 1,15.10
10
;
1,4
= 1,07.10
12

Cu
2+
+ NH
3
Cu(NH
3
)
2+
;
1
=
] NH ][ Cu [
] ) NH ( Cu [
3
2
3
+
+
= 9,77.10
3
(1)
Cu
2+
+ 2NH
3
+ 2
2 3
) NH ( Cu ;
1,2
=
2
3
2
2
2 3
] NH ][ Cu [
] ) NH ( Cu [
+
+
= 2,13.10
7
(2)
Cu
2+
+ 3NH
3
+ 2
3 3
) NH ( Cu ;
1,3
=
3
3
2
2
3 3
] NH ][ Cu [
] ) NH ( Cu [
+
+
= 1,15.10
10
(3)
Cu
2+
+ 4NH
3
+ 2
4 3
) NH ( Cu ;
1,4
=
4
3
2
2
4 3
] NH ][ Cu [
] ) NH ( Cu [
+
+
= 1,07.10
12
(4)
Theo nh lut bo ton khi lng:
+ 2
Cu
C = [Cu
2+
] + [Cu(NH
3
)
2+
] + + + (5)
+ 2
2 3
) NH ( Cu
+ 2
3 3
) NH ( Cu
+ 2
4 3
) NH ( Cu
= [Cu
2+
] ([1 +
1
[NH
3
] +
1,2
[NH
3
]
2
+
1,3
[NH
3
]
3
+
1,4
[NH
3
]
4
]) (6)
t
o
=
+
+
2
2
Cu
C
] Cu [
(7)

o
=
4
3 4 1
3
3 3 1
2
3 2 1 3 1
1
1
] NH [ ] NH [ ] NH [ ] NH [
, , ,
+ + + +
= 9,25.10
13
(8)

1
=
+
+
2
2
3
Cu
C
] ) NH ( Cu [
=
1
[NH
3
]
o
= 9,77.10
3
. 1 . 9,25.10
13
= 9,03.10
9
(9)

2
=
+
+
2
2
2 3
Cu
C
] ) NH ( Cu [
=
1,2
[NH
3
]
2

o
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= 2,13.10
7
. 1
2
. 9,25.10
13
= 1,97.10
5
(10)

3
=
+
+
2
2
3 3
Cu
C
] ) NH ( Cu [
=
1,3
[NH
3
]
3

o
= 1,15.10
10
. 1
3
. 9,25.10
13
= 1,06.10
2


4
=
+
+
2
2
4 3
Cu
C
] ) NH ( Cu [
=
1,4
[NH
3
]
4

o
= 1,07.10
12
. 1
4
. 9,25.10
13
= 9,89.10
1

Khi = 0,01 M chng ta tm c nng cn bng cc dng trong dung dch:
+ 2
Cu
C
[Cu(NH
3
)
2+
] =
1
. = 9,03.10
+ 2
Cu
C
9
. 0,01 = 9,03.10
11
M
=
+ 2
2 3
) NH ( Cu
2
. = 1,97.10
+ 2
Cu
C
5
. 10
2
= 1,97.10
7
M
=
+ 2
3 3
) NH ( Cu
3
. = 1,06.10
+ 2
Cu
C
2
. 10
2
= 1,06.10
4
M
=
+ 2
4 3
) NH ( Cu
4
. = 9,89.10
+ 2
Cu
C
1
. 10
2
= 9,89.10
3
M
T cc kt qu tnh ton trn chng ta thy trong dung dch tn ti ch yu
dng phc (98,9%), c 1,06% dng phc , cn cc dng khc
rt nh khng ng k.
+ 2
4 3
) NH ( Cu
+ 2
3 3
) NH ( Cu
Chng ta xt trng hp tng qut phn ng to phc gia ion kim loi M vi
phi t L. y ion kim loi M c th mang in tch +1; +2; n +n, L phi t
c th dng phn t hay ion. n gin chng ta khng vit in tch v
1
,
2
;

n
hng s bn tng nc.
l phn t s nng kim loi so vi nng ban u.
Phn ng to phc ion kim loi vi phi t L:
M + L ML ;
1
=
] L ][ M [
] ML [
(5.9)
ML + L ML
2
;
2
=
] L ][ ML [
] ML [
2
=
2
1
2
] L ][ M [
] ML [

(5.10)
M
ML
n-1
+ L ML
n
;
n
=
] L ][ ML [
] ML [
n
n
1
=
n
n ,
n
] L ][ M [
] ML [
1 1

(5.11)
Theo nh lut bo ton khi lng:
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C
M
= [M] + [ML] + [ML
2
] + . . . + [ML
n
] (5.12)
Thay cc gi tr t (5.9). (5.10) v (5.11) vo (5.12) ta c:
C
M
= [M] (1 +
1
[L] +
1

2
[L]
2
+ . . .
1
. . .
n
[L]
n
) (5.13)
t
o
=
M
C
] M [
=
n
n
] L [ ... ... ] L [ + + +
1 1
1
1
(5.14)
Thay (5.14) vo (5.13):
[M] =
o
C
M
=
i
i ,
n i
i
M
] L [
C
1
1
1 +

=
=
(5.15)
Chng ta tm c gi tr nng cn bng cc phc trong dung dch :
[ML] =
i
i ,
n i
i
M
] L [
] L [ C
1
1
1
1 +

=
=
(5.16)
[ML
i
] =
i
i ,
n i
i
i
i , M
] L [
] L [ C
1
1
1
1 +

=
=
(5.17)
[ML
n
] =
n
n ,
n i
i
n
n , M
] L [
] L [ C
1
1
1
1 +

=
=
(5.18)
Nng ban u ca phi t L thng ln hn nng ion kim loi C
M
rt
nhiu nn nng ca n sau khi to phc gim khng ng k so vi nng ban
u. V vy c th coi:
[L] = C
L
V vic tm nng cn bng ca cc cu t theo phng trnh (5.15); (5.16);
(5.17); (5.18) tr nn d dng.
Th d 5.3. Tnh nng cn bng ca cc ion v phn t phc cht trong dung
dch Cd (ClO
4
)
2
10
3
M v KI 1M. Trong dung dch c HClO
4
Cd
2+
khng to
phc vi ion OH

.Hng s bn tng cng ln lt phc Cd


2+
vi I
_
: 10
2,88
; 10
3,92
;
10
5,00
; 10
6,10
.
Cd
2+
phn ng vi I

hnh thnh cc phc sau: CdI
+
, CdI
2
, v

3
CdI
2
4
CdI
Theo nh lut bo ton khi lng:
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= [Cd
o
Cd
C
2+
] + [CdI
+
] + [CdI
2
] + [ ] + [ ] = 10

3
CdI
2
4
CdI
3
M
Phng trnh bo ton khilng ca I

= [I
o
I
C

] + [CdI

] + 2[CdI
2
] + 3[ ] + 4 [ ] = 1,0 M

3
CdI
2
4
CdI
Do nng cn bng ca cc ion phc << [I

]
ban u
= 1 M
Theo cng thc (5.15) ta c:
[Cd
2+
] =
4 1 6 3 5 2 92 3 88 2
3
1 10 1 10 1 10 1 10 1
10
. . . .
, , ,
+ + + +

= 10
9,13
mol/l
p dng cng thc (5.16):

[CdI
+
] =
4 1 6 3 5 2 92 3 88 2
3 88 2
1 10 1 10 1 10 1 10 1
10 1 10
. . . .
. .
, , ,
,
+ + + +

= 10
6,25

Tnh tng t ta c cc gi tr sau:
[CdI
2
] = 10
5,21
mol/l; [ ] = 10

3
CdI
4,3
mol/l; [ ] =10
2
4
CdI
3,03
mol/l

Nh vy trong dung dch c d I

ion Cd
2+
ch yu tn ti di dng phc bc
cao nht.
Th d 5.4. Tnh nng cn bng cc ion v phn t trong dung dch Cd (NO
3
)
2

0,01M v HCl 1M. Trong dung dch Cd
2+
to phc vi phi t Cl

c hng s bn
tng cng
1
= 10
1,95
;
1,2
= 10
2,49
;
1,5
= 10
2,34
;
1,4

= 10
1,64.
Phn ng to phc:
Cd
2+
+ Cl

CdCl
+
CdCl
+
+ Cl

CdCl
2
CdCl
2
+ Cl

3
CdCl
+ Cl

3
CdCl



2
4
CdCl
= [Cd
o
Cd
C
2+
] + [CdCl
+
] + [CdCl
2
] + [ ] + [ ] = 10

3
CdCl
2
4
CdCl
2
= [Cd
o
Cd
C
+
2+
] . (1+
1
[Cl

] +
1, 2
[Cl

]
2
+
1, 3
[Cl

]
2
+
1, 2
[Cl

]
3
+
1,4
[Cl

]
4
)
p dng cng thc (5.15) vi [Cl

] = 1,0 M; [Cd
2+
] = 1,0.10
2
M

[Cd
2+
] =
4 64 1 3 343 2 2 49 2 95 1
2
1 10 1 10 1 10 1 10 1
10
. . . .
, , , ,
+ + + +

= 1,5.10
5
M
95
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p dng cng thc (5.16):

[CdCl
+
] =
4 64 1 3 343 2 2 49 2 95 1
95 1 2
1 10 1 10 1 10 1 10 1
1 10 10
. . . .
. .
, , , ,
,
+ + + +

= 1,3.10
3
M
p dng cng thc (5.16), (5.17), (5.18) ta tm c:
[CdCl
2
] = 4,7.10
3
M; [ ] = 3,3.10

3
CdCl
3
; [ ] = 6,6.10
2
4
CdCl
4
M
5.3. S to phc ca etylendiamintetra axetic axit vi cc
ion kim loi.
Mt trong cc axit aminopoli carboxilic c ng dng rng ri v trc nht
trong phn tch th tch xc nh nng cc ion kim loi l axit etylendiamin-
tetra axetic (k hiu EDTA)(H
4
Y).
Cng thc cu to ca EDTA:

H
+
H
+
HO
2
CCH
2
O
2
CCH
2
CH
2
N N
CH
2
CO
2
H
CH
2
CO
2
CH
2

Trong phn t EDTA c 2 nguyn t nit v 4 nhm cacboxyl cha cc cp
electron cha lin kt c kh nng to lin kt phi tr vi cc ion kim loi. Cc loi
thuc th hu c cha hai hay nhiu nhm c kh nng to phc vi ion kim loi
c gi l tc nhn to Chelat (vng cng). Phc to thnh c gi l phc
Chelat. Phng php chun ng dng cc tc nhn to phc Chelat gi l phng
php chun Chelat hay chun complexon.
EDTA l mt a axit c 4 nc phn li:
H
4
Y H
+
+ H
3
Y

;

= 1,10.10
1
a
K
2
=
] Y H [
] Y H ][ H [
4
3
+


(5.19)
H
3
Y

H
+
+ H
2
Y
2
;

= 2,2.10
2
a
K
3
=
] Y H [
] Y H ][ H [

+
3
2
2


(5.20)
H
2
Y
2
H
+
+ HY
3
;

= 6,9.10
3
a
K
7
=
] Y H [
] HY ][ H [

+
2
2
3


(5.21)
HY
3
H
+
+ Y
4
;

= 5,5.10
4
a
K
11
=
] HY [
] Y ][ H [

+
3
4


(5.22)
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EDTA t tan trong nc, v vy thng dng mui dinatri Na
2
H
2
Y c gi l
complexon III hay trilon B. EDTA to phc bn vi nhiu ion kim loi, c t l mol
1 : 1. bn ca phc EDTA vi cc ion kim loi ph thuc rt nhiu vo pH. V
vy, cc php chun complexon thng c tin hnh khi c mt cc cht c
kh nng duy tr pH dung dch m.
Khi pH thay i cc dng ca H
4
Y thay i theo. Hnh 5.1 ch r cc dng tn
ti EDTA ph thuc vo pH.

1,0 -
0,8 -
0,6 -
0,4 -
0,2 -
H
4
Y
H
3
Y
H
2
Y
HY
Y
4
3
2
0 2 4 6 8 10 12 14
pH







Hnh 5.1. Cc dng tn ti ca EDTA ph thuc vo pH
Nu gi l tng nng cc dng ca H
Y H
C
4
4
Y trong dung dch tr dng
phc kim loi vi EDTA.
= [Y
Y H
C
4
4
] +

[HY
3
] + [H
2
Y
2
] + [H
3
Y

] + [H
4
Y] (5.23)
T cc phng trnh (5.19) n (5.22) ta suy ra:
[HY
3
] =
4
4
a
K
] Y ][ H [
+
(5.24)
[H
2
Y
2
] =
3
3
a
K
] HY ][ H [
+
=
4 3
4 2
a a
K K
] Y [ ] H [
+
(5.25)
[H
3
Y

] =
2
2
2
a
K
] Y H ][ H [
+
=
4 3 2
4 3
a a a
K K K
] Y [ ] H [
+
(5.26)
[H
4
Y] =
1
2
3
a
K
] Y H ][ H [
+
=
4 3 2 1
4 4
a a a a
K K K K
] Y [ ] H [
+
(5.27)
Thay cc gi tr t (5.24) n (5.27) vo (5.23):
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= [Y
Y H
C
4
4
]

+ + + +
+ + + +
4 3 2 1 4 3 2 4 3 4
4 3 2
1
a a a a a a a a a a
K K K K
] H [
K K K
] H [
K K
] H [
K
] H [
(5.28)
t
4
=
Y H
C
] Y [
4
4
(5.29)

4
=
4 3 2 1 3 2 1 2 1 1
4 3 2 1
2 3 4
a a a a a a a a a a
a a a a
K K K K ] H [ K K K ] H [ K K ] H [ K ] H [
K K K K
+ + + +
+ +
(5.30)
t D = (5.31)
4 3 2 1 3 2 1 2 1 1
2 3 4
a a a a a a a a a a
K K K K ] H [ K K K ] H [ K K ] H [ K ] H [
+ + + +
+ +

4
=
D
K K K K
a a a a
4 3 2 1
(5.32)
Cn c vo cng thc (5.32) chng ta c th tm c gi tr
4
pH khc nhau.
Bng 5.1. Gi tr
4
ca EDTA cc pH khc nhau.
pH

4
pH

4
2,00 3,7.10
14
7,00 4,8.10
4
3,00 2,5.10
11
8,00 5,4.10
3
4,00 3,6.10
9
9,00 5,2.10
2
5,00 3,5.10
7
10,00 3,5.10
1
6,00 2,2.10
5
11,00 8,5.10
1


12,00 9,8.10
1
Th d 5.4. Tnh nng Ca
2+
trong dung dch gm c 100,00 ml dung dch Ca
2+

0,1000 M v 100,00 ml EDTA 0,1000 M pH = 10,0; hng s bn phc CaY
2
:
5,0.10
10
.

Phn ng to phc Ca
2+
vi EDTA:
Ca
2+
+ Y
4
CaY
2
(1)

Y
4
+ H
+
HY
3
(2)

HY
3
+ H
+
H
2
Y
2
(3)

H
2
Y
2
+ H
+
H
3
Y

(4)
H
3
Y

+ H
+
H
4
Y

(5)

98
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=
/
CaY

2
] Y ][ Ca [
] CaY [
/ +

2
2
(6)
/
CaY

2
c gi l hng s bn iu kin
Ta bit: [Y
/
] =
4
4


] Y [
(7)
Thay (7) vo (6): =
/
CaY

2
] Y ].[ Ca [
] CaY [
+

4 2
2

4
= .
/
CaY

2 4
(8)
S mmol Ca
2+
c trong dung dch :
100,00 x 0,1000 = 10,00 mmol
S mmol EDTA c trong dung dch :
100,00 x 0,1000 = 10,00 mmol

Phn ng theo t l 1 : 1 nn nng CaY
2
:
[CaY
2
] =


00 200
00 10
,
,
= 0,050 M
Hng s bn phc kh ln nn c th xem nng cn bng ca Ca
2+
trong
dung dch : x = [Ca
2+
] = [Y
/
] v [Y
4
] =
4
[Y
/
], vy ta c:


x . . x
,
4
05 0

= 5,0.10
10
x = 1,7.10
6
M
Nng Ca
2+
trong dung dch thi im cn bng: 1,7.10
6
M
Trong trng hp ion kim loi cn tham gia phn ng to phc vi cc phi t
l trong dung dch (thnh phn ca dung dch m, v d nh /NH
+
4
NH
3
) th vic
tnh ton phc tp hn. Hng s bn ca phc kim loi vi EDTA ph thuc khng
ch vo nng H
+
m cn ph thuc vo bn cht v nng cc phi t l.
Th d 5.5. Tnh hng s bn iu kin ca phc NiY
2
trong dung dch m
/NH
+
4
NH
3
bao gm NH
3
1M v NH
4
Cl 1,78 M. Bit rng trong iu kin
nng ban u ca Ni
2+
khng ng k so vi nng NH
3
. Phc ca Ni
2+
vi
Y
4
c hng s bn = 10

2
NiY
18,62
, Ni
2+
vi NH
3
c hng s bn tng cng ln lt:

1
= 10
2,67
;
1,2
= 10
2,80
;
1,3
= 10
6,40
;
1,4
= 10
7,50
v
1,5
= 10
8,40
.
Phn ng to phc:
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Ni
2+
+ Y
4
NiY
2
(1)

=
/
NiY

2
] Y ][ Ni [
] NiY [
/ / +

4 2
2
(2)
Theo nh lut bo ton khi lng:
C
Ni
= [Ni
2+/
] = [Ni
2+
] + [ ] + [ ] + [ ] +
+ 2
3
NiNH
+ 2
2 3
) NH ( Ni
+ 2
3 3
) NH ( Ni
+ [ ] + (3)
+ 2
4 3
) NH ( Ni
+ 2
5 3
) NH ( Ni
Mt khc ta c:
[H
3
O
+
] = .
+
4
NH
K
] NH [
] NH [
3
4
+
= 5,7.10
10
.
1
78 1,
= 1,00.10
9
.
pH = 9,0;
4
= 5,2.10
2


(4)
= [Ni
+ 2
Ni
C
2+/
] = [Ni
2+
] (1 +
1
[NH
3
] +
1,2
[NH
3
]
2
+


1,3
[NH
3
]
3
+
+
1,4
[NH
3
]
4
+
1,5
[NH
3
]
5
) (5)
= 1 +
3
NiNH

1
[NH
3
] +
1,2
[NH
3
]
2
+

1,3
[NH
3
]
3
+
1,4
[NH
3
]
4
+
1,5
[NH
3
]
5
(6)
Thay cc gi tr trn vo (6)
3
NiNH
= 1 + 10
2,67
+ 10
2,8
+ 10
6,4
+ 10
7,5
+ 10
8,1
= 10
8,2
= 1,88.10
8
(7)
[Ni
2+/
] = [Ni
2+
]
3
NiNH
(8)
[Y
/
] =
4
4


] Y [
(9)
Thay (8) v (9) vo (2):
=
/
NiY

2
] Y [ ]. Ni [
]. NiY [
NiNH
+


4 2
4
2
3
= .

2
NiY
3
4
NiNH


= 10
18,62
.
8
2
10 88 1
10 2 5
. ,
. ,

= 3,29.10
8,62
= 2,20.10
9
Trng hp tng qut:
Chng ta xt trng hp kim loi M
n+
ngoi phn ng to phc vi anion Y
4

ca EDTA, cn tham gia phn ng ph vi phi t L to phc ML, ML
2
, ML
3
,
ML
n
v anion Y
4
cn phn ng vi H
+
to thnh HY
3
, H
2
Y
2
, H
3
Y

, H
4
Y. Chng ta
s thnh lp biu thc tnh hng s bn iu kin trong iu kin .
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Phn ng to phc:
M
n+
+ Y
4
MY
(n4)+
(5.33)

=
/
MY
n 4

] Y ][ M [
] MY [
/ / n
) n (
+
+ 4
(5.34)
y: [M
n+
] l tng nng cc dng ca M
n+
tr phc MY
(n-4)+
.
[Y
/
] l tng nng cc dng Y
4
tr phc MY
(n4)+
[M
/
] = [M] + [ML] + [ML
2
] + + [ML
m
] (5.35)
[Y
/
] = [Y
4
] + [HY
3
] + [H
2
Y
2
] + [H
3
Y

] + [H
4
Y] (5.36)
Thay gi tr hng s bn phc gia ion kim loi M
n+
vi phi t L ( n gin
khng vit din tch).
[M
/
] = [M] +
1
[M] [L] +
1,2
[M] [L]
2
++
1,M
[M] [L]
m
= [M] (1 +
1
[L] +
1,2
[L]
2
++
1,m
[L]
m
)
t
ML
= 1 +
1
[L] +
1,2
[L]
2
++
1,m
[L]
m
[M
/
] = [M]
ML
(5.37)
Theo phng trnh (5.28) ta c [Y
/
] =
4
4


] Y [
(5.38)
Thay (5.37) v (5.38) vo (5.34):
=
/
MY
) n ( +

4
] Y [ ]. M [
]. MY [
ML
) n (


4
4
4
= .
4

n
MY
ML

4
(5.39)
T biu thc (5.39) ta thy hng s bn ph thuc vo nng [H
+
] v nng
phi t l trong dung dch cc iu kin ny thay i th hng s bn ca phc
thay i theo. c gi l hng s bn iu kin.
/
MY
) n ( 4

5.4. ng chun trong phng php chun complexon


Th d 5.6. V ng chun 100,00 ml dung dch Ca
2+
0,1000 M bng dung
dch EDTA 0,1000 M pH = 10,00. Hng s bn phc Ca
2+
vi EDTA =
5,00.10

2
CaY
10
.
V
EDTA
= 0,0 ml
[Ca
2+
] = 0,1000 M
pCa = log [Ca
2+
] = log 10
1
= 1,00
V
EDTA
= 5,00 ml
S mmol Ca
2+
c trong dung dch :
100,00 x 0,100 M = 10,00 mmol
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S mmol EDTA0,100 M thm vo:
5,00 x 0,100 M = 0,5000 mmol
S mmol Ca
2+
cn li cha phn ng:
10,00 mmol 0,5 mmol = 9,5 mmol
Nng Ca
2+
dng t do:

ml
mmol ,
105
5 9
= 0,0905 M = 9,05.10
2
M

pCa = log 9,05.10
2
= 1,04
V
EDTA
= 25,0 ml
[Ca
2+
] =
00 125
50 2 00 10
,
, ,
= 6.10
2
M
pCa = log 6,0.10
2
= 1,22
V
EDTA
= 50,0 ml
[Ca
2+
] =
00 150
00 5 00 10
,
, ,
= 0,030 M

pCa = log 3,0.10
2
= 1,48
Ti thi im tng ng, khi thm 100 ml EDTA, ton b lng canxi c
trong dung dch chuyn thnh phc CaY
2
[CaY
2
] =
mol
mmol ,
200
00 10
= 0,050 M
Gi x l nng [Ca
2+
] = [Y
4
], ti thi im cn bng [CaY
2
] = 0,0500 x,
do hng s bn phc ln nn c th b qua x cnh 0,050 M.
Hng s = 5,0.10

2
CaY
10
pH = 10,
4
= 0,35 hng s bn iu kin =
1,8.10
/
CaY

2
10
= 1,8.10
/
CaY

2
10
=
2
0500 0
x
,

x = 1,70.10
6
M = [Ca
2+
]

pCa = log 1,70.10
6
= 5,77
Sau im tng ng, khi thm d EDTA.
V
EDTA
= 150 ml
[CaY
2
] =
00 250
00 10
,
,
= 0,0400 M
=
Y H
C
4
00 250
00 100 00 150
,
0,1000 x , 0,1000 x ,
= 0,020 M

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= 1,8.10

2
CaY
10
=
020 0
0400 0
2
, ]. Ca [
,
+

[Ca
2+
] = 1,1.10
10
M

pCa = log 1,10.10
10
= 9,95

a
pH=7
pH=10
pC
V(ml) EDTA
20 40 60 80 100 120 140
12,0 -
10,0 -
8,0 -
6,0 -
4,0 -
2,0 -
0







Hnh 5.2. ng chun 100 ml dung dch Ca
2+
0,1000 M
bng dung dch EDTA 0,1000 M pH =10,0 v pH = 7.
Hng s bn ca phc complexonat kim loi ph thuc pH ca dung dch v
nng cc phi t l to phc vi ion kim loi. Hnh 5.3 biu din s ph thuc
gi tr hng s bn phc vo nng H
+
dung dch .
0,0
2,0 4,0 6,0 10,0 12,0 14,0
25,0 -
20,0 -
15,0 -
10,0 -
5,0 -
-5,0 -
-10,0 -
- 15,0 -
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o o
x
x
x
x
x
x
x
x
x
x
x
x
x x
x x
x
HgY
2-
2-
HgY
= 6,3.10
21
PbY
2-
= 1,1.10
2-
PbY
18
CaY
2-

CaY
2-
= 5,0.10
10
pH











Hnh 5.3. nh hng ca pH n hng s bn ca phc kim loi vi EDTA
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28 -
26 -
24 -
22 -
20 -
18 -
16 -
14 -
12 -
10 -
8 -
0 2 4 6 8 10 12 14
MY
n-4 lg
3+
Fe
In
Th
Hg
3+
Se
3+
3+
4+
Ga
Lu
Vo
Cu
Zn
Al
La
Fe
Mn
Co
Cd
Sm
Y , Pb
Ni
3+
3+
3+
3+
3+
2+
2+
2+
2+
2+
2+
2+
3+
3+
3+
Ca
Mg
Sr
2+
2+
2+
1
2
3
pH













Hnh 5.4. Gi tr pH thp nht c kh nng chun
hiu qu ion kim loi bng EDTA
Cn c vo th hnh 5.4 chng ta c th thy cc ion kim loi Fe
3+
, In
3+
,
Th
4+
, Se
3+
, Hg
2+
to phc bn trong mi trng c pH < 2, cc ion Ga
3+
, Lu
3+
, Ni
2+
,
Cu
2+
, Pb
2+
, Zn
2+
, Al
3+
, Cd
2+
, Co
2+
, Mn
2+
, Fe
2+
, La
3+
to phc bn trong mi trng c
pH = 4 7, cc ion Sr
2+
, Mg
2+
to phc bn trong mi trng c pH > 7.
5.5. Xc nh im cui trong phng php chun complexon
ch th mu kim loi.
xc nh im kt thc chun ngi ta phi dng mt s cht ch th
Reli v Barna ngh mt danh sch gm 200 cht mu hu c c kh nng
lm ch th trong phng php chun complexon. Chng l nhng axit baz
hu c yu, mu ca dng phc vi kim loi khc mu bn thn ch th, thay i
theo pH. V vy khi chn ch th ngi ta ph chn pH thch hp phn ng xy
ra hon ton.
Gi s k hiu Ind l dng ch th c kh nng to phc vi ion kim loi M.
Ind + M MInd (5.40)
Mt khc Ind cng phn ng vi ion H
+
to thnh HInd
2
v H
2
Ind


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Ind + H
+
HInd
2
= 10
1
a
K
11,5
HInd
2
+ H
+
H
2
Ind

= 10
2
a
K
6,30
t [Ind
/
] l tng nng cc dng ca ch th tr phc MInd
[Ind
/
] = [Ind] + [HInd
2
] + [H
2
Ind

]
[Ind
/
] = [Ind] .

+ +
+ +
2 1 2
2
1
a a a
K K
] H [
K
] H [
(5.41)
t
Ind
= 1 +
2 1 2
2
a a a
K K
] H [
K
] H [
+ +
+ (5.42)
Theo phng trnh (5.40) ta c:
=
/
MInd

] Ind ][ M [
] MInd [
/
=
Ind
] Ind ][ M [
] MInd [

(5.43)
[M] =
Ind
/
] Ind [
] MInd [


log [M] = log + log
/
MInd

Ind
log
] Ind [
] MInd [

Khi t s
] Ind [
] MInd [
thay i, mu ca hai dng ch th thay i theo, tuy nhin mt
ca chng ta ch nhn bit c khi dng ny hn dng kia 10 ln. Vy ta c:
pM = pK
/
1 (5.44)
Biu thc (5.44) ch r khong chuyn mu ca ch th kim loi. Hnh 5.5.
ch r khong chuyn mu ca ch th murexit v eriocrom T en.






Hnh 5.5. Bin i mu ch th kim loi
6,0 -
4,0 -
2,0 -
4 6 8 10 12
H
4
Ind
tm
H
3
Ind
tm
2
H
2
Ind
xanh
H
2
Ind


3
CaH
4
Ind
+
vng da
cam
CaH
3
Ind
tm


3
Ind
da cam
2
HInd
xanh
H
2
Ind

4 6 8 10 12
6,0 -
4,0 -
2,0 -
(a) (b)
MgInd

Mg(OH)
2
kt ta
8
,
0
14
a) Xc nh Ca
2+
vi ch th murexit
b) Xc nh Mg
2+
vi ch th eriocromT en (ETOO)
105
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106
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5.6. Cc phng php chun complexon
5.6.1. Phng php chun trc tip.
Phng php chun trc tip l phng php n gin nht. xc nh
trc tip cc ion kim loi, iu u tin cn phi c l phn ng gia ion kim loi
vi EDTA phi tho mn yu cu i vi cc phn ng dng trong phn tch th
tch. Khi xc nh trc tip cc ion kim loi, dung dch phn tch phi iu chnh
v gi tr pH xc nh bng dung dch m, thng thng trong thnh phn dung
dch m c cc cu t c kh nng to phc vi ion kim loi (dung dch m
NH
4
/NH
3
). Vic chun c tin hnh bng cch thm t t dung dch chun
Na
2
H
2
Y t buret n khi nhn c s thay i mu ca ch th. Da trn th tch
v nng dung dch chun Na
2
H
2
Y tiu tn chng ta c th tm c lng
cht cn xc nh c trong mu phn tch.
5.6.2. Chun ngc.
Mt s trng hp phn ng gia ion kim loi vi EDTA xy ra chm,
hoc khng tm c ch th thch hp, hoc pH chun xy ra hin tng
ion kim loi cn xc nh b kt ta nn ngi ta phi dng phng php chun
ngc. tin hnh chun ngi ta thm mt lng d chnh xc dung
dch chun EDTA vo dung dch mu phn tch,sau chun lng EDTA
d bng dung dch chun ion kim loi khc. Tt nhin phi chn ion kim loi
hng s bn to phc ca n vi EDTA nh hn hng s bn phc ion kim loi
cn xc nh vi EDTA.
Phng php chun ngc cng c p dng khi phn tch hn hp
kim loi. Th d nh lng hn hp Al
3+
v Zn
2+
trong mu phn tch trc
tin ngi ta chun tng s Al
3+
v Zn
2+
bng phng php chun ngc,
sau thm lng d NaF to phc vi Al
3+
.
NaF + AlY

+ Na
3
6
AlF
+
+ Y
4
Chun lng Y
4
c gii phng bng dung dch chun mui Zn
2+

hay Mg
2+
. T kt qu chun c th tnh c hm lng cc nguyn t
cn xc nh.

107
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5.6.3. Chun thay th.
Nu khng th chun trc tip ngi ta c th tin hnh chun ngc
hoc chun thay th. Ngi ta thm mt lng d complexonat kim loi
(thng dung complexonat magie hoc km) vo dung dch cn xc nh, xy ra
phn ng trao i gia ion kim loi cn xc nh vi complexonat:
MgY
2
+ M
2+
MY
2
+ Mg
2+



Chun lng ion kim loi c gii phng (Mg
2+
hoc Zn
2+
) bng dung
dch chun EDTA. T kt qu chun ngi ta cng tnh c hm lng
nguyn t cn xc nh.
5.6.4. Chun gin tip.
Trong mt s trng hp nguyn t cn xc nh khng c kh nng
tham gia phn ng trc tip vi EDTA. Chng hn cc anion , .
Trong cac trng hp ny ngi ta kt ta chng bng mt lng d chnh
xc mui Ba
2
4
SO
3
4
PO
2+
, sau lc b kt ta BaSO
4
(nu xc nh ), thu ton b
phn nc lc v nc ra em chun bng dung dch EDTA. Ngi ta
cng c th thu ton b kt ta BaSO
2
4
SO
4
, ra sch sau ho tan kt ta bng
lng d chnh xc dung dch EDTA. T cc kt qu chun ngi ta cng
tnh c hm lng cht cn xc nh.

108
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Chng 6
Cn bng trong dung dch to thnh hp cht t tan
v phng php chun kt ta
6.1 Cn bng trong dung dch to thnh hp cht t tan
Nt c trng ca phn ng to thnh hp cht t tan l vic hnh thnh h mi:
cht rn v dung dch (h d th). Th d, nu ta cho AgCl (rn) vo nc mt phn rt
nh AgCl tan ra:
AgCl (r) (AgCl)
dung dch
Ag
+
+ Cl


(6.1)
mt nhit nht nh mt lng xc nh AgCl tan ra (g/l) hay mol/l. Trong
dung dch tn ti cn bng: tc ho tan bng tc kt ta. Dung dch trng thi
ny c gi l dung dch bo ho, Chng ta c th vit hng s cn bng ca phn
ng T
AgCl
:
T
AgCl
= [Ag
+
] [Cl

] (6.2)
Do tan ca AgCl nh v trong dung dch khng c ion no khc nn c th
xem lc ion trong dung dch bng khng, h s hot bng 1. Nn nng bng
hot , gi tr T
AgCl
c gi l tch s tan v c gi tr khng i mt nhit v
p sut nht nh.
Th d 6.1. Tch s tan ca AgCl 25
o
C l 1,0.10

10
. Tnh nng Ag
+
v Cl



trong dung dch bo ho AgCl.

[Ag
+
] = [Cl

] = S
S
2
= 1,0.10

10
S = 1,0.10

5
M
tan ca AgCl trong nc l

1,0.10

5
M.
Trng hp tng qut khi ho tan kt ta M
m
A
n
vo nc:
M
m
A
n
mM
n+
+ nA
m

(6.3)
ho tan
kt ta
= .
n m
A M
T
m
M
a
n
A
a
Trong dung dch ngoi ion M
n+
v A
m

khng cn c ion no khc v tan ca


kt ta M
m
A
n
b, c th xem h s hot bng 1, nng bng hot :

= [M]
n m
A M
T
m
[A]
n
(6.5)
109
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T biu thc (5.4) chng ta c th ni iu kin to thnh hp cht t tan khi tch
s nng cc ion trong dung dch vt qu tch s tan ca hp cht .
Trng hp tch s tan ca cc ion trong dung dch cha vt qu tch s tan, kt
ta s tip tc hnh thnh. Dung dch trng thi ny gi l dung dch cha bo ho.
Bng 1. iu kin to thnh, ho tan kt ta.
Quan h tch s nng - tch s tan Tnh cht ca dung dch Trng thi pha rn
Tch s nng < tch s tan Cha bo ho tip tc kt ta
Tch s nng = tch s tan Bo ho Dung dch Kt ta
Tch s nng > tch s tan Qu bo ho Kt ta hnh thnh n
nh
cb
Th d 6.2. Tnh tan ca PbI
2
(g/l) nu = 7,1.10
2
PbI
T

9

PbI
2
Pb
2+
+ 2I


= [Pb
2
PbI
T
2+
] [I

]
2
Nu ta t S l tan ca kt ta PbI
2
:
S = [Pb
2+
] v [I

] = 2S
S . (2S)
2
= 7,1.10

9
S =
3
9
4
7,1.10

= 1,2.10

3
M
tan ca kt ta PbI
2
:
1,2.10

3
mol/l . 461,0 g/mol = 0,55 g/l
Th d 6.3. Tnh nng cc ion trong dung dch (trng thi cn bng) khi trn 25,0
ml dung dch AgNO
3
0,100 M vi 35,0 ml dung dch K
2
CrO
4
0,0500 M. Tnh % Ag
+

cn li trong dung dch, = 1,1.10
4 2
Ag
T
CrO

12

Phn ng to thnh kt ta:
2 Ag
+
Ag
- 2
4
CrO
2
CrO
4

S mmol AgNO
3
: 25,0 x 0,1000 = 2,50 mmol
S mmol K
2
CrO
4
: 35,0 x 0,0500 = 1,75 mmol
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Tng th tch ca dung dch 60,0 ml. S mmol cn li khng tham gia vo
phn ng kt ta:
- 2
4
CrO
1,75 mmol
2
50 2,
mmol = 0,500 mmol
Nng trong dung dch trng thi cn bng:
- 2
4
CrO
[ ] =
- 2
4
CrO
0 60
50 0
,
,
+ S = 0,0083 + S 0,0083 M
y, S l tan ca Ag
2
CrO
4
, c th xem rt nh so vi nng d.
- 2
4
CrO
[Ag
+
] = 2S
[K
+
] =
0 60
50 3
,
,
= 0,0583 M
[ ] =

3
NO
0 60
50 2
,
,
= 0,0417M
[Ag
+
]
2
[ ] = 1,1.10
- 2
4
CrO

12

[2S]
2
. 8,3.10

3
= 1,1.10

12


S =
3
12
10 4
1,1.10

8,3. x
= 5,8.10

6
M
[Ag
+
] = 2 . (5,8.10

6
) = 1,16.10

5
M
Phn trm Ag
+
cn li trong dung dch :

l
l l
mmo ,
m / mmo
50 2
1,16.10 x ml 60,0
5


x 100 = 0,028 %
6.2 Quan h tch s tan v tan ca kt ta
tan ca mt cht l nng ca cht trong dung dch bo ho. tan c
th biu din theo cc n v khc nhau g/l, mol/l. Thng thng theo n v mol/l.
tan v tch s tan c mi quan h vi nhau. Chng ta c th tnh tan t tch s
tan v ngc li. tan ph thuc vo nhiu yu t: bn cht cht tan, thnh phn
dung dch, nhit , p sut, trng thi vt l ca pha rn.
6.2.1 Tnh tch s tan t tan
Th d 6.3. Tnh tch s tan ca Ag
2
CO
3
20
o
C, bit rng nhit , tan ca n
bng 3,17.10

2
g/l. B qua tng tc ca cc ion kt ta vi cc ion ca nc.
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Ta c cn bng: Ag
2
CO
3
2Ag
+
+
2
3
CO
Gi thit = 1; = 1
2
3
CO
f
+
Ag
f
= [Ag
3 2
T
CO Ag
+
]
2
[ ]
2
3
CO
S = [ ]; [Ag
2
3
CO
+
] = 2S
(2S)
2
. S = = 4S
3 2
T
CO Ag
3
S =
3
4
T

tan ca Ag
2
CO
3
: S =
g/mol
/ g
276
3,17.10
2
l

= 1,15.10

4
mol/l
Vy = 4 . (1,15.10
3 2
T
CO Ag

4
)
3
= 6,08.10

12
Nu ta k n h s hot ca cc ion Ag
+
v
2
3
CO
Lc ion: =

0,5 (2 x 1,15.10

4
. 1
2
+ 1,15.10

4
. 2
2
) = 3,45.10

4
lg f
Ag
+

= 0,5 . 1
2

4
3,45.10

= 0,92.10

2
lg = 0,5 . 2
2
3
CO
f
2

4
3,45.10

= 3,714.10

2
f
Ag
+

= 0,80 v = 0,92
2
3
CO
f
= 4. (1,15.10
3 2
T
CO Ag

4
)
2
. 1,15.10

4
. (0,80)
2
. 0,92 = 3,582.10

12
Th d 6.5. Tnh tch s tan ca Mg(OH)
2
20
o
C bit rng 0,012g Mg(OH)
2
tan trong
1 lt H
2
O nhit .
tan ca Mg(OH)
2
nhit 20
o
C l:
S =
58
01 0,
= 2,06.10
2

4
mol/l
= [Mg
2
) OH ( Mg
T
2+
] [OH

]
2
= 2,06.10

4
. (2 . 2,06.10

4
)
2
= 3,5.10

11
Nu k n lc ion ca dung dch :
= 0,5 (2,06.10

4
. 2
2
+ 2 . 2,06.10

4
. 1
2
) = 6,18.10

4

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lg = 0,5 . 2
+ 2
Mg
f
2

4
6,18.10

= 4,97.10

2
lg = 0,5 . 1

OH
f
2

4
6,18.10

= 1,24.10

2

+
= 0,891 v = 0,751
2
Mg
f

OH
f
= 2,06.10
2
) OH ( Mg
T

4
. (2 . 2,06.10

4
)
2
(0,89) . (0,751)
2
= 1,755.10

11
T hai th d trn chng ta thy tch s tan c tnh n h s hot v tch s
tan khng tnh n h s hot (tch s tan nng ) khc nhau, nhng s khc nhau
khng nhiu, nu tan cng b th s khc nhau khng ng k.
6.2.2. Tnh tan t tch s tan.
Vic tnh tan t tch s tan ni chung n gin nhng mt s trng hp kh
phc tp do xy ra cc phn ng ph i km vi qu trnh hnh thnh cc hp cht t
tan. Php tnh s n gin ch khi b qua cc qu trnh ph hoc bit mt s gi tr
nh pH, nng cht to phc.
Th d 6.6. Tnh tan ca BaSO
4
trong dung dch bo ho BaSO
4
, bit = 1,04.10
4
BaSO
T

10
.
BaSO
4
Ba
2+
+
2
4
SO
Tch s tan b nn c th xem lc ion trong dung dch bng khng. Gi S l
tan ca kt ta BaSO
4
:
S = [Ba
2+
] = [ ]
2
4
SO
S
2
= = 1,04.10
4
BaSO
T

10
S =
10
1,04.10

= 1,01.10

5
mol/l
Th d 6.7. Tnh tan ca AgCl trong dung dch NaNO
3
0,1 M, bit T
AgCl
= 1,0.10

10
.
AgCl Ag
+
+ Cl


T
AgCl
= 1,0.10

10
= [Ag
+
] [Cl

] = S
2
(Khng tnh n lc ion ca dung dch )
S =
10
1,04.10

= 1,0.10

5
mol/l
Khi tnh n lc ion : = 0,5 (0,1 . 1
2
+ 0,1 . 1
2
) = 0,1
lg = lg f
+
Ag
f
Cl
= 0,5
1 0 1
1 0 1
2
,
,
+
= 0,12
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= f
+
Ag
f
Cl
= 0,75
T = [Ag
+
] [Cl

] . = S
+
Ag
f

Cl
f
2
.
2
Ag
f
+
S =
2
f
T
=
2
10
(o,75)
1,0.10

= 1,3.10

5
mol/l
6.3 Cc yu t nh hng n tan ca kt ta
Trong cc th d nu trn, khi tnh tch s tan v tan, chng ta gi thit cc
ion to thnh hp cht t tan khng tham gia phn ng ph vi bt k mt ion no khc
trong dung dch. Nhng trong thc t cc ion ca kt ta thng tham gia phn ng
ph (to phc), cc anion ca kt ta phn ng vi ion H
+
to thnh hp cht t phn li.
Cc phn ng ph ny gy nh hng n tan ca kt ta, Chng ta s xt ln lt
cc yu t .
6.3.1 nh hng ca ion chung
Ion chung l ion c trong thnh phn ca kt ta. Nu ta thm ion chung vo
dung dch bo ho ca kt ta, lm cho tch s nng cc ion ln hn tch s tan ,
cn bng chuyn dch v pha to thnh kt ta, lm gim tan. Chng ta s xt mt
vi th d c th.
Th d 6.8. Tnh tan ca CaC
2
O
4
trong dung dch (NH
4
)
2
C
2
O
4
5.10

2
M so snh vi
tan ca n trong H
2
O.
= 2,60.10
4 2
CaC
T
O

9
tan ca CaC
2
O
4
trong H
2
O:
S =
4 2
CaC
T
O
=
9
2,6.10

= 5,09.10

5
M
Lc ion ca dung dch khi c mt (NH
4
)
2
C
2
O
4
5,0.10

2
M
= 0,5 (0,1 . 1
2
+ 2
2
. 5,0.10

2
+ 2
2
. 5,09.10

5
+ 2
2
. 5,08.10
5
)


=

0,15
lg = lg = + 2
Ca
f
2
4 6
O C
f
0,15 1
0,15 5 0
+
2 . ,
2
= 0,55
= = 0,28 + 2
Ca
f
2
4 6
O C
f
= S (S + 5,0.10
4 2
CaC
T
O

2
) . 0,28 . 0,28 = 2,6.10

9

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Gi s S << 5,0.10

2

5,0.10

2
. S . (0,28)
2
= 2,6.10

9
S =
2 2
9
28 0 5,0.10
2,6.10
) , .(

= 6,63.10

7
M
tan ca CaC
2
O
4
trong dung dch (NH
4
)
2
C
2
O
4
5,0.10

2
M gim i 130 ln.

6.3.2 nh hng ca nng H
+
(pH)
tan ca kt ta s thay i nu cc ion ca kt ta tham gia phn ng ph vi
cc cht l c mt trong dung dch.Nng cc ion kt ta thay i,lm cho tch s
nng ca cc ion cng thay i theo.Tch s tan tm c trong iu kin mi ny
c gi l tch s tan iu kin. C ngha l tch s tan c tnh n cc yu t nh
hng n tan.
Th d 6.8. Tnh tan ca CaC
2
O
4
trong dung dch HCl 0,001 M. = 2,6.10
4 2
CaC
T
O

9
.
Cc cn bng: CaC
2
O
4


Ca
2+
+ (1)
2
4 2
O C
+ H
2
4 2
O C
+
(2)

4 2
O HC
+ H

4 2
O HC
+
H
2
C
2
O
4
(3)
H
2
O H
+
+ OH

HCl H
+
+ Cl

= [Ca
4 2
CaC
T
O
2+
] [ ] = 2,6.10
2
4 2
O C

9
(4)

Ka
1
=

]
]
4 2 2
4 2
O C [H
O [HC ] [H
+
= 6,5.10

2
(5)

Ka
2
=

]
]

+
4 2
2
4 2
O [HC
O [C ] [H
= 6,1.10

5
(6)
= [H
O
2
H
K
+
] [OH

] = 1,0.10

14
(7)
Theo nh lut bo ton khi lng:

[Ca
2+
] =

[ ] + [ ] + [H
2
4 2
O C

4 2
O HC
2
C
2
O
4
] (8)

[H
+
] =

[Cl

] + [OH

] [ ] [H

4 2
O HC
2
C
2
O
4
] (9)
[Cl

] = 0,0010 M (10)
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Ka
1
>> Ka
2
[ ] >> [H

4 2
O HC
2
C
2
O
4
] v [ ]
2
4 2
O C
[OH

] rt nh v dung dch axit.


Phng trnh trung ho in tch:
[H
+
] + 2 [Ca
2+
] = 2 [ ] + [ ] + [Cl
2
4 2
O C

4 2
O HC

] + [OH

]
Mt khc ta c:
[H
+
] = 0,0010 + [OH

] [ ] [H

4 2
O HC
2
C
2
O
4
]
= 0,0010 [ ] (11)

4 2
O HC
Theo phng trnh (4) ta c: [Ca
2+
] =
] O C [
O

4 2
CaC
4 2
T
(12)
T phng trnh (6) ta c: [ ] =
2
4 2
O C
] H [
] O HC [
+

4 2 a
2
K
(13)
Thay (13) vo (12): [Ca
2+
] =
] O HC [ K
] H .[
a
O

+
4 2
CaC
2
4 2
T
(14)
Ta c Ka
1
>> Ka
2
nn [ ] >> [H

4 2
O HC
2
C
2
O
4
] v [ ], t phng trnh (8) ta
c th vit:
2
4 2
O C
[Ca
2+
] = [ ] (15)

4 2
O HC
Thay (15) vo (11):
[H
+
] 0,0010 [ ] = 0,0010 [Ca

4 2
O HC
+
] (16)
Thay (15) v (16) vo (14):
[Ca
2+
] =
] Ca [ K
]) Ca [ , .(
a
O
+
+

2
2
CaC
2
4 2
0010 0 T

=
] Ca [ . ,
]) Ca [ , (
+
+

2 5
2 9
.10 1 6
0010 0 2,6.10

6,1.10

5
[Ca
2+
]
2
= 2,60.10

12
2,60.10

9
[Ca
2+
]
6,1.10

5
[Ca
2+
]
2
+ 6,9.10

9
[Ca
2+
] 2,60.10

12
= 0
[Ca
2+
] = 1,9.10

4
M
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Th d 6.10. Bao nhiu mol kt ta MA c ho tan trong 1 lit dung dch HCl 0,1 M
nu tch s tan ca MA bng 1,0.10

8
v K
a
ca axit HA 1,0.10

6
.
Trong dung dch c cc cn bng sau:
MA M
+
+ A

T
MA
= [M
+
] . [A

] (1)
A

+ H
+
HA K
a
=
[HA]
] [A ] [H
+
(2)
H
2
O H
+
+ OH

= [H
O
2
H
K
+
] [OH

] (3)
HCl H
+
+ Cl


Theo nh lut bo ton khi lng:
[M
+
] = [A

] + [HA] (4)
[H
+
] = [Cl

] + [OH

] [HA] (5)
Phng trnh trung ho in:
[H
+
] + [M
+
] = [A

] + [Cl

] + [OH

] (6)
Dung dch axit, HA l axit yu, v vy c th xem [A

] << [HA].
T (4) suy ra: [M
+
] = [A

] + [HA] [HA] (7)


Dung dch axit nn [OH

] rt nh nn t (5) suy ra:


[H]
+
= 0,10 + [OH

] [HA] 0,1 [HA] (8)


Theo phng trnh (1): [M
+
] =
]

[A
T
MA
(9)
T (2) suy ra: [A

] =
]
] HA [
+
[H
K
a
(10)
Thay (10) vo (9): [M
+
] =
]
] H .[
[HA K
T
a
MA
+
(11)
Theo gi thit (7) ta c: [M
+
] = [HA] (12)
T phng trnh (8) ta c: [H
+
] 0,10 [HA] 0,10 [M
+
] (13)
Thay (12) v (13) vo (11): [M
+
] =
]
]) M [ , .(
+
+

[M K
10 0 T
a
MA
(14)
[M
+
]
2
=
6
8
0 1,0.1
10 0 1

. ,
(0,1 [M
+
]
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[M
+
]
2
= 1,0.10

2
(0,10 [M
+
]
[M
+
]
2
+ 1,0.10

2
[M
+
] 1,0.10

3
= 0
[M
+
] =
2
10 4 10 0 1 10 0 1
3 2 2 2
+ + . ) . , ( . ,

[M
+
] = 0,027 M
Trong 1 lt dung dch HCl 0,10 M ho tan c 0,027 mol kt ta MA.
6.3.3 nh hng cht to phc
Th d 6.11. Tnh tan ca kt ta AgBr trong dung dch NH
3
0,020 M. Bit hng s
bn
+

2 3
Ag(NH )
= 1,7.10
7
, tch s tan ca T
AgBr
= 5,0.10

13
. Hng s baz ca NH
3
K
b
=
1,75.10

5
.

Cc cn bng xy ra trong dung dch :
AgBr Ag
+
+ Br

(1)
Ag
+
+ 2NH
3
(2)
+
2 3
) Ag(NH
NH
3
+ H
2
O + OH
+
4
NH

(3)
T
AgBr
= [Ag
+
] [Br

] = 5,0.10

13
(4)

+

2 3
Ag(NH )
=
2
2 3
) Ag(NH
] [NH ] Ag [
3
+
+
= 1,7.10
7
(5)
K
b
=
] [NH
] [OH ]
3
+
4
[NH
= 1,7.10

5
(6)
Gi S l tan ca kt ta, ta c:
S = [Br

] = [Ag
+
] + [ ] (7)
+
2 3
) Ag(NH
Theo nh lut bo ton khi lng:
[Br

] = [Ag
+
] + [ ] (8)
+
2 3
) Ag(NH
= 0,020 = [NH
3
NH
C
3
] + [ ] + 2 [Ag(NH
+
4
NH
3
)
2
] (9)
T phng trnh (3) suy ra: [ ] = [OH
+
4
NH

] (10)
Phng trnh ho in tch:
[H
+
] + [Ag
+
] + [ ] + [ ] = [OH
+
4
NH
+
2 3
) Ag(NH

] + [Br

] (11)
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Dung dch NH
3
0,020 M nn [H
+
] rt nh, c th b qua trong phng trnh (11),
thay gi tr [ ] = [OH
+
4
NH

] t (10) vo (11) ta c:
[Ag
+
] + [ ] = [Br
+
2 3
) Ag(NH

] (12)

+

2 3
Ag(NH )
rt ln nn c th xem: [Ag
+
] << [ ]
+
2 3
) Ag(NH
Phng trnh (12) chuyn thnh [ ] = [Br
+
2 3
) Ag(NH

] (13)
Nhn phng trnh (4) vi (5):

] Ag [ ] [NH
] [Ag ] [Br ]
3
+
+ +
2
2 3
) [Ag(NH
= T
AgBr
. +

2 3
Ag(NH )


2
2 3
) [Ag(NH
] [NH
] [Br ]
3
+
= 1,7.10
7
. 5,0.10

13
= 8,5.10

6
(14)

[
+
4
NH ] << [NH
3
] do K
b
nh.
[NH
3
] >> [ ] do t s
+
2 3
) Ag(NH
2
2 3
) [Ag(NH
] [NH
] [Br ]
3
+
nh (8,5.10

6
)
Nh vy c th xem [NH
3
] = 0,020 M.
T phng trnh (5) suy ra:
[ ] =
+
2 3
) Ag(NH
+

2 3
Ag(NH )
. [NH
3
]
2
[Ag
+
]
= 1,70.10
7
(0,020)
2
. [Ag
+
] (15)
Theo phng trnh (13) ta c [ ] = [Br
+
2 3
) Ag(NH

]. Vy phng trnh (15) c th
c vit li:
[Br

] = 6,8.10
3
[Ag
+
] (16)
T phng trnh (4) suy ra: [Ag
+
] =
] [Br

AgBr
T

[Br

] = 6,8.10
3

] [Br

AgBr
T

[Br

] =
13 3
.5,0.10 6,8.10
-
= 5,9.10

5
M
tan ca AgBr trong dung dch NH
3
0,020 M l 5,9.10

5
M.
S c mt tc nhn to phc trong dung dch lm hn ch hay ngn cn qu trnh
to kt ta do ion kim loi to phc vi tc nhn l. S ngn nga khng cho hnh
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thnh kt ta vi mt ion no o bng cch chuyn n thnh phc cht t phn li c
gi l s che. S che c ng dng rng ri trong ho hc phn tch. Vic che cc ion
lm cn tr n php xc nh thng hay dng trong phn tch nh lng.

Th d, khi
kt ta Ni
2+
bng dimetylglyoxim trong mi trng kim, ngi ta phi thm mt
lng axit tactric khi c mt ion Fe
3+
.
Khi kt ta Cd
2+
bng H
2
S nu c mt Cu
2+
ngi ta phi thm vo dung dch
mt t KCN (lng KCN thm vo nhiu hay t tu thuc vo lng ion Cu
2+
c mt
trong dung dch):
KCN K
+
+ CN


Cu
2+
+ CN


2Cu
+
+ (CN)
2
Cu
+
+ 4 CN



3
4
Cu(CN)
Cd
2+
+ 4CN



2
4
Cd(CN)
= 10

3
4
Cu(CN)
30,29
;

2
4
Cd(CN)
= 10
18,85
Phc bn hn phc nn khi cho H
3
4
Cu(CN)
2
4
Cd(CN)
2
S li qua dung dch th ch
c CdS c kt ta.
+ H
2
4
Cd(CN)
2
S CdS + 2CN


+ 2HCN
Th d 6.12. Tch s tan ca kt ta CuI, T
CuI
= 1,0.10

12
, hng s bn phc
( = 7,9.10

2
CuI
2
CuI


4
). Tnh tan ca kt ta CuI trong dung dch KI 1,0.10

4
M.
Cc cn bng xy ra trong dung dch :
CuI

Cu
+
+ I

(1)
CuI + I




(2)

2
CuI
Gi thit cc ion H
+
v OH

khng tham gia phn ng vi ion Cu


+
v I

.
Nu t S l tan ca kt ta CuI trong KI:
S = [Cu
+
] + [ ] (3)

2
CuI
T
CuI
= [Cu
+
] [I

] (4)

2
CuI
=
] I [
]

2
[CuI
(5)
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Theo nh lut bo ton khi lng:
[I

]
t
= C
KI
+ [Cu
+
] [ ] (6)

2
CuI
Phng trnh ho in tch: b qua [H
+
] v [OH

]

[Cu
+
] + [K
+
] = [I

] + [ ] (7)

2
CuI
Thay C
KI
= [K
+
] = 1,0.10
4
vo (6):

[I] = 1,0.10

4
+ [Cu
+
] [ ]

2
CuI

(8)
Tch s tan ca CuI nh v hng s bn ca phc cng rt nh nn c th
gi thit ([Cu

2
CuI
+
] [ ]) << 1,0.10

2
CuI

4
. Vy ta c:
[I

] = 1,0.10

4
M (9)
Thay gi tr [I

] phng trnh (9) vo (4):


[Cu
+
] =
] [I
T
CuI

=
] [1,0.10
1,0.10
4
12

= 1,0.10

8
M
Thay gi tr [I

] = 1,0.10

4
vo phng trnh (5):
[ ] =

2
CuI

2
CuI
[I

] = 7,9.10

4
. 1,0.10

4
= 7,9.10

8
M
tan ca kt ta CuI trong dung dch KI 1,0.10

4
M:
S = [Cu
+
] + [ ] = 1,0.10

2
CuI

8
+ 7,9.10

8
= 8,9.10

8
mol/l
Gi thit tan ca kt ta [Cu
+
] v [ ] nh hn rt nhiu so vi gi tr
1,0.10

2
CuI

4
M l hp l.
Th d 6.13. Tnh tan ca kt ta CuCl trong dung dch NaCl 1,0.10

4
M. Bit hng
s bn phc = 3,2.10

2
CuCl
2
CuCl

5
; T
CuCl
= 1,9.10

7
.
Cc cn bng xy ra trong dung dch :
CuCl

Cu
+
+ Cl


T
CuCl
= [Cu
+
] [Cl

] = 1,9.10
7
(1)
Cu
+
+ 2Cl

2
CuCl
=
2
CuCl

2
2
[CuCl
] Cl [ ] Cu [
]
+

= 3,2.10
5
(2)
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Nhn (1) vi (2) ta c:
T
CuCl
. = 1,9.10
2
CuCl


7
. 3,2.10
5
=

] Cl [
]

2
[CuCl
(3)
= 6,08.10
2
=
] Cl [
]

2
[CuCl


Phng trnh ho in tch:
[Cu
+
] + [Na
+
] = [Cl

] + [ ] (4)

2
CuCl
[Cl

] = [Cu
+
] + [Na
+
] [ ]

2
CuCl
=
] Cl [
T

+ C
NaCl
6,08.10
2
[Cl

]

[Cl

] =
]

[Cl
1,9.10
7
+ 1,0.10
4
6,08.10

2
[Cl

] (5)
[Cl

]
2
= 1,9.10

7
+ 1,0.10
4
[Cl

] 6,08.10

2
[Cl

]
2
[Cl

]
2
+ 6,08.10

2
[Cl

]
2
1,0.10
4
[Cl

] 1,9.10

7
= 0
[Cl

]
2
(1 + 6,08.10

2
)

1,0.10
4
[Cl

] 1,9.10

7
= 0
[Cl

]
2
1,0.10
4
[Cl

] 1,9.10

7
= 0
[Cl

] =

2
10 6 7 10 1,0.10
7 8 4
+ + . ,

=

2
10 77 8 1,0.10
4 4
+ . ,
= 4,88.10
4
(6)

[Cl

] = 4,88.10

4
mol/l
S = [Cu
+
] + [ ] =

2
CuCl
4
7
4,88.10
1,9.10

+ 6,08.10

2
.4,88.10

4
= 4,1.10

4
mol/l (7)
6.4 Kt ta phn on
Nu c hai ion kim loi M
1
v M
2
cng to kt ta vi ion A thnh hai hp cht
M
1
A v M
2
A c tch s tan khc nhau nhiu, th c th tin hnh kt ta ln lt tng
ion mt.
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Th d 6.14. Tnh nng Cl

cn li khi Ag
2
CrO
4
bt u kt ta trong dung dch
gm c NaCl 0,1 M, K
2
CrO
4
10

2
M v AgNO
3
. Tch s tan ca = 1,1.10
4 2
Ag
T
CrO

12
v
T
AgCl
= 1,0.10

10
.



AgCl bt u kt ta, nng Ag
+
cn c:
[Ag
+
] =
] [Cl
1,0.10
10

=
1
10
10
1,0.10

= 10

9
mol/l
= [Ag
4 2
Ag
T
CrO
+
]
2
[ ] = 1,7.10
2
4
CrO

12

[ ] = 10
2
4
CrO

2
= [Ag
+
] =
2
12
10
1,7.10

= 1,05.10

5

Khi Ag
2
CrO
4
kt ta, nng Ag
+
trong dung dch 1,05.10
5
mol/l v nng Cl

:
[Cl

] =
] [Ag
T
AgCl
+
=
5
10
1,05.10
1,0.10

= 9,5.10

6
Nng Cl

trong dung dch bng 9,5.10

6
mol/l, ngha l cn
1
6
10
9,5.10

x 100 =
9,5.10

3
%.
C th xem nh Cl

kt ta hon ton mi xut hin kt ta Ag


2
CrO
4
. Da trn
nguyn tc ny nh ho hoc ngi c K.F. Mohr ngh s dng K
2
CrO
4
lm
cht ch th trong phng php chun kt ta xc nh ion Cl

, Br

. Vn ny s
c trnh by trong phn tip theo.

6.5 Phng php chun kt ta
Trong thc t c rt nhiu phn ng to thnh hp cht t tan nhng ch mt s t
phn ng c ng dng trong phng php chun kt ta. Cc phn ng ny phi
tho mn cc yu cu i vi mt phn ng dng trong phn tch th tch:
Phn ng phi xy ra nhanh v hon ton (khng c hin tng to thnh dung
dch qu bo ho).
Phn ng phi chn lc. Hin tng hp ph v cng kt xy ra khng ng k.
Phi c kh nng xc nh c im tng ng. Trong s cc phn ng to
thnh hp cht t tan, quan trng nht l phn ng gia AgNO
3
vi cc ion
halogenua- c gi l phng php o bc. Chng ta s xem xt k phng php
chun ny.
6.5.1 ng chun trong phng php chun kt ta
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Th d 4.15. Tnh gi tr pCl trong qu trnh chun 100,00 ml dung dch Cl

0,100
M bng dung dch AgNO
3
0,1 M.
= 0,00 ml
3
AgNO
V
pH = lg[Cl

] = log 0,1000

= 1,000
= 20,00 ml
3
AgNO
V
S mmol Ag
+
thm vo:
20,00 ml x 0,1000 mmol/ml = 2,000 mmol
S mmol Cl


c trong dung dch ban du:
100,00 ml x 0,1000 mmol/ml = 10,000 mmol
S mmol Cl


cn li sau phn ng:
10,00 mmol 2,000 mmol = 8,000 mmol
[Cl

] =
ml ,00 120
mmol 8,000
= 0,0667 M
pCl = log 0,0667 = 1,18
= 99,00 ml
3
AgNO
V
S mmol Ag
+
thm vo:
99,00 ml x 0,1000 mmol/ml = 9,900 mmol
[Cl

] =
00 199
9,9000 10,000
,

= 5,0.10

4
M
pCl = log 5,0.10

4
= 3,26
= 99,50 ml
3
AgNO
V
S mmol Ag
+
thm vo:
99,50 ml x 0,1000 mmol/ml = 9,950 mmol
[Cl

] =
50 199
9,950 10,000
,

= 2,50.10

4
M
pCl = log 2,50.10

4
= 3,60
= 100,00 ml. Ti thi im ny Cl
3
AgNO
V


phn ng ht vi AgNO
3
.
[Cl

] =
AgCl
T =
10
10 0 1

. , = 10

5
M
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pCl = log 10

5
= 5,00
= 100,50 ml
3
AgNO
V
S mmol Ag
+
thm vo:
100,50 ml x 0,1000 mmol/ml = 10,05 mmol
Nng [Ag
+
] d sau phn ng:
[Ag
+
] =
50 200
10,00 - 10,05
,
= 0,024 M
[Cl

] =
] Ag [
+
T
=
2
10
2,40.10
1,00.10

= 4,20.10

9
M
pCl = log 4,20.10

9
= 8,38
= 110,0 ml
3
AgNO
V
S mmol Ag
+
thm vo:
110,50 ml x 0,1000 mmol/ml = 11,00 mmol
Nng [Ag
+
] d sau phn ng:
[Ag
+
] =
00 210
10,00mmol - 11,00mmol
,
= 4,76.10

3
M
[Cl

] =
] Ag [
+
AgCl
T
=
3
10
4,76.10
1,00.10

= 2,10.10

8
M
pCl = log 2,10.10

8
= 7,67









0
14,0 -
12,0 -
10,0 -
8,0 -
6,0 -
4,0 -
2,0 -
20 40 60 80 100 120 140 V(ml) AgNO
3
pCl
I
Br
Cl
125
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Hnh 6.1. ng chun 100,00 ml Cl


0,1M; Br


0,10 M; I


0,10 M
bng dung dch AgNO
3
0,100 M.
T hnh 6.1 cho chng ta thy, khi tch s tan cng b bc nhy trn ng
chun cng di.
T
AgI
= 1,0.10

16
; T
AgBr
= 4,0.10

13
v T
AgCl
= 1,0.10

10
Bc nhy trn ng chun ion cn ph thuc vo nng cc cht chun
. Trong trng hp dung dch qu long v kt ta c tan ln th php chun
khng chnh xc.
6.5.2 Cc phng php xc nh im cui trong phng php chun o bc
1 Phng php Mohr
K
2
CrO
4
c dng lm ch th trong phng php chun xc nh mt s
halogenua bng AgNO
3.
. Khi ion Cl


c kt ta hon ton, d git dung dch
AgNO
3
u tin s phn ng vi ion lm xut hin kt ta mu bc cromat
Ag
2
4
CrO
2
CrO
4

2Ag
+
+ Ag
2
4
CrO
2
CrO
4
Ti im tng ng nng Ag
+
bng 10

5
M nng ln hn
2,0.10
2
4
CrO

2
M. Chun qu nng ny c mu cromat qu m, trong thc t ngi ta
dng dung dch K
2
CrO
4
c nng 0,002 - 0,005 M. Phng php Morh c ng
dng xc nh Cl


, Br

, ch khng xc nh I, SCN


v cc ion ny s hp ph xy ra
mnh. nhy ca ch th cng ph thuc vo pH ca dung dch . Phng php Mohr
thng c tin hnh chun pH = 8. Nu dung dch chun pH < 6, mt
phn ch th tn ti dng H . Nh vy kt ta Ag

4
CrO
2
CrO
4
xut hin cn phi c
mt lng ln Ag
+
trong dung dch . Chun pH > 8, s xut hin kt ta Ag
2
O
cng vi Ag
2
CrO
4
, kh nhn im tng ng.
2 Phng php Volhard
Phng php Volhard da vo phn ng chun Ag
+
bng ion thioxianat SCN



dng ion Fe
3+
lm ch th:
Ag
+
+ SCN


AgSCN
Ti im cui chun xut hin mu ca ion phc FeSCN
2+
.
Phng php c ng dng chun trc tip thioxianat bng AgNO
3
hoc
chun cc anion halogenua (Cl

, Br

) bng phng php chun ngc - (thm d


126
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dung dch AgNO
3
ri chun Ag
+
d bng dung dch thioxianat. Phng php
thng c tin hnh trong mi trng axit HNO
3
.
X


+ Ag AgX + Ag
+
(d)
Ag
+
(d) + SCN


AgSCN
Xc nh im cui bng cch thm Fe
3+
.
Fe
3+
+ SCN


Fe(SCN)
2+
( mu)
Nu tch s tan ca AgX nh hn AgSCN th khng cn phi tch AgX trc khi
chun Ag
+
bng thioxianat. Th d khi chun I

, Br

. Tuy nhin i vi trng


hp I

, ngi ta thm AgNO


3
d trc khi thm Fe
3+
lm ch th v nu khng th Fe
3+

s oxi ho ioua.
2 Fe
3+
+ 2 I

2Fe
2+
+ I
2
Khi chun ion Cl

ngi ta phi thm AgNO


3
d kt ta ht ion Cl

di
dng AgCl. Sau lc b AgCl ra khi dung dch ri mi tin hnh chun Ag
+

bng thioxianat. Nu tin hnh chun c mt AgCl s xy ra phn ng sau:
AgCl

Ag
+
+ Cl


Ag
+
+ SCN

AgSCN
AgCl + SCN

AgSCN + Cl

Fe(SCN)
2+
+ AgCl AgSCN + Fe
2+
+ Cl



Mun xut hin mu mu phc FeSCN
2+
th phi thm lng thuc th SCN


ln hn lng cn thit.
lc kt ta AgCl d dng ngi ta phi um si huyn ph trong vi pht
nhm ng t keo AgCl v gii hp Ag
+
, hoc thm KNO
3
cht ng t keo, sau
un si trong mt vi pht.
Cng c th thm nitrobenzen vo dung dch trc khi chun Ag
+
d bng
SCN


ngn cn tc dng ca AgCl vi SCN

.
3 Phng php Fajans - Ch th hp ph
Fajans v cc cng tc vin a ra mt lot cht mu axit hu c yu c mu
sc thay i khi b hp ph vo b mt kt ta tch in. Trong dung dch cht ch th
tn ti dng ion In


. Khi chun NaCl bng AgNO
3
, trc im tng ng Cl


d,
kt ta tch in m.
(AgCl)
n
: Cl


M Na
+
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Sau im tng ng d Ag
+
, b mt kt ta tch in dng:
(AgCl)
n
: Ag
+
:

3
NO
Trc im tng ng ch th khng b hp ph vo b mt kt ta, sau im
tng ng khi c d Ag
+
, th xy ra cn bng trao i.
(AgCl)
n
, Ag
+
M + In

3
NO


(AgCl)
n
: Ag
+
M In

3
NO
Ch th b hp ph ln b mt kt ta v c mu khc vi mu ca bn thn ch th
trong dung dch . S thay i mu ny lm cho chng ta nhn bit im kt thc chun .
chnh xc ca php chun vi ch th hp ph ph thuc vo mt s yu t sau:
1. nh hng ca pH.
Cht mu b hp ph ch yu dng anion, nng ca n ph thuc vo pH, v
vy cn duy tr pH thch hp sao cho nng anion ln lm chuyn dch cn bng.
Bng 6.1. Mt vi ch th hp ph.
Cht ch th Php chun pH dung dch
Fluoretxein Cl

bng Ag
+
7 8
Diclorofluoretxein Cl

bng Ag
+
4
Bromocresol xanh SCN

bng Ag
+
4 5
Eosin Br

, I

, SCN

bng Ag
+
2
Metyl tm Ag
+
bng Cl

Dung dch axit
Rodamin 6G Ag
+
bng Br

HNO
3
0,3M
Bromophenol xanh Hg
2+
bng Cl

Dung dch 0,1 M
Ortocrom T
Pb
2+
bng
2
4
CrO
Trung tnh dung dch 0,02 M
Fluoretxin l axit yu (K
a
= 10
7
) do khng th chun pH < 7 v khi
ch th tn ti dng khng phn li, kh nng hp ph b hn ch. Diclorofluoretxein l
axit mnh hn (K
a
= 10
4
) kh nng hp ph ca anion ny mnh hn nn c th chun
pH thp. Eosin l axit cn mnh hn nn c th chun pH bng 2.


2. Tnh cht b mt ca kt ta.
S hp ph ph thuc nhiu vo din tch b mt kt ta. Nu kt ta b ng t
khi chun th cht ch th hp ph km. trnh hin tng ng t ngi ta thng
thm cht keo bo v chng ng t.
128
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Th d chun Cl

ngi ta thm dextrin, gelatin. Cng khng nn chun


dung dch qu c v d xy ra hin tng ng t.

129
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Chng 7
Cn bng oxi ho - kh
7.1 Th oxi ho - kh - Phng trnh Nernst
Phn ng oxi ho - kh l phn ng lin quan n bin i mc oxi ho cc
cht phn ng do c s chuyn electron t mt cht phn ng ny n mt cht phn
ng khc. Qu trnh trong mt cht nhng electron gi l qu trnh oxi ho.
Cht nhng electron gi l cht kh. Qu trnh ngc li mt cht nhn electron
gi l qu trnh kh. Cht nhn electron gi l cht oxi ho. Cht oxi ho nhn
electron v b kh thnh dng kh lin hp. Cht kh nhng electron v b oxi ho
thnh dng oxi ho lin hp
Mt cch tng qut:
Ox
1
+ Kh
2
Kh
1
+ Ox
2
(7.1)
y: Ox
1
b kh thnh Kh
1
.
Kh
2
b oxi ho thnh Ox
2

Ox
1
l cht oxi ho
Kh
2
: l cht kh.
Khi b oxi ho th s oxi ho tng.
Khi b kh th s oxi ho gim.
Th d: Sn
2+
+ 2Fe
3+
Sn
4+
+ 2Fe
2+
Sn
2+
2e Sn
4+
Fe
3+
+ 1e Fe
2+
Tng qut: Me
a
+

ne

Me
(a-n)+
(7.2)
Kh nng oxi ho ca mt cht c th hin qua kh nng thu nhn electron
khi tham gia phn ng oxi ho - kh. c trng cho tnh cht ny ngi ta dng
i lng th in cc hay th oxi ho - kh.
Mt cht cng d nhn electron th n c tnh cht oxi ho cng mnh, ngc
li mt cht nhng electron cng d th n c tnh kh cng mnh. Trong mt cp
oxi ho - kh lin hp nu tnh oxi ho cng mnh th tnh kh lin hp cng yu.
Chng ta tin hnh mt th nghim nh sau: em nhng mt thanh kim loi
vo dung dch mui ca n, cc cation t mng li tinh th kim loi chuyn vo
129
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dung dch nm st b mt kim loi (qu trnh oxi ho) v ngc li mt phn nh
cation kim loi trong dung dch c kh nng phng in tch thnh kim loi (qu
trnh kh). Tc cc qu trnh ny xy ra theo hng ngc chiu nhau, t gi tr
bng nhau khi h t ti trng thi cn bng ng. Khi trong mt n v thi
gian c bao nhiu ion kim loi trong dung dch phng in to thnh kim loi th c
by nhiu ion kim loi ri khi mng li i vo dung dch. iu ny dn n b
mt kim loi mang in tch m, s ht mt lng ion mang in tch tri du nm
st b mt kim loi hnh thnh lp in tch kp. Xut hin hiu in th trn b mt
phn chia kim loi dung dch .
Vic o trc tip hiu in th kim loi dung dch rt kh khn, nhng d
dng o c hiu in th gia hai h sau khi ni chng thnh nguyn t ganvanic.
Mt nguyn t ganvanic bt k cng bao gm hai bn nguyn t. Mi bn nguyn t
l mt cp oxi ho - kh.
Bng thc nghim xc nh c gi tr th oxi ho - kh ca cc cp khc nhau,
gi tr th o c khng ch ph thuc vo cng ca cc cp oxi ho - kh m
cn ph thuc vo t s nng ca chng (chnh xc hn hot ca chng). Gi tr
th o c nng dng oxi ho bng nng dng kh c gi l th oxi ho -
kh tiu chun.
xc nh th oxi ho - kh ca cc cp khc nhau ngi ta phi kt hp vi
cp tiu chun. in cc hiro c dng lm in cc tiu chun qui c th ca
cp ny bng khng.
in cc hiro tiu chun bao gm mt bnh ng dung dch H
2
SO
4
c nng
ion H
+
bng 1 ion g/l, nhng vo y mt dy dn Pt, pha cui c bn Pt ph
lp mui Pt t trong ng bo ho kh H
2
c p sut 1 atm. Th in cc hiro tiu
chun qui c bng khng.
xc nh th oxi ho - kh tiu chun ca mt cp no , th d Fe
3+
/Fe
2+

ngi ta kt hp n vi in cc hiro tiu chun trong nguyn t ganvanic.
S nguyn t ganvanic:
H
2
(Pt) / H
+
(H
+
) = 1 / / Fe
3+
, Fe
2+
(Pt)
= 1 atm
2
H
P
Theo s bn tri l in cc hiro, bn phi l in cc nghin cu. y
in cc Pt nhng vo dung dch Fe
3+
/ Fe
2+
. Hai vch / / ch s tip xc 2 pha lng
(dung dch Fe
3+
, Fe
2+
v dung dch H
+
) qua cu ni ng hnh ch U ng dung dch
KCl bo ho. Khi ni hai in cc bng dy dn c thm vn k o hiu in th.
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in cc tiu chun hiro cc m, in cc Pt l cc dng. Giai on u tin qu
trnh nhng electron ca phn t H
2
:
H
2
2e 2H
+
Cc electron s chuyn theo dy dn n cc Pt, ion Fe
3+
nhn cc electron, b
kh thnh Fe
2+
.
2 Fe
3+
+ 2e 2 Fe
2+
Phng trnh chung ca 2 qu trnh:
H
2
+ 2 Fe
3+
2 Fe
2+
+ 2H
+
Hiu in th: = + 0,77 V
o
Fe / Fe
E
+ + 2 3
o
H / H
E
2
2
+
= 0 do = + 0,77 V
o
H / H
E
2
2
+
o
Fe / Fe
E
+ + 2 3
Nu thay cp bng cp Cl
o
Fe / Fe
E
+ + 2 3 2
/2Cl

ta o c gi tr = + 1,36 V
ln hn . Hot oxi ho ca Cl
o
Cl / Cl
E
2
2
o
Fe / Fe
E
+ + 2 3 2
ln hn Fe
3+
.
T y ta suy ra th oxi ho - kh tiu chun ca mt cp cng ln th tnh cht
oxi ho cng mnh, tnh kh dng lin hp cng yu. Nh vy th ca mt cp oxi
ho - kh lin hp c th dng lm i lng o cng ca cp . ph thuc
gia th oxi ho kh ca mt cp no vo nng (hot ) ca dng oxi ho v
dng kh c biu din bng phng trnh Nernst.
E = E
o
+
nF
RT
ln
] Kh [
] Ox [
(7.4)
y: E
o
: th in cc tiu chun bng E, khi [Ox] = [Kh]
R: hng s kh 8,314 J.K
1
. mol
1
T: nhit Kelvins
n: s electron trao i.
F: s Faraday 96485 C
Ln: logarit t nhin = 2,303 log.
Thay cc gi tr v chuyn thnh logarit thp phn
E = E
o
+
n
,059 0
log
] Kh [
] Ox [
(7.5)

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Dng tng qut:
aA + bB + . . . + ne cC + dD +. . .
E = E
o

n
,059 0
log
b a
d c
] B [ ] A [
] D [ ] C [
(7.6)
Th d 7.1. Vit biu thc phng trnh Nernst mt s phn ng sau:
Zn
2+
+ 2e Zn E = +
o
Zn / Zn
E
+
2
059 0,
log [Zn
2+
]
Fe
3+
+ e Fe
2+
E = + 0,059 lg
o
Fe / Fe
E
+ + 2 3
] Fe [
] Fe [
+
+
2
3

2 H
+
+ 2e H
2
E = +
o
H / H
E
2
2
+
2
059 0,
log
2
2
H
P
] H [
+

+ 5e + 8 H

4
MnO
+
Mn
2+
+ 4 H
2
O
E = +
o
Mn / MnO
E
+ 2
4
5
059 0,
log
] [Mn
] [H ] MnO [
+
+
2
8
4

AgCl + e Ag + Cl

E = + 0,059 log
o
Ag / AgCl
E
] [Cl

1

7.2 Cc yu t nh hng n in th oxi ho - kh
Th oxi ho - kh tiu chun iu kin
Th oxi ho - kh ph thuc hot (nng ) dng oxi ho v dng kh, v
vy khi thay i hot (nng ) ca cc dng ny dn n thay i th oxi ho
kh. Cc yu t lm thay i hot dng oxi ho, dng kh thng l nng H
+

(pH), phn ng to thnh hp cht t phn li hay hp cht t tan. Th oxi ho - kh
tiu chun o c trong iu kin c gi l th oxi ho - kh tiu chun iu
kin. Chng ta s xem xt ln lt cc yu t nh hng n th oxi ho - kh.
7.2.1 nh hng nng H
+
Ion H
+
hay OH

tham gia vo nhiu bn phn ng oxi ho - kh. Chng ta c


th thay i th ca cp oxi ho - kh bng cch thay i pH ca dung dch .
Th d cp As(V)/As (III)
H
3
AsO
4
+ 2H
+
+ 2e

H
3
AsO
3
+ H
2
O (7.7)
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*) E = +
o
AsO / AsO
E
3
3
3
4
2
059 0,
log [H
+
]
2
+
2
059 0,
log
] AsO H [
] AsO H [
3 3
4 3
(7.8)
E = E
o
0,059 pH +
2
059 0,
lg
] AsO H [
] AsO H [
3 3
4 3
(7.9)
= E
/
o
E
o
0,059 pH;
y E
o
: th tiu chun ca cp . Trong dung dch HCl 0,1 M
(pH = 1) = E
3
3
3
4
AsO / AsO
/
o
E
o
0,059.
Trong dung dch tnh pH = 7 th:
= E
/
o
E
o
0,059 x 7 = E
o
0,41
Trong dung dch axit mnh H
3
AsO
4
oxi ho c I

thnh I
2
+ 2I
3
4
AsO


+ 2H
+
+ I
3
3
AsO
2
+ H
2
O
nhng trong dung dch trung tnh, ca cp bng 0,146 V b hn
th E
/
o
E
3
3
3
4
AsO / AsO
o
ca cp I
2
/2I

(E
o
I
2
/2I = 0,54 V) nn phn ng xy ra theo hng I
2
oxi ho
H
3
AsO
3
thnh H
3
AsO
4
.
+ I
3
3
AsO
2
+ H
2
O + 2I
3
4
AsO


+ 2H
+
7.2.2. nh hng ca phn ng to thnh hp cht t tan.
Nu trong bn phn ng oxi ho - kh c cha hp cht t tan, th oxi ho -
kh thay i.
Th d 7.2. Th oxi ho - kh tiu chun ca cp Cu
2+
/Cu
+
E
o
= 0,153 V. Tnh th
oxi ho - kh tiu chun iu kin ca cp Cu
2+
/Cu
+
khi c mt lng d SCN


to kt ta CuSCN. Tch s tan ca CuSCN T = 10
14,32
.
Bn phn ng oxi ho - kh.
Cu
2+
+ e

Cu
+
E = + 0,059 log
o
Cu / Cu
E
+ + 2
] Cu [
] Cu [
+
+ 2
(1)
Khi c mt lng d SCN

Cu
2+
+ e

+ SCN

CuSCN
E = + 0,059 log [SCN] [Cu
o /
Cu / Cu
E
+ + 2
2+
] (2)
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E = khi [Cu
o /
E
2+
] [SCN

] = 1 (3)
Mt khc [Cu
+
] [SCN

] = T
CuSCN
(4)
Chia (3) cho (4)
] Cu [
] Cu [
+
+ 2
=
CuSCN
T
1
(5)
Thay (5) vo (1):
= + 0,059 log
/
o
E
o
E
CuSCN
T
1
(6)
= 0,153 0,059 log T
/
o
E
CuSCN
= 0,153 0,059 lg 10
14,32
= 0,998 V
Do to thnh kt ta CuSCN m th E
o
tng gn 7 ln.
7.2.3 nh hng ca phn ng to thnh hp cht t phn li

Trong trng hp dng oxi ho hoc dng kh hay c hai tham gia vo phn
ng to phc vi phi t l c trong dung dch th th oxi ho - kh thay i, mc
thay i ph thuc vo bn ca phc cht to thnh.
Th d 7.3. Tnh th oxi ho - kh ca bn phn ng Cu
2+
/Cu
+
khi c mt NH
3
1M.
Nu trong dung dch c mt NH
3
, to phc vi Cu
2+
v Cu
+
.
Cu
2+
+ 4 NH
3
;
+ 2
4 3
) NH ( Cu
2
= 5,62.10
11

Cu
+
+ 2 NH
3
;
+
2 3
) NH ( Cu
2
= 7,20.10
10

Bn phn ng oxi ho - kh khi c mt NH
3
+ e + 2NH
+ 2
4 3
) NH ( Cu
+
2 3
) NH ( Cu
3

*) E = + 0,059 lg
/
o
E
2
2 3
2
4 3
] [NH ] ) NH ( Cu [
] ) NH ( Cu [
3
+
+
(1)
Khi khng c NH
3
:
Cu
2+
+ e Cu
+
E = E
o
+ 0,059 lg
] Cu [
] Cu [
+
+ 2
(2)
T gi tr hng s bn ca phc Cu
2+
v Cu
+
vi NH
3
ta suy ra:
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[Cu
+
] =
2
3
10
2 3
10 20 7 ] NH [ . ,
] ) NH ( Cu [
+
(3)
[Cu
2+
] =
4
3
11
2
4 3
10 62 5 ] NH [ . ,
] ) NH ( Cu [
+
(4)
Thay (3) v (4) vo (2)
*) E = E
o
+ 0,059 log
4
3 2 3
2
3
2
4 3
] NH .[ 5,62.10 . ] ) NH ( Cu [
] NH .[ 7,20.10 . ] ) NH ( Cu [
11
10
+
+

= E
o
+ 0,059 log
11
10
5,62.10
7,20.10
+ 0,059 log
2
2 3
2
2
4 3
] [NH ] ) NH ( Cu [
] ) NH ( Cu [
3
+ +
+

E = khi [ ] = [ ]; NH
/
o
E
+ 2
4 3
) NH ( Cu
+
2 3
) NH ( Cu
3
= 1 M
E = = E
/
o
E
o
+ 0,059 log
11
10
5,62.10
7,20.10
= 0,100 V
Khi c mt NH
3
to phc vi Cu
2+
v Cu
+
th th gim t 0,153 V
xung 0,100 V. Tuy nhin y mc gim khng nhiu do nng Cu
o
Cu / Cu
E
+ + 2
2+
v Cu
+

u gim tng ng vi mc to phc ca c Cu
2+
v Cu
+
.
Th d 7.4 Hng s bn phc Fe
3+
v Fe
2+
vi EDTA:
=1,3.10

FeY
25
; = 2,1.10
2
FeY

14
Hy tnh ca cp Fe
/
o
E
3+
/Fe
2+
c mt EDTA.
T gi tr hng s bn ca phc Fe
3+
v Fe
2+
vi EDTA ta c:
Fe
3+
+ e = Fe
2+
FeY


+ e FeY
2



E = + 0,059 lg
/
o
E
] [FeY
] [FeY
2


[Fe
3+
] =
] [Y 1,3.10
] [FeY
25

4
v [Fe
2+
] =
] [Y 2,1.10
] [FeY
14

4
2

Th oxi ho - kh ca bn phn ng Fe
3+
/Fe
2+
E = E
o
+ 0,059 log
] [Fe
] [Fe
+
+
2
3

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= 0,77 + 0,059 lg
] [Fe
] [Fe
+
+
2
3

Thay gi tr nng Fe
3+
v Fe
2+
vo
E = 0,77 + 0,059 log
] [Y . , ]. [FeY
] [Y . , ]. [FeY


4 14 2
4 25
10 1 2
10 3 1

E = 0,77 + 0,059 log
14
25
10 1 2
10 3 1
. ,
. ,
+ 0,059 log
] [FeY
] [FeY

2

E = = 0,77 + 0,059 log
/
o
E
14
25
10 1 2
10 3 1
. ,
. ,
khi [FeY

] = [FeY
2
]
= 0,77 + 0,059 log 6,20.10
/
o
E
10
= 0,13 V
Th ca cp Fe
3+
/Fe
2+
gim t 0,77V xung cn 0,13 V do Fe
3+
v Fe
2+

tham gia phn ng to phc bn vi EDTA.
7.3 Hng s cn bng ca phn ng oxi ho - kh
Th d 7.5. Tnh hng s cn bng ca h phn ng:
Cu/Cu
2+
(0,0200 M) / / Ag
+
(0,0200 M) / Ag
Cu
2+
+ 2e Cu (r) E
o
= 0,33 V
Ag
+
+ e

Ag (r) E
o
= 0,799 V
E
mch
= E
catot
E
anot
, khi t cn bng th E ca h bng khng E
catot
= E
anot
=
E
Ag
+ = E
Cu
2+
Cu + 2 Ag
+
2 Ag + Cu
2
Chng ta c: K
cb
=
2
2
] [Ag
] [Cu
+
+


o
Ag
E
+
2
059 0,
log
2
1
] [Ag
+
=
o
Cu
E
+ 2
2
059 0,
log
] [Cu
+ 2
1

=
o
Ag
E
+
o
Cu
E
+
2
059 0,
log
2
1
] [Ag
+

2
059 0,
log
] [Cu
+ 2
1

=
o
Ag
E
+
o
Cu
E
+
2
059 0,
log
2
1
] [Ag
+
+
2
059 0,
log [Cu
2+
]
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log
2
2
] [Ag
] [Cu
+
+
= log K
cb
=
059 0
2
2
,
) E E (
o
Cu
o
Ag
+ +


K
cb
=
059 0
2
2
10
,
) E E (
o
Cu
o
Ag
+ +


K
cb
= 10
15,61
= 4,1.10
15
Th d 7.6. Tnh hng s cn bng ca phn ng:
2 + 3 Mn

4
MnO
2+
+ 2 H
2
O 5 MnO
2
+ 4H
+
2 + 8 H

4
MnO
+
+ 6 e 2 MnO
2
+ 4 H
2
O; E
o
= + 1,695 V
3 MnO
2
+ 12 H
+
+ 6 e 3 Mn
2+
+ 6 H
2
O; E
o
= +1,23 V
Khi h t cn bng: =

4
MnO
E
2
MnO
E
1,695
6
059 0,
log
8
1
] [H ] [MnO
4
+
= 1,23
6
059 0,
log
12
3 2
] [H
] [Mn
+
+


059 0
23 1 6
,
) , (1,695
= log
8
1
] [H ] [MnO
4
+
+ log
3 2
12
] [Mn
] [H
+
+


059 0
23 1 6
,
) , (1,695
= log
8 3 2
12
] [H ] [Mn ] [MnO
] [H
2
4
+ +
+

lg K
cb
= log
3 2
4
] [Mn ] [MnO
] [H
2
4
+
+
= 47,1
K
cb
= 10
47
Trng hp tng qut:
b A
kh
+ a B
ox
bA
ox
+ a B
Kh
(7.10)
b A
ox
+ ba e

bA
Kh

a BB
ox
+ ba e aB

Kh

Khi t cn bng: E
A
= E
B
E = +
o
A
E
ab
,059 0
log
b
Kh
b
ox
] A [
] A [
= +
o
B
E
ab
,059 0
log
a
Kh
a
ox
] B [
] B [

=
o
B
E
o
A
E
ab
,059 0
log
a
ox
b
Kh
a
Kh
b
ox
] B [ ] A [
] B [ ] A [
=
ab
,059 0
K
cb

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log K
cb
=
059 0,
) E E ( ab
o
A
o
B

(7.11)
K
cb
=
059 0
10
,
) E E ( ab
o
A
o
B


7.4 Cht oxi ho v cht kh a bc
Cht oxi ho v cht kh a bc l cht c th b kh hay b oxi ho theo
nhiu nc.
Th d Vanadi ho tr VI ( ) l cht oxi ho a bc, c th b kh ln lt
xung V(IV); V(III); V(II) v V(0).
+ 2
2
VO
+ 2e + 2H
+
2
VO
+
VO
2+
+ H
2
O = + 1,00 V (7.12)
o
E
1
VO
2+
+ e + 2H
+
V
3+
+ H
2
O; = + 0,337 V (7.13)
o
E
2
V
3+
+ e V
2+
= 0,255 V (7.14)
o
E
3
V
2+
+ 2e V(0) = 1,18 V (7.15)
o
E
4
Mn(VII) cng l cht oxi ho a bc b kh xung Mn(VI), V(IV), Mn(II).
+ e = + 0,52 V

4
MnO
2
4
MnO
o
E
1
+ 2e + 2 H
2
4
MnO
2
O MnO
2
+ 4OH

= + 0,38 V
o
E
2
MnO
2
+ 4H
+
+ 2e Mn
2+
+ 2H
2
O

= + 1,23 V
o
E
3
Mn
2+
+ 2e Mn(0) = 1,29 V
o
E
4
Bit c th oxi ho - kh tiu chun ng vi hai nc th tnh c th oxi ho
- kh ca nc th ba t hai nc trn.
Th d 7.7. Bit E
o
ca cc h a ra trn (7.12), (7.13), (7.14) v (7.15). Hy tnh
E
o
ca h V(V)/V(III).
+ 2e + 2H
+
2
VO
+
V
3+
+ H
2
O
E = +
o
V / VO
E
+ + 3
2
2
059 0,
lg
] V [
] [H ] VO [
2
+
+ +
3
2
(7.16)
T cc bn phn ng oxi ho - kh nu ra trn chng ta c th vit:
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E = + 0,059 lg
o
VO / VO
E
+ + 2
2
] VO [
] [H ] VO [
2
+
+ +
2
2
(7.17)
E = + 0,059 lg
o
V / VO
E
+ + 3 2
] V [
] [H ] VO [
2
+
+ +
3
2
(7.18)
Cng phng trnh (7.17) v (7.18) vi nhau
2 E = + + 0,059 lg
o
VO / VO
E
+ + 2
2
o
V / VO
E
+ + 3 2
] V [
] [H ] VO [
2
+
+ +
3
2
(7.19)
E =
2
3 2 2
2
o
V / VO
o
VO / VO
E E
+ + + +
+
+
2
059 0,
lg
] V [
] [H ] VO [
2
+
+ +
3
2
(7.20)
So snh phng trnh (7.20) vi (7.16) ta c:
=
o
V / VO
E
+ + 3
2
2
3 2 2
2
o
V / VO
o
VO / VO
E E
+ + + +
+
= 0,6685 V (7.21)
Chng ta c th tnh t gi tr v
o
V / V
E
0 3+
o
V / V
E
+ + 2 3
o
V / V
E
0 2+
V
3+
+ 3e V
0

E = +
o
V / V
E
0 3+
3
059 0,
lg [V
3+
] (7.22)
V
3+
+ e V
2+
E = + 0,059 lg
o
V / V
E
+ + 2 3
] V [
] V [
+
+
2
3
(7.23)
V
2+
+ 2e V
0
E = +
o
V / V
E
+ 2
2
059 0,
lg [V
2+
] (7.24)
Cng phng trnh (7.23) vi (7.24) ta c:
3 E = + 2 + 0,059 lg
o
V / V
E
+ + 2 3
o
V / V
E
+ 2
] V [
] V ][ V [
+
+ +
2
2 3

E =
3
2
0 2 2 3
o
V / V
o
V / V
E E
+ + +
+
+
3
059 0,
lg [V
3+
] (7.25)
So snh phng trnh (7.22) vi (7.25) ta c:
=
o
V / V
E
0 3+
3
2
0 2 2 3
o
V / V
o
V / V
E E
+ + +
+
=
3
18 1 3 255 0 , . ,
= 1,265 V

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Chng 8
Phng php chun oxi ho - kh
8.1 ng chun oxi ho - kh
Trong qu trnh chun nng cht oxi ho v cht kh thay i, nn th
ca h cng thay i. ng biu din s ph thuc gia th vi th tch thuc th
dng c gi l ng chun . Th ti cc im chun c tnh da trn
phng trnh Nernst.
Trc im tng ng, nng cht phn tch cn d nhiu so vi nng
thuc th nn th ca h tnh theo cp oxi ho - kh cht phn tch.
Sau im tng ng, nng cht phn tch cn li v cng nh, nn th
ca h tnh theo cp oxi ho - kh ca thuc th.
Ti im tng ng, th ca h tnh theo th hai cp oxi ho - kh: cht
phn tch v thuc th. Thng c tnh theo cng thc sau:
E
t
=
Z Z
E Z E Z
o
Kh
o
ox
2 1
2 1
+
+
(8.1)
y v : th oxi ho - kh tiu chun ca cht oxi ho v cht kh.
o
ox
E
o
Kh
E
Z
1
v Z
2
: s electron nhn v cho ca cht oxi ho v cht kh.
Th d 8.1. Tnh th oxi ho - kh ca h trong qu trnh chun 50,00 ml dung
dch Fe
2+
0,0500M bng dung dch Ce
4+
0,1000M trong mi trng H
2
SO
4
1,00M.
Phn ng chun :
Ce
4+
+ Fe
2+
Ce
3+
+ Fe
3+
Fe
2+
e Fe
3+
; E
o
= +0,68 V (H
2
SO
4
1M)
Ce
4+
+ e Ce
3+
; E = 1,44 V (H
2
SO
4
1M)
Trc im tng ng th ca h tnh theo cp Fe
3+
/Fe
2+
. Sau im tng
ng th ca h tnh theo cp Ce
4+
/Ce
3+
.
Thi im ban u khi cha cho thm Ce
4+
trong dung dch ch c Fe
2+
,
lng Fe
3+
v cng b nn khng th tnh c th thi im ny.
Bt u chun = 5,00 ml.
+ 4
Ce
V
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Trong dung dch tn ti cc ion: Fe
2+
, Fe
3+
, Ce
3+
, cn lng Ce
4+
v cng nh.
Th ca h tnh theo cp Fe
3+
/Fe
2+
.
E = + 0,059 log
o
Fe / Fe
E
+ + 2 3
] Fe [
] Fe [
+
+
2
3
(1)
[Fe
3+
] =
00 55
00 5
,
1,000 x ,
[Ce
4+
]
00 55
5000 0
,
,
M (2)
[Fe
2+
] =
00 55
00 5 00 50
,
0,1000 x , 0,0500 x ,
+ [Ce
4+
]
00 55
0000 2
,
,
M (3)
Thay gi tr (2) v (3) vo (1):
E = + 0,059 log
o
Fe / Fe
E
+ + 2 3
0000 2
5000 0
,
,

= 0,68 + 0,059 log
0000 2
5000 0
,
,
= 0,64 V
Ti im tng ng:
Th ca h c tnh theo t hp th ca 2 cp oxi ho - kh.
E
t
= + 0,059 log
o
Fe / Fe
E
+ + 2 3
] Fe [
] Fe [
+
+
2
3

E
t
= + 0,059 log
o
Ce / Ce
E
+ + 3 4
] Ce [
] Ce [
+
+
3
4

2 E
t
= + + 0,059 log
o
Fe
E
+ 3
o
Ce
E
+ 4
] Ce [ ] Fe [
] Ce [ ] Fe [
+ +
+ +
3 2
4 3

Ti im tng ng ta c:
Fe
3+
= [Ce
4+
]
Fe
2+
= [Ce
4+
]
Vy: E
t
=
2
4 3
o
Ce
o
Fe
E E
+ +
+
=
2
68 0 1,44 , +
= 1,06
Sau im tng ng:
+ 4
Ce
V = 25,10 ml. Nng Fe
2+
cn li khng ng k, c th b qua. Th ca
h tnh theo cp Ce
4+
/Ce
3+
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E = + 0,059 log
o
Ce / Ce
E
+ + 3 4
] Ce [
] Ce [
+
+
3
4

[Ce
3+
] =
10 75
00 25
,
0,1000 x ,
[Fe
2+
]
10 75
5000 2
,
,
M
[Ce
4+
] =
10 75
00 50 10 25
,
0,0500 x , 0,1000 x ,
+ [Fe
2+
]
10 75
0100 0
,
,
M
E = + 0,059 log
o
Ce / Ce
E
+ + 3 4
5000 2
0100 0
,
,
= 1,30 V
Bng 8.1. Kt qu tnh th ca h khi chun 50,00 ml dung dch Fe
2+
0,0500M
bng dung dch Ce
4+
0,1000M; {H
+
] = 1,000M.
Th tch Ce
4+
thm vo (ml) E (V) Th tch Ce
4+
thm vo (ml) E (V)
5,00 0,64 25,00 1,30
15,00 0,72 25,10 1,30
20,00 0,76 26,00 1,36
24,00 0,82 30,00 1,40
24,90 1,06 40,00 1,43





Fe
2+
+ Ce
4+
Fe
3+
+ Ce
3+

U
4+
+2Ce
4+
+H
2
O + 2Ce
+ 2
2
UO
3+
+4H
+

1,5
1,3
1,1
0,9
0,7
0,5
0,3
*
*
E(V)
0 5,0 10,0 15,0 20,0 25,0 30,0
V(ml) Ce
4+
0,1000 M
Hnh 8.1. ng chun 50,00 ml dung dch Fe
2+
0,05000M v
50,00 ml U
4+
0,02500 M bng dung dch Ce
4+
0,1000 M
142
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Th d 8.2. V ng chun 50,00 ml dung dch U
4+
0,050M bng dung dch
KMnO
4
0,0200M, [H
+
] = 1,0 M.
Phn ng chun :
2 + 5U

4
MnO
4+
+ 2H
2
O 2Mn
2+
+ 5 + 4 H
+ 2
2
UO
+
(1)
Phn ng oxi ho kh:
+ 5e + 8H

4
MnO
+
Mn
2+
+ 4H
2
O
E = +
o
Mn / MnO
E
+ 2
4
5
059 0,
lg
] Mn [
] H [ ] MnO [
+
+
2
8
4
(2)
U
4+
2e + 2H
2
O + 4H
+ 2
2
UO
+
(3)
E = +
o
U / UO
E
+ + 4 2
2
2
059 0,
lg
] U [
] H ][ UO [
+
+ +
4
4 2
2
(4)
[H
+
] = 1,0 M
Trc im tng ng th ca h c tnh theo cp /U
+ 2
2
UO
4+

E = +
o
U / UO
E
+ + 4 2
2
2
059 0,
lg
] U [
] UO [
+
+
4
2
2
(5)
Khi = 0,00 ml, [ ] 0 nn khng tnh c th ca h.
4
KMnO
V
+ 2
2
UO
Khi = 10,00 ml.
4
KMnO
V
S mmol KMnO
4
0,020 M thm vo:
10,00 ml x 0,0200 M = 0,2000 mmol
S mmol U
4+
c trong dung dch ban u:
50,00 ml x 0,0500 M = 2,500 mmol
Nng U
4+
cn li sau phn ng:
[U
4+
] =
ml ,
MnO mmol
U mmol
2
5
. mmol 0,2 mmol ,
4
00 60
5000 2
4


+
= 3,33.10
2
M (6)
Nng to thnh sau khi thm 10,00 ml KMnO
+ 2
2
UO
4
0,0200 M:
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[ ] =
+ 2
2
UO
ml ,
Mn mmol
UO mmol
2
5
x mmol ,
2
2
2
00 60
2000 0

+
+
= 8,33.10
3
M (7)
Thay cc gi tr (6) v (7) vo (5):
E = +
o
U / UO
E
+ + 4 2
2
2
059 0,
log
2
3
10 33 3
10 33 8

. ,
. ,
= 0,316 V
Tnh tng t nh trn ta tm c gi tr th ca h cc thi im thm
25,00; 49,00; 49,90 ml KMnO
4
0,0200 M.
Khi thm 50,00 ml KMnO
4
0,0200M. Ton b lng U
4+
b oxi ho chuyn
thnh , th ca dung dch c tnh theo th ca hai cp:
+ 2
2
UO
E = +
o
U / UO
E
+ + 4 2
2
2
059 0,
log
] U [
] H [ ] UO [
+
+ +
4
4 2
2
(8)
E = +
o
Mn / MnO
E
+ 2
4
5
059 0,
log
] Mn [
] H [ ] MnO [
+
+
2
8
4
(9)
+
[H
+
] = 1,00M
2 E = 2 + 0,059 log
o
U / UO
E
+ + 4 2
2
] U [
] UO [
+
+
4
2
2
(10)
5 E = 5 + 0,059 log
o
Mn / MnO
E
+ 2
4
] Mn [
] MnO [
+

2
4
(11)
Ti im tng ng ta c:
[ ] =
+ 2
2
UO
2
5
[Mn
2+
] (12)
[U
4+
] =
2
5
[ ] (13)

4
MnO
Cng hai phng trnh (10) v (11) vi nhau:
7 E = 2 + 5 + 0,059 log
o
U / UO
E
+ + 4 2
2
o
Mn / MnO
E
+ 2
4
] Mn ][ U [
] MnO ][ UO [
+ +
+
2 4
4
2
2
(14)
Thay cc gi tr (12) v (13) vo (14) v gin c:
7 E = 2 + 5
o
U / UO
E
+ + 4 2
2
o
Mn / MnO
E
+ 2
4
144
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E =
7
5 2
2
4
4 2
2
o
Mn / MnO
o
U / UO
E E
+ + +
+
(15)
E =
7
2 1,51 x 5 0,334 x +
= 1,17 V (16)
Sau khi thm 50,10 ml KMnO
4
0,0200M:
Lng U
4+
xem nh phn ng ht vi KMnO
4
, th ca dung dch c tnh
theo cp /Mn

4
MnO
2+
:
E = +
o
Mn / MnO
E
+ 2
4
5
059 0,
log
] Mn [
] [H ] MnO [
8
+
+
2
4
(17)
[H
+
] = 1M
S mmol KMnO
4
thm vo:
50,10 ml x 0,0200 = 1,0020 mmol
S mmol Mn
2+
to thnh:
50,00 ml x 0,0500 x
5
2
= 1,0000 mmol
Tng th tch dung dch : 100,10 ml
[ ] =

4
MnO
dch 10 100
1 0020 1
dung ml ,
mmol ,0000 mmol ,
=
10 100
0020 0
,
,
M
[Mn
2+
] =
10 100
0000 1
,
,
M
E = 1,51 +
5
059 0,
log 0,002 = 1,48 V (18)
Bng 8.2. Gi tr th ca dung dch 50,00 ml U
4+
0,0500M sau khi thm
KMnO
4
0,0200M; [H
+
] = 1,0M
Th tch KMnO
4
0,0200M
thm vo (ml)
E (V) Th tch KMnO
4
0,0200M
thm vo (ml)
E (V)
10,00 0,316 50,00 1,17
25,00 0,334 50,10 1,48
49,00 0,384 55,00 1,49
49,90 0,414 60,00 1,50
145
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0
10 20 30 40 50 60
1,5 -
1,0 -
0,5 -
0,1 -
E (V)









V (ml) 0,02M

4
MnO
Hnh 8.2. ng chun 50,00 ml dung dch U
4+
0,0500M
bng dung dch KMnO
4
0,0200M; [H
+
] = 1,0M.
T cc th d nu ra trn, chng ta thy khong bc nhy trn ng chun
ph thuc vo gi tr hng s cn bng phn ng hay hiu s th oxi ho - kh
ca 2 cp (cht phn tch v dung dch chun). Hiu s th oxi ho - kh cng ln
hoc bng s cn bng ca phn ng cng ln th bc nhy cng di. Hnh 8.3 ch
r nh hng mc hon ton ca phn ng n khong bc nhy trn ng
chun .
1
,
0
0
,
80
0
,
60
0
,
40
0
,
20
0
E (V)
A
B
C
D
E
0
10,0 20,0 30,0
V(ml)
cht chun 0,1000M
E
T
E K
o
A cb
A 1,00 V 8.10
16
B 0,80 V 3.10
13
C 0,60 V 1.10
10
D 0,40 V 6,0.10
6
E 0,20 V 2,0.10
3









Hnh 8.3. nh hng ca hng s cn bng phn ng v hiu s th
oxi ho - kh n khong bc nhy trn ng chun .
146
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8.2 Chun a bc
Trong trng hp cht cn xc nh l mt h oxi ha - kh nhiu bc c th
in cc khc xa nhau th c th chun tng nc nh trong trng hp chun
a axit bng kim.
Th d 8.3. Hy thnh lp biu thc tnh th oxi ha - kh trong qu trnh chun
V
o
(ml) dung dch V
2+
c nng C
o
mol/l bng dung dch KMnO
4
C mol/l; [H
+]
=
1,0M.
Vanadi c cc trng thi oxi ha - kh khc nhau V(II); V(III); (V(IV) v
V(V) vi th in cc tiu chun.
V
3+
+ e V
2+
; = 0,255 V
o
V / V
E
+ + 2 3
VO
2+
+ 2H
+
+ e V
3+
+ H
2
O; = + 0,337 V
o
V / VO
E
+ + 3 2
+ 2H
+
2
VO
+
+ e VO
2+
+ H
2
O; = + 1,00 V
o
VO / VO
E
+ + 2
2
Th > > v > nn V
o
VO / VO
E
+ + 2
2
o
V / VO
E
+ + 3 2
o
V / V
E
+ + 2 3
o
Mn / MnO
E
+ 2
4
o
VO / VO
E
+ + 2
2
2+
s
c chun bng dung dch KMnO
4
trong mi trng axit.
+ 5V

4
MnO
2+
+ 8H
+
Mn
2+
+ 5 V
3+
+ 4 H
2
O (1)
+ 5V

4
MnO
3+
+ H
2
O Mn
2+
+ 5VO
2+
+ 2 H
+
(2)
+ 5VO

4
MnO
2+
+ H
2
O Mn
2+
+ 5 + 2 H
+
2
VO
+
(3)
Khi bt u thm V ml KMnO
4
phn ng (1) xy ra, trong dung dch tn ti
ch yu Mn
2+
, V
2+
, V
3+
. Th ca h c tnh theo cp V
3+
/V
2+
:
E = + 0,059 log
o
V / V
E
+ + 2 3
] V [
] V [
+
+
2
3
(4)
[H
+
] = 1,0M
[Mn
2+
] =

+
o
V V
C . V
1
1
M. Theo phn ng (1) [Mn
2+
] =
5
1
[V
3+
]
[V
3+
] =

+
o
V V
C . V
1
1
5 M (5)
[V
2+
] =

o
o o
V V
C . V C V
1
1
5
M (6)
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Thay (5) v (6) vo (4):
E = + 0,059 log
o
V / V
E
+ + 2 3

C . V C V
C . V
o o 1
1
5
5
(7)
Ti im tng ng 1. Trong dung dch tn ti cc ion: V
2+
, V
3+
, Mn
2+
,
VO
2+
, th ca h tnh theo th ca cp V
3+
/V
2+
v VO
2+
/V
3+
. Phn ng (2) bt u
xy ra ng thi vi phn ng (1).
E
t1
= + 0,059 log
o
V / V
E
+ + 2 3
] V [
] V [
+
+
2
3

E
t1
= + 0,059 log
o
V / VO
E
+ + 3 2
] V [
] VO [
+
+
3
2

2 E
t1
= + + 0,059 log
o
V / V
E
+ + 2 3
o
V / VO
E
+ + 3 2
] V [ ] V [
] VO [ ] V [
+ +
+ +
3 2
2 3
(8)
E
t1
=
2
3 2 2 3
o
V / VO
o
V / V
E E
+ + + +
+
+
2
059 0,
log
] V [
] VO [
+
+
2
2
(9)
Theo phng trnh (1) ti im tng ng (1) ta c:
5 V
1
. C = V
o
. C
o
(10)
Mt khc ta c:
[ ] + [Mn

4
MnO
2+
] =
1
1
d
td o
t
V V
V C
+
[Mn
2+
] (11)
[V
2+
] + [V
3+
] + [VO
2+
] + [ ] =
+
2
VO
o
o o
V V
V C
td
+
(12)
Nng [ ] << [V
+
2
VO
3+
] v [VO
2+
] nn b qua
[V
2+
] + [V
3+
] + [VO
2+
] =
o
o o
1
V V
V C
td
+
(13)
Phng trnh bo ton electron:
5 [Mn
2+
] = [V
3+
] + 2 [VO
2+
] + 3 [ ]
+
2
VO
= [V
3+
] + 2 [VO
2+
] (14)
Thay (11) vo (14):
148
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1td
1td
5
V V
CV
o
+
= [V
3+
] + 2 [VO
2+
] (15)
Thay (10) v (13) vo (15) ta c:

1td
o o
V V
V C
o
+
= [V
2+
] + [V
3+
] + [VO
2+
] = [V
3+
] + 2[VO
2+
]
Sau khi n gin:
[V
2+
] = [VO
2+
] (17)
Thay (17) vo (9):
E
t1
=
2
3 2 2 3
o
V / VO
o
V / V
E E
+ + + +
+
(18)
Thay cc gi tr th v :
o
V / V
E
+ + 2 3
o
V / VO
E
+ + 3 2
E
t1
=
2
360 0 255 0 , , +
= + 0,0525 V
Sau im tng ng 1.
Phn ng chun xy ra nh sau:
2 + 5 V

4
MnO
2+
+ 6H
+
2Mn
2+
5 VO
2+
+ 3 H
2
O (19)
Th ca h c tnh theo cp VO
2+
/V
3+
:
E = + 0,059 log
o
V / VO
E
+ + 3 2
] V [
] VO [
+
+
3
2
(20)
Theo phng trnh (19) ta c th vit:
[VO
2+
] =
2
5
[Mn
2+
]
[Mn
2+
] =
V V
CV
o S
S
+
1
1
[VO
2+
] =
2
5

V V
CV
o S
S
+
1
1
(21)
[V
3+
] =
V V
CV / C V
o S
S o o
+

1
1
2 5
(22)
Thay (21) v (22) vo (20):
E
1
= + 0,059 log
o
V / VO
E
+ + 3 2

CV C V
CV
S o o
S
1
1
5 2
5
(23)
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Ti im tng ng 2.
Trong dung dch tn ti ch yu cc ion V
3+
, VO
2+
, . V vy th ca h
tnh theo th ca hai cp:
+
2
VO
VO
2+
/V
3+
v /VO
+
2
VO
2+
E
t2
= + 0,059 log
o
V / VO
E
+ + 3 2
] V [
] VO [
+
+
3
2
(24)
E
t2
= + 0,059 log
o
VO / VO
E
+ + 2
2
] VO [
] VO [
+
+
2
2
(25)
+
2 E
t2
= + + 0,059 log
o
V / VO
E
+ + 3 2
o
VO / VO
E
+ + 2
2
] VO [ ] V [
] VO [ ] VO [
+ +
+ +
2 3
2
2

E
t2
=
2
2
2
3 2
o
VO / VO
o
V / VO
E E
+ + + +
+
+
2
059 0,
log
] V [
] VO [
+
+
3
2
(26)
Theo nh lut bo ton khi lng:
[ ] + [Mn

4
MnO
2+
] =
V V
CV
o td
td
+
2
2
[Mn
2+
] (27)
[V
2+
] + [V
3+
] + [VO
2+
] + [ ] =
+
2
VO
o 2
o o
V V
V C
td
+
(28)
[V
2+
] << [V
3+
] v [VO
2+
], nn phng trnh (28) c vit:
[V
3+
] + [VO
2+
] + [ ] =
+
2
VO
td2
o o
V V
V C
o
+
(29)
Theo nh lut bo ton electron ta c:
5 [Mn
2+
] = [V
3+
] + 2[VO
2+
] + 3 [ ] (30)
+
2
VO
Ti im tng ng 2: 2 C
o
V
o
= 5 C.V
t2
(31)
2[V
3+
] + 2 [VO
2+
] + 2 [ ] = 5 [Mn
+
2
VO
2+
] (32)
Thay (30) vo (32):
2 [V
3+
] + 2 [VO
2+
] + 2 [ ] = [V
+
2
VO
3+
] + 2 [VO
2+
] + 3 [ ]
+
2
VO
Sau khi gin c ta c: [V
3+
] = [ ] (33)
+
2
VO
Thay (33) vo (26):
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E
t2
=
2
2
2
3 2
o
VO / VO
o
V / VO
E E
+ + + +
+
(34)
Thay cc gi tr vo (34) ta c:
E
t2
=
2
000 1 360 0 , , +
= 0,68
Sau im tng ng 2.
Phn ng chun :
3 + 5 V

4
MnO
2+
+ 4H
+
3Mn
2+
+ 5 + 2 H
+
2
VO
2
O (35)
Trong dung dch tn ti ch yu cc ion: VO
2+
, , Mn
+
2
VO
2+
th ca h c
tnh theo cp /VO
+
2
VO
2+
.
E = + 0,059 log
o
VO / VO
E
+ + 2
2
] VO [
] VO [
+
+
2
2
(36)
Ta c: [ ] =
+
2
VO
3
5
[Mn
2+
] (37)
[Mn
2+
] =
V V
CV
o S
S
+
2
2
[ ] =
+
2
VO
3
5

V V
CV
o S
S
+
2
2
(38)
[VO
2+
] =
V V
CV / C V
o S
S o o
+

2
2
3 5
(39)
Thay (38) v (39) vo (36):
E
2
= + 0,059 log
o
VO / VO
E
+ + 2
2
CV C V
CV
S o o
S
2
2
5 3
5

(40)
Ti im tng ng 3.
Trong dung dch tn ti ch yu , VO
+
2
VO
2+
, Mn
2+
v . V vy th ca
h c xc nh theo th ca 2 cp /Mn

4
MnO

4
MnO
2+
v /VO
+
2
VO
2+
.
[H
+
] = 1 M
E
t3
= + 0,059 log
o
VO / VO
E
+ + 2
2
] VO [
] VO [
+
+
2
2
(41)
E
t3
= +
o
Mn / MnO
E
+ 2
4
5
059 0,
log
] Mn [
] MnO [
+

2
4
(42)
+
6 E
t3
= + 5 + 0,059 log
o
VO / VO
E
+ + 2
2
o
Mn / MnO
E
+ 2
4
] VO [ ] Mn [
] VO [ ] MnO [
+ +
+
2 2
2 4
(43)
Theo phng trnh (3) ta c:
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[VO
2+
] = 5 [ ] (44)

4
MnO
[ ] = 5 [Mn
+
2
VO
2+
] (45)
Thay (44) v (45) vo (43):
E
t3
=
6
5
2
4
2
2
o
Mn / MnO
o
VO / VO
E E
+ + +
+
+
6
059 0,
log
] MnO [ ] Mn [
] Mn [ ] MnO [
+
+
4
2
2
4

=
6
5
2
4
2
2
o
Mn / MnO
o
VO / VO
E E
+ + +
+
(46)
Thay gi tr vo (46): E
t3
=
6
51 1 5 00 1 , x , +
= 1,425 V
Bng 7.3. Kt qu chun 50,00 ml dung dch V
2+
0,0500M
bng dung dch KMnO
4
0,0250M; [H
+
] = 1,0M.
Th tch KMnO
4
(ml) Cng thc tnh E Gi tr E (V)
5,00
E = 0,255 0,059 log
CV
CV V C
o o
1
1
5
5

0,257
9,00 --------------- 0,255
9,90 --------------- 0,254
10,00
E
t1
=
2
3 2 2 3
o
V / VO
o
V / V
E E
+ + + +
+

+ 0,052
10,10
E
1
= 0,360 0,059 log
CV
CV V C
S
S o o
1
1
5
5 2

+ 0,331
15,00
E
1
= 0,360 0,059 log
CV
CV V C
S
S o o
1
1
5
5 2

+ 0,347
19,90 ----------------- + 0,360
20,00
E
t2
=
2
2
2
3 2
o
VO / V
o
V / VO
E E
+ + + +
+

+ 0,680
20,10
E
2
= 1,00 0,059 log
CV
CV V C
S
S o o
2
2
5
5 3

+ 0,982
25,00 ------------- + 0,991
29,90 -------------- + 0,999
30,00
E
t3
=
6
5
2
4
2
2
o
Mn / MnO
o
VO / VO
E E
+ + +
+

+ 1,425
35,00
E
3
= +
o
Mn / MnO
E
+ 2
4
5
059 0,
log
V
V V
td
td Std
3
3 3


+ 1,500
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Sau im tng ng 3.
Trong dung dch tn ti ch yu cc ion , Mn
+
2
VO
2+
, . V vy th ca h
c tnh theo cp /Mn

4
MnO

4
MnO
2+
.
E
3
= +
o
Mn / MnO
E
+ 2
4
5
059 0,
lg
] Mn [
] MnO [
+

2
4
(47)
[Mn
2+
] =
V V
CV
o S
td
+
3
3
(48)
[ ] =

4
MnO
V V
C V C V
o S
td S
+

3
3 3
(49)
Thay (48) v (49) vo (47):
E
3
= +
o
Mn / MnO
E
+ 2
4
5
059 0,
lg
3
3 3
S
td S
V
V V
(50)
y: V
S3
: th tch KMnO
4
thm vo sau im tng ng 3.
V
t3
: th tch KMnO
4
thm vo ti thi im tng ng 3.
10 20 30 40
1,5 -
1,0 -
0,5 -
0,0
E (V)
- 0,5 -
V (ml) KMnO
4
0,025M










Hnh 8.4. ng chun 50,00 ml dung dch V
2+
0,0500M
bng dung dch KMnO
4
0,0250M; [H
+
] = 1,0M.
8.3 Cht ch th trong phng php chun oxi ho - kh
8.3.1 Chun khng dng cht ch th
Trong phng php chun oxi ho - kh, mt s trng hp ngi ta khng
dng ch th, mu xut hin khi d mt git dung dch chun. Th d khi chun
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mt vi cht kh bng dung dch KMnO
4
. Mu hng xut hin khu d mt git
KMnO
4
.
8.3.2 Php chun dng cht ch th
i b phn trng hp php chun oxi ho - kh phi dng ch th, c
chia lm 2 nhm:
S thay i mu khng lin quan n thay i th oxi ho - kh, cht ch th
khng tham gia phn ng vi cht oxi ho hay cht kh. Th d h tinh bt l cht
ch th trong php chun it bng dung dch Na
2
S
2
O
3
v h tinh bt to c mu
xanh vi it. Kali thioxyanat to phc mu vi Fe(III) c s dng lm ch th
khi chun Fe(III) bng dung dch Ti(III) sunfat. im cui c nhn bit bi s
mt mu phc Fe(III) vi ion SCN

.
S thay i mu ca dung dch lin quan n thay i th oxi ho - kh,
ngi ta gi ch th oxi ho - kh. Vy ch th oxi ho - kh l cht c th b oxi ho
hoc b kh thun nghch, mu dng oxi ho khc vi mu ca dng kh.
Nu chng ta k hiu dng oxi ho: Ind
ox
v dng kh Ind
kh
Ind
ox
+ ne

Ind
kh
Gi tr th oxi ho - kh c xc nh bng phng trnh Nernst:
E = +
o
Ind
ox
E
n
,059 0
log
] Ind [
] Ind [
kh
ox

y: l th oxi ho - kh tiu chun khi t s nng oxi ho bng
dng kh:
o
Ind / Ind
kh ox
E
] Ind [
] Ind [
kh
ox
= 1.
Khi ta thm vo dung dch cn chun mt vi git cht ch th oxi ho -
kh, mt gi tr th oxi ho kh c thit lp. Khi t s nng dng oxi ho v
dng kh thay i th gi tr th cng thay i, mu ca dung dch cng thay i
ph hp vi gi tr th oxi ho - kh. Nhng cng ging nh ch th dng trong
phng php chun axit baz, khng phi bt k mt s thay i mu no, mt
chng ta cng nhn bit c, m ch c th nhn bit c khi t s nng hai
dng hn km nhau 10 ln.
E = +
o /
Ind / Ind
kh ox
E
n
,059 0
log
1
10

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E = +
o
Ind
kh / ox
E
n
,059 0

E = +
o
Ind / Ind
kh ox
E
n
,059 0
log
10
1

E =
o
Ind / Ind
kh ox
E
n
,059 0

Khong chuyn mu ca ch th:
E =
o
Ind / Ind
kh ox
E
n
,059 0

Bng 8.4. Mt s cht ch th thng dng.
Cht ch th Mu dng
oxi ho
Dng kh I(V) chuyn
mu
iu kin
1,10-Phenantrolin (phc Fe(II) xanh nht 1,11 H
2
SO
4
1M
Diphenylamin sunfonic axit tm khng mu 0,85 axit long
Diphenylamin tm khng mu 0,76 axit long
Metyllen xanh xanh khng mu 0,53 axit 1M
Indigotetrasunfonat xanh khng mu 0,36 axit 1M
5-Nitro-1,10-phenatrolin xanh nht tm 1,25 H
2
SO
4
1M
mu ch th bin i r rng khi chun , sai s php chun b, khong
chuyn mu ca ch th phi nm trong khong bc nhy trn ng chun . Th
d khi chun Fe(II) bng kalidicromat K
2
Cr
2
O
7
6 Fe
2+
+ + 14H
2
7 2
O Cr
+
6 Fe
3+
+ 2 Cr
3+
+ 7 H
2
O
Bc nhy trong khong 0,94 V n 1,302 V, ch th diphenylamin chuyn
mu th E
o
= 0,760 V nn khng dng c cho php chun ny. Nhng nu
thm axit H
3
PO
4
khong bc nhy c ko di c th dng diphenylamin lm ch
th khng gp phi sai s.
Nhc im c bn ca ch th oxi ho - kh l thng gi tr th oxi ho - kh
bin i ph thuc vo pH. S thay i mu ca mt vi cht ch th xy ra tng
i chm, hay to thnh hp cht trung gian.

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Mt s cht ch th hay dng.
*) Diphenylamin c pha trong dung dch H
2
SO
4
, khi b oxi ho - kh c
chuyn thnh diphenylbenzidin mu tm.

NH N
H H
N
+ 2H + 2e
+
Diphenylamin
(khng mu)
Diphenylamin benzidin (khng mu)



N
H H
N
+ +
+ 2e
Diphenylbenzidin (tm)


Th ca diphenylbenzidin trong H
2
SO
4
0,5 1,0M c gi tri 0,76 V.
*) Axit diphenylamin sunfonic, sn phm oxi ho c mu tm. C ch phn ng
tng t nh i vi diphenylamin. Th thay i mu 0,80 V pH = 0.
*) N-phenylantranilic axit, c th thay i mu E
o
= 1,08V [H
+
] = 1,0M.
COOH
NH N
COOH
+ H + e
+

*) Feroin, Feroin l hp cht phc gia.
o-phenantrolin C
12
H
5
N
2
vi Fe(II) c mu .

N N
+ Fe
2+
N N
3
2+
Fe
o-phenantrolin
Fe(C
12
H
8
N
2
)
3
2+
mu tm


Fe(C
12
H
8
N
2
) Fe(C
+ 2
3 12
H
8
N
2
) + e
+ 3
3
tm xanh nht

Th thay i mu E
o
= 1,06V trong H
2
SO
4
hoc HCl 1M.
8.4 Mt s phng php chun oxi ho - kh ng dng
trong thc t
Trong phng php chun oxi ho - kh cht phn tch phi dng oxi ho
hoc dng kh v c kh nng phn ng nh lng vi dung dch chun ca cht
oxi ho hay cht kh. Th d xc nh Mn ngi ta phi tm cch oxi ho ton b
Mn c trong mu phn tch thnh , sau chun lng bng cht

4
MnO

4
MnO
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kh thch hp. V vy trc ht chng ta xt n mt vi cht kh v cht oxi ho
hay dng trong phng php chun oxi ho - kh.
1. Mt s cht kh thng dng
Cc kim loi v hn hng kim loi l nhng cht kh tt. Cc kim loi c s
dng dng bt, dy hay vin, hoc dng ct kh kiu Jones v kiu Waldens.

Ct kh Jones l loi cht hn hng km kim loi vi HgCl
2
:
2 Zn (r) + Hg
2+
(b) Zn
2+
+ Zn(Hg) (r)
Hn hng km thng c np vo ct thu tinh c ng knh 2 cm, chiu
di hn hng 40 50 cm. Khi cho dung dch phn tch chy qua ct kh, cht phn
tch c kh v ho tr thch hp. Th d kh Fe(III) v Fe(II), Cr(III) v Cr(II),
Ti(IV) v Ti(III), V(V) v V(II).
Ct kh Waldens bc c tnh kh trong dung dch HCl 1M, kh Fe(III)
thnh Fe(II), U (VI) v U(IV), Cu
2+
thnh Cu
+
.
Ngoi cc ct kh nu trn, cn c cc cht kh thng c ng dng trong
ho phn tch: SnCl
2
trong HCl 1M; hidrazin dng clorua hay sunfat sn phm kh
l nit khng c hi cho qu trnh phn tch. N thng c ng dng kh
As(V) thnh As(III), Sb(V) thnh Sb(III) trong mi trng axit.
2. Mt s cht oxi ho thng dng
+) Natribimutat NaBiO
3
dng bt, c tnh oxi ho mnh. N c kh nng oxi
ho nh lng Mn(II) thnh nhit phng, oxi ho Ce(III) thnh Ce(IV)
trong dung dch H

4
MnO
2
SO
4
.
+) Amonipesunfat (NH
4
)
2
S
2
O
8
. Amonipesunfat oxi ho Cr(III) thnh
trong mi trng axit, Mn(II) thnh c Ag
2
7 2
O Cr

4
MnO
+
lm xc tc, Ce(III) thnh
Ce(IV).
+) Natripeoxit Na
2
O
2
v hiropeoxit H
2
O
2
. y l nhng cht oxi ho trong
mi trng kim.
3. Mt s phng php chun oxi ho - kh
+) Phng php pemanganat.
KMnO
4
l cht oxi ho mnh, trong mi trng axit ion b kh thnh
ion Mn

4
MnO
2+
khng mu:
157
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+ 8 H

4
MnO
+
+ 5e Mn
2+
+ 4 H
2
O E
o
= 1,51V
Trong mi trng trung tnh hay axit yu b kh thnh MnO
2
.
+ 2 H

4
MnO
2
O + 3e MnO
2
+ 4 OH


E
o
= 0,588V
Pemanganat l cht oxi ho mnh, nn trong thnh phn ca n lun cha
mt lng nh MnO
2
. N cng d dng b phn hu bi cc cht kh nh cc
cht hu c c trong nc, bi ri vo nc, do nng ca dung dch
KMnO
4
mi chun b khng n nh. Ngi ta phi xc nh li sau 7 10 ngy.
Cng chnh v vy khng th chun b dung dch KMnO
4
c nng chnh xc
t lng cn ban u.
thit lp li nng KMnO
4
ngi ta thng dng dung dch chun
H
2
C
2
O
4
hay dung dch K
4
[Fe(CN)
6
].
5 + 2 + 16 H
2
4 2
O C

4
MnO
+
10 CO
2
+ 2Mn
2+
+ 8H
2
O
+) Phng php dicromat.
Kali dicromat c tnh oxi ho trong mi trng axit:
+ 14 H
2
7 2
O Cr
+
+ 6e 2Cr
3+
+ 7 H
2
O E = 1,33V
Dung dch chun K
2
Cr
2
O
7
rt bn, c th pha dung dch c nng chnh xc
t lng cn ban u. Phng php dicromat thng c ng dng xc nh nng
Fe(II). Khi chun cc cht oxi ho ngi ta thm lng d Fe(II), sau
chun lng Fe(II) d bng dung dch K
2
Cr
2
O
7
.
Th d 8.5. Ly 5 ml ru mnh pha long thnh 1 lt bng bnhg nh mc, sau
ly ra 25,0 ml thm vo 50,00 ml K
2
Cr
2
O
7
0,0200M oxi ho ru etylic thnh
CH
3
COOH theo phn ng:
3 C
2
H
5
OH + 2 + 16 H
2
7 2
O Cr
+
4Cr
o
t 3+
+ 3CH
3
COOH + 11H
2
O
Sau khi lm lnh, thm vo 20,00 ml dung dch Fe
2+
0,1253M, lng Fe
2+
d
c chun bng dung dch K
2
Cr
2
O
7
ht 7,46 ml vi ch th diphenylamin sunfonic
axit. Tnh % C
2
H
5
OH c trong ru mnh trn (46,07 g/mol).
Tng s mmol K
2
Cr
2
O
7
thm vo:
(50,00 + 7,46) ml K
2
Cr
2
O
7
x 0,0200 (mmol K
2
Cr
2
O
7
/ml) =
= 1,1492 mmol K
2
Cr
2
O
7
Lng K
2
Cr
2
O
7
phn ng vi Fe
2+
thm vo:
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20,00ml Fe
2+
x 0,1253 (mmol Fe
2+
/ml Fe
2+
)
+ 2
7 2 2
Fe mmol
O Cr K mmol
6
1
= 0,41767 mmol
Lng K
2
Cr
2
O
7
phn ng vi ru C
2
H
5
OH:
(1,1492 0,41767) mmol K
2
Cr
2
O
7
= 0,73153 mmol
Khi lng ru C
2
H
5
OH c trong mu phn tch:
0,73153 mmol K
2
Cr
2
O
7
.
7 2 2
5 2
O Cr K mmol
OH H C mmol
2
3
x 0,0460
OH H C mol m
OH H C g
5 2
5 2

= 0,050552 g C
2
H
5
OH
% C
2
H
5
OH =
ml 1000,00
ml 25,00
x mu 00 5
050552 0
ml ,
OH H C g ,
5 2
x 100 % = 40,4 %
+) Phng php it.

Iot l cht oxi ho yu. Bn phn ng oxi ho - kh
+ 2e

3
I

3I

E
o
= 0,536V
Iot t tan trong nc ( tan 20
o
C l 1,33.10
3
M), nhng d dng tan trong
KI nn ngi ta chun b dung dch it c mt KI vi lng d.
I
2
+ I

= (K = 7,1.10

3
I
2
)
Iot phn ng vi hu ht cc cht hu c, nn khng dng nt lie hoc cao su
nt cc chai ng dung dch it. Khng ng dung dch it trong chai mu sng,
oxi khng kh oxi ho iodua thnh it lm thay i nng it.
4 I

+ O
2
+ 4H
+
2 I
2
+ 2H
2
O
H tinh bt c s dng lm ch th trong phng php chun iot
thiosunfat. Khi cho h tinh bt vo dung dch iot long th xut hin mu xanh c
trng. Ngi ta tin hnh chun it bng dung dch thiosunfat n mt mu xanh.
Nhng gim sai s ca php chun , ngi ta thm h tinh bt khi gn t
im tng ng (dung dch chuyn sang mu vng rm).
Dung dch h tinh bt thng c chun b trc khi dng, thm vo mt t
cht bo v nh: HgI
2
, thimol, glixerin, focmandehit nhm hn ch hot ng ca vi
khun.
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iu kin tin hnh chun theo phng php it:
+) Cn tin hnh chun nhit phng. nhy ca h tinh bt gim khi
tng nhit .
+) Khng tin hnh chun trong mi trng kim bi v it phn ng vi
kim to thnh ion hipoiodid (IO

) c tnh oxi ho mnh hn iot, oxi ho thiosunfat


thnh sunfat:
I
2
+ 2 OH

IO

+ I

+ H
2
O
+ 4 IO

3 2
O S

+ 2 OH

4 I

+ 2 + H
2
4
SO
2
O
Nng kim trong dung dch cng ln, lng thiosunfat chuyn thnh sunfat
cng nhiu, phn ng chun cng km chnh xc.
+) Tc phn ng gia cht oxi ho cn xc nh vi KI thng xy ra
chm nn ch tin hnh chun sau khi thm dung dch KI vo mu phn tch
mt thi gian.
+) Hn hp phn ng gia cht oxi ho cn xc nh vi ion iodua cn trong
ch ti, bi v nh sng c tc dng oxi ho I

thnh iot bi oxi khng kh.
4 I

+ 4 H
+
+ O
2
2 I
2
+ H
2
O
Phng php iot thng c ng dng xc nh cc cht oxi ho nh: xc
nh hm lng clo hot ng trong clorua vi, xc nh hm lng Cu
2+
, asen
Mt ng dng quan trng ca phng php iot l xc nh hm lng nc
trong mt s cht lng hu c. Ngi ta gi phng php ny l phng php s
dng thuc th Phis (Karl Fischer). Thuc th Phis gm c: it, pyrindin, lu
hunh dioxit vi t l mol (1 : 3 : 1) c ho tan trong metanol khan. Thuc th tc
dng vi nc theo phng trnh:
C
5
H
5
N . I
2
+ C
5
H
5
N.SO
2
+ C
5
H
5
N + H
2
O 2C
5
H
5
N. HI + C
5
H
5
N. SO
3
C
5
H
5
N . SO
3
+ CH
3
OH C
5
H
5
N(H)SO
4
CH
3
Trc y ngi ta nhn bit im cui bng mt da vo mu nu khi d mt
git thuc th. Nhng ngy nay ngi ta dng phng php chun o th xc
nh im cui, c chnh xc cao hn nhiu.
160
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+) Phng php Bromat.
Trong mi trng axit b kh thnh bromua:

3
BrO
+ 6 H

3
BrO
+
+ 6e Br

+ 3 H
2
O
Lng d oxi ho Br

3
BrO

thnh brom t do:


+ 5 Br

3
BrO

+ 6 H
+
3 Br
2
+ 3 H
2
O
Dung dch c mu vng ca brom t do, nhng mu vng rt nht khng s
dng nhn bit im cui ca php chun . Brom c kh nng oxi ho cc cht
mu hu c, nn ngi ta ng dng mt s cht ch th axit baz trong phng
php chun bromat. im cui c xc nh bi mt mu ca ch th. Cht ch
th loi ny khng phi cht ch th oxi ho - kh. Phng php bromat c ng
dng xc nh mt s cht As(III) v Sb(VI), mt s cht hu c c kh nng
tham gia phn ng bromua ho.
Th d 8.6. Cn 0,2981g mu bt khng sinh em ho tan vo trong dung dch
HCl, pha long thnh 100,00 ml. Ly ra 20,00 ml cho vo bnh c nt nhm, thm
tip vo 25,00 ml dung dch KBrO
3
0,01767 M c cha lng d Br

, y nt,
yn 10 pht. Sau thm vo mt lng KI, chun lng I
2
gii phng bng
dung dch Na
2
S
2
O
3
0,1215M ht 12,92 ml. Tnh phn trm sunfanilamit (NH
2
)C
6
H
4
NH
2

172,21 g/mol) c trong bt khng sinh.
Cc phn ng xy ra:
+ 5 Br

3
BrO

+ 6 H
+
3 Br
2
+ 3 H
2
O
NH
2
SO
2
NH
2
NH
2
SO
2
NH
2
Br
Br
+ 2Br
2 + 2H + 2Br
+



Br
2
+ 2 I

2 Br

+ I
2
(d KI)
I
2
+ 2 2 + 2 I
2
3 2
O S
2
6 4
O S

Tng s mmol Br
2
to thnh:
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25,00 ml KBrO
3
x 0,01767
3
3
KBrO ml
KBrO mmol
x
3
2
KBrO Mmol
Br mmol 3

= 1,32525 mmol Br
2
.
Lng Br
2
phn ng vi I

to thnh I
2
12,92 ml Na
2
S
2
O
3
x 0,1215
3 2 2
3 2 2
O S Na ml
O S Na mmol
x
3 2 2
2
O S Na Mmol
I mmol
2
1

= 0,78489 mmol Br
2
Lng Br
2
tham gia vo phn ng bromua ho:
1,32525 0,78489 = 0,54036 mmol Br
2
Khi lng sunfanilamit c trong mu:
0,54036 mmol Br
2
x
2
Br mol m
t unfanilami mmol
2
s 1
x 0,17221 (g/mol)
= 0,046528 g
% sunfanilamit =
ml 20,00 x g ,
g ,
mu 2981 0
ml 100 x 046528 0
x 100 %
= 80,4 %
Mt th d quan trng khc ng dng phng php bromat xc nh
8-oxiquinolin.
N
OH
+ 2Br
2
N
OH
Br
Br
HBr + 2



Da trn c s ny ngi ta xc nh gin tip nhm theo nguyn tc:
Al
3+
+ 3 HOC
9
H
6
N Al(OC
= 9 4 pH
9
H
6
N)
3
+ 3 H
+
Al(OC
9
H
6
N)
3
3 HOC
o
t 4M, HCl
9
H
6
N)
3
+ Al
3+
3 HOC
9
H
6
N + 6 Br
2
3 HOC
9
H
6
NBr
2
+ 6 HBr
Phn ng xy ra theo t l:
1 mol Al
3+
3 mol HOC
9
H
6
N 6 mol Br
2
2 mol KBrO
3
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Chng 9
Phng php phn tch khi lng
9.1 Nguyn tc chung ca phng php phntch khi lng
Phng php phn tch khi lng ch yu da trn o chnh xc khi lng
hp cht to thnh. Phng php phn tch khi lng c chnh xc cao nht
trong s cc phng php phn tch, gii hn pht hin 0,10 %, cng 0,2 %.
Ngi ta tin hnh phn tch theo phng php khi lng nh sau: ho tan
mu cha nguyn t cn xc nh trong dung mi thch hp, sau thm lng
thuc th gp 1,5 ln kt ta nguyn t cn xc nh, sau lc ra, ri sy,
nung n khi lng khng i. Khi lng nguyn t cn xc nh c tnh theo
cng thc:
m
A
= m
B
F
a
100
%
m
B
: Khi lmg cn c dng cn B
F: H s chuyn t s khi lng mol nguyn t cn c xc nh vi khi
lng mol ca dng cn.
a: Khi lng mu phn tch
Th d 9.1. Cn 1,132 g qung st, em ho tan trong dung dch HCl c v HNO
3
,
st c oxi ho thnh Fe
3+
, kt ta Fe
3+
bng NH
3
, sau lc, ra, nung nhit
cao chuyn Fe
3+
v dng cn Fe
2
O
3
. Tnh % Fe c trong mu qung. Khi lng mol
ca Fe
2
O
3
l 159,69 g/mol. Khi lng mol ca Fe: 55,84 g/mol. Khi lng Fe
2
O
3

cn c: 0,5394 g.
Mun tm lng Fe trong Fe
2
O
3
ta c th vit:
Trong 1 mol Fe
2
O
3
c 2 mol Fe
Vy trong 0,5394 g Fe
2
O
3
c xg Fe
x = 0,5394 .
84 150
84 55
,
2 x ,
= 0,3772 gam
Vy hm lng % Fe c trong mu qung:
% Fe =
1324 1
377200 0
,
,
x 100 % = 33,32 %
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Th d 9.2. Ngi ta cn 0,3592 g mu bt NaHCO
3
thng mi, em nung nhit
thch hp. Sau cn khi lng mu cn li 0,2302 g. Tnh % Na
2
CO
3
tinh
khit c trong mu?
Khi nung mu NaHCO
3
xy ra phn ng:
2 NaHCO
3
Na
2
CO
3
+ CO
2
+ H
2
O
Khi lng trc khi nung v sau khi nung khc nhau do lng CO
2
v H
2
O
thot ra khi mu. Theo phng trnh phn ng 2 mol NaHCO
3
thot ra 1 mol CO
2

v 1 mol H
2
O.
% Na
2
CO
3
c trong mu:

3592 0
01 44
2362 0 3592 0
,
18,01 ,
84,01 x 2
x ) , , (
+

x 100 % = 92,76 %
Vy hm lng % Fe c trong mu qung:
% Fe =
1324 1
377200 0
,
,
x 100 % = 33,32 %
T hai th d trn chng ta thy c hai cch xc nh khi lng cht cn
phn tch. Tuy nhin, trong thc t cch cn khi lng cht xc nh to thnh
thng c s dng nhiu hn.
Phng php phn tch khi lng thng c chnh xc cao, sai s gp
phi rt nh, tuy nhin thi gian phn tch ko di, ch thch hp khi phn tch cc
nguyn t c hm lng ln. Phng php phn tch khi lng thng c s
dng lm phng php tiu chun xc nh hm lng mt s nguyn t. Nhng
mt iu quan trng l phi ch n chn thuc th kt ta, iu kin kt ta,
trng thi dng kt ta. Chng ta s xt ln lt mt s iu kin c th.
9.2. iu kin kt ta hon ton.
Mun mt hp cht kh tan ca mt nguyn t c th dng trong phng
php phn tch khi lng th phi tho mn mt s yu cu. Trong phng php
phn tch khi lng thng kt ta phi em nung nhit nht nh, trong qu
trnh nung nhiu kt ta chuyn t dng ny sang dng khc. Nh vy, gia dng kt
ta v dng cn khc nhau. Dng kt ta l hp cht c tch ra khi cho thuc th
tc dng vi cht cn xc nh. Dng cn l dng hp cht em cn tnh kt qu
cui cng. Trong mt s trng hp dng cn v dng kt ta l mt. Th d xc
nh di dng kt ta BaSO
2
4
SO
4
. BaSO
4
khng bin i trong qu trnh nung.
Nh vy mi mt dng c yu cu ring ca n.
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9.2.1. Yu cu i vi dung dch kt ta.
Dng kt ta phi c tan nh. iu ny l cn thit v khi mi kt
ta hon ton cht cn xc nh. mt kt ta c s dng trong phng php
phn tch khi lng phi c tan nh hn 10
8
M.


Kt ta phi d lc, ra nhanh. Thng thng dng kt ta tinh th thun
li hn dng kt ta dng v nh hnh. Nht l loi kt ta v nh hnh dng
keo Fe(OH)
3
, Al(OH)
3
c din tch b mt ln, d dng hp ph cht bn, nn
kh ra sch.
Dng kt ta d dng chuyn sang dng cn.
9.2.2. Yu cu i vi dng cn
Yu cu i vi dng cn l phi c thnh phn ng dng cng thc ho hc
Dng cn phi kh bn, khng thay i thnh phn sau khi nung, kt ta
khng ht hn nc, kh CO
2,
,khng t phn hu.
Hm lng nguyn t cn xc nh trong dng cn phi cng nh cng
tt, v trong trng hp ny sai s ca php nh phn s t nh hng n kt
qu cui cng.
Trong qu trnh kt ta, dng kt ta d hp ph cc cht bn hoc nhng
ion l c trong dung dch, trong c c ion lm kt ta m chnh cn phi ra
sch. V cy, cn phi chn cht d bay hi lm cht kt ta, v nu ra khng sch
th khi nung n cng bay hi ht. Th d, kt ta Fe(OH)
3
bng dung dch NH
3
ch
khng dng NaOH hay KOH, kt ta Ba
2+
bng dung dch H
2
SO
4
khng dng mui
Na
2
SO
4
hoc K
2
SO
4
. Nhng khng phi lc no cng tm c cht kt ta thch
hp. Chng hn, khng th kt ta Cu(OH)
2
bng dung dch NH
3
v Cu
2+
d to phc
tan vi NH
3
, buc phi dng NaOH hay KOH, trong trng hp ny phi ra sch
ion Na
+
hoc K
+
.
9.2.3. iu kin kt ta dng tinh th
Qu trnh hnh thnh kt ta phc tp hn vic d on theo phng trnh
phn ng. Th d phn ng:
Ba
2+
+ BaSO
2
4
SO
4
to thnh BaSO
4
phi c s lng tng i ln ion Ba
2+
v tng tc
vi nhau v c s sp xp hp l trong khng gian ca cc ion ny. D nhin mi u
khng phi to ngay nhng tinh th tng i ln m ch nhng tinh th mm v
2
4
SO
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cng nh, cc ht nh ny khng th tch ra thnh kt ta, mun c kt ta tch ra
phi lm cho cc ht nh ln dn ln. Tu theo tnh cht c bit ca cc hp cht kt
ta trc ht tan cng nh iu kin lm kt ta m qu trnh pht trin ca cc
ht s cp c th xy ra theo hai cch khc nhau. Tng ng vi hai cch m ta
c kt ta tinh th hoc kt ta v nh hnh.
Mun kt ta tinh th khng hnh thnh dng ht nh d chiu qua giy lc,
chng ta cn phi kt ta iu kin nh sau:
Phi tin hnh kt ta nh th no sut thi gian kt ta dung dch cng
t qu bo ho so vi cht kt ta cng nhiu cng tt. Mun cho khi kt ta dung
dch cng t qu bo ho th trc ht cn phi:
1- Lm kt ta t nhng dung dch long, vi thuc th long.
2- Thm thuc th rt chm, tng git mt.
3- Dng a thu tinh khuy u trnh hin tng qu bo ho cc b.
4- Lm kt ta t dung dch nng, bng thuc th nng v a s kt ta c
tan tng theo nhit .
5- Trong khi lm kt ta nn thm vo dung dch mt cht c kh nng lm
tng tan kt ta. Th d, khi lm kt ta BaSO
4
ta thng thm HNO
3
,
v axit ny lm tng tan ca BaSO
4
(do hnh thnh anion ). Sau
khi lm kt ta xong, tan ca BaSO

4
HSO
4
s c gim i bng cch dng
d mt t thuc th.
Khi kt ta tinh th thng khng lc ngay, phi yn mt thi gian
(thng sang ngy hm sau). Sau khi yn kt ta c lm ngui, cc tinh th
nh ln dn ln. Sau khi lm ngui kt ta khng ch thu c kt ta tinh th d
lc, m cn c kt ta tinh khit hn, do kt ta dng ht ln t hp ph cht bn
v cn c qu trnh kt tinh li tinh th t hon chnh thnh tinh th hon chnh hn,
mt phn tp cht thi ra khi tinh th.
9.2.4. iu kin to thnh kt ta v nh hnh.
cho kt ta v nh hnh ng t v lng xung, ngi ta phi tm cch
trung ho in tch cc ht keo, thng thm vo dung dch cht in li no c
ion khc du vi ion b hp ph, cc ht keo b trung ho in tch lng xung. Vic
tng nhit trong qu trnh ng t, gim s hp ph. Nh vy, mt trong nhng
im cn ch l phi ngn nga s hnh thnh dung dch keo bng cch kt ta t
dung dch nng, phi thm cht in li, thm nhanh thuc th. gim hp ph cn
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phi lc ngay. Mt khc, do kim kh ln nn cn lc ngay trnh ho tan dng
c thu tinh lm bn kt ta. gim hp ph cht bn bi kt ta v nh hnh,
ngi ta thng thm mt lng nc nng sau khi kt ta xong, lm cho cn bng
hp ph b ph v mt phn ion b hp ph s ri b mt kt ta i vo dung dch .
9.3. Mt s th thut cn ch khi thc hin phng php
phn tch khi lng
Nh trn trnh by phng php phn tch khi lng thng c tin
hnh qua nhiu cng on, phi tun th mt s yu cu nht nh nu khng s dn
n sai s php xc nh rt ln. Sau khi kt ta hnh thnh cc giai on tip theo l
lc, ra, sy, nung, cn kt ta.
1) Lc kt ta: lc, ra kt ta l nhng ng tc rt quan trng. chnh
xc ca kt qu phn tch ph thuc rt nhiu vo giai on ny.
Trong phn tch khi lng khi lc ta thng dng giy lc khng tn. Giy
lc khng tn c nhiu loi dy, mng khc nhau ng vi kch thc ca cc phn t
kt ta cn lc. V d, kt ta v nh hnh rt kh lc, phi dng giy lc chy
nhanh (giy lc bng ), kt ta c tinh th nh cn dng loi giy lc bng xanh.
+) Cch ra kt ta.
Mc ch ra kt ta l ui ht cht bn, k c cc ion c trong dung
dch. Ngi ta thng dng dung dch long cht lm kt ta ra nhm lm gim
tan kt ta trong qu trnh ra. Thnh phn dung dch ra phi l cht d bay hi
hon ton khi nung. ngn nga hin tng pepti ho khng s dng nc ct
ra, v d dn n kt ta chuyn thnh dung dch keo chui qua giy lc. Mt khc,
khi ra kt ta bng nc ct, kt ta d b thu phn lm tng tan ca kt ta
hoc lm cao dng cn khng ng cng thc ho hc.
i b phn dung dch ra cn c un nng gim nht, lc nhanh.
qu trnh loi b cht bn nhanh cn phi ra bng cch lng gn, cho nc ra
vo cc ng kt ta, khuy u yn ri gn nc vo phu lc, qu trnh ny
c lp li nhiu ln, cui cng mi cho kt ta ln phu lc. Trng ra cc,
chuyn ton b kt ta ln phu lc.
+) Cch lm kh v nung kt ta.
Sau khi kt ta c ra sch, kt ta cng giy lc c chuyn vo cc s
(hay cc thch anh hoc chn pletin) tu thuc vo dng kt ta, ghi mu, a vo t
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sy v sy nhit 90 105
o
C trong khong 30 pht. Mt s loi kt ta khng
qua giai on nung th tin hnh sy i sy li n khi lng khng i. i vi
i b phn kt ta cn qua giai on nung, chuyn kt ta cng giy lc vo chn
nung, nhit l nung c tng dn, nung khong 1 2 gi, sau ly chn ra t
vo bnh phng m ch ngui ri em cn, qu trnh c lp li vi ln n khi
lng khng i.
9.4. Cch tnh kt ta trong phng php phn tch khi lng
Th d 9.3. Cn 0,3516 g mu phtphat sau khi phn hu ht cht hu c, em ho tan
trong HCl nng, chuyn phtpho thnh H
3
PO
4
, kt ta di dng MgNH
4
PO
4
.6H
2
O.
Kt ta lc, ra ri em nung chuyn thnh dng Mg
2
P
2
O
7
, cn c 0,2161 g. Tnh
phn trm phtpho c trong mu. Khi lng mol ca Mg
2
P
2
O
7
l 222,57 g/mol,
khi lng mol ca phtpho l 30,974 g/mol.
Trong 1 mol Mg
2
P
2
O
7
c 2 mol phtpho
Vy khi lng phtpho trong mu:

57 222
2
,
30,974 x
x 0,2161 = 0,060147 gam P
% P =
3516 0,
0,06015
x 100 % = 17,10 %
T th d trn ta thy lng cht cn xc nh x chnh l tch gia hai tha s,
trong c mt tha s thay i ph thuc vo lng cht nghin cu ly. Tha
s th 2 l t s gia khi lng mol ca cht cn xc nh v khi lng mol ca
kt ta dng cn, khng thay i c th tnh sn dng cho hng lot php phn
tch cng loi. T s ny c gi l tha s chuyn (h s chuyn), k hiu F. Vy
ta c:
x = a . F
a: khi lng dng cn




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Ph lc
Bng 1. Cc hng s phn li axit 25
o
C
Tn gi axit Cng thc Ka
1
Ka
2
Ka
3
Ka
4
Axetic CH
3
COOH 1,75.10
5

Alanic CH
3
CH(NH
2
)COOH
a
4,5.10
3
1,3.10
10

Asenic H
3
AsO
4
6,0.10
3
1,0.10
7
3,0.10
12

Aseno H
3
AsO
3
6,0.10
10
3,0.10
14

Benzoic C
6
H
5
COOH 6,3.10
5

Boric H
3
BO
3
6,4.10
10

Cacbonic H
2
CO
3
4,3.10
7
4,8.10
11

Cloaxetic ClCH
2
COOH 1,5.10
3

Xitric HOOC(OH)C(CH
2
COOH)
2
7,4.10
4
1,7.10
5
4,0.10
7

Etylendiamin-
tetraaxetic
(CO
2
)
2
NH
+
CH
2
CH
2
NH
+
(CO
2
)
2
a
1,0.10
2
2,2.10
5
6,9.10
7
5,5.10
11
Fomic HCOOH 1,76.10
4

Glixin H
2
NCH
2
COOH
b
4,5.10
3
1,7.10
10

Hiroxianic HCN 7,2.10
10

Hirofluoric HF 6,7.10
4

Hirosunfua H
2
S 9,1.10
8
1,2.10
15

Hiroclor HOCl 1,1.10
8

Iodic HIO
3
2,0.10
4

Lactic CH
3
CHOHCOOH 1,4.10
4

Leucin (CH
3
)
2
CHCH
2
CH(NH
2
)COOH
b
4,7.10
3
1,8.10
10

Maleic cis-HOOCCH : CHCOOH 1,5.10
2
2,6.10
7

Malic HOOCCHOHCH
2
COOH 4,0.10
4
8,9.10
6

Nitr HNO
2
5,1.10
4

Oxalic HOOCCOOH 6,5.10
2
6,1.10
5

Phenol C
6
H
5
OH 1,1.10
10

Photphoric H
3
PO
4
1,1.10
2
7,5.10
8
4,8.10
13

Photphor H
3
PO
3
5,0.10
2
2,6.10
7

o-Phtalic C
6
H
4
(COO)
2
1,2.10
3
3,9.10
6

Picric (NO
2
)
3
C
6
H
5
OH 4,2.10
1

Propanoic CH
3
CH
2
COOH 1,3.10
5

Salixilic C
6
H
4
(OH)COOH

1,0.10
3

Sunfamic NH
3
SO
3
H 1,0.10
1

Sunfuric H
2
SO
4
>>1,0

1,2.10
2



Sunfur H
2
SO
3
1,3.10
2
5,0.10
6

Tricloaxetic Cl
3
COOH 1,29.10
1


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Bng 2. Cc hng s phn li baz 25
o
C

Tn gi baz Cng thc K
b1
K
b2
Amoniac NH
3
1,75.10
5

Anilin C
6
H
5
NH
2
4,0.10
10

1-Butylamin CH
3
(CH
2
)
2
CH
2
NH
2
4,1.10
4

Dietylamin (CH
3
CH
2
)
2
NH

8,5.10
4

Dimetylamin (CH
3
)
2
NH

5,9.10
4

Etanolamin HOC
2
H
4
NH
2
3,2.10
5

Etylamin CH
3
CH
2
NH
2
4,3.10
4

Etylendiamin NH
2
C
2
H
4
NH
2
8,5.10
5
7,1.10
8
Glyxin HOOCCH
2
NH
2
2,3.10
12

Hirazin H
2
NNH
2
1,3.10
6

Hiroxylamin HONH
2
9,1.10
9

Metylamin CH
3
NH
2
4,8.10
4

Piperidin C
5
H
11
N

1,3.10
3

Piridin C
5
H
5
N

1,7.10
9

Trietylamin (CH
3
C

H
3
)
3
N

5,3.10
4

Trimetylamin (CH
3
)
3
N

6,3.10
5

Tri (hidroxylmetyl) aminometan (OHCH
2
)
3
CNH
2
1,2.10
6

Km hiroxit Zn(OH)
2

4,4.10
5












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Bng 3. Tch s tan ca mt s hp cht 25
o
C
Tn cht Cng thc T Tn cht Cng thc T
Nhm hiroxit Al(OH)
3
2.10
32
Ch oxalat PbC
2
O
4
4,8.10
10
Bari cacbonat BaCO
3
8,1.10
9
Ch sunfat PbSO
4
1,6.10
8
Bari cromat BaCrO
4
2,4.10
10
Ch sunfua PbS 8,0.10
28
Bari florua BaF
2
1,7.10
6
Magie amoniphotphat MgNH
2
PO
4
2,5.10
13
Bari iodat Ba(IO
3
) 1,5.10
9
Magie cacbonat MgCO
3
1,0.10
5
Bari manganat BaMnO
4
2,5.10
10
Magie hiroxit Mg(OH)
2
1,2.10
11
Bari oxalat BaC
2
O
4
2,3.10
8
Magie oxalat MgC
2
O
4
9,0.10
5
Bari sunfat BaSO
4
1,0.10
10
Mangan hiroxit Mn(OH)
2
4,0.10
14
Beri hiroxit Be(OH)
2
7,0.10
22
Mangan sunfua MnS

1,4.10
15
Bimutylclorua BiOCl 7,0.10
9
Thu ngn bromua HgBr
2
5,8.10
25
Bimutin Bi
2
O
3
1,0.10
97
Thu ngn (I) clorua Hg
2
Cl
2
1,3.10
18
Catmi cacbonat CdCO
3
2,5.10
14
Thu ngn iodua Hg
2
I
2
4,5.10
29
Catmi sunfua CdS 1,0.10
28
Thu ngn sunfua HgS

4,0.10
53
Canxi cacbonat CaCO
3
8,7.10
9
Bc asenat AgAsO
4
1,0.10
22
Canxi flurua CaF
2
4,0.10
11
Bc bromua AgBr

4,0.10
13
Canxi hiroxit Ca(OH)
2
5,6.10
6
Bc cacbonat Ag
2
CO
3
8,2.10
12
Canxi oxalat CaC
2
O
4
2,6.10
9
Bc clorua AgCl

1,0.10
10
Canxi sunfat CaSO
4
1,9.10
4
Bc clromat Ag
2
CrO
4
1,1.10
12
ng (I) bromua CuBr 5,2.10
9
Bc xianua Ag[Ag(CN)
2
] 5,0.10
12
ng (I) clorua CuCl 1,2.10
6
Bc iodat AgIO
3
3,4.10
8
ng (I) iodua CuI 5,1.10
12
Bc iodua AgI 1,0.10
16
ng(I) thioxianat CuSCN 4,8.10
15
Bc photphat Ag
3
PO
4
1,3.10
20
ng(II) hiroxit Cu(OH)
2
1,6.10
19
Bc sunfua Ag
2
S 2,0.10
49
ng (II) sunfua CuS

9,0.10
36
Bc thioxianat AgSCN 1,0.10
12
St (II) hiroxit Fe(OH)
2
8,0.10
16
Stronti oxalat SrC
2
O
4
1,6.10
7
St (III) hiroxit Fe(OH)
3
4,0.10
38
Stronti sunfat SrSO
4
3,8.10
7
Lantan iodat La(IO
3
)
3
6,0.10
10
Tali clorua TlCl 2,0.10
4
Ch clorua PbCl
3
1,6.10
8
Tali sunfua Tl
2
S 5,0.10
22
Ch cromat PbCrO
4
1,8.10
14
Km ferixianua Zb
2
Fe(CN)
6
4,1.10
16
Ch iodua PbI
2
7,1.10
9
Km oxalat ZnC
2
O
4
2,8.10
8
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Km sunfua ZnS 1,0.10
21

Bng 4. Hng s bn phc ca mt s kim loi vi EDTA 25
o
C

Nguyn t Cng thc

Nhm AlY

1,35.10
16
Bitmut BiY

1,00.1023

Bari BaY

5,75.10
7
Catmi CdY
2
2,88.10
16
Canxi CaY
2
5,04.10
10
Coban (Co
2+
) CoY
2
2,04.10
16
Coban (Co
3+
) CoY

1,00.10
36
ng CuY
2
6,30.10
18
Gali GaY

1,86.10
20
Indi InY

8,91.10
24
St (Fe
2+
) FeY
2
2,14.10
14
St (Fe
3+
) FeY

1,3.10
14
Ch PbY
2
1,10.10
18
Magie MgY
2
4,90.10
8
Mangan MnY
2
1,10.10
14
Thu ngn HgY
2
6,30.10
21
Niken NiY
2
4,16.10
18
Scandi ScY

1,30.10
23
Bc AgY
2
2,09.10
7
Stronti SrY
2
4,26.10
8
Thori ThY

1,6.10
23
Titan (Ti
3+
) TiY

2,00.10
24
Titan (TiO
2+
) TiOY
2
2,00.10
17
Vanadi (V
2+
) VY
2
5,01.10
12
Vanadi (V
3+
) VY

8,00.10
25
Vanadi (VO
2+
) VOY
2
1,23.10
18
Ytri YY

1,23.10
18
Km ZnY
2
3,16.10
16
172
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Bng 5. Th oxi ho - kh tiu chun v th oxi ho - kh iu kin ca mt
vi cp oxi ho - kh lip hp.
Bn phn ng oxi ho - kh Th oxi ho - kh E
o
(V)
F
2
+ 2 H
+
+ 2e

= 2 HF 3,06
O
3
+ 2 H
+
+ 2e

= O
3
+ H
2
O 2,07
2
8 2
O S + 2e

= 2
2
4
SO
2,01
Co
3+
+ e

= Co
2+
1,842
H
2
O
2
+ 2 H
+
+ 2e

= 2 H
2
O 1,77

4
MnO + 4 H
+
+ 3e

= MnO
2
+ 2 H
2
O
1,695
1,70 (HClO
4
) 1M
1,61 HNO
3
1M
Ce
4+
+ e

= Ce
3+

1,44 H
2
SO
4
1M
HClO + H
+
+ e

= 1/2 Cl
2
+ H
2
O 1,63
H
5
IO
6
+ H
+
+ 2e

= + 3 H

3
IO
2
O
1,60

3
BrO + 6 H
+
+ 5e

= 1/2 Br
2
+ 3 H
2
O
1,52

4
MnO + 8 H
+
+ 5e

= Mn
2+
+ 4 H
2
O
1,51
Mn
3+
+ e

= Mn
2+
1,51 (H
2
SO
4
1M)

3
ClO + 6 H
+
+ 5e

= 1/2 Cl
2
+ 3 H
2
O
1,47
PbO
2
+ 4 H
+
+ 2e

= Pb
2+
+ H
2
O 1,455
Cl
2
+ 2e

= 2 Cl

1,359
2
7 2
O Cr + 14 H
+
+ 6e

= 2 Cr
3+
+ 7 H
2
O
1,33
Tl
3+
+ 2e

= Tl
+
1,25 0,77 (HCl 1M)

3
IO + 2 Cl

+ 6H
+
+ 4e

= + 3 H

2
ICl
2
O
1,24
MnO
2
+ 4 H
+
+ 2e

= Mn
2+
+ 3 H
2
O 1,23
O
2
+ 4 H
+
+ 4e

= 2 H
2
O 1,229
2 + 12 H

3
IO
+
+ 10e

= I
2
+ 6 H
2
O
1,20
2
4
SeO + 4 H
+
+ 2e

= H
2
SeO
3
+6 H
2
O
1,15
Br
2
(aq) + 2e

= 2Br

1,087
a

Br
2
(I) + 2e

= 2Br

1,065
a

3
ICl + e

= I
2
+ 2Cl

1,06
+
2
VO + 2 H
+
+ e

= VO
2+
+ H
2
O
1,00
HNO
2
+ H
+
+ e

= NO + H
2
O 1,00
Pd
2+
+ 2e

= Pd

0,987

3
NO + 3 H
+
+ 2e

= HNO
2
+ H
2
O
0,94
2 Hg
2+
+ 2e

=
+ 2
2
Hg
0,920
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Bn phn ng oxi ho - kh Th oxi ho - kh E
o
(V)
H
2
O
2
+ 2e

= 2OH

0,88
Cu
2+
+ I

+ e

= CuI 0,86
Hg
2+
+ 2e

= Hg 0,854
Ag
+
+ e

= Ag 0,799 0,228 (HCl 1M);
0,792 (HClO
4
1M)
+ 2
2
Hg + 2e

= 2 Hg
0,789 0,274 (HCl 1M)
Fe
3+
+ e

= Fe
2+
0,771
H
2
SeO
3
+ 4 H
+
+ 4e

= Se + 3 H
2
O 0,740
2
4
PtCl + 2e

= Pt + 4 Cl
0,73
C
6
H
4
O
2
(quinon) + 2H
+
+ 2e

= C
6
H
2
(OH)
2
0,699 0,696 (HCl, H
2
SO
4
,
HClO
4
1M)
O
2
+ 2 H
+
+ 2e

= H
2
O
2
0,682
2
6
PtCl + 2e

= + 2 Cl
2
4
PtCl

0,68
I
2
(aq) + 2e

= 2I

0,6197
a

Hg
2
SO
4
+ 2e

= 2Hg +
2
4
SO
0,615
Sb
2
O
5
+ 6 H
+
+ 4e

= 2 SbO
+
+ 3 H
2
O 0,581

4
MnO + e

=
2
4
MnO
0,564
H
3
AsO
4
+ 2 H
+
+ 2e

= H
3
AsO
3
+ H
2
O 0,559 0,577 (HCl, HClO
4
1M)

3
I + 2e

= 3I

0,5355
I
2
(s) + 2e

= 2 I

0,5345
a

Mo
6
+ e

= Mo
3+
0,53 (HCl 2M)
Cu
+
+ e

= Cu 0,521


H
2
SO
3
+ 4 H
+
+ 4e

= S + 3 H
2
O 0,45
Ag
2
CrO
4
+ 2e

= 2Ag +
2
4
CrO
0,446
VO
2+
+ 2 H
+
+ e

= V
+
+ H
2
O 0,361
3
6
) CN ( Fe + e

=
4
6
) CN ( Fe
0,36 0,72 (HClO
4
, H
2
SO
4
1M)
Cu
2+
+ 2e

= Cu 0,337
+ 2
2
UO + 4 H
+
+ 2e

= U
4+
+ 2 H
2
O
0,334
BiO
+
+ 2 H
+
+ 3e

= Bi + H
2
O 0,32
Hg
2
Cl
2
(8) + 2e

= 2Hg + 2Cl

0,268 0,242 (KCl bh),
0,282 (KCl 1M)
AgCl + e

= Ag + Cl

0,222 0,228 (KCl 1M)
2
4
SO + 4 H
+
+ 2e

= H
2
SO
3
+ H
2
O
0,17

4
BiCl + 3e

= Bi + 4 Cl

0,16
174
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Bn phn ng oxi ho - kh Th oxi ho - kh E
o
(V)
Sn
4+
+ 2 e

= Sn
2+
0,154 0,14 (HCl 1M)
Cu
2+
+ e

= Cu
+
0,153
S + 2 H
+
+ 2e

= H
2
S 0,141
TiO
2+
+ 2 H
+
+ e

= Ti
3+
+ H
2
O 0,1
Mo
4+
+ e

= Mo
3+
0,1 (H
2
SO
4
4M)
2
6 4
O S + 2e

= 2
2
3 2
O S
0,08
AgBr + e

= Ag + Br

0,071
3
2 3 2
) O S ( Ag + e

= Ag + 2
2
3 2
O S
0,01
2H
+
+ 2e

= H
2
0,000
Pb
2+
+ 2e

= Pb 0,126
2
4
CrO + 4 H
2
O + 3e

= Cr(OH)
3
+ 5OH

0,130
Sn
2+
+ 2e

= Sn 0,136
AgI + e

= Ag + I

0,151
CuI + e

= Cu + I

0,185
N
2
+ 5H
+
+ 4e

=
+
5 2
H N

0,230
Ni
2+
+ 2e

= Ni 0,250
V
3+
+ e

= V
2+
0,255
Co
2+
+ 2e

= Co 0,277

2
) CN ( Ag + e

= Ag + 2CN

0,310
Tl
+
+ e

= Tl 0,336 0,551 (HCl 1M)
PbSO
4
+ 2e

= Pb +
2
4
SO
0,356
Ti
3+
+ e

= Ti
2+
0,370
Cd
2+
+ e

= Cd 0,403
Cr
3+
+ e

= Cr
2+
0,410
Fe
2+
+ 2e

= Fe 0,440
2 CO
2
(g) + 2 H
+
+ 2e

= H
2
C
2
O
4
0,490
Cr
3+
+ 3e

= Cr 0,740
Zn
2+
+ 2e

= Zn 0,763
2H
2
O + 2e

= H
2
+ 2 OH

0,828
Mn
2+
+ 2e

= Mn 1,180
Al
3+
+ 3e

= Al 1,660
Mg
2+
+ 2e

= Mg 2,37
Na
+
+ e

= Na 2,714
Ca
2+
+ 2e

= Ca 2,870
Ba
2+
+ 2e

= Ba 2,900
K
2+
+ e

= K 2,925
Li
+
+ e

= Li 3,045




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Bng 6. Mt s ch th axit baz (pH)
STT Ch th pH Khong pH chuuyn mu
1 Cresol hng 0,2 1,8 vng
2 m-Cresol ta 1,2 2,8 vng
3 Thymol xanh 1,2 2,8 vng
4 p-xylenol xanh 1,2 2,8 vng
5 2,2,2,4,4-Pentametoxytriphenylcarbizon 1,2 3,2 khng mu
6 2,4-Dinitrophenol khng mu 2,8 4,7 vng
7 4-Dimetylaminoazobenzen 2,9 4,0 vng da cam
8 Bromoclophenol xanh vng 3,0 4,6 ta
9 Bromophenol xanh vng 3,0 4,6 ta
10 Metyl da cam 3,1 4,4 vng da cam
11 Bromocresol xanh vng 3,8 5,4 xanh
12 2,5-Dinitrophenol khng mu 4,0 5,8 vng
13 Alizarinsunfonic axit natri vng 4,3 6,3 tm
14 Metyl 4,4 6,2 vng da cam
15 Mui natri metyl 4,4 6,2 vng da cam
16 Clorophenol vng 4,8 6,4 ta
17 Hematoxylin vng 5,0 7,2 tm
18 Qu 5,0 8,0 xanh
19 Bromophenol vng da cam 5,2 6,8 ta
20 Bromocresol ta vng 5,2 6,8 ta
21 4-Nitro phenol khng mu 5,4 7,5 vng
22 Bromo xylenol xanh vng 5,7 7,4 xanh
23 Alizarrin vng 5,8 7,2
24 Bromothymol xanh vng 6,0 7,6 xanh
25 Phenol vng 6,4 8,2
26 3-Nitrophenol khng mu 6,6 8,6 vng da cam
27 trung tnh 6,6 8,0 vg da cam
28 4,5,6,7-Tetrabromophenolphtalein khng mu 7,0 8,0 ta
29 Cresol da cam 7,0 8,8 ta
30 1-Naphtolphtalein hi nu 7,1 8,3 xanh l cy
31 m-cresol ta vng 7,4 9,0 ta
32 Thymol xanh vng 8,0 9,6
33 p-xylenol xanh vng 8,0 9,6 xanh l cy
34 Phenolphtalein khng mu 8,2 9,8 tm
35 Thymolphtalein khng mu 9,3 10,5 xanh l cy
36 Alizarrin vng GG vng nht 10,2 12,1 vng hi nu
37 Epsilon xanh da cam 11,6 13,0 tm
176
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Ti liu tham kho
1. Nguyn Tinh Dung. Ho hc phn tch.
Cn bng ion trong dung dch.
Nh xut bn Gio dc 2000
2. Nguyn Tinh Dung. Ho hc phn tch.
Cc phng php nh lng ho hc
Nh xut bn Gio dc 2002
3. T Vng Nghi. Ho hc phn tch.
C s l thuyt cc phng php ho hc phn tch
Nh xut bn i hc Quc gia H Ni 2000
4. Douglas A. Skoog, Donald M. Wost, F. Yames Holler Stanley R. Crouch
Analytical Chemistry
Saunders College publishing 1999
5. Gary D. Christian Analytical Chemistry
John wiley G SONS.INC 2003
6. D. Kealey Analytical Chemistry
Bios Scientific publishers Limited 2002
7. George M. Bodner, Harry L. Pardue
Chemistry
John wiley SONS, INC 2001
8. Paul Lois Fabre Chimie
Chimie des sehition
Ellipses Edition Marketing S. A. 2001












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Mc lc
Trang
M u 1
Chng 1. Phn ng phn tch Cn bng ho hc Hot 6
1.1. Phn loi cc phn ng phn tch 6
1.2. iu kin xy ra cc phn ng 7
1.2.1. nh hng ca nhit
7
1.2.2. nh hng ca mi trng phn ng
8
1.2.3. nh hng nng cht phn ng
10
1.3. nh lut tc dng khi lng ng dng i vi cc phn ng phn tch 10
chng 2. i cng v phng php phn tch th tch
12
2.1. Nguyn tc chung phng php phn tch th tch 12
2.2. Phn loi cc phng php chun 13
2.3. Nng dung dch 14
2.4. iu ch dung dch c nng xc nh 16
2.5. Cch tnh kt qu trong phn tch th tch 17
2.6. Sai s trong phn tch nh lng 20
2.6.1. Cc loi sai s trong phn tch nh lng 20
2.6.2. Mt s i lng c trng thng c ng dng x l s liu thc
nghim theo phng php ton hc thng k
22
2.6.3. nh gi kt qu phn tch 24
Chng 3. Cn bng axit - baz 26
3.1. nh ngha axit - baz 26
3.2. Tnh cht axit - baz ca dung mi nc 28
3.3. Hng s cn bng axit v baz trong dung dch nc 29
3.4. pH ca dung dch n axit trong dung mi nc 30
3.4.1. pH ca dung dch axit mnh 30
3.4.2 . pH ca dung dch n axit yu 31
3.5. pH ca dung dch n baz trong dung mi nc 34
3.5.1. pH ca dung dch baz mnh 34
3.5.2. pH ca dung dch n baz yu 34
3.6. pH ca dung dch a xit - baz lin hp. Dung dch m 36
3.7. pH ca dung dch hn hp axit 40
3.7.1. pH ca dung dch hn hp axit mnh v axit yu 40
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3.7.2. pH ca dung dch hn hp hai axit yu 42
3.8. pH ca hai dung dch hn hp hai baz 44
3.8.1. pH ca dung dch hn hp baz mnh v baz yu 44
3.8.2. pH ca dung dch hn hp hai baz yu 45
3.9. pH ca dung dch a axit v mui ca chng 46
3.9.1. pH ca dung dch a axit 46
3.9.2. pH ca dung dch mui a axit 49
Chng 4. Phng php chun axit baz 50
4.1. Cht ch th axit - baz 50
4.2. ng chun trong phng php chun axit - baz 53
4.2.1. Chun axit mnh bng baz mnh 53
4.2.2. Chun baz mnh bng axit mnh 56
4.2.3. Chun axit yu bng baz mnh 58
4.2.4. Chun baz bng axit mnh 62
4.3. ng chun a axit v a baz 66
4.3.1. Chun a axit bng baz mnh 66
4.3.2. Chun a baz bng axit mnh 73
4.3.3. Chun aminoaxit
4.3.4. Phng php phn tch Kjeldahl 79
Chng 5. Cn bng to phc v phng php chun phc cht 86
5.1. Hng s cn bng phn ng to phc 86
5.2. Tnh nng cn bng cc cu t trong dung dch phc cht 88
5.3. S to phc ca Etylendiamintetraaxetic axit vi cc ion kim loi 93
5.4. ng chun trong phng php chun complexon 98
5.5. Xc nh im cui trong phng php chun complexon .
Ch th mu kim loi
101
5.6. Cc phng php chun complexon 104
5.6.1. Phng php chun trc tip 104
5.6.2. Phng php chun ngc 104
5.6.3. Phng php chun thay th 105
5.6.4. Phng php chun gin tip 105
chng 6. Cn bng trong dung dch to thnh hp cht t tan v
phng php chun kt ta.
106
6.1. Cn bng trong dung dch to thnh hp cht t tan 106
6.2. Quan h tch s tan v tan ca kt ta 108
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6.2.1. Tnh tch s tan t tan 108
6.2.2. Tnh tan t tch s tan 110
6.3. Cc yu t nh hng n tan ca kt ta 111
6.3.1. nh hng ca ion chung
111
6.3.2. nh hng ca nng ion H
+
112
6.3.3. nh hng ca cht to phc
115
6.4. Kt ta phn on 119
6.5. Phng php chun kt ta 120
6.5.1. ng chun trong phng php chun kt ta 120
6.5.2. Cc phng php xc nh im cui trong phng php chun kt ta 123
Chng 7. Cn bng phn ng oxi ho - kh 126
7.1. Th oxi ho - kh. Phngtrnh Nernst 126
7.2. Cc yu t nh hng n th oxi ho - kh.
Th oxi ho kh tiu chun iu kin
129
7.2.1. nh hng ca nng ion H
+
129
7.2.2. nh hng ca phn ng to thnh hp cht t tan
130
7.2.3. nh hng ca phn ng to thnh hp cht t phn li
131
7.3. Hng s cn bng ca phn ng oxi ho - kh 133
7.4. Cht oxi ho v cht kh a bc 134
Chng 8. Phng php chun oxi ho - kh 137
8.1. ng chun trong phng php chun oxi ho - kh
137
8.2. Chun a bc 144
8.3. Cht ch th trong phng php chun oxi ho - kh 150
8.3.1. Php chun khng dng cht ch th 150
8.3.2. Php chun dng cht ch th 151
8.4. mt s phng php chun oxi ho - kh ng dng trong thc t
153
Chng 9. Phng php phn tch khi lng 160
9.1. Nguyn tc chung ca phng php phn tch khi lng 160
9.2. iu kin kt ta hon ton 161
9.3. Mt s th thut cn ch khi thc hin phng php phn tch khi lng 164
9.4. Cch tnh kt qu trong phng php phn tch khi lng 165
Ph lc 166
Ti liu tham kho 174
Mc lc 175

180

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