Thí Nghiệm Hóa Phân Tích

TRNG I HC BCH KHOA H NI
B MN HA PHN TCH

2
M M C C L L C C

Mc lc.....................................................................................................................................1
Li ni u...............................................................................................................................6
Nhng iu cn bit khi tin hnh phn tch nh lng....................................................7
Gii thiu mt s dng c, thit b c bn ......8 khi lm th nghim phn tch nh lng
X l thng k cc s liu thc nghim...............................................................................12
Phn 1: Cc phng php phn tch ha hc ....................................................................14
Chng I: .................................... 14 Phn tch bng phng php trng lng
Bi 1: Xc nh
2
4
SO

(sunfat) theo phng php khi lng.................................16
Bi 2: Xc nh st theo phng php khi lng...................................................18
Bi 3: ...............................................................................20 Xc nh niken trong thp
Chng II: ......................................... 22 Phn tch bng phng php th tch
Dng c dng o th tch dung dch .....................................................................22
Tnh ton v pha ch dung dch trong phn tch th tch........................................26
Cht ch th ...................................................................................................................33
Cc bi th nghim......................................................................................... 41
Bi 4: Pha ch v chun dung dch HCl ...................................................................41
Bi 5: Xc nh nng dung dch naoh bng dung dch HCl ....................................43
Bi 6: Xc nh hm lng Na CO trong Na CO k thut.........................................44
2 3 2 3
Bi 7: Xc nh nng NaOH v Na CO trong hn hp..........................................45
2 3
Bi 8: Xc nh hm lng axit c trong dm v ru vang.........................................48
Bi 9: Pha ch v xc nh nng dung dch kmno .................................................49
4
Bi 10: Xc nh hm lng canxi trong vi............................................................51
Bi 11: Xc nh nng dung dch Fe bng KMnO ...............................................53
2+
4
Bi 12: Xc nh st trong dung dch FeCl bng KMnO ............................................54
3 4
Bi 13: Xc nh hm lng Mn trong thp hp kim....................................................56
Bi 14: Xc nh nng Fe bng K Cr O ...............................................................57
3+
2 2 7
Bi 15: Xc nh crm trong thp hp kim...................................................................60
Bi 16: Chun dung dch Na S O theo phng php it ........................................61
2 2 3
Bi 17: Xc nh ng trong CuSo ..............................................................................65
4
Bi 18: Xc nh antimon trong antimon k thut ........................................................67

3
Bi 19: Xc nh Cl bng dung dch chun AgNO .................................................... 68
3
Bi 20: Xc nh Cl bng dung dch chun Hg(NO ) ................................................ 69
3 2
Bi 21: Xc nh km (Zn ) bng feroxianua kali theo phng php kt ta ............ 70
2+
Bi 22: Xc nh nng complexon III bng dung dch ZnSO ................................ 71
4
Bi 23: Xc nh cng chung ca nc bng complexon III................................... 73
Bi 24: Xc nh Ca bng phng php complexon..................................................... 74
Bi 25: Xc nh Al bng complexon III theo phng php nh phn ngc ............ 75
Bi 26: Xc nh Ni bng complexon III ...................................................................... 76
Bi 27: Xc nh coban bng complexon III................................................................. 77
Phn 2: Cc phng php phn tch ha l....................................................................... 78
Chng 1: Phng php trc quang.............................................................. 78
Bi 28: Nghin cu ph hp th ca phc Fe-axit sunfosalisilic.................................. 82
Bi 29: Xc nh st bng axit sunfosalixilic................................................................ 83
Bi 30: Xc nh hm lng st trong nc t nhin ................................................... 85
Bi 31: Xc nh MnO v Cr O trong dung dch hn hp ..................................... 87
4
2 7
2

Bi 32: Xc nh Ni bng dimetylglyoxim................................................................. 88
2+
Bi 33: Xc nh amoni trong nc .............................................................................. 89
Bi 34: Xc nh Cl bng thy ngn thyoxyanate ....................................................... 91
Bi 35: Phng php o quang xc nh thnh phn phc phc Cu(II)nitrozo-r-sol ............ 92
Bi 36: Xc nh ng theo phng php o quang vi sai ........................................... 95
Bi 37: Ph in t ca ion NO .................................................................................. 97
2
Chng 2: Phng php in phn ............................................................. 100

Bi 38: Phng php in phn khi lng xc nh ng ........................................ 104
Bi 39: Phng php in phn c kim tra th catot xc nh Pb trong oxit km.... 106
Chng 3: Phng php cc ph................................................................ 108
Bi 40: Xc nh Zn trong dung dch.......................................................................... 110
Bi 41: Xc nh Cd trong dung dch....................................................................... 111
2+
Bi 42: Phng php vonampe xc nh Pb .......................................................... 113
2+
Bi 43: Phng php von-ampe xc nh Zn , Cd , Pb , Cu khi chng c mt ng thi.. 114
2+ 2+ 2+ 2+
Chng 4: Phng php in th................................................................ 116
Bi 44: Xc nh nng HCl bng NaOH (in cc quinhydron bo ha).............. 118
Bi 45: Xc nh nng NaOH v Na CO bng HCl (in cc thy tinh)............. 119
2 3

4
Bi 46: Xc nh Cl , I trong dung dch hn hp bng AgNO 0,1N........................122

3
Bi 47: Chun Fe bng K Cr O ..........................................................................123
3+
2 2 7
Chng 5: Phng php sc k trao i ion ...............................................................125
Bi 48: Phng php trao i ion trn nha cationit tch niken v coban..................126
Bi 49: Tch v xc nh Fe , Zn trong dung dch hn hp....................................128
3+ 2+
Chng 6: Phng php chit o quang.................................................. 130
Bi 50: Xc nh vi lng ng(II) khi c niken(II) lng ln bng phng php chit-
o quang ......................................................................................................................134
Ti liu tham kho ..............................................................................................................136

5

HNG DN TH NGHIM HA PHN TCH
2007

B mn Ha Phn tch Trng i hc Bch Khoa H Ni
Department of Analytical Chemistry Hanoi University of Technology
a ch: S 1 i C Vit H Ni. Phng 411 Ta nh C1 H Bch Khoa H Ni
in thoi: (+84) 04. 8692206 E.mail: hpt@mail.hut.edu.vn
Bn gc Hng dn th nghim Ha Phn tch nm 1992, 1996: Trn Bnh, Nguyn Ngc Thng
Bn nm 2007 b sung cc bi: 35,36,37,42,43 do GS.TSKH. T Vn Mc son
3,6,8,18,24,30,32,45 do Nguyn L Huy son
33 do V Th Hng n son
Ch bn v bin tp: Nguyn L Huy
Hon thnh ngy 10 thng 5 nm 2007. In tiu chun trn kh A4 (210x297mm)

6

L L I I N N I I U U

Ha hc phn tch l ngnh khoa hc v phng php gip nghin cu cc hiu ng v
chuyn ha ha hc, nghin cu cc hp cht v vt liu mi, gip cc nh k thut nhng
ch dn iu khin v t ng ha cc qu trnh cng ngh; gip cc nh kinh t v qun
l nhng c s nh gi cht lng sn phm v hoch nh k hoch pht trin.
Ha hc phn tch l ngnh khoa hc ng dng tng hp cc thnh tu ca cc ngnh
khoa hc khc c lin quan nh: ha hc, vt l, ton tin, sinh hc, y hc, mi trng, v tr,
a cht, a l y l ngnh c s tch hp cao ca nhiu ngnh khoa hc t nhin nhm
em li li ch ti a cho khoa hc, i sng v s pht trin ca con ngi. Bn cnh vic
nghin cu phn tch nh tnh v phn tch nh lng cc nguyn t v hp cht, ngy nay
phn tch cu trc cng thuc ngnh phn tch.
Trong ti liu ny chng ti trnh by cc bi th nghim phn tch nh lng cc cht
v c p dng phng php phn tch ha hc v phng php phn tch ha l tng i
n gin c tnh cht gio khoa gip sinh vin bc u lm quen vi cng tc phn tch ha
hc. Ti liu cng bc u cung cp mt s phng php phn tch cu trc n gin bng
php o quang vng t ngoi v nhn thy nhm gip sinh vin bc u c khi nim cho
cng tc nghin cu khoa hc sau ny.
Xu hng pht trin ca ha hc phn tch trong nhng nm sp ti l:
- Nghin cu c bn v phn tch cu trc (phng php nhiu x tia X; nhiu x
noton; cng hng t ht nhn; o quang vng hng ngoi, nhn thy, t ngoi;
ph Raman; khi ph; quang ph in t)
- Nghin cu c bn v phn tch v nguyn t c bit l phn tch hn hp cc
cht hu c, pht hin nguyn t dng vt, siu vt p dng cc k thut sc k
hin i.
- Nghin cu c bn v phn tch qu trnh phc v s nghip cng nghip ha v
hin i ha t nc. p dng cng ngh t ng ha v tin hc ha vo cng
tc phn tch sn xut.
- o to nhn lc ph hp vi mc tiu pht trin ca x hi.
- Xy dng cc phng phn tch hin i, uy tn.

7

N NH H N NG G I I U U C C N N B BI I T T K KH HI I T TI I N N H H N NH H P PH H N N T T C CH H N NH H L L N NG G

I. Chun b th nghim
Mt th nghim phn tch nh lng thng bao gm nhiu giai on. Nu mi giai
on th nghim u c tin hnh cn thn, ng nguyn tc th kt qu cui cng mi c
th chnh xc.
Bi vy sinh vin phi chun b tht k trc khi lm th nghim:
- Nm vng c s l thuyt ca th nghim, hiu thu o ngha ca tng thao
tc th nghim.
- Nm vng cch s dng cc dng c th nghim, cch pha ch, chun b cc
ha cht cn thit.
- Trnh t th nghim.
- Cch ghi chp v tnh ton kt qu th nghim.
gip sinh vin chun b tt, cui mi bi th nghim u c cu hi v bi tp. Sinh
vin cn hon thnh y cc phn ny trc mi bi th nghim.
II. Tin hnh th nghim
Mun tin hnh th nghim c kt qu tt trong thi gian nh sn, khng lng ph ha
cht, lm h hng dng c, thit b, sinh vin cn ch mt s qui tc sau:
1. Sp xp ch lm vic
Ch lm vic phi sch s, kh ro, cc dng c phi b tr thun tin cho vic s
dng, trnh xy ra va chm, v..
2. Chun b dng c, thit b
Cc dng c thy tinh, s phi bo m sch s trc khi dng, cn kim tra dng
c thit b trc khi dng v bn giao y cho phng th nghim sau khi hon thnh th
nghim.
3. Ghi chp
Mi hin tng, s liu trong khi th nghim u phi ghi vo s th nghim, khng ghi
vo mnh giy ri hoc ghi ln bn.

Trc v trong khi lm th nghim nu cn iu g cha nm vng sinh vin phi
hi thy, c gio hng dn.

8
G GI I I I T TH HI I U U M M T T S S D D N NG G C C , , T TH HI I T T B B C C B B N N
K KH HI I L L M M T TH H N NG GH HI I M M P PH H N N T T C CH H N NH H L L N NG G

I. Dng c thy tinh
C nhiu loi dng c bng thy tinh c s dng khi tin hnh phn tch nh lng.
V c bn c th chia thnh ba loi sau:
Loi dng ng, bo qun, cha nh bnh, chai, l...
Loi dng un nng nh cc c m, bnh nn hay bnh tam gic...
Loi dng o nh bnh nh mc, ng ong, buret, pipet...

a - Bnh nn (bnh tam gic) b - Cc c m dung tch 100ml c ng ong

d Bnh nh mc - pipet e Buret v autoburet
Hnh 1: Mt s loi dng c thy tinh thng dng trong phn tch nh lng
Ni chung cc dng c thy tinh u d b kim n mn, b HF ph hy. c bit dng
c thy tinh u d b v khi va chm, nh ri, dn n t ngt.
Lu rng ch c un nng cc dng c thy tinh chu nhit. Khng c un dung
dch bng cc bnh nh mc hoc trong cc chai l thng thng dng ng.

9
II. Dng c bng s

Bt s, cc s, chn s... u l loi dng
c chu c nhit tng i cao, c th chu
c nhit ti 1000
o
C, bn vi cc axit v c,
bn c hc tt. Tuy nhin chng chu kim km
v khng th s dng thc hin cc phn ng
kim chy.
Hnh 2: Chn nung bng s
III. Dng c bch kim
Bt, chn, in cc bch kim l nhng vt dng t tin, chng chu c nhit rt
cao (bch kim nng chy 1770
o
C), bn vi cc loi axit v c (k c HF). Tuy nhin bch
kim cng b cng thy ph hy v vy tuyt i khng c ha tan mu bng cng thy
khi s dng dng c bch kim.
c bit bch kim d to hp kim vi Pb, Sb, As, Bi, Sn, Ag, Au, C... v vy khng
nung cc cht ny trong bt, chn bch kim v trnh nung dng c bch kim trn ngn la c
khi (C). Khng thc hin phn ng kim chy c cht oxy ha v khi Pt s b ha tan
lm hng chn.
IV. L nung
C nhiu loi l nung c s dng trong phng th nghim ha phn tch, da theo
nhit ti a m chng c th t c ngi ta chia lm ba loi l sau:
1. Loi l nung c th t 800
o
C
1000
o
C: loi ny thng dng si t Niken-
Crom qun xung quanh mt hp lm bng vt
liu chu la. iu chnh nhit ngi ta
s dng cp nhit in ni vi cc rle v b
ngun cung cp in p
o
C
1200
o
C: loi ny dng si t l mt hp kim
c bit, c th chu nhit cao hn (v d
nh Tantan), cc si t c sp xp sao
cho gn vt nung nht c th.
Hnh 3: L nung
o
C 1400
o
C: loi ny khng dng si t thng thng
m phi dng cc thanh t l vt liu ca hp cht silic, l thanh cacbuasilic. Vt nung
c t vo ng hnh tr t gia cc thanh cacbuasilic.

10
V. Cn phn tch v nhng lu khi s dng cn
1. Cn phn tch
Cn l thit b thng xuyn phi dng trong cc phng th nghim ha phn tch. l
thit b chnh xc, t tin v d hng. C hai loi cn chnh l cn k thut v cn phn tch.

Hnh 4: Cn k thut v cn phn tch in t hin s
Cn k thut: dng cho php cn km chnh xc, c th cn s b trc khi cn phn
tch; cn cc vt, ha cht c hi m khng cn sy sau xc nh li nng bng cc
cht chun. Sai s ca php cn ny t 0,01 n 0,1 gam.
Cn phn tch thng cn cc vt c khi lng cn ti a khng qu 200 gam, c
chnh xc ti 10
4
10
5
gam, bao gm hai loi chnh l cn c hc v cn in t.
Cn c hc ngy nay t c s dng trong cc phng th nghim, nguyn l hot
ng ca cn n gin l dng qu cn v n cn o khi lng ca vt cn. Quang
cn v n cn c bng cc li dao hp kim chu mi mn tt. Cn Mettler c cu
to gm hai li dao cn (hnh 5), mt li dng treo quang cn, li dao cn li dng
nng n cn v tr cn bng. Khi a vt vo cn ta phi ly bt qu cn ra vi khi
lng tng ng gi cho n cn v li v tr cn bng ban u.

Hnh 5: Cn k thut v s lm vic ca cn Mettler

11
Ngy nay cn in t ra i s dng k thut s v hin th bng mn hnh tinh th
lng nn gim bt c rt nhiu thao tc cho ngi phn tch. Nguyn l hot ng ca
cn in t l vt cn ko a cn xung vi lc F = m.g vi m l khi lng ca vt cn; g
l gia tc trng trng. Cn in t s dng mt lc phn hi in t ko a cn v v tr
ban u ca n. Khi t vt cn vo a cn, do khi lng ca vt cn ko a cn xung,
iu s c detector pht hin v gi tn hiu n b chnh dng, dng phn hi c
sinh ra a ti ng c tr. Dng in cn thit sinh ra lc phn hi t l vi khi lng
ca vt v c hin th trn mn hnh hin s.

Hnh 6: Cn in t v nguyn l hot ng
2. Nhng lu khi s dng cn
- Trc khi cn phi kim tra thng bng ca cn qua bt nc ca b phn iu
chnh thng bng, bt nc phi nm gia vng trn gii hn.
- Khi cn phi i din vi cn, mi thao tc phi nh nhng trnh va p.
- Ngun in cp cho cn phi ng, bt cng tc ngun, i cho cn n nh, mn
hnh hin th ch 0,0000 g.
- Khng c cho vt qu khi lng gii hn ca cn (khi lng ny c ghi trn
tng loi cn c th).
- t vt cn chnh gia a cn.
- Ch cn vt nhit bng nhit xung quanh khng gian ca cn v vy i vi
nhng vt ly l nung, t sy... ra nht thit phi t vo bnh ht m ti nhit
phng ri mi c cn.
- Trong thi gian cn cc ca t cn phi ng kn.
- Trong bt k trng hp no cng khng t trc tip ha cht ln a cn (phi
ng trong cc cc cn, thuyn cn hoc giy cn ph hp). Khi cn cc cht d bay
hi phi ng trong bnh c nt kn.
- Cn xong phi tt cn, rt ngun v v sinh sch s cn.

12
X X L L T TH H N NG G K K C C C C S S L LI I U U T TH H C C N NG GH HI I M M

Ngay c nhng quan st chnh xc cng c th dn n nhng kt lun khng chnh
xc nu cc s kin th nghim c x l khng ng. V vy vic x l cc kt qu thc
nghim l mt giai on quan trng khi thc hin cng vic th nghim v nghin cu. C s
v cc thut ng ca cng vic da trn nhng l thuyt v xc sut v thng k ton, di
y ch trnh by ni dung ca phng php ny di dng cc v d c th sinh vin c
th p dng ngay khi x l cc s liu th nghim.
V d 1: Xc nh axit phophoric bng phng php th tch da trn vic chun axit
phophoric bng dung dch chun NaOH khi c mt cht ch th metyl da cam. Lng NaOH
tiu tn sau 7 ln lm th nghim c ghi li nh sau:
x
1
=7,75ml; x
2
=7,70ml; x
3
=7,78ml; x
4
=7,75ml; x
5
=7,76ml; x
6
=7,05ml; x
7
=7,70ml
Ta tnh cc c trng.
K vng mu:
1
1 7, 75 7, 07 7, 78 7, 75 7, 76 7, 05 7, 70
7, 64
7
n
i
i
x x m
n
=
+ + + + + +
= = =
l
nu s dng chng trnh Microsoft Excell ta dng hm AVERAGE (X)
Phng sai mu iu chnh
*2 2 2
1
1
( ) (0, 2625)
1
n
i
i
S x x
n
=
= =

lch chun
*
0, 2625 S =
nu s dng chng trnh Microsoft Excell ta dng hm STDEV (X)
Lp bng
V (NaOH) ml ( )
i
x x
2
( )
i
x x
1 7,75 0,1086 0,011788
2 7,70 0,0586 0,003431
3 7,78 0,1386 0,019202
4 7,75 0,1086 0,011788
5 7,76 0,1186 0,014059
6 7,05 -0,5914 0,349788
7 7,70 0,0586 0,003431
Ta nhn thy kt qu o 6, gi tr tuyt i ca lch so vi gi tr trung bnh
vt qu 2.S
*
(0,5914 > 0,2625 . 2 = 0,5250) nn kt qu ny phi loi b.
Nh vy vi s ln o n=6 ta c c cc kt qu sau:
{7,75ml; 7,70ml; 7,78ml; 7,75ml; 7,76ml; 7,05ml; 7,70ml}

13
S dng chng trnh Excell tnh
c trng Lnh trong Excell Kt qu
K vng ( x ) =AVERAGE (X) 7,74
lch chun (S
*
) =STDEV (X) 0,0329
Phn v vi tin cy 95% (t
0,05; 5
) =TINV (0,05; 5) 2,5706
p dng cng thc:
* *
S S
x t m x t
n n

< < +
ta tm c khong tin cy ca gi tr trung bnh vi tin cy 95% l 7,74
0,035ml NaOH.
Nu tin cy l 98% th khong tin cy ca gi tr trung bnh s l 7,74
0,045ml NaOH. Nh vy nu tng tin cy, khong tin cy cng ln theo, v vy trong
thc hnh ngi ta khng chn tin cy qu cn 1.
V d 2: Tin hnh phn tch song song domomit xc nh %CaO trong , ngi ta
thu c mt s kt qu phn tch sau:
x
1
=29,22%; x
2
=28,82%; x
3
=28,94%; x
4
=29,02%; x
5
=29,56%; x
6
=29,22%; x
7
=29,78%
Lp bng:
% CaO ( )
i
x x
2
( )
i
x x
1 29,22 -0,002857143 0,000008163
2 28,82 -0,402857143 0,162293878
3 28,94 -0,282857143 0,080008163
4 29,02 -0,202857143 0,041151020
5 29,56 0,337142857 0,113665306
6 29,22 -0,002857143 0,000008163
7 29,78 0,557142857 0,310408163
K vng: x = 29,22%
lch chun S
*
= 0,3434
Phn v t
0,05; 6
= 2,4469
Nh vy vi xc sut 95% c th ni hm lng %CaO trong mu nm trong gii hn
29,22% 0,34 ngha l bng 28,88 29,56%.

14
P PH H N N 1 1: : C C C C P PH H N NG G P PH H P P P PH H N N T T C CH H H H A A H H C C

CHNG I
PHN TCH BNG PHNG PHP TRNG LNG

Phng php phn tch trng lng l phng php phn tch nh lng ha hc da
vo vic cn khi lng sn phm c tch ra bng phn ng kt ta tm c hm
lng ca cht cn phn tch hay cn nh lng.
y l phng php c chnh xc cao nht trong cc phng php phn tch ha
hc (sai s nh hn 0,1% nu hm lng ln hn 1%). C phm vi ng dng rng ri; xc
nh c nhiu cht, nhiu nguyn t nhng phng php ny i hi thi gian tin hnh
phn tch lu (vi gi cho ti c bui).
Ni chung mt quy trnh phn tch thng c tin hnh qua cc giai on:
- Ch ha mu phn tch, a mu vo dng dung dch.
- To kt ta: thc hin phn ng to ra kt ta.
- Tch kt ta ra khi dung dch (gn, lc, ly tm).
- Lm sch kt ta.
- Sy, nung, cn kt ta thu c.
Trong phn tch trng lng ngi ta lc kt ta bng giy lc khng tn. Giy lc
khng tn l loi giy lc khi t chy, khi lng cn li t 3.10
-5
8.10
-5
g tro (ty theo
tng loi). Thc t khi lng ny khng nh hng ti kt qu phn tch ( chnh xc ca
cn phn tch l 0,0001g).
Giy lc bng xanh l loi giy lc mn, xp nh nht, dng lc cc kt ta tinh
th nh nh BaSO
4
, PbSO
4
... Giy lc bng trng, bng vng l loi giy lc c xp trung
bnh, dng lc cc kt ta hydroxit kim loi. Giy lc bng l loi giy lc c xp
ln nht, dng lc cc kt ta tinh th ln.
Thao tc gp giy lc v k thut lc trong phn tch nh lng c m t qua cc
hnh 7 v 8.
Trong chng ny trnh by hai bi th nghim rt c bn trong phn tch trng lng
l: xc nh sunfat (kt ta tinh th), xc nh st (kt ta v nh hnh) v mt bi th
nghim c tnh ng dng cao ph hp vi yu cu sn xut.

15

Hnh 7: Thao tc gp giy lc trong phn tch trng lng

Hnh 8: K thut lc gn dung dch trong phn tch trng lng
Hnh 9: K thut ra kt ta trn giy lc

16
Bi 1
XC NH (SUNFAT) THEO PHNG PHP KHI LNG
2
4
SO

I. C s phng php
2
4
SO

c kt ta bi ion Ba
2+
theo phn ng:

2 2+
4 4
SO + Ba BaSO

lc, ra kt ta, sy kh v nung ti khi lng khng i. T khi lng BaSO
4
suy
ra lng
2
4
SO

Phng php ny thng c dng xc nh lu hunh trong tt c cc trng hp
khi lu hunh c th bng cch ny hay cch khc oxi ha thnh ion SO
4
2
II. Cch xc nh
1. iu kin th nghim
- Lng mu cn ly: BaSO
4
l kt ta tinh th nn theo kinh nghim thc t cn ly
lng mu sao cho lng BaSO
4
vo khong 0,5g.
- Tin hnh th nghim theo ng nhng iu kin bit v s to thnh kt ta tinh
th: dung dch mu v thuc th long, nng, tc thm thuc th chm, dung dch c tnh
axit (pH = 2).
- Cn tch cc ion cn tr: SiO
3
2
, WO
4
2
, SnO
3
2
(v c th to kt ta: H
2
SiO
3
, H
2
WO
4
,
H
2
SnO
3
), cng cn tch hoc che cc ion d cng kt nh Fe
3+
, Al
3+
, Cl
, MnO
4
.
- Khi nung, BaSO
4
c th b kh mt phn bi C ca giy lc:
BaSO
4
+ 2C = BaS + 2CO
2

Nu c khng kh th BaS li b oxi ha thnh BaSO
4
.
Nh vy, nung n khi lng khng i th khng cn BaS:
BaS + 2O
2
= BaSO
4
2. Cch tin hnh
Ly chnh xc 10,00ml dch cha SO
4
2
cho vo cc c m loi 250ml, pha thm nc ct n
150ml, thm vo dung dch khong 2ml HCl 2N v khong 2ml axit picric 1%, sau un dung
dch n gn si. Ly khong 6ml dung dch BaCl
2
5% cho vo cc c m loi 100ml, pha
long bng nc ct n 50ml v un dung dch n gn si.
Rt t t dung dch BaCl
2
vo dung dch cha SO
4
2
, khuy lin tc. Khi rt gn
ht, kim tra xem SO
4
2
kt ta ht cha. Mun vy, lng kt ta, nh thm vi git
dung dch BaCl
2
theo thnh cc, nu khng thy dung dch vn c na th tc l s kt ta
hon ton.
un cch thy cc ng kt ta khong 1 gi, sau ly ra ngui lc qua giy lc
dy (bng xanh). Cc thao tc gp giy lc thu kt ta c m t hnh 7.
Ra kt ta 34 ln, mi ln dng 2030ml nc ct.

17

Cch lm nh sau: trc ht gn dung dch
qua giy lc, nc vo cc c kt ta khuy u
nh nhng, lng kt ta ri li gn dung dch
qua giy lc (thao tc gn dung dch phi rt qua
a thy tinh c m t hnh 10). Lp li thao
tc ny nhiu ln ti khi hu nh ht ion Cl
. Cui
cng chuyn ton b kt ta ln trn giy lc.
Dng tng ming giy lc nh dm nt v vt ht
cc kt ta trong cc cho ln giy lc trn phu. Hnh 10: Thao tc gn lc kt ta
Tip tc dng nc ct ra kt ta trn giy lc cho n khi kim tra thy trong nc
ra khng cn Cl
th thi (dng dung dch AgNO

3
th).
cho giy lc ro nc, cho c giy lc v kt ta vo chn s nung v cn trc
ghi khi lng m
0
.
Sy chn nung trn bp in v cho giy lc chy t t thnh than (khng c bc
chy thnh ngn la, v kt ta s bn ra ngoi). a chn vo l nung, nung nhit
800
o
C trong 2025pht. Sau ly chn nung ra, cho vo bnh ht m, ngui ri cn.
Li cho chn nung vo l, nung thm 1015pht v lp li thao tc trn cho n khi
thy khi lng cn khng thay i th kt thc th nghim ghi khi lng m
1
.
Tnh khi lng :
2
4
SO

2
4
1 0
96
( ).
233, 33
SO
m m m
= .
Tnh hm lng /lt.
2
4
SO

III. Ha cht v dng c cn thit
- Dung dch phn tch (H
2
SO
4
).
- Dung dch BaCl
2
5%.
- Dung dch HCl 2N, axit picric 1%.
- Dung dch thuc th AgNO
3
.
- Cc c m 100ml, 250ml, phu lc, pipet, ng ong, giy lc bng xanh...
Cu hi v bi tp
1) Gii thch cc iu kin trong th nghim trn.
2) Ti sao phi kt ta BaSO
4
khi c mt HCl?
3) Phn ng g xy ra i vi BaSO
4
khi tro ha giy lc? Ti sao phi nung kt ta
n khi lng khng i?
4) Tnh s gam H
2
SO
4
trong 1lt dung dch nu dng BaCl
2
kt ta BaSO
4
ta thu
c BaSO
4
c khi lng 0,2126g.
(.S: 0,089gam)

18
Bi 2
XC NH ST THEO PHNG PHP KHI LNG

I. C s ca phng php
Kt ta Fe
3+
bng NH
4
OH theo phn ng:
Fe
3+
+ 3NH
4
OH = Fe(OH)
3
+ 3NH
4
+
Khi nung, Fe(OH)
3
chuyn thnh Fe
2
O
3
2Fe(OH)
3
= Fe
2
O
3
+ 3H
2
O
T lng cn Fe
2
O
3
suy ra c lng st.
(Th nghim ny c tnh gio khoa, thc t ngi ta hay dng phng php th tch).
II. Cch xc nh
1. iu kin th nghim
- Fe(OH)
3
l mt kt ta v nh hnh in hnh, rt d b bin thnh dung dch keo.
trnh hin tng ny, phi tin hnh kt ta theo ng nhng iu kin ti u khi to kt ta
v nh hnh: dung dch phn tch v thuc th tng i c, tin hnh phn ng trong dung
dch nng c thm cht in ly lm ng t (NH
4
NO
3
), kt ta xong pha long v lc ngay,
ra kt ta bng nc c pha thm cht in ly mnh.
- Dung dch mui Fe(III) d b thy phn, khi un nng s thy phn xy ra cng mnh:
FeCl
3
+ 2H
2
O Fe(OH)
2
Cl + 2HCl
Fe(OH)
2
Cl + H
2
O Fe(OH)
3
+ HCl
Kt ta do phn ng thy phn to ra dng nhy, bm cht vo cc rt kh lc, ra
sch. Bi vy phi ngn nga s thy phn bng cch thm HNO
3
, sau ny HNO
3
s b
NH
4
OH trung ha to ra NH
4
NO
3
ng vai tr cht in ly lm ng t keo.
- Phi tch ht ion Cl
v n c th to thnh FeCl
3
, khi nung cht ny bay hi mt
phn lm mt mt phn st.
- Khng nung nhit qu cao (>900
o
C) v qu lu v c th mt phn Fe
2
O
3
bin
thnh Fe
3
O
4
lm sai kt qu:
6Fe
2
O
3
= 4Fe
3
O
4
+ O
2
2. Cch tin hnh
Ly chnh xc 10,00ml dung dch FeCl
3
, cho vo cc c m 250ml, thm 5ml dung dch
HNO
3
2N, un nh trn bp in (khng un si). Cho thuc th NH
4
OH 10% lin tc vo
dung dch FeCl
3
ang nng, khuy lin tc cho n khi trong cc c mi NH
3
bc ra. un
nng sn khong 100ml nc ct, vo dung dch v khuy nh. yn cho kt ta lng ri
th li xem kt ta hon ton hay cha (dng vi git dung dch NH
4
OH nh theo thnh
cc, nu khng thy vn c th s kt ta l hon ton), sau lc kt ta ngay, dng giy lc
trung bnh (bng trng).

19
Ra kt ta vi ln bng nc ct nng c pha NH
4
NO
3
2%. Lc gn v ra kt ta
theo cch nh bi kt ta BaSO
4
.
Chuyn ton b kt ta ln giy lc. Tip tc ra bng nc ra trn cho n khi trong
nc lc ht ion Cl
(th nh bi kt ta BaSO
4
).
giy lc ro nc, chuyn c kt ta v giy lc v chn s nung v cn trc,
sy kh ri t chy giy lc trn bp in. a chn nung vo l, nung 900
o
C khong 40
pht. Ly chn nung cho vo bnh ht m ngui ri cn.
Nung v cn li cho n khi khi lng chn v kt ta khng i.
Tnh hm lng FeCl
3
(g/l)
- Dung dch phn tch FeCl
3

- Dung dch NH
4
OH 10%
- Dung dch HNO
3
2N
- Dung dch NH
4
NO
3
2%
- Dung dch thuc th AgNO
3

- Cc c m 100ml, 250ml, bnh tam gic 250ml
- Pipet, ng ong, phu lc, a thy tinh, giy lc bng trng.
Cu hi v bi tp
1) Gii thch cc iu kin trong th nghim trn (axit ha dung dch; s c mt ca
NH
4
NO
3
khi kt ta Fe(OH)
3
, khi ra kt ta; pha long dung dch sau khi kt ta; ra tht
sch Cl
kt ta trc khi nung, khng nung nhit qu cao).

2) Sau khi kt ta Al
3+
, Fe
3+
trong mt dung dch bng NH
4
OH ri nung c Al
2
O
3
,
Fe
2
O
3
. T mt th nghim khc ngi ta xc nh c lng Fe. tnh lng Al ngi ta
lm nh sau: Gi Q l tng khi lng Al
2
O
3
+ Fe
2
O
3
; a l khi lng Fe; b l khi lng Al
b = [Q (a X1,4297)] X 0,5292
Cc h s 1,4297 v 0,5292 l h s g?

20
Bi 3
XC NH NIKEN TRONG THP

I. C s phng php
Thp thng c cha niken vi hm lng tng i ln, phng php ph bin
xc nh hm lng niken trong mu thp l s dng thuc th dimethylglyoxim kt
ta chn lc niken.
H
3
C C
N
HO
CH
3
C
N
OH
+ Ni
2+ Ni
N
N
N
N
C
O
CH
3
O
H
O
O
H
C
H
3
C
C
H
3
C
C
CH
3
+ 2H
+

nh hng ca ion st (III) c th b loi tr bng cch thm axit tactric vo dung dch
khi phn tch. Lu rng v thuc th dimethylglyoxim pha trong cn cho nn cn khng
ch lng thuc th a vo lm kt ta do mt nng cao cn s c th ha tan ng k
kt ta niken dimethylglyoxim lm kt qu phn tch b thp so vi thc t. Tuy nhin nu
cho khng lng thuc th s khng kt ta c hon ton lng niken c trong mu v
gy sai s m.
II. Cch tin hnh
Ly mu i din v lm kh mu ti khi lng khng i 110
o
C trong t nht 1 gi.
Cn chnh xc mt lng mu (cha khong 30~35mg niken) cho vo cc 500ml. Ha
tan mu bng 50ml HCl 6M, un nh, sau thm tht cn thn 15ml HNO
3
6M vo dung
dch. un si k ui nit oxyt ra khi dung dch.
Pha long dung dch bng 200ml nc sau li un si tr li. Tip tc thm vo
30ml axit tactric 15% v NH
4
OH ti khi thy c mi NH
3
thot ra, cho d khong 1~2ml
NH
4
OH na. (Nu dung dch khng trong sut do c Fe
2
O
3
.xH
2
O c hnh thnh khi cho
NH
4
OH vo, ta axit ha dung dch bng HCl, thm axit tactric v thc hin li qu trnh
trung ha. Cch khc l lc kt ta vi dung dch ra l dung dch NH
3
/NH
4
Cl nng).
Axit ha dung dch bng HCl ti khi khng cn mi NH
3
na, un nng dung dch ti
~60
o
C ri thm 20ml dimethylglyoxim 1%. Khuy u, dng dung dch NH
4
OH 6M thm vo
dung dch ti khi thy mi NH
3
thot ra, cho d thm 1~2ml na.
yn cc ng kt ta trong khong 30~60 pht ri tin hnh lc, ra kt ta bng
nc ct ti khi ht ion Cl
.
Tro ha giy lc ri sy kt ta n khi lng khng i 110
o
C.
Tnh hm lng phn trm niken c trong mu, bit rng dng cn c cng thc ha
hc l Ni(C
4
H
7
O
2
N
2
)
2
(288,92 g/mol)

21
III. Ha cht v dng c
- Dimethylglyoxim 1% (w/v): Ha tan 10g dimethylglyoxim trong 1lt ethanol
- Axit tactric 15% (w/v): Ha tan 225g axit tactric trong 1500ml nc ct. Lc trc
khi s dng nu dung dch khng trong sut.
- Cc axit HCl 6M, HNO
3
6M
- NH
4
OH 10%
- AgNO
3

- Bp in, l nung, chn s, cc chu nhit, a thy tinh, phu lc

=============================================================
Gi phn tch mt s cation v c bng phng php phn tch trng lng

=============================================================
=============================================================
Gi phn tch mt s anion v c bng phng php phn tch trng lng

=============================================================

22
CHNG II
PHN TCH BNG PHNG PHP TH TCH

Da vo bn cht ca phn ng trong phn tch th tch c th phn loi cc phng
php phn tch sau:
- Phng php trung ha: da vo phn ng gia axit - baz nh lng trc tip
hay gin tip axit, baz, mui.
- Phng php oxy ha kh: da vo phn ng oxy ha kh nh lng cc
nguyn t chuyn tip, mt s cht hu c v c th nh lng mt cch gin tip
cc anion v c.
- Phng php kt ta: da vo phn ng to thnh cc hp cht kt ta (hp cht t
tan).
- Phng php to phc: da vo phn ng to phc cht ca cht cn phn tch v
thuc th. N nh lng c a s cc cation kim loi v mt s anion. Thuc th
c dng nhiu nht l Complexon.

DNG C DNG O TH TCH DUNG DCH
Khng k cc dng c ha hc thng thng, trong phn tch th tch cc dng c
dng o chnh xc th tch dung dch c mt vai tr rt quan trng. Di y s gii thiu
ba loi dng c o th tch chnh xc dung dch thng xuyn gp khi tin hnh phn tch
nh lng.
I. Bnh nh mc
Bnh nh mc l bnh thy tinh pha di c dng trn, y bng; c di, b c vch
nh mc. Bnh nh mc dng ong th tch dung dch, pha ch cc dung dch c
nng xc nh. Th tch cht lng ng trong bnh c biu din bng mililit (cc bnh
nh mc thng c dung dch khc nhau t 25 ti 2000ml).
Khi lm vic vi bnh nh mc cn trnh tip xc tay vo bu bnh, ch cm tay vo
phn trn c bnh, v nhit t tay s truyn vo thnh bnh lm thay i dung tch bnh.
Trc khi lm y bnh nh mc, phi t bnh v tr bng phng v c chiu sng r.
II. Pipet
Pipet l ng thy tinh di, b; c th phnh ra gia; trn ng c cc vng vch mc
hoc vch chia 0,1-1ml vi cc pipet o dung tch nh. Pipet dng o nhng th tch nh
dung dch v chuyn mt th tch xc nh dung dch t bnh ny sang bnh khc. Th tch
cht lng cha trong pipet c biu din bng mililit (cc pipet c dung tch khc nhau t 1
ti 100ml).
Khi lm vic vi pipet, khng c chm tay vo phn gia ca pipet, nhit t tay s
lm thay i dung tch ca pipet.

23

Hnh 11: Ly dung dch bng pipet s dng qu bp cao su thng dng
a Ht dung dch ln b iu chnh mc cht lng trong pipet
Tay cm u trn ca pipet bng ngn ci v ngn gia ca tay thun ri nhng u
di ca pipet vo dung dch (gn n y bnh). Tay khng thun cm qu bp cao su bp
li ri a vo u trn pipet ht dung dch vo pipet n khi dung dch trong pipet cao
hn vch mc 2 3cm. Dng ngn tay tr bt nhanh u trn ca pipet cht lng khng
chy ra khi pipet. Dng tay khng thun nng bnh ng dung dch ln, iu chnh nh
nhng ngn tay tr cht lng tha t t chy ra khi pipet. Khi mt cong di ca cht
lng trng vi vch ca pipet th dng ngn tay tr bt cht u trn pipet li v chuyn pipet
c cha mt th tch chnh xc cht lng sang bnh chun . Khi iu chnh pipet phi
vch pipet ngang vi mt.
Khi chuyn cht lng sang bnh chun phi cho chy t t th cht lng mi chy
ht khi pipet. Nu cho chy nhanh, do lc chy ca cht lng m mt phn ng k s cn
li trong pipet. Pipet phi v tr thng ng khi chy.
Mc d cht lng chy ht khi pipet nhng u pipet vn cn mt t cht lng, v
vy ta phi chm u pipet vo bnh phn khng c dung dch cht lng chy ra ht.
III. Buret
Buret l nhng ng thy tinh nh c khc theo chiu di. u di ca buret tht li
v lp thm mt kha thy tinh qua dung dch t buret chy ra.

Hnh 12: Thao tc chun phng php
phn tch th tch
Hnh 13: c th tch buret khi mt cc v
tr khc nhau

24
Ngi ta thng khc vch trn buret thnh ml v mt phn mi ml.
Trn buret ngi ta khc nhng vch v nhng con s o th tch dung dch tiu tn
khi chun . Vch 0 nm phn trn ca buret.
Cc buret 25ml ngi ta khc vch vi chnh xc n 0,1ml, khong gia hai vch
chia gn nhau c c lng bng mt; iu cho php o vi chnh xc ti mt phn
trm mililit. Ngi ta o th tch cc dung dch khng mu theo phn di mt li cn dung
dch c mu theo phn trn mt li.

Hnh 14: c buret ng dung dch trong
sut. c 24,87ml
Hnh 15: c buret khi dung dch khng trong
sut. c 25,62ml
Khi lm vic vi buret ta phi kp buret vo v tr thng ng. Trc mi ln chun
ta phi dung dch chun vo buret ti vch 0 v ch lm y c phn cui v c kha
buret. Khi c ch s trn buret, mt phi v tr ngang vi vch li (hnh 14). C th c
theo phn cong xung hay cong ln ca mt cong dung dch, nhng tt c cc ln c k c
khi c vch 0 v khi c mc dung dch sau khi chun u phi ging nhau.
Khi tin hnh chun phi cho dung dch chy ra khi buret mt cch t t tt c
cht lng chy ht ra khi buret, iu ny c ngha c bit khi chun vi cc dung mi
khc nc. Cui qu trnh chun phi nh tng git dung dch, cn tin hnh chun vi
ln. Kt qu ca qu trnh chun l gi tr trung bnh ca mt s php xc nh song song.
Th tch dung dch chun tiu tn trong qu trnh chun khng c ln hn dung tch
ca buret. Php chun c coi l kt thc khi hiu th tch gia cc ln chun song
song khng qu 0,1ml.
IV. Lm sch dng c o th tch dung dch
Bnh nh mc, buret, pipet ch c coi l sch khi khng thy mt vt bn no v khi
trng nc ct thnh pha trong dng c khng ng git no.
Nu trn thnh dng c cn bm, ng nhng git nc l bnh b bn bi cc cht
du, m. Mun lm sch dng c khi cc vt du, m; ta ra bnh bng hn hp cromic,
dung dch kim pemanganat, hn hp ru-ete, dung dch kim-ru-kali, dung dch
trinatriphotphat nng...

25
Hn hp cromic c pha ch bng cch cn 9,2g K
2
Cr
2
O
7
( tn thnh bt) cho vo
cc ri thm 100ml axit sunfuric m c. un cch thy v khuy u ti khi tinh th
K
2
Cr
2
O
7
tan hon ton. Lu rng hn hp cromic c tnh oxy ha rt mnh nn khi lm
vic cn ht sc thn trng. Hn hp cromic lm phng da, khi ri vo qun o s lm chy
qun o hoc to thnh cc vt bn khng lm sch c. Ra xong li hn hp cromic
cn li vo bnh.
Mun lm sch thm cc bnh o, ngi ta dng mt phng
php c bit gi l hp bng hi nc. Mun vy ta kp mt bnh
ng nc vo gi v un si. Khi nc si, hi nc s phun vo
thnh bnh; nc ngng t trn thnh bnh nh mc s chy qua phu
tr li bnh un. Tin hnh hp khong 1 gi, sau khi hp trn thnh
bnh s khng cn dnh nhng git nc v th tch dung dch rt vo
bnh s hon ton chnh xc. Bnh sch khi mt cong hnh cu bn
trong hay phn c bnh pha trn mt lm dung dch khng cn dnh
nc khi trng bng nc ct.
Hnh 16: Hp bnh nh mc

26
TNH TON V PHA CH DUNG DCH TRONG PHN TCH TH TCH

I. Nng dung dch v cc cch biu din nng
1. Khi lng mol v mol ng lng
- Khi lng mol (M): khi lng ca 6,023.10
23
ht (phn t, nguyn t, ion...).
Khi lng mol ca mt cht l hng s, n v l g/mol.
- Mol ng lng (ng lng gam - ): ng lng gam ca mt cht l s gam
ca cht v mt ha hc tng ng vi mt mol hydro hay mt mol hydroxyl trong
phn ng m ta xt. ng lng gam ca mt cht khng phi l mt hng s, n ph
thuc vo phn ng ha hc m cht tham gia.
=
M
n

(n: s in tch hay s e ca mt phn t tham gia trao i trong phn ng)
V d:
[ ] [ ]
[ ]
3 4
3 4
4 6
3 4 2 4 2
H PO
3 4 2 4 2
H PO
4 6 4 6 2
K Fe(CN)
H PO + NaOH = NaH PO + H O
M
1 = =98
1
H PO + 2NaOH = Na HPO + 2H O
M
2 49
2
K Fe(CN) + 2CuSO = Cu Fe(CN) + 2K SO
M 378
4 94, 5
4 4
n g
n g
n g
=
= = =
= = = =
4

4
4
4 4 2 4 2 4 3 4 2 4 2
KMnO
FeSO
10FeSO +2KMnO +8H SO Fe (SO ) +2MnSO +K SO +8H O
M 158
5 31, 6
5 5
M 152
1 152
1 1
n g
n g
= = = =
= = = =

2. Mt s cch biu din nng
- Nng th tch ca mt cht lng l t s gia th tch ca cht lng v th tch
ca dung mi (thng l nc).
V d: HCl 1:4 (hoc 1/4) l dung dch gm 1 th tch dung dch HCl c v 4
th tch nc
- Nng phn trm (theo khi lng) s gam cht tan c trong 100gam dung dch
k hiu l C%.

m.100
C%=
m+q

m: s gam cht tan
q: s gam dung mi

V d: NaCl 20% c ngha c 20g NaCl trong 100g (ml) nc nguyn cht.

27
- Nng mol/l (nng M): s mol cht tan c trong 1lt dung dch.

M
m
C =
M.V

m: s gam cht tan
M: phn t gam cht tan
V: lt dung dch

- Nng ng lng: (nng N): s mol ng lng cht tan c trong 1lt dung
dch hay s ng lng gam cht tan c trong 1lt dung dch.

N
a
C =
.V

a : s gam cht tan trong V (lt) dung dch
: s ng lng gam cht

- chun (T): s gam (hay mg hoc g) cht tan c trong 1ml dung dch

R
a
T =
V

a : s
R
gam (mg) cht tan trong V(ml) dung dch
T : chun ca dung dch R

V d: Ha tan 7,64g NaOH thnh 500ml dung dch, th chun ca dung dch NaOH
bng bao nhiu?
NaOH
7, 64
0 01528 15 28
500
T = = = , , g/ml mg/ml
- chun theo cht cn xc nh (T
A/B
): s gam cht cn xc nh B tc dng va ht
(tng ng) vi 1ml dung dch chun cht A (A l thuc th, B l cht nh phn).
V d 1: Tnh chun ca dung dch K
2
Cr
2
O
7
0,05N theo Fe khi xc nh Fe bng
phn ng chun sau:
6Fe
2+
+ Cr
2
O
7
2-
+ 14H
+
2Cr
3+
+ 6Fe
2+
7H
2
O
Gii: T
K
2
Cr
2
O
7
0,05N/
Fe
= 0,0028g/ml.
V d 2: Tnh chun dung dch KMnO
4
theo st, bit rng khi chun dung dch
cha 0,1170gam Fe
2+
th tn ht 20ml dung dch KMnO
4
.
Gii:
4
KMnO /Fe
0,1170
T = = 0, 00585
20, 0
g/ml

V d 3: chun ca dung dch KMnO
4
theo st bng bao nhiu nu ha tan 3,1610g
KMnO
4
thnh 1lt dung dch.
Theo phn ng chun :
4
4
2+
2+ - + 3+ 2+
2
KMnO
Fe
5Fe +MnO +8H Fe +2Mn +4H O
M 158
5 31, 6
5 5
M 55, 85
1 55, 85
1 1
n g
n g
= = = =
= = = =

S ng lng gam KMnO
4
trong 1ml dung dch bng 0,0001 v cng bng s ng
lng gam Fe
2+
b oxy ha. Vy chun ca KMnO
4
l:

4
KMnO /Fe
3,161.55,85
T = = 0, 005585
32, 61.1000
g/ml

28
Tng qut:
A/B
a
T = .
V
B
A

a s
A B
: gam thuc th trong V( ) dung dch
, : ng lng gam ca thuc th v cht nh phn
ml

3. nh lut tc dng ng lng: cc cht phn ng vi nhau va theo s ng
lng gam bng nhau.
A + B = C + D
S ng lng gam A = s ng lng gam B
- Nu A v B u dng dung dch:
N
A
, V
A
ln lt l nng ng lng v th tch ca dung dch A
N
B
, V
B
ln lt l nng ng lng v th tch ca dung dch B
th: N
A
.V
A
= N
B
.V
B
- Nu A tnh t lng cn cn B l dung dch:
Chng hn, c a (gam) cht tan A tc dng va vi V
B
(ml) cht B th:

=
B B
A
N .V ( ) a( )
1000
ml g

V d: Cn 0,106 gam Na
2
CO
3
tinh khit, sau ha tan trong mt th tch nc ty cho
ti khi tan ht. Chun dung dch Na
2
CO
3
bng dung dch HCl ht 16ml. Tnh nng HCl.
= = = =
2 3 2 3
HCl HCl
HCl
Na CO Na CO HCl
a.1000 0,106.1000
N 0
. 53.16
N .V a( )
1000 V
g
,125

II. Pha ch dung dch chun
1. Cht gc trong phn tch th tch
Dung dch chun, dung dch gc l dung dch c bn trong phn tch th tch, khi
chun da vo n xc nh hm lng cc cht trong cht phn tch. Vic pha ch mt
dung dch c nng chnh xc cn phi tun theo nhng quy tc c bit v tnh chnh xc
v cn thn nghim ngt khi lm vic. V th cc cht gc cn tha mn cc yu cu sau:
- Phi c tinh khit cao (tinh khit phn tch tkpt).
- Thnh phn ha hc ca cht tn ti trong thc t phi ng ng vi cng thc
dng tnh ton lng phi cn.
- Cc cht gc phi bn vng, khng ht m, khng tc dng vi khng kh, khng
chy khi cn, khi pha thnh dung dch nng ca n phi khng i theo thi gian.
- Phn t lng ca cht gc cng ln cng tt v nh th s lm gim c sai s
khi cn.
Do phi tha mn cc yu cu trn nn trong thc t phn tch nh lng ch c mt
s cht c chn lm cht gc, cho php o c th. V d trong phng php trung ha:
H
2
C
2
O
4
.2H
2
O v Na
2
B
4
O
7
.10H
2
O; phng php oxy ha-kh: K
2
Cr
2
O
7
v H
2
C
2
O
4
.2H
2
O;
phng php Complexon: Na
2
H
2
Y.2H
2
O.

29
thun li hn khi pha ch cc dung dch chun trn th trng c bn sn mt s
loi ha cht thng dng c cha trong ng thy tinh gi l fixanal. Trn mi ng
fixanal nh sn xut ghi r dung tch cn pha thu c nng xc nh.
V d: ng fixanal ng tinh th H
2
C
2
O
4
.2H
2
O trn c ghi N/10 c ngha khi pha
vo bnh nh mc loi 1000ml s thu c dung dch axit oxalic c nng 0,1N hay
0,05M.
1
2

Hnh 17: ng fixanal ng cc dung dch chun
(cc im 1, 2 trn hnh 11 l cc im cn phi chc thng bng a thy tinh chuyn vo
bnh nh mc)
2. Pha dung dch long t dung dch c
a. Nng c biu th bng nng M, N, T
1 1 2 2
2 1
. .
( )
n
C V C V
V V V
=
= +

C
1
, C
2
nng ca dung dch c v dung dch long ca cht cn pha
V
1
, V
2
th tch ca dung dch c v dung dch long
V
n
th tch nc cn phi thm vo V
1
ml dung dch nng C
1
c V
2
ml dung
dch nng C
2
.
V d: Cn ly bao nhiu ml dung dch HCl 12M c 250ml dung dch HCl 0,1M.
1 1 2 2
1 1
. .
0,1.250
12. 0,1.250 2, 085
12
C V C V
V V
=
= = = ml

b. Nng c biu th theo %khi lng
2 2
1 1 1 2 2 2 1 2
1 1
.
. . . . .
.
C d
C d V C d V V V
C d
= =
C
1
, C
2
; d
1
, d
2
; V
1
, V
2
: nng , t trng, th tch dung dch c v dung dch long cn pha.
V d: Cn bao nhiu ml dung dch H
2
SO
4
98% (d=1,84) pha 1lt dung dch H
2
SO
4

5% (d=1,00)?
2 2
1 2 1
1 1
. 5.1, 00
. .1000 27, 73
. 98.1,84
C d
V V V
C d
= = = ml
)

c. Trn hai dung dch cng mt cht c nng khc nhau
Nu trn V
1
ml dung dch cht no c nng C
1
vi V
2
ml dung dch cht c
nng C
2
c dung dch C v th tch V ml. Chng ta c:
1 1 2 2 1 1 2 2 1 2
. . . hay . . .( C V C V CV C V C V C V V + = + = +

30
V d: Cn thm bao nhiu ml dung dch HCl c 12M (37%) vo 200ml dung dch
HCl 0,8M c c mt dung dch HCl nng 1M.
1 1 2 2 1 2
2 2 2
1
1
. . .( )
. . 1.200 0, 8.200
3, 63
12 1
C V C V C V V
CV C V
V m
C C
+ = +

= = =

l

d. Quy tc ng cho pha dung dch
* Tnh theo nng phn trm
V d: Cn bao nhiu ml dung dch H
2
SO
4
96% v nc ct c dung dch H
2
SO
4

30%.

30
96
30
66
0
Nh vy nu trn 30 gam dung dch H
2
SO
4
96% vi 66 gam nc ta s c dung dch
H
2
SO
4
30%
* Tnh theo t trng
V d: C dung dch H
2
SO
4
t trng 1,57 g/ml, lm th no pha c dung dch
H
2
SO
4
c t trng 1,20 g/ml.
0,20

1,57
1,2
0,37
1,00

Nh vy nhn cc s bn phi ca s vi 100 ta c 20 v 37. Ngha l trn 20g
dung dch H
2
SO
4
t trng 1,57g/ml vi 37ml H
2
O s c dung dch H
2
SO
4
t trng 1,2 g/ml.
Nu mun c lng dung dch H
2
SO
4
t trng 1,2 g/ml nhiu hn ta ch cn nhn 20 v 37
vi n ln mong mun.
III. Quan h gia chnh xc ca php o v chnh xc ca tnh ton
Kt qu phi tm khng th no chnh xc hn chnh xc ca phng php phn tch
dng, v vy vic tnh ton trong phn tch th tch phi c tin hnh vi chnh xc
sao cho ph hp vi vic o th tch dung dch chun bng buret.
Cc buret dung tch 25 50ml chia thnh nhng vch 0,1ml th chnh xc ca vic
c th tch dung dch trn buret y t c mt phn trm mililit. Cc microburet c th
tch 1 2ml chia thnh nhng vch 0,01ml th chnh xc ca vic c trn buret t c
mt phn nghn mililit.

31
1. Ch s c ngha
a. phn nh mc tin cy ca mt s o thc nghim, ta ch c php ghi s o
ny bng cc ch s c ngha.
b. i vi mi s o vi s t nhin thng thng, ta phn bit hai loi ch s c
ngha sau:
- Ch s c ngha khng tin cy: l ch s ng sau cng v bn phi ca s o. Ch
duy nht mt ch ch s c ngha khng tin cy trong mi s o.
- Ch s c ngha tin cy: l tt c ch s ng trc ch s c ngha khng tin cy v
tn cng v bn tri bng mt ch s khc ch s 0.
Mt s o c th c mt hay nhiu ch s c ngha tin cy. Cng nhiu ch s c
ngha th php o cng chnh xc.
V d: c trn buret, ta ghi c s o 12,65ml. S ny c tt c 4 ch s c ngha.
Phn loi nh sau: 5 l ch s c ngha khng tin cy; 1, 2, 6 l cc ch s c ngha tin cy.
S d gi 1, 2, 6 l cc ch s c ngha tin cy v trn buret c chia chnh xc ti 0,1ml th
ai cng c r c ch s ny. Ch s 5 thuc loi ch s c ngha khng tin cy v ngi
c phi c lng bng mt v do c s chnh lch; c khi c thnh 12,64ml hoc
12,66ml.
* S o c khng tin cy tuyt i: 0,01ml.
* S o c khng tin cy tng i l
0, 01 1
12, 65 1265
=
khng tin cy tng i mi c gi tr biu th chnh xc ca php o, n cng
nh th php o cng chnh xc.
c. i vi mi s o thuc loi s logarit th cc ch s c ngha ch tnh t ch s
khc khng u tin sau du phy. i vi mi s o thuc loi s m th cc ch s c ngha
cng ch tnh t ch s khc khng sau du phy (thuc phn m ca s m)
V d: logx = 4,3756 c 4 ch s c ngha (khng tnh ch s 4).
x = 10
3,246
c 3 ch s c ngha (khng tnh ch s 3)
Lu : Cc quy nh v ch s c ngha s logarit v cc s m trn ch ng khi x
(trong logx hoc 10
x
) l s o trc tip. Trong mt s php o, ngi ta o trc tip y=logx
hay y = 10
x
khi y tr thnh s t nhin thng thng v tun theo quy nh mc b.
V d: Cc my o pH cho php o trc tip pH=loga
H
+ , pH = 4,7 v s o ny c 2
ch s c ngha. T y chuyn ra a
H
+ th php ghi a
H
+ cng c 2 ch s c ngha
a
H
+ = 10
4,7
= 0,1995.10
4
= 0,20.10
4
hay a
H
+ = 2.10
5
.
2. Lm trn s cho s o gin tip
S o gin tip l s o tnh c t cc s o trc tip thng qua mt biu thc ton
hc no . Sai s ca s o trc tip lan truyn sang s o gin tip nn ta phi ghi s o
gin tip cng bng nhng ch s c ngha.

32
Khi tnh ton thng c nhiu s l, cn phi lm trn s. Mun vy ta phi tm ra s
cht trong mi biu thc tnh ton s o gin tip.
a. Php cng v tr: S cht c coi l s hng c khng tin cy tuyt i ln nht
V d: Tnh trng lng phn t ca BaO. Tra bng nguyn t lng, ta c c:
Ba: 137,34 (chp nhn khng tin cy l 0,01)
O: 15,9994 (chp nhn khng tin cy l 0,0001)
Nh vy BaO c khi lng l 153,3394 (lm trn thnh 153,34)
b. Php nhn v chia: S cht c coi l tha s c khng tin cy tng i ln
nht. S cht c bao nhiu ch s c ngha th s kt qu cng c by nhiu ch s c ngha.
V d: Ly 10,00ml HCl em chun bng dung dch NaOH 0,09215M th ht
2,45ml. Tnh C
HCl
.
HCl
0, 09215.2, 45
0, 0225767
10, 00
C M = =
lm trn thnh 0,0226M v s cht l 2,45.
c. Trong cc php tnh hn hp cn lm trn trong tng khu vc biu thc ri mi lm
trn ln cui cng.

33
CHT CH TH
I. Cht ch th cho chun axit baz trong mi trng nc
1. nh ngha
Cht ch th axit baz l nhng axit hoc baz hu c yu c kh nng bin i mu
nhng gi tr pH nht nh v mu ca dng axit khc mu ca baz.
Cht ch th axit baz bin i mu di tc dng ca axit baz. S bin i mu
ph thuc vo mc thay i nng ca ion hydro hay pH ca dung dch
Gi s c cht ch th HInd, trong dung dch c cn bng sau:
HInd H
+
+ Ind
(K
a,Ind
)
axit baz
(cht cho proton) (cht nhn proton)
mu A mu B
y HInd: dng phn t ca cht ch th; Ind
-
: dng ion ca cht ch th
Nu cn bng ca phn ng chuyn dch v pha bn phi th dung dch c mu ca
dng ion cht ch th. Nu cn bng chuyn dch v pha bn tri th dung dch c mu ca
phn t cht ch th.
V d: metyl da cam l mt axit tng i mnh (pK
a
=3,7) nn trong dung dch trung
ha c mu vng v trong dung dch dng ion chim u th.
HInd H
+
+ Ind

dng mu dng mu vng
Phenolphthalein l mt axit yu (pK
a
=9,2) nn trong dung dch trung ha cn bng
chuyn dch v pha bn tri v dng phn t chim u th hn dng ion.
HInd H
+
+ Ind

dng khng mu dng mu
2. Khong pH i mu ca cht ch th
Hng s in ly ca cht ch th c biu din bng cng thc:
K
a,Ind
= [H
+
].[Ind
-
]/[HInd]
pH = pK
a,Ind
lg([HInd]/[Ind])
V K
a,Ind
l mt hng s nn thm axit vo dung dch th [H
+
] v [HInd] s tng v
[Ind
] s gim, ngha l tng mu ca dng phn t cht ch th. Thm kim vo dung dch s
xy ra qu trnh ngc li, lm tng mu dng ion ca cht ch th.
Khong pH m trong thy c s bin i mu ca cht ch th gi l khong
chuyn mu ca cht ch th. Gi tr pH thch hp ca dung dch cn chun , m gi tr
thy r nht s bin i mu ca cht ch th l bng chng kt thc s chun c
gi l ch s chun v c k hiu bng ch pT.

34
Mu ca cht ch th c quyt nh bi t s nng ca dng phn ly v khng
phn ly, ngha l vo t l:
[Ind
-
]/[HInd] = K
a,Ind
/[H
+
] hay [HInd]/[Ind
-
] = [H
+
]/K
a, Ind
Mt thng c th nhn c mu ca cht ch th dng axit HInd khi [HInd] ln gp
10 ln [Ind
] hoc ngc li. Tc l:

[ ]
HInd
Ind

10: mu ca HInd pH pK
HInd
1
v
[ ]
HInd
Ind

1
10
: mu ca Ind
-
pH pK
HInd
+ 1.
Khong pH (pK
HInd
1; pK
HInd
+1) c gi l khong i mu ca cht ch th.
HInd Khong i mu Ind
-
pH

pK
HInd
1 pK
HInd
+ 1

3. Ch s chun ca cht ch th
Thay cho khong chuyn mu ca cht ch th, trong phn tch ngi ta cn dng ch
s chun ca cht ch th (pT). pT l gi tr pH ti u, gi tr pH cht ch th c
dng l tt nht cho qu trnh chun , gi tr pT gn trng pK
a,Ind
.
4. Chn cht ch th
iu kin quan trng nht khi chun l phi chn ng cht ch th, nu iu
kin ny khng c tun theo th khng th nhn c nhng kt qu phn tch chnh xc
ngay c khi cc giai on phn tch khc c tin hnh cn thn.
Khong chuyn mu ca cht ch th c chn phi nm trong bcnhy pH (hay
bc nhy chun ) ca h cho; cn ch s chun (pT) ca cht ch th phi trng vi
pH im tng ng.
V vy khi chn cht ch th, trc tin ta phi tnh ton khong pH ca dung dch,
trong c bc nhy pH, sau mi chn xem cht ch th no c khong pH chuyn mu
nm trong bc nhy pH tnh.
Ngoi ra, cng cn ch ti nh hng ca cc yu t c trng ca ng cong
chun nh cht ch th metyl da cam ch dng c khi chun dung dch HCl 0,1N v
1N, cn khi chun dung dch axit 0,01N th khng dng c.
Bng 1 di y trnh by c tnh v cch pha ch mt s loi cht ch th axit-baz
trong mi trng nc thng gp. Cc s liu chi tit v y v cc cht ch th c th
c tm thy trong cc s tay ha hc.

35
Bng 1: : Mt s cht ch th axit baz trong mi trng nc thng gp

Mu ca dng
TT Cht ch th Khong pH
axit baz
Cch pha
1. Metyl tm 0,0 1,6 Vng Tm 0,05% trong nc
2. Cresol 0,2 1,8 Vng
0,1g trong 26,2ml NaOH 0,01M
sau thm ~225ml nc
3. Thylmol xanh 1,2 2,8 Vng
sau thm ~225ml nc
4. Cresol ta 1,2 2,8 Vng
sau thm ~225ml nc
5. Dinatri erythrosine 2,2 3,6 Da cam 0,1% trong nc
6. Methyl da cam 3,1 4,4 Da cam Vng 0,01% trong nc
7. Congo 3,0 5,0 Tm 0,1% trong nc
8. Ethyl da cam 3,4 4,8 Da cam Vng 0,1% trong nc
9. Bromocresol xanh 3,8 5,4 Vng Xanh
sau thm ~225ml nc
10. Methyl 4,8 6,0 Vng
0,02g trong 60ml ethanol, thm
40ml nc
11. Chlorophenol 4,8 6,4 Vng
0,1g trong 23,6ml NaOH 0,01M,
thm ~225ml nc
12. Bromocresol ta 5,2 6,8 Vng ta
sau thm ~225ml nc
13. p-Nitrophenol 5,6 7,6 Khng mu Vng 0,1% trong nc
14. Litmus 5,0 8,0 Xanh 0,1% trong nc
15. Bromthymol xanh 6,0 7,6 Vng Xanh
0,1g trong 16ml NaOH 0,01M sau
thm ~225ml nc
16. Phenol 6,4 8,0 vng
sau thm ~225ml nc
17. trung tnh 6,8 8,0 Vng 0,01g trong 50ml ethanol + 50ml nc
18. Cresol 7,2 8,8 Vng
sau thm ~225ml nc
19. -naphttholphthalein 7,3 8,7 Hng Xanh m 0,1g trong 50ml ethanol, 50ml nc
20. Cresol ta 7,6 9,2 Vng ta
sau thm ~225ml nc
21. Thylmol xanh 8,0 9,6 Vng Xanh
sau thm ~225ml nc
22. Phenolphtalein 8,0 9,6 Khng mu 0,05g trong 50ml ethanol + 50ml nc
23. Thylmolphtalein 8,3 10,5 Khng mu Xanh 0,04g trong 50ml ethanol + 50ml nc
24. Alizarin vng 10,1 12,0 Vng cam 0,01% trong nc
25. Nitramine 10,8 13,0 Khng mu Cam sm 0,1g trong 70ml ethanol + 30ml nc
26. Tropeolin O 11,1 12,7 Vng Da cam 0,1% trong nc
27. Orange G 11,5 14,0 Vng 0,1% trong nc
28. Indigocacmin 11,6 14,0 Xanh tm Vng 0,25g trong 50ml ethanol + 50ml nc

36
II. Cht ch th cho chun axit-baz trong mt trng khng nc

Bng 2: Mt s cht ch th axit-baz trong mi trng khng nc
TT Cht ch th Dung mi
Lng
dng
S i mu Cht cn xc nh
1. Azo tm Piridin 0,1% Da cam Xanh Phenol, enol, imit
2. p-Aminoazo-bezen Cloroform 0,1% Vng Resorsin
3. Benzoinayrain axit axetic 0,1% Vng Tm Axit amin
4. Bromcresol xanh Cloroform 0,5% Xanh m Khng mu Amin bc 1, bc 2
5. Bromtimol xanh Piridin, axit axetic 0,1% Vng Xanh Axit hu c
6. Bromphenol xanh
Clobenzen, Cloroform,
ethanol
0,1% Tm Vng Ancaloit, amin, sunfamit
7. Congo metanol, dioxan 0,1% Xanh Amin
8. Methyl vng Cloroform 0,1% Vng Amin, nicotin
9. Methyl
Cloroform, metanol,
axit axetic
0,1% Vng photphat
10. Methyl da cam Axeton, metanol 0,1% Vng sm
Nhm marcotic ca
morphin
11. Methyl tm Clobenzen, axit axetic 0,1% Xanh Vng dn xut ca antipirin
12. Nitrophenol Clobenzen 0,1% Vng Khng mu Baz hu c
13. p-oxyazobezen Axeton 0,1% Khng mu Vng Axit cacboxylic
14. Phenol Ethanol 0,1% Vng Axit formic
III. Cht ch th cho chun oxy ha kh
Cht ch th oxy ho kh l nhng cht hu c c kh nng oxy ho - kh, mu ca
dng oxy ho khc mu ca dng kh. Trong dung dch n c th i mu theo in th
nhng gi tr xc nh.
Ind
Ox
+ ne = Ind
Kh
[ ]
[ ]
= +
Ox 0
Ind Ind
Kh
Ind
0, 059
E E lg
n Ind

Mu ca cht ch th c quyt nh bi t s nng 2 dng [Ind
Ox
]/[Ind
kh
]. Khi E
dd

thay i lm cho t s ny thay i th mu ca cht ch th cng thay i.
Thng th ta thy mu dng oxy ha khi [Ind
ox
] gp 10 ln [Ind
Kh
] v ngc li.
Tc l
[ ]
[ ]
Ox
Kh
Ind
Ind
10 : mu ca Ind
ox
+
0
dd Ind
0, 059
E E
n

[ ]
[ ]
Ox
Kh
Ind
Ind

1
10
: mu ca Ind
Kh

0
dd Ind
0, 059
E E
n

Khong
0
Ind
0, 059
E
n
gi l khong in th i mu ca cht ch th oxy ho - kh.

37
Ind
Kh
Khong i mu Ind
ox
E

0
Ind
0, 059
E
n

0
Ind
0, 059
E
n
+
Thc t gi tr
0, 059
n
kh nh nn coi nh cht ch th i mu qua E
0
.
Ind
Kh
Ind
ox
E

E
0

Bng 3: Mt s cht ch th oxy ha kh thng gp
Mu ca dng
TT Cht ch th E
0
(V)
oxy ha kh
Cch pha
1. 2,2 dipiridyl (phc vi Ru) +1,33 Khng mu Vng Trong HNO
3
1M
2. o-nitrophenantrolin+FeSO
4
+1,25 Xanh nht Trong H
2
SO
4
1N
3. 2,2 dipiridyl (phc vi Fe
2+
) +1,14 Xanh nht Trong H
2
SO
4
1N
4. Xylenol xanh BC +1,09 Vng 1% trong etanol
5. Axit phenylantranilic +1,08 Tm Khng mu
0,1g ch th trong 100ml
Na
2
CO
3
0,2% un nng
6. Feroin +1,06 Xanh nht
1,63g ch th+0,7g FeSO
4

trong 100ml nc
7. p-Nitrophenylamin +1,06 Tm Khng mu 1% trong etanol 96%
8. Natri diphenylaminsunfonat +0,84 Tm Khng mu 0,1% trong nc
9. Diphenylamin +0,76 Xanh tm Khng mu 0,1% trong H
2
SO
4
un nng
10. Metylen xanh +0,36 Xanh da tri Khng mu 0,2g ch th trong 100ml nc
IV. Cht ch th cho chun Complexon
Trong phng php complexon, ngi ta thng dng cc cht ch th c kh nng to
vi ion kim loi phc c mu khc vi mu ring ca cht ch th. Cht c gi l cht
ch th kim loi. Nh vy php chun ion kim loi bng EDTA gm 2 giai on sau:
- Phn ng gia ion kim loi t do v complexon.
- Phn ng gia complexon v ion kim loi trong phc.
C ch chuyn mu:
+
+
144444424444443
n
Me

dungdch m pH + CTKL

Phc cht [CTKL + Me
n+
] + H
2
Y
2-
= MeY
(4-n)-
+ 2H
+
+ CTKL t do
Mu A Mu B
Cht ch th nguyn cht rt kh s dng v ch cn mt lng nh i khi lm cho
mu dung dch qu m, khng th quan st c s i mu ti im tng ng. d
s dng ngi ta phi pha long chng bng nhng ha cht khc nhau.

38
Bng 4: Mt s cht ch th thng gp trong chun complexon
TT Cht ch th Ion cn xc nh pH, iu kin S thay i mu Cch pha
1 2 3 4 5 6
Ca
2+
>12; NaOH Tm
Cu
2+
, Ni
2+
, Co
2+
~8; NH
3
Da cam Tm 1 Murexide
Ag
2+
10-11,5; NH
3
Xanh tm
0,25% trn vi
NaCl tinh th
Al
3+
, t him
7-8; chun ngc bng
mui km c pyridin
Ba
2+
, Ca
2+

10; c mt complexonat
magie; m amn
Bi
3+
9-10; chun ngc bng
mui km
Cd
2+
, Co
3+
, Mg
2+
,
Zn
2+
, Cr
3+
10; NH
3
; chun ngc
bng mui Mn
Fe
3+
, Ti
4+
chun ngc bng mui
km c pyridin
Ga
3+
6,5-9,5; chun ngc
bng mui km
Hg
2+
9-10; thm complexonat
magie
Mn
2+
10, thm hydroxylamin
Ni
2+
, Pb
2+
10, chun ngc bng
mui km
Tl
3+
10, chun ngc bng
mui magie
2 Eriocrom en T
V
4+
10, chun ngc bng
mui Mn
nho Xanh
0,1% trn vi
NaCl (KNO
3
)
tinh th
t him 6-7 Xanh
Bi
3+
2-3; HNO
3
Vng
cam
Pb
2+
5-6 Xanh tm
Ni
2+
, Cd
2+
, Co
2+
9, m amn
3
Bromopyrogallol
(PBR)
Mg
2+
, Mn
2+
, Pd
2+
,
Tl
3+
, Fe
3+,
In
3+
,
Ga
3+
10, m amn, chun
ngc bng mui ch
hoc bitmut
Xanh nho
0,5% trong
ethanol 50%
Bi
3+
1-3, HNO
3
Th
4+
1,7-3,5; HNO
3
Zn
4+
HNO
3
1M; 90
o
C
Se
2+
2,2-5
Zn
2+
3-3,5; m axetac
Hg
2+
, Tl
3+
4-5; m axetac
Cd
2+
, Fe
2+
5-6; m urotropin
Vng
Co
2+
5-6; m urotropin; 80
o
C tm Vng
t him 5-6; m urotropin
Zn
2+
5-6; m axetac
Pb
2+
5; m axetac
Vng
4 Xylenol da cam
Al
3+
, Fe
3+
, Ga
3+
,
Ni
2+
, Pb
2+
, Sn
4+
,
U
4+
, VO
2+
Chun ngc vi mui
Th
4+
Xanh tm
Vng
0,5% trong
ethanol
Ca
2+
14,5; NH
3
12,5-13; NaOH
Cd
2+
11,5; NH
3
5 Canxon
Mg
2+
, Mn
2+
, Zn
2+
10, m amn
Hng Xanh
Trn vi Na
2
SO
4

tinh th (1/100)

39
1 2 3 4 5 6
Bi
3+
1-3; HNO
3
Vng xanh
Cd
2+
5-6; m axetic
HngVng
xanh
Cu
2+
3-5; m axetac; ~80
o
C Tm Vng
In
3+
2,3-2,5; m axetac Vng
Ni
2+
4; metanol 25%; ~60
o
C Tm Vng
Th
4+
2-3,5; HNO
3
6
(Piridin-2-azo) 1-
naphatol-2 (PAN)
Al
3+
, Ca
2+
, Co
2+
,
Fe
3+
, Hg
2+
, Ga
3+
,
Mg
2+
, Mn
2+
,
Mo
5+
, Ni
+
, Pb
2+
,
t him
Chun ngc bng mui
Cu
2+
Vng
0,1% trong
ethanol 96%
Bi
3+
1-2; HNO
3
Tl
3+
1,7
In
3+
2,3-2,5; ~70
o
C
Vng
Hg
2+
3-6 Da cam
Cd
2+
6-11,5; m NH
3
Vng
Cu
2+
5; m axetac
11,5; m NH
3
Vng
hoc Xanh
Mn
2+
9; m NH
3
Ni
2+
5; m axetac; ~90
o
C
Pb
2+
5-9,6; m urotropin
t him 6; m urotropin
7
(Piridin-2-azo)-4
resorsin (PAR)
Y
3+
, Zn
2+
5-11; m urotropin
Vng
0,1% trong nc
8 Axit sunfosalixilic Fe
3+
2-3; m axetac Vng 5% trong nc
Ca
2+
, Cd
2+
11,5; NH
3
Xanh
Mg
2+
, Zn
2+
10; m amoniac Xanh
V
4+
HCl 0,01-0,2M Xanh
9 Eriocrom xanh en B
Zr
4+
HCl 0,01-0,5M; metanol
50%
Xanh
0,4% trong
methanol
Ba
2+
, Sr
2+
10-11; m amoniac
Ca2+ 12; NH
3
hoc NaOH
Mg
2+
10-11,5; m amoniac
Xanh Xm
Bi
3+
1-3; HNO
3
Cd
2+
, Co
2+
5-6; m urotropin
Xanh Vng
Cu
2+
11,5; NH
3
Xanh
Khng mu
hoc xm
Fe
2+
4,5-6,5; m urotropin
Hg
2+
6; m urotropin
In
3+
3-4; m axetac
Mn
2+
6-6,5; m urotropin
11,5; m NH
3
Pb
2+
6; m urotropin
t him 6; m urotropin
Sn
2+
5,5-6; piridin+axetac+F
-
Zn
2+
6-6,5; m urotropin
12; NH
3
Xanh Vng
Zr
4+
1-2; axit cloaxetic;
~90
o
C
Xanh
10 Metylthymol xanh
Ga
3+
, In
3+
4,5-6; m axetac
mt mu
hunh quang
Trn vi KNO
3

rn (1/100) hoc
0,1%
Zn
2+
9-10; m amoniac
11 Zincon
Ca
2+
, Ge
4+
, Co
2+
,
Cu
2+
, Fe
3+
, In
2+
,
Mn
2+
, Pb
2+

9-10; chun ngc bng
mui km
Xanh Vng
0,130g ch th v
2ml NaOH 1M
trong 100ml
nc

40
V. Cht ch th hp ph
Cht ch th hp ph l nhng cht hu c yu, trong dung dch c th phn ly thnh
ion. Mu dng ion ca cht ch th hp ph khi trng thi t do khc mu khi n b hp ph
ln b mt kt ta.
Bng 5: Mt s cht ch th hp ph thng gp
TT Cht ch th Ion cn xc nh
Ion
chun
S thay i mu Cch pha
1 Alizarin S Fe(CN)
6
4-
Pb
2+ Vng hng 0,4 1% trong
nc
2 Bengal hng A
I
-
(vi s c mt ca
Cl
-
)
Ag
+ Hng tm
0,5 % trong nc
3 Bromcresol xanh Cl
-
Ag
+ Tm xanh 1% trong etanol
20%
4 Bromphenol xanh Cl
-
, Br
-
, SCN
-
, I
-
Ag
+ Vng xanh 1% trong etanol
20%
5 Diphenylamin Zn
2+
Fe(CN)
6
4- Xanh xanh l m 1% trong H
2
SO
4

96%
SCN
-
,

Ag
+
,

tm
6 Diphenylcacbazit
Cl
-
Br
_
Hg
2+
Khng mu tm
0,1% trong etanol
96%
Cl
-
sng tm
Br
-
, I
-
Vng xanh l m 7 Diphenylcacbazon
SCN
-
Ag
+
xanh
0,2% trong ethanol
96%
Cl
-
xanh
8 Cng g
Br
-
, I
-
Ag
+

0,1% trong nc
Cl
-
Vng xanh hng
Br
-
, SCN
-

9
Flureocin
(muiNa)
I
-
Ag
+
Vng xanh da
cam
0,2% trong nc
hoc ethanol
Cl
-
tm hng
Br
-
, I
-
Da cam hng
10 Fucsin (Rosanilin)
SCN
-
Ag
+
Xanh hng
1% trong ethanol
96%
11 Eosin Br
-
, I
-
, SCN
-
Ag
+ Da cam hng sm 0,5% trong nc
hoc ethanol 65%
12 Erytrosin MnO
4
2-
, I
-
Pb
2+
Da cam sm 0,5% trong nc
13 Rolamin 6 G Ag
+
Cl
--
, Br
-
Vng tm 0,1% trong nc

41
CC BI TH NGHIM

Bi 4
PHA CH V CHUN DUNG DCH HCl

Axit HCl c l cht d bay hi v hp th hi nc c trong khng kh. V vy
khng th ly mt th tch xc nh dung dch HCl c bn th trng pha mt dung
dch HCl c nng chnh xc nh trc, m sau khi pha ch cn phi xc nh li nng
ca dung dch .
Mun th cn dng nhng cht tinh khit, c th cn hoc pha ch thnh dung dch
c nng chnh xc nh trc ri dng cht ny xc nh nng dung dch HCl
Nhng cht nh th gi l cht gc (cht khi u hay cht c s)
Thng ngi ta dng Na
2
B
4
O
7
(borax) hoc Na
2
CO
3
, nhng Na
2
B
4
O
7
l cht thng
dng hn v d tinh ch, phn t lng ln trong khi Na
2
CO
3
kh tinh ch, d ht m v
phn t lng b.
I. C s phng php
Khi ha tan vo nc, Na
2
B
4
O
7
b thy phn:
Na
2
B
4
O
7
+ 7H
2
O 2NaOH + 4H
3
BO
3
(1)
H
3
BO
3
l axit yu, NaOH l kim mnh do dung dch borax c tnh cht kim
mnh, c th nh phn bng cc axit, v d bng HCl
Khi tc dng vi HCl phn ng xy ra:
NaOH + HCl = NaCl + H
2
O (2)
Gp hai phn ng (1) v (2) ta c
Na
2
B
4
O
7
+ 2HCl + 5H
2
O = 2NaCl + 4H
3
BO
3
im tng ng, dung dch cha hn hp NaCl v H
3
BO
3
, pH c xc nh theo
axit yu H
3
BO
3
, tnh ra pH 5.
Bi vy cht ch th tt nht xc nh im tng ng l metyl (pT = 5,5).
Cng c th dng metyl da cam (pT = 4) v tnh ra ch s nh phn ca cht ny vn nm
trong bc nhy pH.
II. Cch xc nh
1. Pha ch dung dch chun Na
2
B
4
O
7
Na
2
B
4
O
7
l cht kt tinh ngm 10 phn t nc (Na
2
B
4
O
7
.10H
2
O).
Tnh lng Na
2
B
4
O
7
.10H
2
O cn ly pha 200ml dung dch Na
2
B
4
O
7
0,1N:
ng lng gam ca
2 4 7 2
381, 4
Na B O .10H O 190, 7
2 2
M
g = = =
Lng Na
2
B
4
O
7
.10H
2
O cn ly pha 200ml dung dch 0,1N: 190,7x0,1x0,2 = 3,814g

42
Cn mt lng chnh xc Na
2
B
4
O
7
.10H
2
O trong khong 34g (khng nht thit phi
c cn cho ng lng tnh trn) cho vo cc c m 100ml, thm nc ct, un nh cho
tan ht. Chuyn dung dch vo bnh nh mc 200ml, trng cc nhiu ln bng nc ct v
tt c vo bnh nh mc. Sau thm cn thn nc ct vo bnh nh mc cho n vch
mc. Xo trn u dung dch.
T lng cn thc t tnh li nng dung dch Na
2
B
4
O
7
.
2. Pha ch dung dch HCl 0,1N
Axit HCl c c d = 1,19g/ml, cha 38% HCl nguyn cht.
T tnh th tch HCl c cn ly pha mt th tch nh trc dung dch HCl 0,1N.
Dng mt cc c m (dung tch tu theo th tch cn pha ch), thm vo lng
nc ct cn thit. Dng mt ng ong nh ly th tch HCl c cn thit tnh, cho vo
cc nc ct, khuy u (lm trong t ht hi c). Rt sang bnh cha.
pha c 1lt HCl 0,1N cn ly khong 8ml HCl c
3. Xc nh nng dung dch HCl
Ra sch buret, dng 1015ml dung dch HCl pha trng buret v trng cc ng
dung dch HCl. Sau dung dch HCl vo buret, chnh n vch 0. Ch trong phn
ui ca buret khng cn bt kh.
Dng pipet ly chnh xc 10,00ml dung dch Na
2
B
4
O
7
cho vo bnh nn ra sch,
thm 12 git cht ch th metyl .
M kha buret cho dung dch HCl nh t t xung bnh ng Na
2
B
4
O
7
, lc u. Khi
dung dch trong bnh nn t ngt chuyn t mu vng sang mu hng th kt thc nh
phn. Ghi th tch HCl dng.
- HCl c 38% (d=1,19g/ml)
- Na
2
B
4
O
7
.10H
2
O tinh khit phn tch (M=381,37)
- Dung dch metyl (0,1% trong cn)
- Bnh nh mc c dung tch 200ml
- Buret, pipet, ng ong, cc c m, bnh nn, a khuy
Cu hi v bi tp
1) Vit cc phn ng xy ra trong qu trnh nh phn Na
2
B
4
O
7
bng HCl.
2) Tnh pH ca dung dch H
3
BO
3
nng 0,1M bit pK
H
3
BO
3
= 9,24.
3) Ti sao trong trng hp nh phn (pK
1
) ny ngi ta dng metyl lm
cht ch th?
4) Tnh s ml HCl c d = 1,19g/ml; 38% cn thit pha 250ml dung dch HCl 0,1N.
5) Cn ly bao nhiu ml HNO
3
c d=1,4g/ml; 68% pha 5 lt dung dch HNO
3
0,1N?
(S: Khong 33,1ml.)

43
Bi 5
XC NH NNG DUNG DCH NaOH BNG DUNG DCH HCl

th rn, NaOH rt d ht m trong khng kh, dung dch NaOH hp th CO
2
trong
khng kh to thnh Na
2
CO
3
. Bi vy khng th pha dung dch NaOH c nng chnh xc
nh trc theo lng cn. Hn na sau khi pha ch v xc nh nng trong tng thi gian
bo qun, trc khi dng ngi ta phi xc nh li nng ca n.
I. C s ca phng php
Dng dung dch HCl bit nng chnh xc lm dung dch chun xc nh nng
dung dch NaOH theo phn ng:
2
O
y l trng hp nh phn mt baz mnh bng mt axit mnh, c th dng metyl
, metyl da cam hay phenolphtalein lm cht ch th.
II. Cch xc nh
Np dung dch HCl bit chnh xc nng vo buret.
Dng pipet ly chnh xc 10,00ml dung dch NaOH cho vo bnh nn 100ml, thm 23
git cht ch th metyl da cam ri nh phn bng dung dch HCl cho n khi dung dch chuyn
t mu vng sang mu da cam. Ghi th tch dung dch HCl dng.
Li ly chnh xc 10,00ml dung dch NaOH cho vo bnh nn sch, thm 78 git
cht ch th phenolphtalein ri tin hnh chun bng dung dch HCl cho ti khi ton b
dung dch chuyn t mu hng sang khng mu th dng qu trnh chun . Ghi th tch
HCl tiu tn.
So snh th tch HCl tiu tn trong qu trnh chun vi 2 cht ch th trn. Nhn
xt kt qu thu c.
- Dung dch NaOH cn xc nh nng
- Dung dch HCl
- Cht ch th metyl da cam v phenolphtalein
- Cc dng c cn thit cho phn tch th tch
Cu hi v bi tp
1) Ti sao khi dng metyl v phenolphtalein lm cht ch th trong trng hp nh
phn dung dch NaOH tip xc lu vi khng kh bng dung dch HCl th kt qu khc
nhau?

44
2) Tm nng ng lng gam v chun ca dung dch KOH nu ly 0,1485g
axit succinic H
2
C
4
H
4
O
4
ha tan ri nh phn bng dung dch KOH th ht 25,20ml dung
dch KOH?
(S: 0,1005N)
3) Cho 9,777g axit nitric m c vo nc pha long thnh 1lt. nh phn 25ml
dung dch NaOH 0,1040N cn 25,45ml dung dch HNO
3
va pha trn. Tnh nng phn
trm ca dung dch HNO
3
m c.
(S: 65,85%)
4) Tnh s gam H
3
PO
4
c trong dung dch, nu khi nh phn dung dch bng dung
dch NaOH 0,2000N dng phenolphtalein lm cht ch th th tn ht 25,50ml dung dch
NaOH.
(S: 0,2499g)

Bi 6
XC NH HM LNG Na
2
CO
3
TRONG Na
2
CO
3
K THUT

I. C s phng php
Phng php trung ha l phng php c bn c la chn xc nh hm lng
natri cacbonat.
Na
2
CO
3
+ HCl = NaHCO
3
+ NaCl (1)
NaHCO
3
+ HCl = H
2
CO
3
+ NaCl (2)
C hai im tng ng quan st c trn ng chun Na
2
CO
3
. Ti im tng
ng u tin, tng ng vi phn ng chuyn cacbonat thnh hydrogen cacbonat, pH ca
dung dch c 8,3; ti im tng ng th hai khi sn phm ca phn ng l axit cacbonic
v cacbon dioxit, pH ca dung dch c 3,8. im tng ng th hai c la chn nh
lng cacbonat do bc nhy pH y ln hn nhiu so vi im tng ng th nht.
php xc nh c chnh xc hn ngi ta tin hnh un si nh dung dch trong thi gian
ngn nhm loi ra cc sn phm trung gian ca phn ng l axit cacbonic v cacbon
dioxyt. Thao tc ny s lm thay i nhiu pH ca dung dch v c th lm thay i mu ca
dung dch.
H
2
CO
3
CO
2
+ H
2
O
Cht ch th c la chn cho phn ng chun l bromocresol xanh hoc metyl da cam.
Mt cch khc cng hay c s dng l cho d mt lng axit chun sau chun
ngc bng dung dch kim chun.

45
II. Cch tin hnh
Sy kh mu Na
2
CO
3
110
o
C trong khong 2 gi, lm ngui v nhit phng trong
bnh ht m.
Cn chnh xc mt lng mu (khong 0,2g) cho vo bnh nn 250ml ri ho tan hon
ton bng khong 50ml nc ct. Thm vo 2~3 git cht ch th bromocresol xanh ri
chun bng dung dch chun HCl 0,10N cho ti khi ton b mu xanh lam ca dung dch
chuyn thnh mu xanh l cy. un si dung dch khong 2~3 pht, ri lm ngui v
nhit phng (mu ca dung dch s chuyn t mu xanh l cy v mu xanh lam, nu mu
sc khng i chng t chun d axit) ri tip tc chun ti khi ton b dung dch c
mu xanh l cy.
Tnh hm lng phn trm natri cacbonat c trong mu.

Bi 7
XC NH NNG NaOH V Na
2
CO
3
TRONG HN HP

Cc cht kim hp th CO
2
trong khng kh chuyn thnh mui cacbonat tng ng:
2NaOH + CO
2
= Na
2
CO
3
+ H
2
O
Do dung dch NaOH lun lun cha Na
2
CO
3
. C nhng trng hp phi bit hm lng
ring ca NaOH v Na
2
CO
3
gii quyt vn ny c th dng 2 phng php:
Phng php 1: da trn vic xc nh 2 im tng ng trn ng nh
phn Na
2
CO
3
.
Phng php 2: nh phn dung dch NaOH sau khi kt ta CO
3
2
bng ion Ba
2+
.

Phng php 1
I. C s ca phng php
Dng dung dch chun HCl cho tc dng vi hn hp NaOH v Na
2
CO
3
, phn ng xy
ra ln lt nh sau:
2
O (1)
Na
2
CO
3
+ HCl = NaHCO
3
+ NaCl (2)
NaHCO
3
+ HCl = H
2
CO
3
+ NaCl (3)
Khi nh phn hn hp NaOH+Na
2
CO
3
, lc kt thc phn ng (1) v (2) pH ca dung
dch khong 8,3 (xem cch tnh pH ca cht lng tnh). Nu trong dung dch c mt cht
ch th phenolphtalein th thi im ny cht ch th s mt mu hng.

46
Tip tc cho HCl tc dng, khi phn ng (3) kt thc, ton b NaHCO
3
chuyn thnh
H
2
CO
3
, pH ca dung dch khong 3,8 (xem cch tnh pH ca dung dch a axit). Lc nu
trong dung dch c mt cht ch th metyl da cam th mu ca n s chuyn t vng sang da cam.
Nh phn l thuyt ch r, H
2
CO
3
c hng s K
1
, K
2
m t s
4 1
2
10
K
K
< bc nhy
pH im tng ng th nht (to thnh NaHCO
3
) khng ln, bi vy vic i mu
ca cht ch th im ny cng khng r rng v do vic xc nh im tng ng
km chnh xc.
Mt trong nhng nguyn nhn lm gim chnh xc ca php xc nh cn do s hp
th CO
2
trong khng kh (hoc trong nc), v th m mt phn NaOH bin thnh Na
2
CO
3

ngay trong khi nh phn. V th, khi phn tch cn:
- Pha long dung dch bng nc khng cha CO
2
- nh phn ngay khi ly hn hp
- Khi gn kt thc nh phn (vi cht ch th phenolphtalein) thm HCl tng i
chm trnh to thnh H
2
CO
3
t do
- ng lc dung dch qu mnh (nu khng, s tng cng s hp th CO
2
)
- Dng mt lng phenolphtalein tng i ln (810 git), nu dng t qu th cht ch th
c th mt mu sm trc im tng ng do phenolphtalein nhy vi CO
2
.
II. Cch xc nh
Dng pipet ly chnh xc 10,00ml hn hp NaOH+Na
2
CO
3
cho vo bnh nn, thm
78 git dung dch cht ch th phenolphtalein ri nh phn bng dung dch HCl 0,1N cho
n khi mt mu hng. c v ghi th tch dung dch HCl tiu tn. Thm tip vo dung dch
12 git cht ch th metyl da cam, dung dch s c mu vng. Chun tip cho n khi dung
dch t mu vng chuyn sang mu da cam. c v ghi th tch HCl dng.
Phng php 2
I. C s ca phng php
Dng dung dch HCl 0,1N nh phn hn hp NaOH+Na
2
CO
3
, dng metyl da cam lm
cht ch th. Ta bit c th tch dung dch HCl tiu tn tc dng vi ton b NaOH v Na
2
CO
3
Sau ly mt mu khc, kt ta CO
3
2
bng dung dch BaCl
2
, CO
3
2
s to kt ta
BaCO
3
Na
2
CO
3
+ BaCl
2
= BaCO
3
+ 2NaCl
Dung dch cn li l NaOH. Khng cn lc kt ta, dng HCl nh phn dung dch vi
cht ch th phenolphtalein, bit c th tch dung dch HCl cn tc dng vi ring NaOH.
T suy ra th tch dung dch HCl cn tc dng vi Na
2
CO
3
, phng php ny chnh
xc hn phng php 1.

47
II. Cch xc nh
Dng pipet ly chnh xc 10,00ml dung dch hn hp NaOH+Na
2
CO
3
cho vo bnh
nn, thm 12 git cht ch th metyl da cam ri nh phn bng dung dch HCl cho n khi
dung dch c mu da cam. Ghi th tch HCl tiu tn (V
1
).
Li ly chnh xc 10,00ml dung dch hn hp nh trn, cho vo bnh nn sch, thm
57ml dung dch BaCl
2
5% v 810 git cht ch th phenolphtalein. Khng cn lc kt ta,
nh phn dung dch bng dung dch HCl cho n khi mt mu. Ghi th tch HCl tiu tn cho
php nh phn ny (V
2
).
(V
1
V
2
) chnh l th tch dung dch HCl tc dng vi Na
2
CO
3
.
- Dung dch hn hp NaOH + Na
2
CO
3

- Dung dch HCl 0,1N
- Dung dch BaCl
2
5%
- Cht ch th phenolphtalein, metyl da cam
- Cc dng c cn thit cho vic phn tch th tch.
Cu hi v bi tp
1) Ti sao phng php xc nh NaOH v Na
2
CO
3
trong cng mt dung dch bng
HCl vi 2 cht ch th khng chnh xc?
2) Trong phng php th 2, nu sau khi kt ta CO
3
2
bng BaCl
2
, chun dung
dch NaOH cn li bng HCl vi cht ch th phenolphtalein th khng cn lc kt ta
(BaCO
3
) nu dng cht ch th metyl da cam c c khng? Gii thch.
3) Tnh lng KOH v K
2
CO
3
trong mt mu sn phm KOH k thut nu sau khi ha
tan mu, chun dung dch bng dung dch HCl 0,09500N vi cht ch th phenolphtalein
th ht 22,40ml cn vi cht ch th metyl da cam th ht 25,80ml dung dch HCl.
(S: 0,046g K
2
CO
3
v 0,1013g KOH)
4) Khi nh phn 25,00ml hn hp Na
2
CO
3
v NaHCO
3
bng dung dch H
2
SO
4

0,1200N vi cht ch th phenolphtalein th ht 9,46ml cn vi cht ch th metyl da cam th
ht 24,80ml dung dch H
2
SO
4
ni trn.
Tnh s gam Na
2
CO
3
v NaHCO
3
trong 250ml dung dch hn hp ni trn.
(S: 1,203g Na
2
CO
3
v 0,5989g NaHCO
3
)
5) Sau khi ha tan 1 mu CaCO
3
vo 50,00ml dung dch HCl 0,200N, ngi ta cn
dng 10,00ml dung dch NaOH chun lng d HCl. Bit rng chun 25,00ml
dung dch HCl ni trn cn 24,00ml dung dch NaOH. Tnh s gam CaCO
3
c trong mu
phn tch.
(S: 0,3962g)

48
Bi 8
XC NH HM LNG AXIT C TRONG DM V RU VANG

I. C s phng php
Tng lng axit c trong dm hoc ru vang c th xc nh bng mt baz chun
theo phng php chun thng thng. Tng lng axit xc nh c trong dm c
tnh theo axit axetic bi axit ny chim ch yu trong mc d cng c nhng axit khc
trong mu. Tng t nh vy, tng lng axit c trong ru vang c tnh theo phn trm
axit tactric, cho d trong mu cn c nhng axit khc.
Hm lng axit trong hu ht cc mu dm u vo khong 5% (trng lng/th tch)
quy ra axit axetic v cc mu ru vang l di 1% (trng lng/th tch) quy ra axit tactric.
II. Cch tin hnh
Vi mt mu dm (lng axit c trong chai dm c th b gim i nu ngoi
khng kh, do vy mu ly phn tch phi ly t chai c y nt kn): Dng pipet ly
chnh xc 25,0ml mu cho vo bnh nh mc 250ml ri nh mc bng nc ct ti vch,
lc u. T bnh nh mc ny ly ra 50,00ml dung dch cho vo bnh nn loi 250ml ri
thm khong 50ml nc ct na. Thm vo 1~2 git cht ch th phenolphthalein (lng
ch th c th tng ln m bo s thay i mu c th nhn thy c l d dng nht)
ri chun bng dung dch chun NaOH 0,1M ti khi dung dch c mu hng (khng mt
mu trong khong 30 giy)
Tnh lng axit trong mu dm theo hm lng phn trm (trng lng/th tch) axit
axetic CH
3
COOH (60,053g/mol)
Vi mt mu ru vang: Dng pipet ly chnh xc 50,00ml mu cho vo bnh nn
loi 250ml ri thm khong 50ml nc ct. Thm vo 1~2 git cht ch th
phenolphthalein chun bng dung dch chun NaOH 0,1M ti khi dung dch c mu hng
(khng mt mu sau khong 30 giy).
Tnh lng axit c trong mu ru vang theo hm lng phn trm (w/v) axit tactric
C
2
H
4
O
2
(COOH)
2
(150,09g/mol)
III. Ha cht v dng c
- Dung dch NaOH 0,1M (fixanal)
- Cht ch th phenolphthalein

49
Bi 9
PHA CH V XC NH NNG DUNG DCH KMnO
4

I. C s ca phng php Pecmanganat
KMnO
4
l cht oxi ha mnh, thng c dng xc nh nhiu loi cht kh khc
nhau.
Phn ng oxi ha ca KMnO
4
c th tin hnh trong mi trng axit hay mi trng
kim, nhng phn ng trong mi trng axit hay c dng hn.
Trong mi trng axit, MnO
4
khi b kh chuyn thnh ion Mn

2+
MnO
4
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
Nu lng axit khng th ch xy ra phn ng (trong mi trng axit hoc kim
cng vy).
MnO
4
+ 4H
+
+ 3e MnO
2
+ 2H
2
O
Khi tng nng ion H
+
, phn ng tip tc:
MnO
2
+ 4H
+
+ 2e Mn
2+
+ 2H
2
O
Khi dng dung dch KMnO
4
chun , sau im tng ng (d KMnO
4
) dung
dch c mu hng tm, nn khng cn dng cht ch th.
II. Pha ch v bo qun dung dch KMnO
4
Trong phng th nghim phn tch, thng pha ch dung dch KMnO
4
c nng 0,1N;
0,05N; 0,02N; 0,01N v ni chung hay dng dung dch KMnO
4
c nng 0,05N.
KMnO
4
l cht rn, tinh th mu tm en v thng c tp cht, nht l MnO
2
, ngoi ra
v l cht oxi ha rt mnh nn khi ha tan vo nc KMnO
4
b phn hy bi cc cht kh
c trong nh NH
3
, cc cht hu c, bi v.v... v vy sau khi pha ch xong, nng dung
dch gim dn, phi sau 710 ngy nng mi n nh.
Do khng th (v cng khng cn thit) pha dung dch chun KMnO
4
bng cch ly
lng cn tht chnh xc, m sau khi pha 710 ngy ri xc nh li nng ca dung
dch. (Nu un si dung dch KMnO
4
, qu trnh oxi ha xy ra nhanh, sau vi gi c th lc
b kt ta v c dung dch KMnO
4
c nng n nh)
Khng c cho dung dch KMnO
4
tip xc vi cao su, nt bc, giy v.v.. v vy
mun lc dung dch th dng chn lc th tch y xp hoc xiphng.
Phi bo qun dung dch KMnO
4
trong ti hoc trong chai mu thm trnh phn
ng xy ra khi b nh sng kch thch:
KMnO
4
+ H
2
O = MnO
2
+ KOH + O
2

50
III. Cch xc nh nng dung dch KMnO
4
C th dng H
2
C
2
O
4
.2H
2
O, Na
2
C
2
O
4
, As
2
O
3
, K
4
[Fe(CN)
6
].3H
2
O v.v... xc nh
nng dung dch KMnO
4
, nhng hay dng nht l H
2
C
2
O
4
.2H
2
O v Na
2
C
2
O
4
v l nhng
cht c cng thc xc nh, d tinh ch.
Di y l cch xc nh nng dung dch KMnO
4
bng H
2
C
2
O
4
.2H
2
O
1. C s ca phng php
Trong mi trng axit, KMnO
4
oxy ha H
2
C
2
O
4
theo phn ng:
5H
2
C
2
O
4
+ 2KMnO
4
+ 3H
2
SO
4
= 2MnSO
4
+ K
2
SO
4
+ 10CO
2
+ 8H
2
O
C
2
O
4
2
2e = 2CO
2
MnO
4
+ 8H
+
+ 5e = Mn
2+
+ 4H
2
O
- im tng ng c xc nh khi dung dch c mu hng nht (mu ca KMnO
4

d), khng mt sau khong 30 giy.
- Phn ng tin hnh trong mi trng H
2
SO
4
- Lc u phn ng xy ra chm nn tng tc phn ng, trc khi chun cn
un nng dung dch H
2
C
2
O
4
(khng un si trnh H
2
C
2
O
4
b phn hy).
2. Cch tin hnh
a) Pha ch dung dch H
2
C
2
O
4
0,05N
Cn mt lng H
2
C
2
O
4
.2H
2
O 0,05N cn thit, v d pha 200,0ml th ly:
0,05 X 63,03 X 0,2 = 0,6303g
Cho vo cc c m sch, thm nc ct, un nh cho n khi tan ht. Chuyn vo bnh
nh mc 200ml (trng cc nhiu ln bng nc ct v tt c vo bnh nh mc),
ngui, thm nc ct n vch, xo trn u dung dch.
Tnh v ghi li nng chnh xc ca dung dch H
2
C
2
O
4
va pha.
b) nh phn dung dch KMnO
4
bng H
2
C
2
O
4
Ly chnh xc 10,00ml dung dch H
2
C
2
O
4
cho vo bnh nn, thm 57ml H
2
SO
4

6N, un nng trn bp in ti 7080
o
C.
Cho dung dch KMnO
4
ln buret iu chnh ti vch s 0 ri cho chy t t dung
dch trn buret xung bnh nn ng H
2
C
2
O
4
(lc u cho tng git KMnO
4
xung mt, sau
khi sinh ra lng Mn
2+
lm xc tc cho phn ng th c th tng nhanh tc chun
ln) ng thi lc nh cho ti khi ton b dung dch trong bnh nn xut hin mu hng
nht, khng mt mu sau khong 30 giy.
Lu rng khi kt thc chun dung dch trong bnh nn phi cn m (>40
o
C)

51
- Dung dch KMnO
4
cn chun
- Tinh th H
2
C
2
O
4
.2H
2
O tinh khit phn tch (P.A)
- Dung dch H
2
SO
4
6N
- Cc dng c cn thit cho phn tch th tch.

Cu hi v bi tp
1) Ti sao khng th pha dung dch KMnO
4
c nng nh trc theo lng cn
chnh xc?
2) Gii thch cc iu kin th nghim: thm H
2
SO
4
, un nng dung dch, tc thm
thuc th vo dung dch ban u phi rt chm.
3) Ti sao khi nh phn, lu mu ca KMnO
4
dung dch li bin mt.
4) Ly 0,2000g mu qung cha MnO
2
, ch ha bng H
2
C
2
O
4
d v H
2
SO
4
. Th tch
dung dch H
2
C
2
O
4
ly l 25,0ml v chun lng H
2
C
2
O
4
d cn 20,0ml dung dch
KMnO
4
0,020N. Bit rng 25,0ml dung dch H
2
C
2
O
4
tc dng va ht 45,00ml dung dch
KMnO
4
trn. Tnh % Mn trong qung.
(S: 6,87%)

Bi 10
XC NH HM LNG CANXI TRONG VI

Thnh phn ch yu ca vi l CaCO
3
, ngoi ra cn c mt lng nh SiO
2
, Fe
2
O
3
,
Al
2
O
3

I. C s phng php
Ha tan vi trong axit HCl:
CaCO
3
+ 2HCl = CaCl
2
+ CO
2
+ H
2
O
Kt ta ion Ca
2+
bng H
2
C
2
O
4
Ca
2+
+ C
2
O
4
2
= CaC
2
O
4

Lc ly kt ta CaC
2
O
4
, ra sch ri ha tan trong H
2
SO
4
CaC
2
O
4
+ H
2
SO
4
= CaSO
4
+ H
2
C
2
O
4
Chun H
2
C
2
O
4
to ra bng dung dch KMnO
4
bit nng :
2KMnO
4
+ 5H
2
C
2
O
4
+ 3H
2
SO
4
= 2MnSO
4
+ K
2
SO
4
+ 10CO
2
+ 8H
2
O

52
II. Cch xc nh
Cn chnh xc mt lng vi cho mu vo cc c m dung tch 100ml tm t mu
bng vi git nc, cho t t dung dch HCl 1:1 vo cc cha mu, un nh trn bp in
cho ti khi mu tan ht.
Chuyn dung dch vo bnh nh mc 250ml, trng nhiu ln cc cha mu bng nc
ct ri vo bnh nh mc. nh mc bng nc ct ti vch, lc u.
Dng pipet ly chnh xc 10,00ml dung dch cho vo bnh tam gic thm vi git metyl
da cam, 5060ml nc ct, 10ml dung dch H
2
C
2
O
4
5%, un nng ti 7080
o
C v thm t t
tng git dung dch NH
4
OH 10% cho n mt mu hng (chuyn sang mu da cam)
Cho cc ln bp cch thy un khong 20 pht.
ngui, lc qua giy lc dy (bng xanh) c gng gn nc trong ln giy lc. Sau
ra kt ta trong cc v trn giy lc nhiu ln bng nc ct ngui cho tht ht ion
C
2
O
4
2
(kim tra gin tip bng cch th ion Cl
)
Ha tan kt ta ngay trn giy lc v trong cc bng dung dch H
2
SO
4
6N, bnh
ng kt ta di phu, un nng dung dch H
2
SO
4
di ln giy lc v dng a thy tinh
chc thng giy lc cho kt ta tri xung (di axit H
2
SO
4
34 ln, dng khong 5060ml).
Cui cng ra giy lc 23 ln bng nc ct nng.
un nng dung dch n 7080
o
C, chun H
2
C
2
O
4
trong dung dch bng KMnO
4

- Dung dch HCl 1:1
- Dung dch NH
4
OH 10%, dung dch H
2
SO
4
6N
- Dung dch KMnO
4
0,1N
- Cht ch th metyl da cam
- Ci, chy s; ci, chy m no. Cc dng c cn thit cho phn tch th tch

Cu hi v bi tp
1) Ti sao phi tm t mu trc khi thm HCl
2) Ti sao phi trung ha dung dch khi kt ta CaC
2
O
4
? Ti sao ch ch cn trung ha
ti khi metyl da cam chuyn t mu sang mu da cam
3) Tnh s gam Ca trong 250ml dung dch CaCl
2
nu sau khi thm 40,00ml dung dch
(NH
4
)
2
C
2
O
4
0,100N vo 25,00ml dung dch CaCl
2
v sau khi tch kt ta CaC
3
O
4
ra, chun
lng (NH
4
)
2
C
2
O
4
cha tc dng cn dng 15,00ml dung dch KMnO
4
0,02N
(S: 0,7415g)

53
Bi 11
XC NH NNG DUNG DCH Fe
2+
BNG KMnO
4

I. C s phng php
Chun ion Fe
2+
bng KMnO
4
theo phn ng:
5Fe
2+
+ MnO
4
+ 8H
+
= 5Fe
3+
+ Mn
2+
+ 4H
2
O
y l phn ng t ch th: trc im tng ng dung dch khng c mu sau im
tng ng dung dch c mu pht hng do khi d mt git dung dch KMnO
4
d dng xc nh im tng ng cn lm mt mu vng do to ra ion Fe
3+
.

Mun vy ngi ta thm axit H
3
PO
4
to phc khng mu: [Fe(PO
4
)
2
]
3

II. Cch tin hnh
Ly chnh xc 10,00ml dung dch Fe
2+
cho vo bnh nn, thm khong 57ml hn hp
hai axit H
2
SO
4
+H
3
PO
4
.
Trn buret np y dung dch KMnO
4
va xc nh nng bng cch chun vi
dung dch axit oxalic, iu chnh ti vch s 0 ri cho chy t t dung dch trn buret xung
bnh nn ng dung dch Fe
2+
cho ti khi xut hin mu hng nht v khng mt mu sau
khong 30 giy.
Ghi th tch KMnO
4
tiu tn, tnh nng Fe
2+
trong dung dch.
- Dung dch KMnO
4
bit chnh xc nng
- Dung dch Fe
2+
cn phn tch
- Hn hp 2 axit H
2
SO
4
v H
3
PO
4
(cho 150ml H
2
SO
4
c (d=1,84g/ml) tht cn thn
vo 500ml nc, ngui, thm 150ml H
3
PO
4
c (d=1,70g/ml) sau pha long dung dch
thnh 1 lt)
- Cc dng c cn thit cho phn tch th tch.

54
Bi 12
XC NH ST TRONG DUNG DCH FeCl
3
BNG KMnO
4

I. C s ca phng php
Hm lng ca st ch c th xc nh c sau khi kh ion Fe
3+
thnh Fe
2+
. Sau
chun ion Fe
2+
bng KMnO
4
theo phn ng:
5Fe
2+
+ MnO
4
+ 8H
+
= 5Fe
3+
+ Mn
2+
+ 4H
2
O
5FeCl
2
+ KMnO
4
+ 8HCl = 5FeCl
3
+ MnCl
2
+ KCl + 4H
2
O
c th kh Fe
3+
bng cc cht kh khc nhau nh Zn, SnCl
2
v.v Trong th nghim
ny kh Fe
3+
bng SnCl
2
:
FeCl
3
+ SnCl
2
= 2FeCl
2
+ SnCl
4
Lng

SnCl
2
d phi c loi b khi dung dch v n cng b oxi ha bi KMnO
4
.
Mun vy ngi ta cho HgCl
2
vo dung dch, phn ng xy ra:
SnCl
2
+ HgCl
2
= SnCl
4
+ Hg
2
Cl
2

Hg
2
Cl
2
l kt ta mt mu trng. Nu SnCl
2
ch d rt t, Hg
2
Cl
2
to ra t th tc phn
ng gia Hg
2
Cl
2
v KMnO
4
khng ng k, khng gy sai s cho php xc nh.
Cn ch mt s iu kin sau:
Khng c dng d qu nhiu SnCl
2
, nu khng s c phn ng xy ra:
SnCl
2
+ Hg
2
Cl
2
= Hg + SnCl
4
Kt ta to ra mu xm en, tc dng vi KMnO
4
lm sai kt qu xc nh.
trnh d nhiu SnCl
2
, cn cho tng git dung dch SnCl
2
cho ti khi mt mu vng
ca FeCl
3
sau cho d thm mt vi git dung dch SnCl
2
.
Khi nh phn Fe
2+
trong mi trng HCl c phn ng ph xy ra gia KMnO
4
v
Cl
(xem phn phn ng lin hp).

ngn nga ngi ta thm mt t ion Mn
2+
.
d dng xc nh im tng ng, cn lm mt mu vng ca ion Fe
3+
. Mun
vy ngi ta thm H
3
PO
4
to phc khng mu [Fe(PO
4
)
2
]
3
.
Thc t khi nh phn Fe
2+
trong dung dch c Cl
ngi ta thm hn hp Zimecman

(gm MnSO
4
, H
3
PO
4
v H
2
SO
4
).
Sau khi kt thc nh phn, do phn ng gia KMnO
4
v Hg
2
Cl
2
mu hng nht ca
dung dch s mt nhanh. Do nu sau 30 giy, dung dch khng mt mu th coi nh php
xc nh kt thc.
II. Cc xc nh
Ly mt th tch chnh xc dung dch FeCl
3
(cha khong 0,03g Fe) cho vo bnh
nn, thm 10ml HCl 1:1, un gn si. Ngng un, thm tht cn thn, tng git mt dung
dch SnCl
2
cn i vi giy, quan st mu ri mi nh tip git khc.

55
Khi dung dch gn ht mu vng th pha long dung dch SnCl
2
gp i, tip tc nh
dung dch SnCl
2
vo dung dch Fe
3+
cho ti khi va mt mu, thm 12 git dung dch
SnCl
2
na.
Lm ngui dung dch, pha thm nc ri thm 10ml dung dch HgCl
2
(rt c, cn
thn), lc u dung dch.
Nu thy kt ta trng mt nh voan l tt; nu kt ta c, xp, nht l nu c mu
xm hoc khng thy xut hin kt ta th phi b th nghim , lm li t u.
Thm khong 100ml nc na v 5ml Zimecman ri nh phn dung dch bng
KMnO
4
cho ti khi xut hin mu hng nht, khng mu mu sau khong 30 giy.
III. Ho cht v dng c
- Dung dch KMnO
4
0,05N
- Dung dch SnCl
2
: ha tan 150g SnCl
2
.2H
2
O trong 100ml HCl c pha long thnh 1lt
- Hn hp Zimecman: ha tan 67g MnSO
4
.4H
2
O

trong 500600ml nc thm 139ml
H
3
PO
4
(d=1,7g/ml) v 130ml H
2
SO
4
c sau pha long thnh 1lt.
- Dung dch HCl 1/1
Cu hi v bi tp
1) Thm dung dch HCl 1:1 vo dung dch FeCl
3
v un gn si lm g?
2) Ti sao phi thm cn thn SnCl
2
khng qu d? Du hiu g cho bit lng
SnCl
2
cha hoc d nhiu?
3) Gii thch tng thnh phn trong hn hp Zimecman.
4) Tnh hm lng % ca st trong mt loi qung nu sau khi ha tan 0,2500g qung
trong HCl, kh Fe
3+
thnh Fe
2+
ri nh phn dung dch Fe
2+
bng dung dch KMnO
4

0,01990M th tn ht 28,00ml KMnO
4

(S: 62,24%)
5) Cn ly mt lng qung st bao nhiu (cha 70% Fe
2
O
3
) sau khi ch ha ri
nh phn dung dch Fe
2+
thu c bng dung dch KMnO
4
0,1N th cn dng 2030ml dung
dch ny.
(S: t 0,23g n 0,34g)

56
Bi 13
XC NH HM LNG Mn TRONG THP HP KIM

I. C s phng php
Ha tan mu trong cc axit, oxi ha Mn
2+
thnh MnO
4
bng (NH
4
)
2
C
2
O
8
c AgNO
3

lm xc tc. Chun dung dch HMnO
4
to thnh bng dung dch chun Na
3
AsO
3
+NaNO
2
.
Cc phn ng xy ra nh sau:
3MnS + 14HNO
3
= 3Mn(NO
3
)
2
+ 3H
2
SO
4
+ 8NO + 4H
2
O
Mn
3
C + 8HNO
3
= 3Mn(NO
3
)
2
+ C + 2NO + 4H
2
O
2Mn(NO
3
)
2
+ 5(NH
4
)
2
S
2
O
8
+ 8H
2
O

= 2HMnO
4
+

5(NH
4
)
2
SO
4
+4HNO
3
+ 5H
2
SO
4
Vai tr xc tc ca AgNO
3
c gii thch theo c ch sau:
2(NH
4
)
2
S
2
O
8
+ 2H
2
O

=

2(NH
4
)
2
SO
4
+ 2H
2
SO
4
+ O
2

4AgNO
3
+ O
2
+ 2H
2
O = 2Ag
2
O
2
+ 4HNO
3
2Mn(NO
3
)
2
+ 5Ag
2
O
2
+ 6HNO
3
= 2HMnO
4
+ 10AgNO
3
+ 2H
2
O
2HMnO
4
+ 5Na
3
AsO
3
+ 4HNO
3
= Mn(NO
3
)
2
+ 5Na
3
AsO
4
+ 3H
2
O
2HMnO
4
+ 3Na
3
AsO
3
+ H
2
O

= 3Na
3
AsO
4
+ MnO(OH)
2

MnO(OH)
2
+ NaNO
2
+ 2HNO
3
= Mn(NO
3
)
2
+ NaNO
3
+ 2H
2
O
Phng php ny thng dng xc nh Mn trong gang, thp khi hm lng ca n
khong 0,28%
Nu trong mu c coban th khng xc nh c im tng ng v c ion Co
2+

mu hng.
Nu c crm (>2%) cng tr ngi cho vic xc nh im tng ng v Cr
3+
b oxy
ha n Cr
2
O
7
2
mu vng.
II. Cch xc nh
Cn chnh xc mt lng mu (0,30,4gam) cho vo cc c m (hoc bnh nn)
250ml, thm 1520ml hn hp axit (xem phn ha cht cn thit) un nh cho ti khi tan ht
mu, sau un si k ui ht NO (khong 1520 pht)
Thm vo dung dch khong 50ml nc ct nng, 35ml AgNO
3
0,5%, khong 10ml
dung dch (NH
4
)
2
S
2
O
8
20%, un ti si v si nh khong 1 pht. yn dung dch 34
pht sau lm ngui tht nhanh dung dch, thm 10ml H
2
SO
4
1:1 v 3ml dung dch NaCl
0,1N ri chun nhanh bng dung dch arsenit nitrit cho ti khi mt mu hng.
- Hn hp axit: H
2
SO
4
+H
3
PO
4
+HNO
3
: Chun b khong 500ml nc, thm rt t t
125ml H
2
SO
4
c (d=1,84g/ml) vo, ngui ri thm 100ml H
3
PO
4
(d=1,7g/ml) v 275ml
HNO
3
c (d=1,4g/ml).

57
- Dung dch AgNO
3
0,5%
- Dung dch H
2
SO
4
1:1
- Dung dch NaCl 0,1N
- Dung dch hn hp arsenit nitrit: un nng 125ml NaOH 16% + 6,6g As
2
O
3
+

500ml nc. Trung ha dung dch bng H
2
SO
4
1:2 (th vi giy qu). Thm d 23ml H
2
SO
4

na. Thm vo dung dch 4,25g NaNO
2
, khuy cho tan hon ton, pha long thnh 5lt. Xc
nh chun ca dung dch theo mu thp chun c hm lng Mn bit chnh xc.
Cu hi v bi tp
1) xc nh hm lng Mn trong thp, ngi ta ly 0,300g mu ha tan trong axit, oxi
ha bng (NH
4
)
2
S
2
O
8
c AgNO
3
lm xc tc. Chun dung dch thu c bng dung dch
Na
3
AsO
3
c T
Na
3
AsO
3
/
Mn
= 0,0001510g/ml th ht 12,80ml. Tnh % Mn
(S: 0,64%)
2) xc nh chun ca Na
3
AsO
3
theo Mn ngi ta ly 0,3182g thp cha 0,84%
Mn. Cn dng 22,27ml dung dch Na
3
AsO
3
chun HMnO
4
thu c. Tnh
T
Na
3
AsO
3
/
Mn
(g/ml).
(S: 0,000120 g/ml)

Bi 14
XC NH NNG Fe
3+
BNG K
2
Cr
2
O
7

I. C s chung ca phng php Cromat
K
2
Cr
2
O
7
l cht oxi ha mnh, c th dng lm cht khi u xc nh nhiu loi
cht kh khc nhau, lc Cr
2
O
7
2
chuyn thnh Cr
3+
:
Cr
2
O
7
2
+ 14H
+
+ 6e = 2Cr
3+
+ 7H
2
O
Trong phn ng ny
K
2
Cr
2
O
7

=
249, 2
49, 03
6 6
M
= =
Th oxi ha tiu chun ca cp Cr
2
O
7
2
/
2Cr
3+
=
+
1,36V (b hn th tiu chun ca cp
MnO
4
/
Mn
2+
= 1,51V)
So vi KMnO
4
th K
2
Cr
2
O
7
c nhng u im sau:
- D dng tinh ch c K
2
Cr
2
O
7
tinh khit bng cch kt tinh li v sy 200
o
C. Do
c th pha ch dung dch chun t mt lng cn chnh xc nh trc.

58
- Dung dch K
2
Cr
2
O
7
ng trong bnh kn rt bn, khng b phn hy ngay c khi un
si trong dung dch axit, v vy nng dung dch K
2
Cr
2
O
7
khng thay i trong thi gian
bo qun.
- C th chun cht kh trong mi trng HCl m khng s K
2
Cr
2
O
7
oxi ha v
E
0
Cl
2
/
2Cl
= +1,36V. Tuy nhin nu nng HCl>2N cng nh khi un si, s oxy ha c th

xy ra.
K
2
Cr
2
O
7
cng c nhc im: Trong qu trnh chun ion Cr
3+
to ra c mu xanh
gy kh khn cho vic nhn bit im tng ng.
Trong phng php nh phn bng K
2
Cr
2
O
7
hay dng cht ch th diphenylamin hoc
axit phenylantranilic.
II. C s ca phng php xc nh st
Sau khi ch ha mu (qung, hp kim v.v) st thng dng Fe
3+
. xc nh,
trc ht phi kh Fe
3+
thnh Fe
2+
bng SnCl
2
hoc Zn.
Fe
3+
+ Zn = Fe
2+
+ Zn
2+
c th d dng lc b Zn d. Sau chun dung dch Fe
2+
bng K
2
Cr
2
O
7
theo phn ng:
6Fe
2+
+ Cr
2
O
7
2
+ 14H
+
= 6Fe
3+
+ 2Cr
3+
+ 7H
2
O
Fe
2+
e = Fe
3+
Cr
2
O
7
2
+ 14H
+
+ 6e = 2Cr
3+
+ 7H
2
O
C th dng axit phenylantranilic (E
0
= 1,08V) lm cht ch th (dung dch t khng
mu chuyn thnh ta) hoc diphenylamin (E
0
= 0,76V) lm cht ch th (dung dch
chuyn t khng mu chuyn thnh xanh tm).
Khi dng ch th diphenylamin lm cht ch th cn ch :
- Ch dng 12 git dung dch cht ch th, nu dng nhiu cht ch th s to ra sn
phm mu xanh khng thay i nn khng nhn bit c im tng ng.
- c th dng diphenylamin, phi thm vo dung dch phn tch mt lng H
3
PO
4

(xem thuyt v nh phn bng phng php oxy hakh hc).
- Ngoi ra cn to mi trng axit kh cao, v vy trc khi nh phn ngi ta thm
vo dung dch hn hp H
2
SO
4
+H
3
PO
4
.
III. Cch xch nh nng dung dch Fe
3+
Ly chnh xc 10,00ml dung dch FeCl
3
cho vo bnh nn nh, thm khong 5ml HCl
1/1. Thm 45 ht km (nghing bnh v cho km vo nh nhng, trnh lm v bnh). t
bnh ln bp in un gn si (lm trong t ht) cho ti khi dung dch mt mu vng hon
ton (nu thy c kt ta trng l mui baz ca km th phi cho thm HCl ti khi tan ht).

59
Dng khong 10ml nc ct ngui cho thm vo bnh nn. Ly bnh nn ra khi t
ht v lm ngui nhanh dung dch, lc b km d bng giy lc chy nhanh, hng dung dch
vo bnh nn loi 250ml. Dng nc ct trng ra nhiu ln bnh nn nh v phu lc. Thm
nc ct ti khong 100ml (nu cn), thm vo 57ml hn hp hai axit H
2
SO
4
+H
3
PO
4

v 12 git dung dch cht ch th diphenylamin ri nh phn dung dch bng dung dch
chun K
2
Cr
2
O
7
cho ti khi xut hin mu xanh tm (cho thm nc ct l gim mu xanh
ca Cr
3+
, d nhn thy s i mu ca cht ch th).
IV. Ha cht v dng c cn thit
- Dung dch HCl 1:1
- Km ht (Zn)
- Hn hp hai axit H
2
SO
4
+H
3
PO
4
(cho 150ml H
2
SO
4
c 98% (d=1,84g/ml) tht cn
thn vo 500ml nc, ngui, thm 150ml H
3
PO
4
c (d=1,70g/ml) sau pha long
thnh 1lt).
- Cht ch th diphenylamin.
- Dung dch K
2
Cr
2
O
7
0,05N.
- Bnh nn, phu lc, a thy tinh v cc loi ng ong, pipet
Cu hi v bi tp
1) Dng K
2
Cr
2
O
7
lm dung dch chun xc nh Fe c u im v nhc im g so
vi dng KMnO
4
.
2) Ti sao phi lm ngui dung dch cha ion Fe
2+
ri mi lc b km d?
3) Gii thch vai tr ca hn hp axit H
2
SO
4
+H
3
PO
4
cho vo dung dch trc lc nh
phn.
4) Cn ly bao nhiu gam qung cha Fe
2
O
3
sau khi ha tan mu trong HCl v
chuyn thnh FeCl
2
.

Sau chun dung dch ny cn dng mt th tch dung dch (tnh
bng ml) K
2
Cr
2
O
7
0,02N ng bng hm lng Fe
2
O
3
trong qung tnh bng %.
(S: 0,1597g)

60
Bi 15
XC NH CRM TRONG THP HP KIM

I. C s ca phng php
Trong hp kim crm thng tn ti dng Cr
4
C; Cr
3
C
2
; 3Cr
3
C
2
.Fe
3
C; Cr
3
Si
Sau khi ha tan mu Cr dng Cr
2+
, d b oxi ha bi oxi ca khng kh thnh Cr
3+
.
Cr + H
2
SO
4
= CrSO
4
+ H
2

4CrSO
4
+ 2H
2
SO
4
+ O
2
= 2Cr
2
(SO
4
)
3
+ H
2
O
4Cr + 6H
2
SO
4
+ O
2
= 2Cr
2
(SO
4
)
3
+ 2H
2
O + 4H
2

Sau oxi ha Cr
3+
thnh Cr
2
O
7
2
bng (NH
4
)
2
S
2
O
8
c AgNO
3
lm xc tc.
Cr
2
(SO
4
)
3
+ 3(NH
4
)
2
S
2
O
8
+ 7H
2
O = H
2
Cr
2
O
7
+ 6H
2
SO
4
+ 3(NH
4
)
2
SO
4
C ch xc tc ca AgNO
3
:
(NH
4
)
2
S
2
O
8
+ Ag
2
SO
4
+ 2H
2
O

= (NH
4
)
2
SO
4
+ 2H
2
SO
4
+ Ag
2
O
2
Cr
2
(SO
4
)
3
+ 3Ag
2
O
2

+

H
2
O = H
2
Cr
2
O
7
+ 3Ag
2
SO
4
Cui cng chun dung dch bng dung dch Fe
2+
hoc cho mt lng Fe
2+
d tc
dng vi dung dch v chun lng Fe
2+
d bng KMnO
4
ri suy ra lng Fe
2+
tc
dng H
2
Cr
2
O
7
vi to ra.
Cr
2
O
7
+ 6Fe
2+
+ 14H
+
= 2Cr
3+
+ 6Fe
3+
+ 7H
2
O
Thng mu thp c Mn nn Mn
2+
b oxi ha thnh HMnO
4
mu tm (xem bi xc
nh Mn trong thp) cng l du hiu chng t Cr
3+
b oxi ha hon ton v:
E
0
MnO
4
/
Mn
2+
> E
0
Cr
2
O
7
2
/
2Cr
3+
(1,51V) (1,36V)
Trong trng hp cn phi loi b MnO
4
trc khi chun Cr

2
O
7
2
bng cch
thm HCl hoc NaCl vo dung dch:
2HMnO
4
+ 14HCl = 2MnCl
2
+ 5Cl
2
+ 8H
2
O
II. Cch xc nh
Cn chnh xc mt lng mu (nu Cr t 610% ly khong 0,3g; Cr>10% ly
khong 0,1g; Cr0,2% ly khong 2g) cho vo cc c dung tch 250ml. Thm 2040ml hn
hp axit H
2
SO
4
+H
3
PO
4
+HNO
3
y np knh ng h, un trn bp ct n tan. Nu mu
khng tan ht, thm 35ml axit HNO
3
c un cho n sn st phn hy ht cacbua.
ngui, thm khong 200ml nc ct, li un si. Sau thm khong 3ml AgNO
3

0,5% v 1520ml (NH
4
)
2
S
2
O
8
20%, tip tc un dung dch cho n xut hin mu tm
(nu trong dung dch khng c Mn th cho vo dung dch khong 0,10,2ml dung dch
MnSO
4
5%)

61
Thm vo dung dch 5ml NaCl 1% hoc HCl 1/20 un khong 810 pht phn hy
hon ton HMnO
4
(mt mu tm, cn li mu vng ca H
2
Cr
2
O
7
)
T buret cho mt th tch dung dch mui Fe
2+
vo mu phn tch cho ti mt mu
vng (cn mu xanh), thm 5ml dung dch mui Mo na cui cng dng dung dch
KMnO
4
chun lng d ca mui Mo (n khi xut hin mu hng nht)
III. Ha cht cn thit
- Dung dch (NH
4
)
2
S
2
O
8
20%.
- Dung dch mui Mo ((NH
4
)
2
SO
4
.FeSO
4
.6H
2
O) 0,05N.
- Dung dch KMnO
4
0,02N, MnSO
4
5%, HCl 1:20.
- HNO
3
c.
- Hn hp 2 axit H
2
SO
4
+H
3
PO
4
(160ml H
2
SO
4
c (d=1,84g/ml) cho t t vo
760ml nc, ngui ri thm 80ml H
3
PO
4
c (d=1,7g/ml)).
- Hn hp axit H
2
SO
4
+H
3
PO
4
+HNO
3
(160ml H
2
SO
4
c (d=1,84g/ml) + 60ml HNO
3

c (d=1,4g/ml) + 80ml H
3
PO
4
c (d=1,7g/ml)).

Bi 16
CHUN DUNG DCH Na
2
S
2
O
3
THEO PHNG PHP IT

I. C s chung ca phng php It
I
2
cng nh cc halogen khc c th nhn e ca cc cht d nhng e, v vy l cht
oxy ha.
I
2
+ 2e = 2I
Th oxy ha- kh tiu chun ca cp I

2
/
2I
tng i b (E
0
= 0,5345V ) nn so vi
cc cht oxi ha bit (KMnO
4
, K
2
Cr
2
O
7
) I
2
l cht oxi ha tng i yu. Ngc li ion
I
li l cht kh mnh hn cc ion Cr

3+
, Mn
2+
.
Do c th xc nh cc cht kh bng dung dch I
2
v c th xc nh cc cht oxi
ha bng cch kh chng bi ion I
.
V d: c th xc nh Na
2
S
2
O
3
, Sn
2+
v.v theo cc phn ng:
2S
2
O
3
2
+ I
2
= 2NaI + S
4
O
6
2
(E
0
=0,08V) (E
0
=0,54V)
2 Na
2
S
2
O
3
+ I
2
= 2NaI

+ Na
2
S
4
O
6

62
SO
3
2
+ I
2
+ H
2
O = SO
4
2
+ 2I
+ 2H
+
(0,17V)
Na
2
SO
3
+ I
2
+ H
2
O = Na
2
SO
4
+ 2HI
Sn
2+
+ I
2
= Sn
4+
+ 2I
(0,15V)
SnCl
2
+ I
2
+ 2HCl = SnCl
4
+ 2HI
hoc xc nh K
2
Cr
2
O
7
, Br
2
v.v theo phn ng :
K
2
Cr
2
O
7
+ 6KI

+ 14HCl = 3I
2
+ 8KCl + 2CrCl
3
+ 7H
2
O
(1,36V) (0,54V)
Br
2
+ 2I
= 2Br
+ I
2
(1,07V) (0,54V)
Br
2
+ 2NaI = 2NaBr + I
2
Khi chun cc cht kh, c th chun trc tip:
- nhn bit im tng ng ngi ta dng cht ch th l mt cht nhy vi I
2

l h tinh bt to vi I
2
mu xanh m.
- Nh vy khi cho I
2
tc dng vi cht kh, trong dung dch c h tinh bt th khi tha
mt git dung dch I
2
, dung dch c mu xanh, ngc li khi cho cht kh tc dng vi dung
dch I
2
(v d cho Na
2
S
2
O
3
tc dng vi I
2
) c thm h tinh bt, khi I
2
tc dng ht th dung
dch mt mu xanh.
chun cc cht oxi ha bng phng php it thng s phn tch nh sau:
1/ KI
d
+ cht oxi ha I
2
2/ Chun I
2
bng Na
2
S
2
O
3
Mt s iu kin khi chun bng phng php it:
a) V E
0
I
2
/2I
khng ln, nhiu phn ng l thun nghch nn phi tm cc iu
kin thch hp cho phn ng xy ra hon ton.
b) I
2
l cht d bay hi nn phi tin hnh phn ng nhit thng. Mt khc
khi tng nhit , nhy ca h tinh bt gim.
c) Khng c tin hnh chun I
2
trong mi trng kim v
I
2
+ NaOH = NaIO + NaI + H
2
O
IO
l cht oxi ha mnh hn I

2
n oxi ha c Na
2
S
2
O
3

S
2
O
3
2
+ 4IO
+ 2SO
4
2
= 4I
+ 2SO
4
+ H
2
O
Do phn ng ph ny, kt qu phn tch s khng chnh xc. V vy phi gi pH < 9
d) Cng khng tin hnh chun trong mi trng axit mnh v axit lm tng
cng phn ng oxi ha gia O
2
khng kh v I

4I
+ O
2
+ 4H
+
= 2I
2
+ 2H
2
O

63
e) V tan I
2
trong nc kh nh nn khi chun cc cht oxi ha (to ra I
2
)
cn dng kh d KI (KI d s ha tan I
2
to phc K[I
3
] ).
S to thnh hp cht ny khng nh hng g n qu trnh nh phn v phn
ng to phc K[I
3
] thun nghch , K[I
3
] s b phn hy dn gii phng I
2
vo
dung dch.
f) D dng KI d (v axit khi cn) vn tc gia cht oxi ha thng khng ln, v
vy sau khi thm cht oxi ha phi i mt thi gian.
g) Trc khi chun cn dung dch trong bng ti hn ch phn ng:
4I
+ 4H
+
+ O
2
= 2I
2
+ 2H
2
O
h) i vi trng hp nh phn I
2
thot ra trong phn ng, ch c thm h tinh
bt khi I
2
tc dng gn ht (dung dch c mu vng nht) Nu thm h tinh
bt khi I
2
cn nhiu, hp cht gia It v h tinh bt to ra nhiu, phn ng chm
vi Na
2
S
2
O
3
do d nh phn qu im tng ng.
II. C s ca phng php chun Na
2
S
2
O
3
Na
2
S
2
O
3
.2H
2
O

l cht kt tinh, mc d c th iu ch c mc tinh khit ha hc
trong nhng iu kin thch hp vn khng th pha ch dung dch Na
2
S
2
O
3
c nng chnh
xc theo lng cn v:
- l hp cht khng bn, c th tc dng vi CO
2
, O
2
trong khng kh, b tc dng
ca vi khun trong nc
V d: Na
2
S
2
O
3
tc dng vi H
2
CO
3
trong nc theo phn ng :
Na
2
S
2
O
3
+ H
2
CO
3
= NaHCO
3
+ NaHSO
3
+ S
V vy khi cho Na
2
S
2
O
3
tc dng vi I
2
th thc cht c 2 phn ng :
HSO
3
+ I
2
+ H
2
O

= HSO
4
(1)
2S
2
O
3
2
+ I
2
= S
4
O
6
2
+ 2I
(2)
ng lng gam ca NaHSO
3
=
2
M
trong khi ng lng gam ca Na
2
S
2
O
3
=
1
M

Nh vy ngi ta khng chun ngay Na
2
S
2
O
3
sau khi pha m sau khong 10 ngy
mi xc nh nng .
ngn nga nh hng ca CO
2
ngi ta dng nc ct mi un si ngui pha
v nu pha 0,1g Na
2
CO
3
vo 1lt dung dch th c th tng n nh ca nng dung dch
Na
2
S
2
O
3
v:
Na
2
CO
3
+ CO
2
+ H
2
O

= 2NaHCO
3

- Sau mt thi gian chun ca dung dch Na
2
S
2
O
3
gim chm do:
Tc dng ca O
2
khng kh.
2 Na
2
S
2
O
3
+ O
2
= 2Na
2
SO
4
+ 2S

64
B vi khun phn hy. ngn nga s phn hy ny ngi ta thm
khong 10mg HgI
2
cho 1lt dung dch ( dit khun)
Sau khi pha ch, thnh thong li phi xc nh li nng dung dch Na
2
S
2
O
3
. C th
dng dung dch chun I
2
pha ch t ha cht tinh khit theo lng cn nhng phng php
ny cng c nhiu bt tin nn ngi ta thng dng cc cht khi u l cc cht oxi ha
nh K
2
Cr
2
O
7
, As
2
O
3
.
C th dng K
2
Cr
2
O
7
da vo cc phn ng sau:
Cho mt lng K
2
Cr
2
O
7
chnh xc vo dung dch KI d, I
2
thot ra v tan vo KI d
K
2
Cr
2
O
7
+ 6KI + 7H
2
SO
4
= K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 3I
2
+ 7H
2
O
Chun I
2
bng dung dch Na
2
S
2
O
3
dng h tinh bt lm ch th
Na
2
S
2
O
3
+ I
2
= Na
2
S
4
O
6
+ 2NaI
T hai phn ng trn, theo lng K
2
Cr
2
O
7
m suy ra nng dung dch Na
2
S
2
O
3
III. Cch xc nh nng dung dch Na
2
S
2
O
3
Dng pipet ly chnh xc 10,00 dung dch K
2
Cr
2
O
7
0,05N cho vo bnh nn chuyn
dng cho chun oxy ha kh theo phng php it (Bnh nn c ming loe v c nt
nhm). Thm khong 57ml dung dch H
2
SO
4
2N, khong 7ml dung dch KI 20%. y nt
bnh chun , tia nc ct ln ming bnh ri vo ch ti khong 5 pht.
Sau ly bnh nn ra, nh nhnh nhc np bnh ln dng bnh tia trng np bnh,
hng vo bnh nn. Tia nc ct vng quanh thnh trong ca bnh ti xp x 100ml. nh
phn bng dung dch Na
2
S
2
O
3
cho ti khi c mu vng chanh sng th thm 12ml dung dch
h tinh bt v nh phn tip cho ti khi mt mu xanh en (ch cn thy mu xanh nht ca
Cr
3+
).
IV. Ha cht cn thit
- Dung dch Na
2
S
2
O
3
khong 0,05N
- Dung dch K
2
Cr
2
O
7
0,05N
- Dung dch KI 20%
- Dung dch H
2
SO
4
2N
- H tinh bt (0,5g tinh bt tan, thm vi ml nc ngui, khuy u. tt c vo
100ml nc si, un si vi pht cho ti khi no h tinh bt trong sutlc nu cn. Thm
vi mg HgI
2
dit khun nhm bo qun ch th h tinh bt c lu hn. Ly 1 git dung
dch I
2
0,02N, thm 50ml nc, 23ml h tinh bt va pha. Dung dch s c mu xanh l.
Nu mu tm, hoc nu chng t h tinh bt hng khng dng c)

65
Cu hi v bi tp
1) Da trn nguyn tc no ngi ta c th chun cc cht oxi ha cng nh cc cht
kh bng phng php it? Cho v d, vit phn ng minh ha.
2) Hy k nhng iu kin cn phi tun theo khi chun bng phng php it
3) Ti sao khng th pha dung dch Na
2
S
2
O
3
c nng nh trc theo lng cn? Lm
th no gi cho dung dch Na
2
S
2
O
3
n nh ?
4) Nu sau khi kt thc nh phn (trong phng php nu trn) thm 1 git dung dch
K
2
Cr
2
O
7
m mu xanh li xut hin tr li th c th kt lun iu g?
5) Nu di tc dng ca CO
2
; Na
2
S
2
O
3
chuyn thnh NaHSO
3
lng tng cng ca
Na
2
S
2
O
3
thay i 1% th nng ng lng ca Na
2
S
2
O
3
bin thin th no?
(S: tng 1%)

Bi 17
XC NH NG TRONG CuSO
4

I. C s ca phng php
Mt trong nhng p dng quan trng ca phng php it l xc nh Cu trong qung,
hp kim v.v
Phng php ny da vo phn ng :
2Cu
2+
+ 4I
= 2CuI + I
2
I
2
thot ra c chun bng dung dch Na
2
S
2
O
3
Suy lun theo gi tr cc th oxy ha kh tiu chun ca cc cp Cu
2+
/
Cu
+

(E
0
= 0,17V) v I
2
/
2I
(E
0
= +0,54V) ta thy ng l phn ng phi xy ra theo chiu ngc
li vi chiu phn ng trn.
Tuy nhin do CuI l cht t tan (T
CuI
= 10
12
, nng CuI thc t rt b v do E ca
cp Cu
2+
/
Cu
+
tng mnh vt gi tr E ca I
2
/
2I

; mt khc do dng d nhiu KI, nng
I
cng ln E
I
2
/
2I
cng gim, E
Cu
2+
/
Cu
+
cng tng v phn ng cng hon ton.
Mc d ion H
+
khng tham gia vo phn ng trn, cn thit phi to mi trng axit
yu thch hp ngn nga phn ng thy phn mui Cu
2+
.
II. Cch xc nh
Dng pipet ly chnh xc 10,00ml dung dch CuSO
4
cho vo bnh nn chuyn dng
cho chun oxy ha kh theo phng php it, thm 56ml dung dch CH
3
COOH 2N,

66
thm tip khong 7ml dung dch KI 20% (hoc hn hp KI+NH
4
CNS). y nt, tia nc ct
ln ming bnh ri vo ch ti khong 5 pht.
Chun bng dung dch Na
2
S
2
O
3
bit chnh xc nng cho ti khi dung dch
phn tch c mu vng trng, thm khong 2ml h tinh bt (dung dch s c mu xanh en),
chun tip cho ti khi dung dch trong bnh nn mt mu xanh en v khng xut hin li
sau vi pht.
III. Ha cht cn thit
- Dung dch phn tch CuSO
4
khong 0,05N
- Dung dch CH
3
COOH 2N, h tinh bt
- Dung dch KI 20% hoc hn hp KI+NH
4
CNS (25g KI+100g NH
4
CNS)
- Dung dch chun Na
2
S
2
O
3
0,05N
Cu hi v bi tp
1) Ti sao phi thm CH
3
COOH vo dung dch CuSO
4
? Ti sao khng dng axit mnh
nng ln hn?
2) Ti sao phi dng KI d nhiu?
3) Ti sao chiu ca phn ng gia cp Cu
2+
/Cu
2+
v I
/I
2
khng xy ra nh d on
theo cc gi tr E
0
ca 2 cp I
2
/2I
v Cu
2+
/Cu
+
.
Ghi ch: Khi dng hn hp KI+NH
4
CNS , phn ng xy ra:
2Cu
2+
+ 4I
2CuI + I
2
2CuI + 2CNS
Cu
2
(CNS)
2
+ 2I
Cu
2
(CNS)
2
rt t tan
4) xc nh chun ca Na
2
S
2
O
3
ngi ta ly 0,1125g I
2
tinh khit, sau khi ha
tan trong KI (ging nh xc nh Cu) chun dung dch ny bng dung dch Na
2
S
2
O
3
dng
ht 18,99ml Na
2
S
2
O
3
.
Tnh: - chun ca dung dch Na
2
S
2
O
3
- chun ca dung dch Na
2
S
2
O
3
theo Cu
(S: 0,01473g/ml v 0,005923g/ml)
5) xc nh Pb trong mt mu qung cn 5,000g mu ha tan trong axit v sau khi
ch ha kt ta Pb
2+
dng PbCrO
4
. Lc, ra v ha tan trong HCl v KI (vit phn ng). I
2

thot ra trong phn ng c chun bng dung dch Na
2
S
2
O
3
0,0500N v dng ht
42.00ml dung dch ny. Tnh % Pb trong qung.
(S: 2,90%)

67
Bi 18
XC NH ANTIMON TRONG ANTIMON K THUT

I. C s ca phng php
xc nh antimon trong antimon k thut bng phng php chun c th p
dng phng php chun iot da vo phn ng oxy ha Sb(III) thnh Sb(V):
SbO
3
3
+ I
2
+ H
2
O SbO
4
3
+ 2I
+ 2H
+
Cn bng ca phn ng ph thuc vo nng ion H
+
c trong dung dch. phn
ng din ra theo chiu t tri sang phi, phng php chung nht c th c p dng l cho
d mt lng NaHCO
3
n phn ng vi ion hydro khi chng c to thnh.
Antimon k thut cha mt lng silica v mt s tp cht khc c th phn hy bng
axit clohydric v un nng. Lu rng qu trnh s hnh thnh antimon (III) clorit rt d bay
hi v vy ngi ta thm KCl vo to phc SbCl
4
hay SbCl
6
3
khng bay hi khi un
nng.
Khi HCl d b trung ha s to thnh mui SbOCl, chng phn ng khng hon ton
vi iot v gy ra kt qu phn tch b thp. iu ny c loi tr bng cch thm axit tactric
to thnh phc (SbOC
4
H
4
O
6
), phc ny d dng b oxy ha bng iot.

II. Cch tin hnh
Sy kh mu ti 110
o
C trong khong 1 gi sau lm ngui ti nhit phng trong
bnh ht m. Cn chnh xc trn cn phn tch ~1,0000g mu (cha 1,52mmol antimon) cho
vo bnh nn 500ml. Thm khong 0,3g KCl v 10ml dung dch HCl c. un nng (khng
un si) dung dch cho ti khi kt ta di y bnh c mu trng hoc mu xm sng l
thnh phn SiO
2
cn li.
Thm 3g axit tactric v un nng thm khong 10~15 pht na. Sau lc nh, thm
nc (thm nc chm bng pipet hoc buret ng thi lc nh kim sot s hnh thnh
mui SbOCl) ti 100ml. Nu Sb
2
S
3
mu c to thnh, ngng pha long, un nng dung
dch tr li kh H
2
S c th thot ra (thm HCl nu cn).
Thm 3 git cht ch th phenolphthalein ri trung ha dung dch bng NaOH 6M
ti khi dung dch xut hin mu hng. Li lm mt mu dung dch bng 1~2 git HCl 6M ri
cho d 1ml dung dch HCl 6M ny.
Tip tc thm 4 ti 5g NaHCO
3
, thm 5ml cht ch th h tinh bt ri tin hnh chun
bng dung dch chun I
2
0,05M ti khi dung dch xut hin mu xanh (khng mt mu
sau khong 30 giy).
Tnh lng Sb trong mu.
III. Ha cht v dng c
- HCl c v HCl 6M, Tinh th KCl, NaHCO
3
, axit tactric
- Cht ch th phenolphthalein, h tinh bt, NaOH 6M, dung dch chun I
2
0,05M

68
Bi 19
XC NH Cl
BNG DUNG DCH CHUN AgNO

3

I. C s phng php
Phn ng xy ra khi nh phn:
Ag
+
+ Cl
= AgCl
im tng ng c xc nh bng cht ch th K
2
CrO
4
(phng php Mohr) v
cht ch th hp ph Fluorexein.
1. Phng php Mo
Sau im tng ng khi tha mt git AgNO
3
phn ng xy ra:
CrO
4
2
+ 2Ag
+
= Ag
2
CrO
4

Ag
2
CrO
4
c mu gch. Cn c vo s xut hin ca kt ta mu ny, ta kt thc
nh phn.
Nh phn l thuyt ch r (xem phng php chun kt ta) Ag
2
CrO
4
xut
hin im tng ng (hoc ln cn, vi sai s cho php) phi tnh ton lng K
2
CrO
4

mt cch cn thn ch khng th tu tin c.
2. Phng php dng ch th hp ph Fluorexein
Fluorexein l cht ch th hunh quang khi khng b hp ph c mu xanh l cy. Khi
b hp ph chuyn sang mu hng.
Trong dung dch Cl
c thm Fluorexein trc im tng ng khi Cl
cn d,
AgCl b hp ph Cl
c in tch m nn khng hp th Fluorexein (ng ra l khng hp

ph anion c mu ca Fluorexein).
Sau im tng ng, Ag
+
d AgCl hp ph Ag
+
mang in tch dng nn kt ta
hp ph anion ca Fluorexein v chuyn sang mu hng.
Khi dng ch th Fluorexein mi trng phi trung tnh v mi trng axit lm gim s
phn ly ca cht ch th thnh anion.
II. Cch xc nh
1. Theo phng php Mo
Ly chnh xc 10,00ml dung dch NaCl cho vo bnh nn thm 0,51ml dung dch
K
2
CrO
4
5% v nh phn dung dch bng dung dch chun AgNO
3
(mi khi dung dch
AgNO
3
xung cn phi lc mnh) cho n khi xut hin mu gch. Kt thc nh phn,
ghi li th tch Ag
+
tiu tn trong php chun
2. Theo phng php dng Fluorexein lm cht ch th
Ly chnh xc 10,00ml dung dch NaCl, thm 35 git cht ch th Fluorexein 0,5%.
Va nh phn va lc mnh dung dch cho ti khi kt ta chuyn thnh mu hng, ghi li
th tch Ag
+
tiu tn sau qu trnh chun .

69
(Lu rng khi chun bng cht ch th hp ph cn phi c bit ch ti mi
trng nu mi trng ca phn ng chun qu axit th mu hng ti im tng ng
s khng c to thnh. Trong trng hp ny, nguyn nhn thng do dung dch AgNO
3

c lng axit ln; phng php x l l s dng dung dch NH
4
OH 10% iu chnh mi
trng)
III. Ha cht cn thit
- Dung dch phn tch NaCl.
- Dung dch AgNO
3
0,1N.
- Dung dch K
2
CrO
4
5%.
- Cht ch th Fluorexein 0,5% pha trong ethanol.
Cu hi v bi tp
1) Ti sao phi ch iu kin mi trng khi nh phn Cl
bng AgNO
3
theo c 2
phng php trn? Gii thch.
2) Trong phng php Mo ngi ta chn nng cht ch th K
2
CrO
4
trn c s no?
Hy tnh xem trong bi th nghim ni trn nng K
2
CrO
4
l bao nhiu? (tnh gn ng
theo nng mol/lit).
3) Da trn hiu ng g ngi ta chn Fluorexein lm cht ch th khi nh phn Cl

bng AgNO
3
.
4) Tnh s gam KCl trong 250ml dung dch nu ly 25,00ml dung dch ny chun
ht 34,00ml dung dch AgNO
3
0,1050N.
(S: 2,662g)

Bi 20
XC NH Cl
BNG DUNG DCH CHUN Hg(NO

3
)
2

I. C s ca phng php
Da vo phn ng:
2NaCl + Hg(NO
3
)
2
= HgCl
2
+ 2NaNO
3
HgCl
2
l mui rt t phn ly.
xc nh im tng ng ngi ta dng cht ch th diphenylcarbazon. Cht ny
to vi ion Hg
2+
(d) kt ta mu xanh m.

70
II. Cch xc nh
Ly chnh xc 10,00ml dung dch NaCl vo bnh nn 250ml, thm 4050ml nc ct,
4ml dung dch HNO
3
0,2N, 10 git dung dch cht ch th diphenylcarbazon. Chun bng
dung dch Hg(NO
3
)
2
cho ti khi xut hin kt ta mu xanh tm.
Dng chun , ghi th tch Hg(NO
3
)
2
tiu tn.
Tnh nng NaCl v chun theo cht xc nh.
III. Ha cht cn thit
- Dung dch phn tch NaCl
- Dung dch HNO
3
0,2N
- Dung dch Hg(NO
3
)
2
0,05N (8,5g Hg(NO
3
)
2
.0,5H
2
O

cho vo cc, thm 2ml dung
dch HNO
3
c + t nc khuy u. Sau khi ha tan pha thm nc ct ti va
1lt).
- Dung dch cht ch th diphenylcarbazon 1% (pha trong ru).

Bi 21
XC NH KM (Zn
2+
) BNG FEROXIANUA KALI THEO PHNG PHP KT TA

I. C s ca phng php
Phng php da trn phn ng to kt ta gia dung dch Zn
2+
(trung tnh hoc hi
axit) vi dung dch chun K
4
[Fe(CN)
6
]
3ZnSO
4
+ 2K
4
[Fe(CN)
6
] = K
2
Zn
3
[Fe(CN)
6
]
2
+ 3K
2
SO
4
xc nh im tng ng ngi ta dng cht ch th oxy ha-kh diphenylamin.
c th dng cht ch th ny ngi ta thm vo dung dch mt lng nh K
3
[Fe(CN)
6
]
to vi K
4
[Fe(CN)
6
] cp oxi ha-kh: [Fe(CN)
6
]
3
/
[Fe(CN)
6
]
4
c th oxy hakh tnh
theo cng thc:
+ =
4
6
3
6
] ) CN ( Fe [
] ) CN ( Fe [
lg 059 , 0 36 , 0 E

i vi diphenylamin E
0
= +0,76V s i mu ca cht ch th diphenylamin (t khng
mu sang xanh tm) c gii thch nh sau:
- Lc thm mt lng nh [Fe(CN)
6
]
3
th oxy ha-kh ca cp E
Feri/
Fero
cn rt
nh, nh hn 0,76V nn [Fe(CN)
6
]
3
khng tc dng vi cht ch th.
- Trong qu trnh nh phn lng [Fe(CN)
6
]
4
gim dn. E
Feri/
Fero

tng dn, khi
[Fe(CN)
6
]
4
tc dng ht (im tng ng) E
Feri/
Fero
tng vt > E
diphenylamin
, lc
diphenylamin b [Fe(CN)
6
]
3
oxy ha chuyn thnh dng mu xanh tm.

71
Lu rng K
3
[Fe(CN)
6
], K
4
[Fe(CN)
6
] khi c mt axit hay mui axit, c bit khi un
nng, th phn hy gii phng axit xyanhydric l cht rt c, th phi rt nguy him ti tnh
mng.
II. Cch xc nh
Ly chnh xc 10,00ml dung dch K
4
[Fe(CN)
6
] cho vo bnh nn, thm 34 git dung
dch K
3
[Fe(CN)
6
], 10ml dung dch H
2
SO
4
6N, 23 git cht ch th diphenylamin v xp x
2gam (NH
4
)
2
SO
4
v thm 50ml nc.
Cho dung dch ZnSO
4
vo buret v nh phn ti khi dung dch chuyn sang mu xanh tm.
Tnh ton kt qu: T
K
4
[Fe(CN)
6
]/
ZnSO
4
(g/ml). Tnh s gam ZnSO
4
trong mu.
- Dung dch ZnSO
4
.
- Dung dch chun K
4
[Fe(CN)
6
] 0,1M.
- Dung dch K
3
[Fe(CN)
6
] 1%.
- H
2
SO
4
6N, (NH
4
)
2
SO
4
tinh th.
- Cht ch th diphenylamin.

Cu hi v bi tp
1) Gii thch cch xc nh im tng ng trong phng php xc nh ZnSO
4
bng K
4
[Fe(CN)
6
] vi cht ch th iphenylamin.
2) Tnh ng lng gam ca ZnSO
4
v K
4
[Fe(CN)
6
] ca phn ng dng trong php
nh phn.

Bi 22
XC NH NNG COMPLEXON III BNG DUNG DCH ZnSO
4

I. C s phng php
Complexon III hay Trilon B (Na
2
C
10
H
14
N
2
O
8
) l mui dinatri ca axit
etylendiamintetraaxetic (EDTA) c cng thc cu to:

N CH
2
CH
2
N
CH
2
COOH NaOOC
COONa
HOOC CH
2
CH
2
CH
2
k hiu l Na
2
H
2
Y

72
C th pha ch dung dch complexon III c nng chnh xc theo lng cn. Cng
c th pha ch dung dch complexon III c nng gn chnh xc sau xc nh li nng
ca dung dch ny bng dung dch chun MgSO
4
hay ZnSO
4
.
Phn ng gia ion kim loi v complexon III xy ra nh sau:

N
CH
2
CH
2
CH
2
COO
OOC CH
2
CH
2
N H
2
C
Me O C O O C O
OH
2
H
2
O
H
2
Y
2
+ Zn
2+
= ZnY
2
+ 2H
+
H
2
Y
2
+ Mg
2+
= MgY
2
+ 2H
+
(Phn ng xy ra theo t l 1:1)
Hnh 18: Phc ca Complexon vi cation kim loi
xc nh im tng ng, thng dng cht ch th Eriocrom en T (ET-00, 1-
oxi-2-naphtylazo-6-nitro-2-naphtol-4-sunfonic) k hiu l H
3
Ind.

N = N
OH
NO
2
-
O
3
S
OH

pH t 8 10 phn ng gia cht ch th ET-00 v Zn
2+
c th biu din theo s :
H
3
Ind 2H
+
+ HInd
2
Zn
2+
+ HInd
2
= ZnInd

+ H
+
Khi chun , im tng ng khi complexon III tc dng ht vi Zn
2+
(phc
ZnY
2
bn hn phc ZnInd
) th:
H
2
Y
2
+ ZnInd

= ZnY
2
+ H
+
+ HInd
2
( pH = 8 11)
ta khng mu xanh
Ch rng v mu ca ET-00 ph thuc pH nn khi nh phn phi cho thm dung
dch m NH
4
Cl+NH
4
OH

c pH khong trn.
II. Cch xc nh
Ly chnh xc 10,00ml dung dch ZnSO
4
0,025M cho vo bnh nn, thm khong
57ml hn hp m NH
4
Cl+NH
4
OH v mt t cht ch th ET-00.
Cho dung dch complexon III vo buret v chun dung dch cho ti khi dung dch
t mu ta chuyn sang mu xanh trong.
Ghi th tch dung dch complexon III tiu tn, t tnh ra nng dung dch
complexon III ny.

73
Bi 23
XC NH CNG CHUNG CA NC BNG COMPLEXON III

I. C s phng php
cng chung ca nc ln hay b ph thuc lng Ca
2+
, Mg
2+
c trong nc.
xc nh cng chung ca nc phng php thng dng hin nay l chun
bng complexon III da vo phn ng ti st im tng ng vi cht ch th ET-00 (xem
bi trc) ti pH = 8 11:
H
2
Y
2
+ CaInd

= CaY
2
+ HInd
2
+ H
+
H
2
Y
2
+ MgInd

= MgY
2
+ HInd
2
+ H
+
cng chung ca nc c biu din bng s mili ng lng gam Ca
2+
, Mg
2+

trong 1lt nc.
II. Cch xc nh
Ly chnh xc 100,0ml nc phn tch cho vo bnh nn 250ml, thm 57ml hn hp
m NH
4
Cl+NH
4
OH thm mt t cht ch th ET-00, lc u.
Cho dung dch complexon III vo buret v chun lng nc ny cho ti khi dung
dch t mu ta chuyn sang mu xanh trong.
Ghi th tch dung dch Complexon III tiu tn, tnh cng chung ca nc.
III. Ha cht cn thit
- Dung dch complexon III 0,05N
- Dung dch m NH
4
OH+NH
4
Cl (27g NH
4
Cl+70ml NH
4
OH

25% pha 1lt)
- Cht ch th ET-00

Cu hi v bi tp
1) Vit cc phn ng xy ra trong qu trnh nh phn dung dch Complexon III bng
ZnSO
4
v trong qu trnh xc nh cng ca nc. Gii thch s i mu ca cht ch th
trong qu trnh trn.
2) Ti sao trong php nh phn cc ion kim loi bng Complexon III dng ET-00
lm cht ch th phi thm dung dch m NH
4
Cl+NH
4
OH ?

74
Bi 24
XC NH Ca BNG PHNG PHP COMPLEXON

I. C s phng php
Sau khi xc nh cng chung ca nc, bng cch xc nh ring phn lng Ca
2+

c trong mu phn tch s suy ra c lng Mg
2+
c trong mu nc phn tch.
Da vo phn ng:
Ca
2+
+ H
2
Y
2
= CaY
2
+ 2H
+
xc nh im tng ng, s dng cht ch th Murexit k hiu l H
3
Ind.
pH12 phn ng gia cht ch th Murexit v Ca
2+
c th biu din theo s
H
3
Ind 2H
+
+ HInd
2
Ca
2+
+ HInd
2
= CaInd

+ H
+
cui qu trnh chun khi complexon III tc dng ht vi Ca
2+
(phc CaY
2
bn
hn phc CaInd
) th:
H
2
Y
2
+ CaInd

= CaY
2
+ H
+
+ HInd
2
( pH12)
ta khng mu tm hoa c
Ch rng v mu ca cht ch th Murexit ph thuc pH nn khi nh phn phi cho
thm dung dch NaOH

vo

c gi tr pH ph hp.
II. Cch xc nh
Ly chnh xc 100,00ml dung dch nc cn phn tch cho vo bnh nn loi 250ml,
thm khong 5~7ml NaOH 10% (kim tra bng giy o pH) ti pH12. Thm mt t cht ch
th murexit vo, dung dch s c mu ta. Chun bng dung dch complexon III ( bit
chnh xc nng ) ti khi ton b dung dch trong bnh nn chuyn sang mu tm hoa c.
Ghi li th tch complexon III tiu tn. Tnh hm lng (mg/l) Ca c trong mu.
III. Ha cht cn thit
- Dung dch complexon III 0,05N
- Dung dch NaOH 10% hoc KOH 10%
- Cht ch th murexit

75
Bi 25
XC NH Al BNG COMPLEXON III THEO PHNG PHP NH PHN NGC

I. C s phng php
Trong mi trng axit yu vic nh phn xc nh Al bng EDTA (complexon III) gp
kh khn do phc hydroxo ca Al tc dng vi complexon III rt chm.
un nng dung dch, vn tc phn ng tng nhng vn khng th dng phn ng ny
nh phn Al trc tip c.
Trong a s trng hp ngi ta xc nh Al bng phng php nh phn ngc,
mt trong cc ng li l: cho mt lng complexon III d sau d chun complexon III
d bng dung dch chun ZnSO
4
dng xylen da cam lm cht ch th.
Al
3+
+ H
2
Y
2
AlY
+ 2H
+
H
2
Y
2
+ Zn
2
+
ZnY
2
+ 2H
+
Zn
2+
+ xylen da cam phc mu (pH=56)
II. Cch xc nh
Ly chnh xc 10,00ml dung dch Al
3+
thm vo khong 30ml dung dch
Complexon III 0,1M, 1ml HCl 1N, un si nh 10 pht.
Lm ngui, dng axetat natri iu chnh pH n 56. Sau thm cht ch th xylen
da cam (xem trong phn ha cht cn thit) v nh phn dung dch bng dung dch chun
ZnSO
4
cho ti khi no dung dch chuyn t mu vng sang mu .
III. Ha cht cn thit
- Dung dch phn tch Al
3+

- Dung dch EDTA (Complexon III) 0,1M
- Dung dch chun ZnSO
4
0,1M
- Hn hp cht ch th (1g xylen da cam + 99gam KNO
3
)
- CH
3
COONa

Cu hi v bi tp
1) Ti sao khng th chun trc tip Al
3+
bng Complexon III theo phng php
thng thng.
2) Ti sao trong phng php trn ngi ta thm d nhiu EDTA v un si tng
i lu?

76
Bi 26
XC NH Ni BNG COMPLEXON III

I. C s ca phng php
Ni
2+
cng nh Cu
2+
, Co
2+
c th xc nh trc tip bng EDTA, dng Murexit lm cht
ch th.
Cc phn ng xy ra trong qu trnh nh phn:
Ni
2+
+ H
2
Y
2
NiY
2
+ 2H
+
Murexit to phc mu vng vi Ni
2+
trong mi trng kim mnh Murexit dng
H
2
F
3
mu tm xanh. im tng ng phn ng xy ra: (phn ng rt chm, phi thm
EDTA t t)
H
2
Y
2
+ [Ni(H
2
F)]
2
H
2
F
3
+ NiY
2
+ 2H
+
Khc vi Co
2+
, Ni
2+
c th nh phn khi c d NH
4
OH. Nhiu ion cn tr php xc
nh ny nn phi tm cch loi, che trc.
III. Cch xc nh
Ly mt th tch chnh xc (10,00ml) dung dch Ni
2+
(c cha axit). Thm vi git ch
th metyl trung ha bng NaOH hoc NH
4
OH n khi no dung dch c mu vng. Thm
5ml dung dch NH
4
Cl vi ba git dung dch Murexit v dung dch NH
4
OH c cho ti khi
no dung dch c mu vng.
un nng dung dch ti khong 40
o
C v nh phn dung dch bng EDTA 0,025M cho
ti khi no dung dch t mu vng t ngt chuyn sang mu xanh tm.
Nu khi nh phn dung dch chuyn sang mu da cam th thm vi git dung dch NH
4
OH
tip tc nh phn, gn im tng ng th phi thm thuc th tht chm.
III. Ha cht cn thit
- Dung dch phn tch Ni
2+
.
- Dung dch EDTA 0,025M.
- Dung dch cht ch th metyl , cht ch th Murexit.
- Dung dch NH
4
Cl 1M.
- Dung dch NH
4
OH hoc NaOH 10%.

77
Bi 27
XC NH COBAN BNG COMPLEXON III

I. C s phng php
Cng nh nhiu ion kim loi khc Co
2+
to phc bn vi EDTA
Co
2+
+ H
2
Y
2
CoY
2
+ 2H
+
(1)
C th xc nh im tng ng ca phn ng bng s i mu ca cht ch th
Murexit. Nu k hiu Murexit bng HF
, F
l ion ca Murexit, th im tng ng

phn ng xy ra:
Co(H
2
F)
+ H
2
Y
2
CoY
2
+ H
3
F
2
+ H
+
mu vng mu tm
S i mu im tng ng rt r, tuy nhin nu thm vo dung dch mt lng
NH
4
OH d nhiu to phc vi Co
2+
rt bn s ph hy phc ca Co
2+
vi cht ch th. Do
, cn phi ch ch thm mt lng NH
4
OH d ti thiu. Nhng nh vy do kh nng
m ca dung dch thp trong qu trnh nh phn pH ca dung dch c th thay i (H
+
to
ra dung dch (1)) hin tng trn c th nhn bit do s xut hin phc mu da cam.
Nu lc thm vi git NH
4
OH phc chuyn ngay thnh [Co(H
2
F)]
mu vng th
s i mu ca im tng ng ca qu trnh nh phn s tr nn r rng. (Phi loi b
cc ion kim loi nng ra khi dung dch v cc ion ny cn tr vic xc nh)
II. Cch xc nh
Ly chnh xc 10,00ml dung dch Co
2+
(dung dch cha axit) thm 1 git dung dch
cht ch th metyl (dung dch s c mu ), trung ha dung dch bng NaOH ti khi no
dung dch chuyn sang mu vng da cam thm 3 git dung dch NH
4
Cl 2M v 3 git dung
dch NH
4
OH

25%.
Thm vi ba git dung dch Murexit, dung dch s c mu vng da cam. Nu trong qu
trnh nh phn pH ca dung dch thay i nhiu (iu ny xy ra khi nng Co
2+
ln) th
mu ca cht ch th s thay i sm trc im tng ng. Trong trng hp thm 1
git dung dch NH
4
OH v li chun tip cho ti khi mu vng ca dung dch chuyn sang
tm.
III. Ha cht cn thit
- Dung dch EDTA 0,05M
- Murexit bo ha (mi pha); cht ch th metyl
- Dung dch NH
4
Cl 2M, dung dch NH
4
OH 25%

78
P PH H N N 2 2: : C C C C P PH H N NG G P PH H P P P PH H N N T T C CH H H H A A L L

CHNG 1: PHNG PHP TRC QUANG

Phng php phn tch o quang l phng php phn tch cng c da trn vic o
nhng tn hiu bc x in t v tng tc ca bc x in t vi cht nghin cu.
Phng php c u im l tin hnh nhanh, thun li. C nhy cao, chnh xc
c ti 10
-6
mol/l. Tu thuc vo hm lng cht cn xc nh m c chnh xc t 0,2 ti
20%.

I. nh lut Lambe-Beer
Khi chiu mt chm bc x n sc (cng bc x ban u l I
0
) i qua mt lp
dung dch c b dy l v c nng l C, th sau khi i qua dung dch cng bc x b
gim i (cng ca bc i ra khi dung dch l I) do qu trnh hp th, phn x, tn x...
hp th quang ca dung dch t l thun vi C v l.
0
I
A =lg =.l.C
I

% truyn qua: T =
0
I
.100
I
(%) A = lgT
trong :
A : hp th
: h s hp th mol (lit.mol
-1
.cm
-1
). c trng cho
kh nng hp th nh sng ca dung dch. Ph thuc
vo bn cht dung dch v bc sng .
l: b dy dung dch (cm)
C: nng dung dch (mol/l)
Hnh 19: Loi cuvet thng c dng
trong my o quang
II. Ph hp th
Dung dch hp th nh sng c tnh cht chn lc. th biu din A = f() (hoc =
f() hoc lg = f()) gi l ph hp th nh sng ca dung dch. Trn ph hp th c th c
mt hoc nhiu cc i, thng th cht mu c mt cc i. Ti
max
ta c A
max
(hoc
max
).

79

Hnh 20: Ph hp th nh sng

III. Tnh cht ca mt quang
Chiu chm nh sng qua qua lin tip 2 dung dch:
Tng hp th quang ca 2 dung dch: A
= lg
0
2
I
I
. Gi hp th quang ca dung
dch 1 l A
1
, dung dch 2 l A
2
.
= = + = +
0 1 0 1
1 2
1 2 1 2
I .I I I
A lg lg lg A A
I .I I I

vy hp th quang c tnh cht cng tnh.
Nu 1 dung dch c nhiu cht cng hp th nh sng th A
dd
= A
cc cht
A
dd
= A
cht phn tch
+A
tp

cht
V vy mun o A
cht phn tch
ta phi tm cch loi b nh hng ca tp cht bng cch
chun b 1 mu trng (dung dch trng).
= =
o dungdch trng cht phn tch
A A A A
IV. S thit b o quang

Hnh 21: S nguyn l thit b o quang

80
1. Ngun sng: cung cp bc x nh sng vng trng thy th dng n si t
Vonfram; vng t ngoi: dng n hydro, deteri, thu ngn
2. H tn sc: h tn sc c nhim v bin chm tia a sc thnh chm tia n sc
(cung cp bc x n sc). Vi cc my th h c s dng t 10 ti 12 knh lc nh sng cho
di ph hp ch khng cho h n sc. Cc my hin i hn th s dng lng knh cho
nh sng n sc. Cc my UV-Vis th h mi s dng cch t (12001800 vch/mm c khi
ti 2400 vch/mm) c phn gii cao t 1 ti 0,2nm.
3. Mu phn tch: cht phn tch c th cho tc dng vi mt thuc th trong mi trng
thch hp nhm to phc cht c nhy m bo tnh nh lng ca phng php. Nu cht
phn tch l cht kh th phi cha mu vo cuvet ng kn. Cuvet dng cho ph UV phi l
cuvet thch anh. Cuvet dng cho ph Vis c th l cuvet nha hoc cuvet thu tinh
4. Detector: trong cc my n gin dng t bo quang in chuyn tn hiu quang thnh
tn hiu in ri cho qua b khuch i hin th kt qu o. Trong cc my th h mi c nhy
cao thng dng detector dng ng nhn quang hoc loi chui diot (DAD). Detector chui diot
thch hp cho vic o ng thi nhiu cu t vi nhiu bc sng khc nhau, thit b kh bn.
V. Cc phng php phn tch nh lng
1. Phng php so mu bng mt
C cc cch ch yu nh lng theo phng php so mu bng mt l:
lp dy mu chun, chun so snh mu v cn bng mu. Phng php cho kt
qu vi chnh xc khng cao, tuy nhin rt n gin khng cn my o ph.
Phng php thch hp trong vic kim tra ngng cho php ca cht no trong
mt sn phm c th xem c t hay khng.
2. Phng php ng chun
Phng trnh c bn ca php o nh lng theo ph UVVis l:
A= . l. C (. l = const vy A = f(C) hm bc nht)
Bng cch chun b mt dy dung dch mu c nng tng dn v bit chnh
xc trc C
1
, C
2
, C
3
, (thng l 57 nng nm trong vng tuyn tnh ca mi
quan h AC) v dung dch mu ca cht cn xc nh nng trong cng iu kin
phn tch nh dy dung dch chun. Nghin cu chn iu kin ph hp nht o ph
ca cc mu chun v mu phn tch nh cc thng s v thi gian, mi trng, loi
cuvet o hp th quang ca cc dung dch chun, dng ng chun theo h
ta AC sau o hp th quang ca dung dch cht mu cn xc nh nng
(gi s l A
x
), ri p vo ng chun ta s c nng C
x
tng ng vi nng
cht cn xc nh.

81

Hnh 22: th chun A-C v cch xc nh nng t A
x
o c
Phng php rt tin li phn tch hng lot mu ca cng mt cht trong mt loi
i tng nghin cu, nhanh chng, hiu sut cao.
3. Phng php thm chun
Ni dung ca phng php l dng ngay mt mu phn tch (nng C
x
) l cht nn
pha ch mt dy mu chun bng cch ly mt lng nht nh mu phn tch v pha
thm vo nhng lng nng chnh xc dung dch chun theo cp s cng. a cc
dung dch v iu kin o quang ti u. Khi ny mi dung dch u cha mt lng nh
nhau mu cn phn tch v nng khc nhau ca dung dch chun. Tin hnh o quang dy
dung dch v xy dng th thm chun vi trc x l nng dung dch chun c thm
vo, y l hp th quang o c. Ngoi suy nng mu phn tch bng cch ko di
ng chun ct trc x ti u chnh l nng mu cn tm.

A

(4) (2) 0 2 4 6 8
C
Nng mu
phn tch (C
x
)
A ca dung dch mu phn tch
(khng c dung dch chun)
A ca dy chun (mu phn tch nh nhau +
dung dch chun c nng thay i)

Hnh 23: ng chun ca phng php thm chun

82
Bi 28
NGHIN CU PH HP TH CA PHC Fe-AXIT SUNFOSALISILIC

I. C s phng php
Axit salixilic cng nh dn sut ca n l axit sunfosalixilic phn ng rt nhy vi cc
ion Fe
2+
, Fe
3+
trong dung dch, to thnh cc cht ni phc c mu v tan trong nc.
OH
COOH
SO
3
H
Fe
3+
Fe 2nH
+
+
+
O
-
COO
-
3-2n
n
n SO
3
H

Ty thuc vo iu kin pH ca dung dch m phc gia st v axit sunfosalixilic c
mu, dng phc khc nhau:
pH = 1,8 2,5 phc c mu tm; n=1. (vit tt l FeSal
+
)
pH = 4 8 phc c mu nu, n=2. (vit tt l FeSal
2
)
pH = 8 11,5 phc c mu vng, n=3 (vit tt l FeSal
3
3
)
(Sal
2-
l anion ca axit sunfosalixilic)
Bng cch s dng cc dung dch m pH thch hp nhm ch ng to cc dng phc
khc nhau v kho st ph hp th trn my o quang s c nhng nh gi quan trng v
kh nng ng dng ca phc st vi axit sunfosalixilic vo phn tch nh lng.
II. Cch tin hnh
Chun b su bnh nh mc dung tch 25ml cho vo th t cc ha cht c thnh
phn nh bng sau:
ml
Bnh
B 1 B 2 B 3 B 4 B 5 B 6
Fe
3+
0,1 mg/ml

2,0

2,0

2,0

Axit sunfosalisilic 10% 2,5 2,5 2,5 2,5 2,5 2,5
HCl 0,1N 2 2

CH
3
COOH+CH
3
COONa

5 5

NH
4
OH 10%

2 2
Nc ct nh mcva ti vch ri lc u
Tin hnh ghi ph hp th (A) trn my o quang phc Fe
3+
vi axit sunfosalixilic
cc bnh 2, 4, 6 vi dung dch trng tng ng bnh 1, 3, 5 trong cc cuvet c b dy
l=1cm. Tnh
max
ca cc phc. Nhn xt cc kt qu thu c

83
Bi 29
XC NH ST BNG AXIT SUNFOSALIXILIC

I. C s phng php
Axit salixilic cng nh dn sut ca n l axit sunfosalixilic phn ng rt nhy vi cc
ion Fe
2+
, Fe
3+
trong dung dch, to thnh cc cht ni phc c mu v tan trong nc.
Vi cc nghin cu ph hp th ca phc st vi axit sunfosalixilic cho thy pH = 8
11,5 phc c mu vng (vit tt l FeSal
3
3
) l nhy v bn nht (hng s khng bn ca
phc ny l K=2,8.10
34
). H s hp th phn t ca phc mu vng
max
= 4.10
3
, c cc i
hp th 424nm.
II. Cch tin hnh
1. Xy dng th chun
Chun b 5 bnh nh mc loi 25,0ml pha ch mt dy dung dch c thnh phn nh
bng sau:
ml
Bnh
B 1 B 2 B 3 B 4 DD trng
Fe
3+
0,10
mg
/ml 0,5 1,0 1,5 2,0 0,0
Axit sunfosalixilic 10% 2,5 2,5 2,5 2,5 2,5
NH
4
OH

10%

2 2 2 2 2
Nc ct nh mc va ti vch ri lc u
Sau khi pha ch xong nhn xt mu v cng mu ca cc bnh trong dy.
Ly cc dung dch trong cc bnh nh mc cho ra cuvet c b dy 1,0cm ri a vo
my o quang = 420nm vi dung dch trng c thnh phn nh bng trn.
T cc s liu hp th quang A o c t cc bnh 1 ti bnh 4 xy dng th
chun AV
Fe
3+
hoc th AC
Fe
3+ trn giy milimet. ( th phi l mt ng thng i
qua gc to ).
2. Xc nh nng Fe
3+

Ly chnh xc 1,0; 1,5 hoc 2,0 ml dung dch Fe
3+
(ty thuc vo hm lng st c
trong mu) cho bnh nh mc loi 25ml. Thm vo khong 2,5ml dung dch axit
sunfosalixilic 10%; 2,5ml dung dch NH
4
OH 10%. Thm nc ct va ti vch, lc u.
o hp th quang ca dung dch ny vi dung dch trng trn. T s liu o c v
th chun, tnh hm lng v nng ca dung dch st.
III. Ha cht v dng c
- Dung dch chun mui st (III) 0,1mg/ml. Cn 0,8636gam NH
4
Fe(SO
4
)
2
.12H
2
O
ha tan vo 5ml H
2
SO
4
c, sau nh mc bng nc ct va 1,0 lt.

84
- Dung dch m CH
3
COOH+CH
3
COONa
- Dung dch axit sunfosalixilic 10%
- Dung dch NH
4
OH 10%
- Bnh nh mc loi 25,0ml
- Pipet loi 2,0ml, ng ong, buret

Cu hi v bi tp
1) Axit sunfosalixilic c nhng c im g c th chn lm thuc th i vi st.
2) Yu t pH nh hng nh th no n qu trnh to phc gia thuc th v ion kim
loi? Ly v d.
3) C nhn xt g khi thc hin phn ng theo trnh t sau:
a) Dung dch Fe
3+
+ axit sunfosalixilic + NH
4
OH d
b) Dung dch Fe
3+
+ NH
4
OH d + axit sunfosalixilic
4) Mt quang ( hp th) ca dung dch ph thuc vo nhng yu t g? Gii
thch nhng yu t t nh lut c bn ca php o quang.
5) Nhng bin php thc nghim no m bo nhn c th AC l mt ng
thng.
6) Dung dch nghin cu c mt quang ( hp th) A=0,9 khi o cht mu cuvet
c l=5,0cm. Trong cng iu kin dung dch, cht mu y vi nng chun 5,0g/ml c
hp th quang A=0,6 khi o cuvt c l=3,0cm. Tm nng ca dung dch nghin cu.
(S: 4,5g/ml)
7) Mt phc mu ca st c h s hp th phn t =4.10
3
. Hi phi chn cuvet c l
bng bao nhiu cm khi o hp th quang c gi tr A=0,4. Bit rng phc mu c
to t 0,05mg Fe trong bnh 50ml.

85
Bi 30
XC NH HM LNG ST TRONG NC T NHIN

I. C s phng php
C nhiu loi thuc th c th to phc mu vi ion st c gi tr trong phng php
o quang. Bn cnh phc gia Fe(III) vi axit sunfosalixilic nghin cu trong cc bi trn
th phc mu cam c to thnh gia Fe(II) v 1, 10 phenanthroline
(orthophenanthroline) c coi l phng php tiu chun xc nh hm lng trong
nc t nhin. Phn ng to thnh phc c vit ngn gn nh sau:
Fe
2+
+ 3phenH
+
Fe(phen)
3
2+
+ 3H
+
Hng s cn bng ca phn ng l 2,5.10
6
(ti 25
o
C). Phc c hnh thnh trong
khong pH t 3 ti 9, ti u l 3,5. Trong phn tch nh lng cn cho d tc nhn kh nh
hydroxylamin hay hydroquynon chuyn hon ton cc dng Fe(III) v Fe(II). Phc to
thnh trong cc iu kin ti u rt bn (hng s khng bn K=5.10
22
) c gi tr ln trong
phn tch o quang.
Phc c hp th quang cc i ti 508nm, vi cc my so mu n gin c th s
dng knh lc mu xanh l cy.
II. Cch tin hnh
1. Xy dng ng chun
u tin dng pipet ly chnh xc 10,00ml dung dch Fe
2+
40g/ml cho vo cc loi
100ml ri thm khong 25ml nc; a cc vo my o pH ri s dng dung dch citrat natri
iu chnh pH ca dung dch ti 3,5. c th tch dung dch citrat natri tiu tn v ghi li
vo s tay th nghim (Gi s dung dch citrat natri tiu tn l Vml). T lng dung dch
citrat natri cn iu chnh pH cho 10ml Fe
2+
s suy ra lng dung dch citrat natri cn ly
cho cc lng dung dch st chun t hoc nhiu hn.
Chun b 5 bnh nh mc loi 50ml, cho vo cc loi ha cht theo th t sau
ml B1 B2 B3 B4 B5
Fe
2+
40g/ml 1,0 2,0 3,0 4,0 5,0
Citrat natri V/10 V/5 V/3,3 V/2,5 V/2
Hydroxylamin 1
Orthophenanthroline 2
yn 5 pht ri nh mc bng nc ct va ti vch ri lc u

Tin hnh o quang ti bc sng 508nm vi dung dch trng gm cc thnh phn tr
khng c st trong cc cuvet c b dy l=1cm. Xy dng th chun AC.

86
2. Xc nh hm lng st trong nc
Ty thuc vo hm lng thc t ca mu nc m ta ly lng mu tin hnh
phn tch cho ph hp. Vi cc mu nc sinh hot, thng thng ta ly chnh xc 100ml
mu, cho vo cc chu nhit, thm 1~2 git HNO
3
c ri un nh trn bp in ti th tch
khong 20ml. ngui ri chuyn ton b dung dch mu c vo bnh nh mc loi
50ml, thm mt th tch dung dch citrat natri ti khi t pH=3,5. Thm 1ml dung dch
hydroxylamin v 2ml dung dch orthophenanthroline vo bnh, yn 5 pht ri nh mc
bng nc ct ti vch. Tin hnh o quang ti 508nm vi dung dch trng ph hp.
T gi tr hp th quang o c v th chun xc nh hm lng st c trong
mu nc phn tch.
III. Ha cht v dng c
- Dung dch Fe
2+
40g/ml: cn chnh xc 0,2810g FeSO
4
.(NH
4
)
2
SO
4
.6H
2
O vo cc
kh, thm 1ml H
2
SO
4
c ri khuy u, thm nc ct ti va 1lt.
- Dung dch citrat natri 25g/l.
- Dung dch hydroxylamin hydroclorit 10%. Dung dch bn c khong 1 tun.
Lu y l cht c, khi lm vic cn cn trng.
- Othophenanthroline: cn 2,5g orthophenanthroline ha tan trong 100ml ethanol
96%, thm nc ct ti 1lt. Dung dch bn trn 1 thng nu trong bng ti.

87
Bi 31
xc nh MnO
4
v Cr
2
O
7
2

trong dung dch hn hp

I. C s phng php
ng cong quang ph hp th Cr
2
O
7
2
c cc i
1max
= 440nm; di sng ny
MnO
4
cng b hp th mt phn. Ion MnO

4
hp th nhiu nht
2max
= 525nm nhng
y s hp th Cr
2
O
7
2
khng ng k.

(1)
A
Hnh 24: Dng th chun v ph hp th ca MnO
4
+ Cr
2
O
7
2
Do c th xc nh nng ca cc ion ny nh sau:
1. o hp th quang ca dy dung dch chun KMnO
4

1max
v
2max
dng hai
ng A-C ng vi hai di sng (ng 1 v 2)
2. o hp th quang ca dy dung dch chun K
2
Cr
2
O
7

1max
A-C ng vi
di sng (ng 3)
3. o hp th quang ca dung dch hn hp c
1max
v
2max
c cc gi tr
tng ng l A(
1
) v A(
2
). V
2max
ion Cr
2
O
7
2
hp th khng ng k nh sng nn
A(
2
) l hp th quang ch ca MnO
4
-
trong hn hp. Da vo ng chun 2, tm c
nng ca MnO
4
l C
1
. Khi tm c nng C
1
, da vo ng chun 1 tm c
hp th quang A'(
1
) ca MnO
4
-
A(
1
) l hp th quang ca c hai ion di sng
1
nn:
A(
1
) - A'(
1
) = A"(
1
Cr
2
O
7
2-
)
A"(
1
Cr
2
O
7
2
) l hp th quang ca Cr
2
O
7
2

1max
. T ng chun 3 tm c
nng Cr
2
O
7
2

trong dung dch hn hp C
2
.
(3)
(2)
C
2

A(
2
)

A"(
1
)

A'(
1
)

C
1

88
II. Cch tin hnh
1) Xy dng ng chun ca KMnO
4
v K
2
Cr
2
O
7
* Chun b 4 bnh nh mc c dung tch 25,0ml ly vo ln lt 0,5 1,0 1,5
2,0ml dung dch chun KMnO
4
0,01N. Thm nc ct va ti vch nh mc ri lc u.
o hp th quang trn my ti = 525nm v = 440nm
* Tip theo, chun b 4 bnh nh mc c dung tch 25,0ml ly vo ln lt 0,5
1,0 1,5 2,0ml dung dch chun K
2
Cr
2
O
7
0,05N. Thm nc ct va ti vch nh mc
ri lc u. o hp th quang trn my ti = 440nm
V 3 th chun trn giy milimet trn cng mt h trc ta . ( th phi l mt
ng thng i qua gc ta )
2) Xc nh hm lng Cr v Mn trong dung dch hn hp
Ly chnh xc 2,0 hoc 3,0ml dung dch hn hp phn tch - o tng hp th quang
ti
max1
v
max2
ri xc nh hm lng Mn v Cr c trong dung dch phn tch.
Tnh nng cc ion theo mg/ml
II. Ha cht
- Dung dch chun KMnO
4
0,01N khi pha cho thm ~5ml H
2
SO
4
+5ml H
3
PO
4
.
- Dung dch chun K
2
Cr
2
O
7
0,05N ~5ml H
2
SO
4
+5ml H
3
PO
4
.
- Dung dch hn hp phn tch KMnO
4
+K
2
Cr
2
O
7

Bi 32
XC NH Ni
2+
BNG DIMETYLGLYOXIM

I. C s phng php
Dimetylglyoxim (thuc th Trugaep) to vi Ni
2+
mi trng kim khi trong dung
dch c cht oxy ha (I
2
, Br
2
, S
2
O
8
2-
, H
2
O
2
) mt hp cht c mu tm. y Ni
2+
b oxy
ha thnh Ni
3+
; hp cht ny c thnh phn Ni
3+
:DM
2
= 1:3 c cc i hp th ti bc sng
max
=470nm, =13000. Phn ng to phc rt nhy nhng b nhiu ion nh Fe
3+
, Cu
2+
, Al
3+

cn tr.
Tuy nhin trong thc t xc nh Ni
2+
nu dng cc cht che nh tatrat, citrat c th
loi tr c mt s cc ion gy cn tr php xc nh.
II. Cch tin hnh
1. Xy dng th chun
Chun b 6 bnh nh mc dung tch 50ml pha ch mt dy dung dch c thnh phn
nh bng sau

89
ml
Bnh
B1 B2 B3 B4 B5 B6
Ni
2+
0,01 mg/ml 0 1 2 3 4 5
Nc ct 20
It 0,05M 0,5 0,5 0,5 0,5 0,5 0,5
NaOH 1N 2,5 2,5 2,5 2,5 2,5 2,5
Dimetylglyoxim 0,5 0,5 0,5 0,5 0,5 0,5
Nc ct nh mc va ti vch lc u
Ly cc dung dch trong cc bnh nh mc cho ra cuvet c b dy l=1,0cm. o hp
th quang ca cc dung dch trn my quang ph o quang ti bc sng =470nm vi dung
dch trng l bnh s 1.
V th A-C trn giy milimet ( th phi l mt ng thng i qua gc ta )
2. Xc nh nng Ni
2+

Dung dch Ni
2+
cha bit nng cng chun b vi trnh t v lng thuc th nh
dy dung dch chun trong bnh nh mc 50ml. Cho dung dch trong bnh nh mc ra cuvet
1cm, o hp th ti =470nm vi dung dch trng l bnh 1.
T kt qu hp th o c tnh nng Ni
2+
trong mu kim tra.
III. Ha cht v dng c
- Dung dch chun Ni
2+
0,01 mg/ml
Cn 0,4786gam NiSO
4
.7H
2
O ha tan trong nc c axit ha bng 2 3ml H
2
SO
4

c v pha bng nc ct ti vch trong bnh nh mc 1lt. Nng dung dch ny l
0,1mg/ml khi cn pha long 10 ln.
- Dung dch It 0,05M
- Dung dch NaOH 1N
- Dung dch dimetylglyoxim 0,05M pha trong etanol

Bi 33
XC NH AMONI TRONG NC

I. Nguyn tc xc nh
Nm 1856, J.Nessler ln u tin xut phng php xc nh amoni bng
phng php so mu vi dung dch kim thy ngn (II) iotdit. Khi thuc th Nessler c
thm vo dung dch amoni th amoni t do trong dung dch s phn ng rt nhanh vi tc
nhn ny, tuy nhin khng phi ton b lng amoni t do u phn ng ngay lp tc do
vy cn c mt thi gian tc ht keo mu vng c to thnh hon ton.

90
Ion st, mangan trong mu cng to phc mu vng vi thuc th Nessler do vy
cn phi cho dung dch kali hoc natri tactrat vo che cc ion ny.
Phn ng vi thuc th Nessler, dung dch kim ca kali tetraiodo thy ngn, vi
amoni:
2NH
3
+ 2K
2
[HgI
4
] = Hg
2
NH
2
I
3
+ 4KI + NH
4
I
Thuc th cho phn ng rt nhy vi amoni, phng php ch c p dng vi dung
dch c hm lng amoni rt nh (0,1mg/l)
II. Cch xc nh
1. Xy dng ng chun:
Chun b 5 bnh nh mc loi 50ml pha ch dy dung dch chun theo ng th t v
c thnh phn nh bng sau:
B1 B2 B3 B4 B5
Nc ct Khong 25ml
NH
4
+
25mg/l 0 1,0 2,0 3,0 4,0
K
4
NaC
4
H
4
O
6
10% 2,0ml ly bng pipet
Thuc th Nessler 2,0ml ly bng pipet
Nc ct khng c amoni nh mc va ti vch ri lc u
yn dung dch khong 5 pht ri cho ra cuvet c b dy l=1cm em o quang trn
my o quang bc sng 400nm vi dung dch trng gm mi thnh phn tr amoni. T
cc s liu hp th quang thu c xy dng th chun AC
NH
4
+ trn giy milimet.
Lu rng trc khi o quang cn quan st dung dch nu thy dung dch c hin
tng c, m (khng trong sut) th phi lm li th nghim.
2. Xc nh nng NH
4
+
trong nc:
Tu thuc vo nng NH
4
+
trong mu phn tch ln hay nh m ta ly vo bnh nh
mc 50ml sao cho nng NH
4
+
khng qu 5mg/l. Pha long dung dch bng nc ct
khng c amoni trc khi cho vo 2,0ml K
4
NaC
4
H
4
O
6
10% v 2,0ml thuc th Nessler.
nh mc bng nc ct va ti vch lc u.
yn 5 pht sau o quang trn my so mu bc sng 400nm.
T cc s liu hp th quang (A) thu c da vo th chun ta s tnh c
nng NH
4
+
(mg/l) trong mu phn tch.
III. Ho cht v dng c
Dung dch chun NH
4
+
: Cn 0,7414g NH
4
Cl sy kh ti khi lng khng i
105
o
C ha tan hon ton bng nc ct khng cha amoni ri chuyn ton b dung dch vo
bnh nh mc 1000ml. Sau khi pha c dung dch ny li dng pipet ly chnh xc

91
10,00ml cho vo bnh nh mc 100ml dng nc ct khng c amoni thm va ti vch
lc u. Nh vy c 100ml dung dch NH
4
+
25mg/l.
Dung dch K
4
NaC
4
H
4
O
6
10% : Cn 10g tinh th K
4
NaC
4
H
4
O
6
pha vo 90ml nc
ct khng c amoni.
Thuc th Nessler: Cn 45,5g HgI
2
v 35g KI tm t, khuy trn u ti khi tan
hon ton. Thm tip 112g KOH khuy n tan ri thm nc ct ti va 1lt. yn
dung dch 24 gi gn ly phn dung dch trong em i lm thuc th. Thuc th ny rt c
nn khi lm vic cn thn trng v bo qun trong bnh nu c nt nhm.
Bnh nh mc 50, 100, 1000ml
ng ong, pipet, qu bp cao su

Bi 34:
XC NH Cl
BNG THY NGN THYOXYANATE

I. C s phng php
Phng php cho php xc nh lng vt anion clorit trong dung dch. Nguyn tc
l ion thyocyanat ca mui thy ngn thyoxyanat b chim ch bi ion clorit v gii phng ra
ion thyoxyanat t do. Vi s c mt ca ion Fe(III) trong dung dch s to ra phc c mu
mu. Cng mu ca phc st vi thyoxyanat tng ng vi hm lng ion clorit
trong dung dch.
2Cl
+ Hg(SCN)
2
+ 2Fe
3+
= HgCl
2
+ 2[Fe(SCN)]
2+

II. Cch tin hnh
1. Xy dng ng chun
Chun 5 bnh nh mc dung tch 25ml cho vo cc loi ha cht sau
ml

Bnh
B1 B2 B3 B4 B5
Cl
2,5 mg/ml 0 0,5 1,0 1,5 2,0

Phn amoni st(III) 0,25M 2 2 2 2 2
Hg(SCN)
2
bo ha 2 2 2 2 2
Nc ct nh mc va ti vch lc u
yn dung dch 10 pht ri a ra cuvet v o hp th quang ti bc sng =
460nm vi dung dch trng bnh 1. Xy dng th chun A C.

92
2. Xc nh Cl
trong mu
Vi cc mu nc t nhin ta ly 20ml mu cho vo bnh nh mc 25ml, thm 2ml
phn st(III) amoni sunfat, thm 2ml Hg(SCN)
2
bo ha. yn mu 10 pht ri nh mc
bng nc ct ti vch. o quang ti =460nm vi dung dch trng l bnh 1.
T hp th quang o c, da vo ng chun s xc nh c hm lng gc
ion Cl
trong dung dch.

III. Ha cht cn chun b
Dung dch Cl
chun 2,5mg/ml: Sy kh tinh th NaCl (tkpt) 180

o
C trong khong
30 pht, cn chnh xc 4,1213g NaCl pha vo 1lt nc ct.
Phn amoni st(III) 0,25M: cn 120g NH
4
Fe(SO
4
)
2
.12H
2
O ha tan v nh mc bng
dung dch HNO
3
6N.
Hg(SCN)
2
bo ha c pha trong ethanol

Bi 35
PHNG PHP O QUANG XC NH THNH PHN PHC
PHC Cu(II) NITROZO-R-SOL

I. C s phng php
Khi hp th bc x in t t min t ngoi ti min trng thy, cc phn t cc cht
hp th t b phn hy, t xy ra s b gy lin kt ha hc. iu ny cho php ng dng
phng php ph hp th nghin cu thnh phn, trng thi cn bng ca dung dch.
Nguyn tc chung p dng phng php ny l gii phng trnh lin quan ti hai nh
lut: nh lut tc dng khi lng v nh lut hp th nh sng.
c im chung ca phng php l da vo th thnh phn tnh cht dung dch
xc nh h s ha hc trong phn ng to phc cht. Cc phng php c bn l phng
php dy ng phn t gam, phng php ng cong bo ha.
1. Phng php dy ng phn t gam
Phng php ng phn t gam c s dng rt ph bin xc nh thnh phn ca
cc phc. Ni dung ca phng php l cho cht phn tch X tc dng vi thuc th R
sinh ra hp cht phc c dng phn t X
n
R
m
th nguyn tc c th l:
- Pha mt dung dch cht X v mt dung dch thuc th R c cng nng phn t gam.
- Pha mt dy dung dch cc hn hp ca X v R bng cch em trn chng vi nhau
theo cc t l th tch khc nhau, nhng c tng th tch l nh nhau cho cc mu u c
tng nng (C
X
+C
R
) l nh nhau.

93
- Chn cc iu kin o quang thch hp ri tin hnh o hp th quang ca dy
dung dch.
- V ng cong biu din mi quan h A C
X
/C
R
.
Nu trong khong nng nghin cu cht X tc dng vi thuc th R ch to thnh
mt phc cht c thnh phn nht nh th cc ng tng ng vi cc dy ng phn t
gam ca X v R c nng khc nhau ch c mt t l nng ca X v R. Tc l cc cc
i ca dy ng phn t gam vi nng khc nhau chng u nm trn mt ng thng
song song vi trc tung v vung gc vi trc honh.
Nu cc nng khc nhau ca dy ng phn t gam ca X v R m cc i ca
cc ng cong c honh khc nhau, tc l t s (C
X
/C
R
) khc nhau, th iu chng t
khi pha long thnh phn hp cht phc b thay i. Ngha l mi t l nng khc nhau
ca X v R phc sinh ra c thnh phn khc nhau.
2. Phng php ng cong bo ha
Nguyn tc ca phng php l gi cho mt thnh phn khng i (thng l cht phn
tch X) cn thnh phn kia (thuc th R) s c bin i lin tc t nh ti ln. Cch lm
theo cch thc sau:
- Pha mt dy cc dung dch chun ca cht X m gi tr nng ca cht X l nh nhau
trong cc mu. Cn nng thuc th R th c thay i tng dn.
- Chn cc iu kin o quang thch hp ri tin hnh o hp th quang ca dy
dung dch.
- Dng ng cong biu din mi quan h A C
X
/C
R
.
Thnh phn ca phc X
n
R
m
c xc nh bng cch v cc ng tip tuyn ng vi
phn ng cong c hp th quang tng nhanh v phn ng cong gn nh song song vi
trc tung ( hp th quang khng tng hoc tng khng ng k).
II. Cch tin hnh
1. Phng php dy ng phn t gam
Ly 9 bnh nh mc c dung tch 25,0ml pha ch 1 dy dung dch c cc thnh phn
nh bng sau:
ml

Bnh

B 1 B 2 B 3 B 4 B 5 B 6 B 7 B 8 B 9
Nitrozo-R-sol 10
3
M 9,0 8,0 7,0 6,0 5,0 4,0 3,0 2,0 1,0
CuSO
4
10
3
M 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0
Na
2
SO
4
0,05M 5,0
H
2
SO
4
pH = 4 Thm va n vch nh mc ri lc u

94
Tin hnh o hp th quang ca phc mi bnh ti bc sng =470nm vi dung
dch so snh l nc ct hoc dung dch H
2
SO
4
pH=4. Xy dng th ph thuc ca A vi
V
Cu
/V
HR
. Tm cc i v xc nh thnh phn ca phc to thnh.

0
0,2
0,4
0,6
0,8
0 1 2 3 4 5 6 7 8 9
V
R
V
Me
9

8

7 6

5

4

3 2 1
A
Hnh 25: th m t s ph thuc A-V
Me
/V
R
theo phng php dy ng phn t
2. Phng php ng cong bo ha
Ly 8 bnh nh mc 25ml pha ch mt dy dung dch c thnh phn nh bng sau
ml
Bnh

B 1 B 2 B 3 B 4 B 5 B 6 B7 B8
Nitrozo-R-sol 10
3
M 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0
CuSO
4
10
3
M 2,0
Na
2
SO
4
0,05M 5,0
H
2
SO
4
pH = 4 Thm ti vch nh mc ri lc u
Tin hnh o hp th quang ca phc mi bnh ti bc sng =470nm vi dung
dch so snh l nc ct hoc dung dch H
2
SO
4
pH=4.
Lp th h to A V
R
/V
Cu
. T th ny tnh ton v xc nh thnh phn phc
theo phng php ng cong bo ha.
0
0,1
0,2
0,3
0,4
0,5
0 0,5 1 1,5 2 2,5 3 3,5 4

Hnh 26: th m t s ph thuc A-V
Me
/V
R
theo phng php ng cong bo ha
2 2 2 2 2 2 2 2
A
V
R
V
Me

95
III. Chun b thuc th
- Dung dch CuSO
4
10
3
mol/l. Cn chnh xc 0,2600g CuSO
4
.5H
2
O ha tan bng dung
dch H
2
SO
4
c pH=4 n 1lt.
- Nitrozo-R-sol 10
3
M. Cn chnh xc 0,3773g Nitrozo-R-sol loi tinh khit ha hc
pha trong nc ct ti 1lt.
- Dung dch H
2
SO
4
pH=4. Ly khong 1ml H
2
SO
4
0,1M ha tan vo gn 2lt nc ct.
o pH ca dung dch trn my o pH. iu chnh pH ca dung dch t n 3,90,1 bng
cch cho tng git dung dch H
2
SO
4
0,1M hoc dung dch NaOH 0,1M.
- Dung dch Na
2
SO
4
0,05M c pH=4. Cn 16,1g Na
2
SO
4
.10H
2
O hoc 7,1g Na
2
SO
4

khan ha tan vo 1lt nc ct. Thm tng git H
2
SO
4
0,1M hoc NaOH 0,1M iu chnh
sao cho pH = 4,0 0,1 trn my o pH.

Bi 36
XC NH NG THEO PHNG PHP O QUANG VI SAI

I. C s phng php
Hm lng ng trong hp kim c xc nh theo phng php quang ph o quang
vi sai dng phc . Phc c cc i hp th
+ 2
4 3
) NH ( Cu
+ 2
4 3
) NH ( Cu
max
=620nm. hp th quang dung dch phn tch c o vi dung dch so snh l dung
dch phc c nng C
+ 2
4 3
) NH ( Cu
0
bit. C hai cch xc nh nng theo phng
php o vi sai l phng php th chun v phng php tnh.
II. Cch tin hnh
1) Phng php th chun
Chun b 5 bnh nh mc loi 25ml pha ch dy dung dch chun c thnh phn nh
bng sau:
ml
Bnh

B 1 B 2 B 3 B 4 B 5
CuSO
4
0,05M 1,0 2,0 3,0 4,0 5,0
NH
4
OH

10%

Khong 5ml, ly bng ng ong
Nc ct Thm va ti vch ri lc u
hp th A
0
A
1
A
2
A
3
A
4

A
1
A
2
A
3
A
4
l hp th ca cc dung dch chun vi dung dch so snh c
nng C
0
(B1) ti =620nm. Ta c phng trnh tnh sau:
A
1
= A
1
- A
0
= l (C
1
- C
0
) (1)

96
A
2
= A
2
- A
0
= l (C
2
- C
0
)

.
(2)

A
n
= A
n
- A
0
= l (C
n
- C
0
)
Trong A
0
, A
1
, A
2
A
n
l hp th ca cc dung dch nu o vi dung dch
trng theo phng php o quang thng thng.
Ta lp th h to A C trn giy milimet
Ly chnh xc mt th tch V
x
dung dch CuSO
4
(mu phn tch), thm khong 5ml
dung dch NH
4
OH 10% em o quang vi dung dch so snh nh trn ti =620nm.

Gi s
ta o c hp th quang ca dung dch nghin cu l A
x
ta s c biu thc tnh sau:
A
x
= A
x
- A
0
= l (C
x
C
0
) (3)
Da vo th chun A C ta d dng tnh c nng C
x
.
2) Phng php tnh
Chun b 3 bnh nh mc c dung tch 25,0ml pha ch mt dy dung dch c thnh
phn nh bng sau:

Dung dch chun Dung dch so snh MKT
5,0ml CuSO
4
C
i
= 3.10
-2
M C
0
= 1.10
-2
M C = x
NH
4
OH 10% Khong 5ml, ly bng ng ong
Nc ct Thm va ti vch ri lc u
hp th A
i
0,00 A
x

o hp th quang ca cc dung dch trn bc sng = 620nm.
T biu thc (2) (3) ta c:
'
0
'
0
x x
i i
A C C
A C C
suy ra:

'
0 '
( )
x
x i
i
A
C C C
A
0
C = +
hay c th vit: C
x
= F . A
X
+ C
0
(
0 i
i
C C
F
A
= )
Nh vy vi phng php tnh ton ta ch cn o hp th quang ca dung dch phn
tch v hp th quang ca mt dung dch chun c nng C
i
thay cho vic phi o
hp th quang ca nhiu dung dch chun nh phng php th chun. T cc kt qu thu
c tnh ton nng CuSO
4
trong mu kim tra theo phng php tnh.

97
Bi 37
PH IN T CA ION NO
2

I. Ni dung nghin cu
Cc phn t, nhm phn t ca cc cht, n cht hay hp cht, cng u c cu to
t cc nguyn t theo nhng cch, kiu lin kt ha hc nht nh ca cc in t (electron)
ha tr (cc electron lp ngoi cng) ca cc nguyn t. Tuy c hng vn cht c to
thnh t cc nguyn t, phn t nhng trong phn t ch c ba loi lin kt ha hc, l
lin kt xicma (), lin kt pi () v lin kt phi tr (cho-nhn). Ngoi ra, nu trong phn t
cha cc nguyn t nh nit, oxy, lu hunh th nguyn t ny c th c mt hoc hai i
in t ha tr cha tham gia lin kt v c k hiu l cp electron n.
Cc electron ha tr khi lin kt trong phn t hnh thnh cc lin kt loi v . Cc
in t ha tr ca lin kt nm trong cc phn lp p, d, f v l cc lin kt loi pp,
dd, ff, df, df. Trong phn t hay nhm nguyn t cc lin kt c nng lng lin kt
ln nht (bn nht); sau , km hn l cc lin kt v cc i in t t do n. Cc phn t
iu kin bnh thng chng tn ti trng thi c bn, trng thi bn vng. Theo c hc
lng t, trng thi c bn phn t khng thu v khng pht bc x. Nhng khi b chiu
mt chm nh sng (chm proton) c nng lng thch hp (kch thch) th cc in t ha
tr trong cc lin kt , v i in t n trong phn t s hp th nng lng ca chm nh
sng (tng tc khng n hi) v chuyn n ln trng thi kch thch c mc nng lng
cao hn. Khi phn t b kch thch nh th chng s c s chuyn mc nng lng:
n
*
n
*

*

*

Kch thch
C bn

Hnh 27: S cc mc nng lng v bc chuyn nng lng trong ph in t

98
Hiu s gia hai mc nng lng c bn E
0
v mc kch thch E* chnh l nng lng
m phn t hp th c t ngun sng (chm sng) v tc ng vo chng theo biu
thc: E
e
= E* E
0
= .h = (h.c)/
Song trong qu trnh phn t b kch thch, tc l phn t cht hp th nng lng
ca chm nh sng chiu vo n, cng vi s chuyn mc nng lng ca electron lin kt
trong phn t cn km theo c s quay v dao ng ca nguyn t trong phn t. V th tng
nng lng m phn t ca cht nhn c khi b kch thch l bao gm ba thnh phn
E
tf
= E*
tf
E
0
tf
= (E*
e
E
0
e
) + (E*
v
E
0
v
) + (E*
j
E
0
j
)
= E
e
+ E
v
+ E
j

V chnh nng lng b mt i ny ca chm nh sng kch thch b cht hp th to
thnh ph hp th phn t ca cht.
Tng nng lng (E
tf
) chnh l tng ng vi nng lng ca cc chm nh sng nm
trong vng bc sng 190800nm (vng UVVis). V th ph hp th loi ny c gi l
ph hp th phn t UVVis. Trong ba thnh phn ny th E
e
>>E
v
>>E
j
v ch c thnh
phn E
e
l c lng t ha, theo cc mc nng lng nht nh ca cc obital phn t
(MO). Cn hai thnh phn kia khng c lng t ha, v th ph hp th phn t ca cc
cht trong vng UVVis khng phi l ph vch v khng n sc nh ph pht x hay ph
hp th nguyn t. Ph y l ph bng, c rng t 10 ti 80nm v c cc gi tr cc i
v cc tiu ti nhng sng nht nh, ty thuc vo cu to phn t ca mi cht.
Cc cht no c nhiu lin kt v lin kt lin hp th s hp th quang ca n
cng mnh. Kh nng hp th quang ny c c trng bi h s hp th ca n. Ngha l
gi tr ca phn t mt cht c lin quan cht ch n cc loi lin kt ha hc ca nguyn
t c trong phn t ca cht, tc l cu trc phn t. V th ph hp th quang phn t vng
UVVis cng l mt i lng c trng cho cu trc phn t ca cht, nhng cht khc
nhau s c nhng nhm ph, nhng cc i hp th quang ca ring n.
Da vo min ph ta phn on, phn nh loi bc chuyn nng lng cng vi m
ph hp th (gn bc chuyn nng lng cho m ph)
Da vo cng m ph (o bng h s tt phn t ):
- Nu ln (>10
3
) m ph vi cng ln
- Nu b (<10
2
) m ph vi cng b
Ta c mt s nt c trng c th dng phn bit cc bc chuyn nng lng cho
cc m ph:
- Chuyn mc n * c nhng c im: cng b, mc ph t ngoi gn, nhn thy.

99
- Chuyn mc * c nhng c im: cng ln, mc ph t ngoi trung bnh, gn.
- Chuyn mc * c nhng c im: cng ln, mc ph t ngoi rt xa.
S dng my UV-Vis kho st s bin thin ca hp th A theo bc sng ta s xc
nh c gi tr bc sng m ti cht nghin cu c hp th ln nht
max
.
max
c hai ngha quan trng l phn tch nh lng v phn tch cu trc phn t.
Trong phng php phn tch cu trc phn t bng ph UV-Vis t gi tr
max
ta d
dng tnh c bc chuyn nng lng in t cc i, h s tt phn t cc i ca dung
dch nghin cu.

max
v
max
l nhng tham s ta nhn dng bc chuyn nng lng in t. T
gip nhn bit cc obital MO phn t trong hp cht. l ni dung phng php ph
in t nghin cu cu trc phn t.
II. K thut thc nghim
T dung dch NO
2
0,01M pha ch ra cc dung dch c nng thch hp (mi nng

lm t nht 2 mu nghin cu).
Cho cc dung dch ny cho ra cuvet thch anh c b dy l=1cm a vo ngn ng
mu ca my UV-VIS (Agilent 8453) chn phng php (Method): kho st ph hp th
(Spectrum/peaks) trong khong bc sng =200nm ti =600nm, vi dung dch so snh l
nc ct.
Nhn xt v ph hp th thu c. Tnh h s
max
, E
max
.
III. Chun b ha cht
- Sy kh tinh th NaNO
2
ti 110
o
C trong khong 30pht. Cn chnh xc 0,6900g
NaNO
2
pha trong mt lt nc ct.

100
CHNG 2: PHNG PHP IN PHN

I. C s phng php
in phn l mt phng php in ha dng tch cc kim loi ra khi dung dch,
ng thi cng l phng php xc nh nng ca kim loi trong dung dch, v sau khi
tch ht ngi ta cn bit lng kim loi bm trn in cc.
Phng php tin hnh nhanh, thun li; c chnh xc cao (sai s ca php phn
tch trong khong 0,1 - 0,28%), chn lc cao. C th tch lng ln, lng nh, tch s
b. Tuy nhin, s nguyn t c th c phn tch bng phng php in phn khng
nhiu, hm lng cht nghin cu cn phi ln.

Hnh 28: S h thng in phn
1- Catot li bch kim
2- Ant bch kim dng dy xon
3- Bin tr
4- Vn k
5- Ampe k

Khi c dng in mt chiu chy qua, cc ion chuyn v cc in cc tri du v xy
ra cc qu trnh in ha.
V d: Khi cho dng in mt chiu i qua dung dch CuCl
2
c nhng cc in
cc ant v catot lm bng kim loi platin, ng c tch ra catot theo qu trnh:
Cu
2+
+ 2e = Cu
Cn trng lng catot trc v sau khi in phn bit nng ng. ant
c qu trnh thot kh clo:
2Cl
2e = Cl
2
C nhng trng hp c cc cation cng b oxy ho trn ant.
V d: Pb
2+
2e + 2H
2
O = PbO
2
+ 4H
+
Mn
2+
2e + 2H
2
O = MnO
2
+ 4H
+
nh lut c bn trong in phn nh bit l nh lut Faraday:
=
D
m I
F
t
m: lng cht thot ra trn in cc (g)
D: ng lng gam ca cht thot ra in cc
F: hng s Faraday = 96.500 C
I: cng dng in (A)
t: thi gian in phn (giy)

101
Tuy nhin c qu trnh in phn xy ra trong dung dch, cn phi bit n nhng
qui tc in ha, ch yu l:
1. Th in cc
Khi nhng thanh kim loi vo dung dch mui ca kim loi th gia b mt phn
chia s xut hin cn bng v do xut hin mt th c gi l th in cc. Th in cc
ny c xc nh theo h thc Nerst:
+
+

= +
0 n
n
Me / Me
RT
E E ln M
nF
e
+
+

= +
0 n
n
Me / Me
0, 059
E E lg M
n
e (ti 25
0
C)
Khi [Me
n+
] gim th gim.
n
Me / Me
E
+
2. S phn cc
Trong qu trnh in phn gia 2 cc lun lun xut hin mt th ngc chiu vi in
p cung cp.
a. S phn cc in ho
Trong qu trnh in phn cc sn phm sinh ra hai cc to thnh pin v c cng
dng in ngc chiu vi cng dng bn ngoi cp vo h.
V d: Khi in phn CuSO
4
, cc qu trnh xy ra ti in cc:
Catot (-)
Cu
2+
Cu
2+
+ 2e = Cu
Anot (+)
SO
4
2-
, H
2
O
2H
2
O - 4e =4H
+
+ O
2

Do vy to thnh pin: () Pt, Cu|CuSO
4
||O
2
,H
+
|H
2
O Pt (+)
+
+
+
=
2 pin
O 4H / H O
Cu / Cu
2 2
E E E
b. Phn cc nng
Khi cha in phn th nng ca ion kim loi l nh nhau ti mi im trong dung
dch. Khi c qu trnh in phn, catot: Cu
2+
+ 2e = Cu lm cho [Cu
2+
] catot gim
i dn ti c s chnh lch nng v to ra pin nng .
+
+
(+) (-)
pin
2
2
anot
catot
[Cu ] 0, 059
E = E - E = lg
2 [Cu ]

Dng in do pin nng to ra c chiu ngc vi chiu ca dng in cung cp cho
qu trnh in phn.

C 2 loi phn cc u cn tr qu trnh in phn cho nn phi loi tr:
- i vi s phn cc in ho: cho vo dung dch cht kh cc tc dng vi sn phm
to thnh trn in cc to ra hp cht khc.

102
V d: Khi in phn ti in cc sinh ra O
2
, Cl
2
. . . l cc cht oxy ho. Cho vo dung
dch mt cht kh chng hn nh hydroxylamin (NH
2
OH.HCl). Khi :
2NH
2
OH.H
+
2e = N
2
+ 2H
2
O + 4H
+
Cl
2
+ 2e = 2Cl
Khi in phn sinh ra H

2
(cht kh) s nh hng n cht lng ca kim loi bm
trn in cc. Cho vo dung dch cht oxy ha nh NH
4
S
2
O
8
, HNO
3
. . . Khi :
NO
3
+ 10H
+
+ 8e = NH
4
+
+ 3H
2
O
H
2
2e = 2H
+
- i vi s phn cc nng : loi b s chnh lch nng bng cch tng nhit ,
khuy trn dung dch. Mc ch l tng cng s chuyn cht ti b mt in cc.
3. Th phn hy
Th phn hy (E
h
) l sc in ng b nht cn t vo hai cc s in phn xy ra
v c duy tr trong mt s iu kin no . Th phn hu phi ln hn hoc bng sc
in ng ca pin do cc in cc to ra (sc in ng phn cc).
E
h
ph thuc vo nng cht trong dung dch, bn cht ca cht phn tch, mi
trng in phn.
4. Qu th
Tuy nhin c th duy tr c qu trnh in phn th ta cn t vo hai in cc
mt th E > E
h
.
E = E
h
+ IR
R: in tr ca h thng in phn.
I: cng dng in phn
Thc t th ta phi vo hai cc mt th E > E. V trong qu trnh in phn thng
km theo nhiu hin tng ph. S gia tng in th t vo hai cc qu trnh in phn
xy ra lin tc gi l qu th ().
E = E
h
+ IR
E
h
= (E
A
+
A
) - (E
K
+
K
)
E
A
: th ca anot c tnh theo phng trnh Nerst.
E
K
: th ca catot c tnh theo phng trnh Nerst.
A
,
K
: qu th anot, qu th catot.
Qu th ph thuc vo bn cht in cc, cc thnh phn ca phn ng in cc, trng
thi b mt ca in cc (b mt nhn bng c ln hn so vi b mt x x), iu kin tin
hnh in phn (nhit , mt dng in).

103
Bnh thng qu th ca cc kim loi trn cc in cc nh coi nh khng ng k.
Nhng qu th ca H
2
trn cc in cc khng th b qua.
Catot (-) Pt Au Fe Cu Zn Hg Pb Sn
2
H
(V)
-0,07 -0,39 -0,56 -0,58 -0,75 -1,04 -1,09 -1,08
25
0
C, mt dng l 0,01A/cm
2
2
H
trn Hg, Pb, Sn l ln nht (rt thun li cho vic tch cc kim loi v H
2
s thot
ra sau cng khng nh hng n qu trnh in phn).
II. iu kin in phn theo yu cu phn tch
i vi mc ch phn tch, qu trnh in phn phi m bo cc yu cu sau:
Cht lng ca kt ta kim loi trn in cc:
ng vi lng kim loi trong dung dch
Ht bm trn in cc chc, d ra sch, sy kh, thnh phn ha hc ng nht
(V d: khi in phn dung dch CuSO
4
ngoi Cu bm trn in cc cn c th c Cu
2
O.

Trng

hp ny khng c chp nhn).
Khng cc kim loi khc c trong dung dch b tch trn in cc cng vi kim
loi xc nh. lm c iu ny phi bit thnh phn nh tnh ca dung dch, th phn
hy ca cc ion kim loi tp cht. Trng hp cn thit phi in phn c kim tra th catot
hoc dng cc cht to phc.
in phn mt dng thch hp (0,001 0,01 A/cm
2
) thu c ht mn, bm
chc vo in cc.
t c nhng yu cu trn:
- Tin hnh in phn th ln hn th thot ca hydro, hydro khng thot ra
c catot. Th thot hydro c tnh theo cng thc:
E = 0,059lg C
H
+
H
C
H
l nng H
+
trong dung dch in phn
H
l qu th ca hydro trn in cc catot trong qu trnh in phn.
Do , dung dch in phn phi c pH nht nh, hoc trong mt s trng hp phi
dng cc cht oxy ha loi tr H
+
catot.
- Tin hnh in phn mt dng trung bnh (khong 0,001 0,01 A/cm
2
), thu
c kt ta ht nh, mn, bm chc trn in cc. Nu mt dng qu nh s thu c kt
ta dng tinh th ht to, bm khng chc vo in cc. mt dng qu ln thu c kt
ta dng bt, to, bm km vo in cc.
- i vi tng cht, ty theo nng ca n, qu trnh in phn hon ton ch sau
mt thi gian nht nh. Do phi kim tra qu trnh in phn bng cc phn ng nh
tnh i vi dung dch sau mt thi gian in phn, hoc nhn xt s thay i mu sc sau
mt thi gian in phn.

104
- i vi dung dch ngoi ion cn xc nh cn c cc ion kim loi khc, phi bit
trc th phn hy ca chng v in phn mt hiu in th nht nh m bo ch cho
ion cn xc nh c kt ta, cn cc ion khc khng cng kt ta vi ion cn xc nh.
Trong trng hp cn thit phi dng phng php in phn c kim tra th catot.
- Trong trng hp cc ion c th phn hy rt st nhau khng thc hin c vic
tch theo cc phng php trn, th phi chn cc cht to phc thch hp v in phn trong
iu kin to phc. Do s to thnh cc phc c bn khc nhau, th phn hy thc t ca
cc ion thay i.
III. Chun b in cc
in cc l b phn quan trng in phn: kim loi thng c dng ch to
in cc l platin, vng, hoc hp Pt-Au. Mt s trng hp c th dng cc in cc bng
thp, niken, nhm v.v ty theo iu kin phn tch c th. in cc thng c dng hnh
tr li khi lp anot v catot c lng vo nhau.
Trc khi dng in cc platin phi c ngm trong dung dch HNO
3
c khong 3 pht.
Sau c ra sch bng nc ri sy kh v em i cn trn cn phn tch. i vi cc kim
loi to c vi Pt thnh hp kim, th trc khi tch kim loi phi ph in cc bng mt
lp Cu hoc Ni, cc kim loi thng l Bi, Pb, Zn.

Bi 38
PHNG PHP IN PHN KHI LNG XC NH NG

I. C s phng php
in phn dung dch CuSO
4
Catot ()
Cu
2+
Cu
2+
+ 2e = Cu
Anot (+)
SO
4
2
, H
2
O
2H
2
O 4e =4H
+
+ O
2

Khi in phn cc dung dch mui nitrat, sunfat, photphat th cc ion ny khng b oxy
ho trn anot thay vo l nc.
Dung dch in phn lun c khuy u v un nng 70-80
o
C trong sut qu trnh
in phn.
Mi trng thc hin qu trnh in phn l hn hp axit H
2
SO
4
+HNO
3
c tc dng
lm tng phn ly ca dung dch v HNO
3
cn l mt cht kh cc nhm trnh thot kh
hydro trn catot m bo cho qu trnh in phn din ra iu kin ti u.

105
II. Cch tin hnh
1. Chun b in cc
in cc c s dng l in cc bch kim, cc thao tc chun b xem phn trn
2. Chun b dung dch phn tch
Ly mt cc c dung tch 250ml c ra sch, trng nc ct. Dng pipet ly
chnh xc 2,0ml dung dch CuSO
4
cho vo cc trn, pha thm khong 150ml nc ct. Dng
ng ong ly khong 5ml HNO
3
6N v 5ml H
2
SO
4
6N cho vo cc chun b.
3. Tin hnh phn tch
Sau khi sy v cn catot ti khi lng khng i, ghi trng lng ca catot.
Lp lng hai in cc vo nhau sao cho cn i, khng chm nhau.
Nhng in cc vo dung dch in phn sao cho ch ngp 4/
5
chiu cao in cc.
Cho my khuy t v thit b gia nhit lm vic.
in phn dung dch th 2,0V trong khong 30 pht. Khi dung dch ht mu xanh
kim tra in phn hon ton cha bng cch thm nc ct ngp ht cc nhn xt mu
ca in cc phn va thm nc ct. Nu cn c mu hung ca ng th in phn tip
khong 10 pht sau kim tra Cu
2+
cn st trong dung dch bng thuc th K
4
[Fe(CN)
6
]
(Phn ng c thc hin trn bn s bng cch ly mt a thy tinh ra, trng sch ly 1
git dung dch in phn cho ln bn s, trung ha bng 1 git CH
3
COONa ri nh 1 git
K
4
[Fe(CN)
6
] . Nu khng thy c kt ta mu nu th chng t dung dch in phn
hon ton).
Sau khi kim tra chng t dung dch in phn khng cn Cu
2+
th dng in phn
nhng khng c ngt mch in m ch tt my khuy t v my gia nhit. Vn gi
nguyn in cc trng thi in phn trn my nng cao in cc ln ly cc ng dung
dch in phn ra. Chun b sn mt cc ng khong 100ml nc ct, nhng vi ln in
cc vo cc nc ct . Thay nc ct trong cc v ra 23 ln nh th. Sau mi ngt
dng in, tho in cc ra khi my, em vo t sy, sy kh ri cn ti khi lng khng
i. Ghi kt qu khi lng cn thu c.
4. Tnh ton kt qu
Hiu khi lng ca in cc sau v trc khi in phn l s gam ca ng ly
in phn. T tnh nng CuSO
4
(mol/l).
5. Ra in cc
Ra sch in cc khi Cu bng cch nhng vo dung dch HNO
3
1/1, cho Cu tan
ht. Ra li in cc bng nc ti khi ht HNO
3
bm trn .

106
III. Ha cht cn thit
- Dung dch phn tch CuSO
4

- Dung dch H
2
SO
4
6N
- Dung dch HNO
3
6N v 1/1
- in cc Pt, cc thy tinh 100, 250ml, ng ong
Cu hi v bi tp
1) Vit phn ng in cc (catot v anot) khi in phn dung dch CuSO
4
. Gii
thch vai tr ca dung dch axit HNO
3
trong qu trnh in phn.
2) Ti sao khi dng in phn khng ngt mch in ngay m phi lm theo trnh t
nh nu trong bi th nghim?
3) Nhng yu t no nh hng ti cht lng ca kim loi bm trn in cc

Bi 39
PHNG PHP IN PHN C KIM TRA TH CATOT
XC NH Pb TRONG OXIT KM

I. Nguyn tc
Ha tan ZnO trong axit nitric. Cho vo dung dch mt lng Citrat axit Natri to
phc v clorua hydroxylamin lm cht kh cc anot ri in phn kt ta Pb trn catot
ph Cu.
II. Thit b
C th in phn vi thit b kim tra th catot nhng cng c th dng thit b kim
tra in p n gin.
Catot l li Pt, in phn ph Cu trc v cn.
III. Cch tin hnh
Cn 1g ZnO ha tan trong 5ml HNO
3
1:1 un nh.
Sau khi mu tan, thm mt t nc ct nng cho ti th tch 1012ml (c 100ml
nc th thm 23 git dung dch HNO
3
2N). Nu thy c mt t ht khng tan th lc v ra
giy lc bng nc nng c pha axit HNO
3
.
ngui dung dch, pha long n 50ml thm 2g citrat axit natri v 1g clorua
hydroxylamin. Dng dung dch NaOH 2N trung ha dung dch ny ti khi xut hin kt ta,

107
sau thm 12 git HNO
3
2N. Pha long dung dch ti th tch 120130ml, pH vo khong
7,27,5.
Lp cc in cc vo my v my khuy (tc 250300 vng/pht) ri nhng in
cc vo dung dch phn tch sao cho ch np 4/5 in cc. Dng in cc calomen lm in
cc so snh kim tra th catot.
u tin t th catot 0,55V so vi in cc calomen (hoc in p ch 0,75V). in
phn trong 34 pht. Sau tng th catot ln 0,6V (in p 0,850,9V) v in phn
trong vng 1015 pht. Cui cng th catot 0,65V (in p 0,951,00V) v in phn
tip thm 1015 pht na.
Kim tra xem Pb kt ta ht cha bng cch h thp cc in cc xung dung dch.
Nu sau 23 pht phn catot ph Cu khng thy Pb kt ta na th ngng in phn.
Nhng khng c ngt dng in ch tt my khuy nng cao in cc ln ra nhanh bng
nc sau bng ru.
Ngt in, sy catot 105110
o
C, ngui ri cn ti khi lng khng i. Hiu s
khi lng in cc trc v sau in phn ch chnh l Pb trong mu ZnO ly phn tch.
Cu hi v bi tp
1) Ti sao li phi ph ng ln trn in cc Pt trc khi in phn kt ta Pb.
2) Vai tr ca citrat natri v clorua hydroxilamin trong th nghim ny l g?
3) Ti sao khng nhng ngp in cc Pt ngay t u.
4) Ti sao ngi ta thng ra in cc (c c kt ta) bng ru hoc ete?

108
CHNG 3: PHNG PHP CC PH

I. C s chung ca phng php
Phng php cc ph cng l phng php in phn, nhng y vic xc nh nng
thng qua vic nghin cu quan h gia in p t vo hai in cc (E) vi dng in (I)
hnh thnh trong qu trnh phn cc.
Quan h I-E c biu din trn th hnh 21

Hnh 29: Sng cc ph Hnh 30: th chun
Trong phn tch, s dng dng gii hn (I
gh
) xc nh nng theo phn tch
Inkovitch:
I
gh
= 605.n.D
1/2
.m
2/3
.t
1/6
.C
n: in tch ca ion kim loi (thc ra l s e tham gia phn ng in cc)
D: h s khuch tn, cm
2
.s
-1
m: khi lng Hg chy ra t mao qun trong 1 giy (g.s
-1
)
t: thi gian to git Hg (s)
C: nng ion kim loi kh in cc (mol/l)
D kh xc nh bng thc nghim v cng t c trong s tay.
m, t l i lng c trng cho mao qun, c th xc nh bng thc nghim; m ph
thuc ng knh trong ca mao qun, chiu cao ct Hg v nhit ; i vi t, ngoi hai yu t
nh hng nh i vi m, t cn ph thuc trng thi dung dch v in th.
Trong thc t c th duy tr D, m, t khng thay i trong cc iu kin thc nghim
xc nh, do phng trnh Inkovitch c th vit di dng:
I
d
= K.C (vi K=const)

109
Phng trnh trn l c s xc nh nng C, thng thng dng phng php
th chun:
- Chun b mt lot dung dch chun c nng bit chnh xc, xy dng th I
theo C . Sau khi xc nh chiu cao cc sng cc ph theo cc nng khc nhau ta v
th quan h h (chiu cao sng) - C (nng )
- Sau ly dung dch nghin cu, tin hnh ghi sng cc ph trong cc iu kin
ging ht nh khi xy dng ng chun, xc nh chiu cao h
x
ca sng cc ph ca dung
dch nghin cu ri theo th chun m tm ra nng cht cn xc nh.
Nu cc iu kin ghi sng cc ph c th gi hon ton ng nht khi tin hnh th
nghim i vi dung dch chun v dung dch nghin cu v bit chc gia I
gh
v C
M
c
quan h tuyn tnh trong mt khong rng, ta c th ch dng mt dung dch chun tnh
nng dung dch nghin cu:
C
x
= C
ch
.
ch
x
h
h

C
ch
: nng dung dch chun; C
x
: nng cn xc nh.
h
x
v h
ch
l chiu cao sng cc ph tng ng ca dung dch nghin cu v dung
dch chun.
II. S nguyn tc ca phng php cc ph

Hnh 31: S nguyn tc ca my cc ph

110
III. iu kin dung dch khi o sng cc ph
c c sng cc ph nh l thuyt, khi o sng cc ph ngi ta thm vo dung
dch cc cht:
- Cht kh hoc ui oxy nh Na
2
SO
3
, sc kh tr v rng oxy trong khng kh lun c
trong dung dch v n cng c sng cc ph ring.
- Gielatin hoc cc cht mu hu c hot ng b mt. Nhng cht ny loi tr nhng
cc i loi 1, loi 2 trn sng cc ph ca cht xc nh. Cc loi cc i trn xut
hin l do hnh thnh v chuyn ng c hc ca git thy ngn u mao qun thy
tinh.
- Cht in ly mnh nh KCl, NH
4
Cl cc cht ny gi l cht nn cc ph.

Bi 40
Xc nh Zn trong dung dch

I. C s phng php
Xem li phn l thuyt v nhng tm tt trn
II. Cch tin hnh
1. Chun b dung dch chun
Chun b 5 bnh nh mc dung tch 25ml nh s t 1 ti 5. Ln lt cho vo cc th
tch dung dch chun ca ZnCl
2
nng 0,1M v cc ha cht cn thit khc theo bng sau:
Bnh
B1 B2 B3 B4 B5
0,1M 0,3 0,6 0,9 1,2 1,5
in 0,2 0,5
l+NH
4
OH Thm va ti vch, lc u
Ln lt ghi sng cc ph ca tng dung dch. Khi o cho vo cc in phn mt
lng Na
2
SO
3
.
2. Ghi sng cc ph ca dung dch phn tch
Dung dch phn tch cng c chun b trong iu kin nh khi chun b cc dung
dch chun. Ghi sng cc ph trong cng iu kin.

111
3. Xy dng th chun
Ghi li cc kt qu I E o c i vi tng dung dch. Xy dng th I E trn
giy milimet. o chiu cao h: h
1
, h
2
, h
3
, h
4
, h
5
, v h
x
ri xy dng th h C (C y
c biu din qua s ml dung dch chun ZnCl
2
0,1M ly khi pha ch dung dch). T
th h C v h
x
, tnh nng ca dung dch ZnCl
2
mu phn tch.
III. Ha cht cn thit
- ZnCl
2
0,10M.
- Gielatin 0,1%.
- NH
4
OH 1M + NH
4
Cl 1M.
- Bt Na
2
SO
3
.

Bi 41
Xc nh Cd
2+
trong dung dch

I. C s phng php
Phn ng xy ra trn vi in cc (catot):
Cd
2+
+ 2e = Cd
Cd
2+
cho sng cc ph r trong nhiu nn khc nhau. Trong nn KCl 2M th E
1/2
=
0,65V; nn NH
4
OH+NH
4
Cl

th

E
1/2
= 0,81V; nn clorua, sunfat khng xut hin cc i.
Chiu cao sng cc ph t l vi nng Cd
2+
trong khong nng rt rng.
II. Cch xc nh
1. Nn NH
4
OH+NH
4
Cl
Chun b 5 bnh nh mc dung tch 25ml ln lt cho vo cc loi ha cht theo bng
sau:
ml
Bnh
B1 B2 B3 B4 B5
Cd(NO
3
)
2
0,1M 0,3 0,6 0,9 1,2 1,5
Bt Na
2
SO
3
~ 5 gam
Gielatin ~ 5 git
NH
4
OH+NH
4
Cl Thm va ti vch, lc u

112
Ghi sng cc ph ca tng dung dch.
Xc nh chiu cao sng, tm E
1/2
.
V th chun theo quan h h C.
Da theo ng chun xc nh nng Cd
2+
trong dung dch nghin cu.
2. Nn KCl
a. Xy dng ng chun
Chun b 5 bnh nh mc dung tch 25ml ln lt cho vo cc loi ha cht theo bng
sau:
ml
Bnh
B1 B2 B3 B4 B5
Cd(NO
3
)
2
0,1M 0,3 0,6 0,9 1,2 1,5
KCl 2N Thm va ti vch, lc u
Ghi sng cc ph ca tng dung dch.
Xc nh chiu cao sng, tm E
1/2
.
V th chun theo quan h h C.
b. Ghi sng cc ph ca dung dch phn tch
Dung dch phn tch cng c chun b trong iu kin nh khi chun b cc dung
dch chun. Ghi sng cc ph trong cng iu kin.
Da vo ng chun tm nng Cd
2+
.
III. Ha cht cn thit
- Dung dch Cd(NO
3
)
2
0,10M.
- Dung dch Cd
2+
mu phn tch.
- Dung dch KCl 2N
- Gielatin 1%
- NH
4
OH 1M + NH
4
Cl 1M.
- Bt Na
2
SO
3

113
Bi 42
PHNG PHP VONAMPE XC NH Pb
2+

I. Bn cht ca phng php
Pb
2+
c mt vi hm lng vt trong nhiu i tng thc t nh cc ngun nc,
trong mu, trong kem nh rng, trong xng khng ch Vic kim sot lng ch c mt
trong cc i tng trn l cn thit. phng php VonAmpe vi in cc lm vic l in
cc thu ngn git treo cho php ta xc nh Pb
2+
trong cc i tng trn mt cch nhanh
chng vi chnh xc v tin cy rt cao. Nu ta s dng dung dch nn l: CH
3
COONa
0,1M, HNO
3
0,05M th th na sng ca Pb
2+
l 404mV.
II. Dng c v thuc th
- Dung dch chun gc Pb
2+
nng 100mg/L
- Dung dch nn CH
3
COONa 0,1M, HNO
3
0,05M
- Bnh kh tr N
2
(hoc ar)
- Micropipet 100L, 1000L v pipet 10,0ml, Bnh nh mc 50ml v 100ml
III. Cch tin hnh
- Ly chnh xc 20,00ml nc ct + 1000L CH
3
COONa 0,1M + 1000L HNO
3
0,05M
cho vo bnh in phn.
- Thm 100L Pb
2+
t mu nghin cu cho vo bnh in phn.
- Tin hnh khuy 300,0s, tc khuy 2000vng/pht; ng thi thi kh tr vo bnh
in phn ui kh oxy ra.
- Bin xung t l 50mV, vi thi gian o l 20,0ms, thi gian xung l 40,0ms, bc
xung l 4mV.
- Thc hin cc chng trnh con:
Khng khuy 10,0s
Ging git thu ngn v treo (HMDE)
in phn tch gp lm giu l 90,0s in p 700mV
Qut th vi U
u
= 700mV; U
cui
= 200mV, tc qut 10mV/s; thi gian
qut tng ng l 51,2s
- Thm dung dch chun vi th tch thm l 100L (nng ca dung dch c
nhp vo trang tnh ton)
- S ln thm ln hn 2, th kt thc chng trnh phn tch
- Hin th kt qu phn tch ln trn mn hnh

114
Bi 43
PHNG PHP VON-AMPE XC NH Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+

KHI CHNG C MT NG THI

I. Bn cht ca phng php
Vic xc nh ng thi cc kim loi km, cadimi, ch, ng khi chng c mt ng
thi l vn kh phc tp. Phng php von-ampe cho php ta gii quyt vn . Ta
bit th na sng ca mt cht nghin cu c th ph thuc vo bn cht cht nghin cu
v cht nn cc ph. Nu ta s dng dung dch nn l (CH
3
COONa 0,1M, HNO
3
0,05M) th
th na sng ca 4 cht nghin cu trn xa khc nhau. iu cho php chng ta xc
nh ng thi cc ion trn khi chng c mt ng thi.
Ion Zn
2+
Cd
2+
Pb
2+
Cu
2+
E
1/
2
, mV 983 562 368 +35
II. Dng c v thuc th
Micropipet 100L
Micropipet 1000L
Pipet 10,00ml
Dung dch chun gc Pb
2+
, Cu
2+
, Cd
2+
, Zn
2+
nng 100mg/l
Dung dch nn CH
3
COONa 0,1M, HNO
3
0,05M
Bnh kh tr: N
2
(hoc Ar)
III. Cch tin hnh
- Ly chnh xc 20,00ml nc ct + 1000L CH
3
COONa 0,1M + 1000L HNO
3
0,05M cho vo bnh in phn.
- Tin hnh khuy 180,0s, tc khuy 2000vng/pht; ng thi thi kh tr vo bnh
in phn ui oxy ra.
- Thm 100L dung dch cha Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
t mu nghin cu cho vo bnh
in phn.
- Khuy 50,0s
- Ngng thi
- Bin xung t l 50mV, vi thi gian o l 20,0ms, thi gian xung l 40,0ms, bc
xung l 4mV.
- Thc hin chng trnh con:
* Ging git thu ngn v treo (HMDE)
* in phn tch gp lm giu l 40,0s in p 1150mV
* Khng khuy 15,0s
* Qut th vi U
u
=1150mV; U
cui
=+150mV, tc qut 13,33mV/s; thi
gian qut tng ng l 98,1s

115
- Thm dung dch chun cha Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
vi th tch thm l 100L (nng
chun ca mi mt ion kim loi c nhp vo trang tnh ton)
- Thc hin chng trnh con.
- Thm dung dch chun cha Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
vi th tch thm l 100L
- Thc hin chng trnh con:
- S ln thm >2 th kt thc chng trnh phn tch
- Hin th kt qu phn tch trn mn hnh

116
CHNG 4 : PHNG PHP IN TH

Phng php phn tch o in th l phng php nh lng in ho da vo vic
o th ca in cc nhng vo dung dch phn tch.
Vi cc dung dch long th gn ng c th coi hot bng nng . Nerst a ra
phng trnh sau :
E = E
0
+
[ ]
[ ]
[ ]
[ ]
= +
0 0
Ox Ox
RT 0, 059
E = E + ln E lg
nF Kh n Kh

E = f(C) l 1 hm ca cht cn phn tch.

Phng php chun in th: Dng mt
dung dch chun chun mt dung dch
phn tch. Trong qu trnh chun th E ca
dung dch thay i, gn ti im tng ng
th E thay i t ngt. Phng php nhm nhn
bit s thay i t ngt ny xc nh im
tng ng.
Kho st s thay i E ca dung dch theo
lng dung dch chun thm vo.
o E ca dung dch (s dng my o in
th) ti tng thi im thm thuc th.
V th E V,
E
V
V, t xc nh
im tng ng.
Hnh 32: B dng c dng trong chun
in th
0
50
100
150
200
250
300
350
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
V (ml)
E

(
m
V
)
0
100
200
300
400
500
600
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
V (ml)
E
/
V
Hnh 33: th xc nh im tng ng theo phng php chun in th
a - th tch phn (E-V) b - th vi sai (E/(V-V))

117
Phng php chun in th c th xc nh c im tng ng ca qu trnh
nh phn cc dung dch c mu. Phng php c chnh xc, chn lc, nhy cao v
c th t ng ho c qu trnh phn tch.
Bn cnh my o th in cc l nhng dng c quan trng trong phng php chun
in th. Mt h in cc hon chnh phi c in cc ch th v in cc so snh.
in cc ch th
+ in cc ch th loi 1: l in cc c ch to t bn hoc dy kim loi nhng vo
dung dch mui tan ca kim loi .
+ in cc ch th loi 2: l in cc c ch to t bn dy kim loi tr (kim loi
qu) nhng vo mt dung dch cha cp oxy ho - kh lin hp.
in cc so snh
in cc so snh: l loi in cc c th n nh, khng i v khng ph thuc vo
nng ion trong dung dch.
in cc so snh thng c ch to t bn hoc dy kim loi c ph bn ngoi mt
lp mui t tan ca kim loi v nhng vo mui cha anion cng tn trong lp ph.

Hnh 34: in cc so snh: in cc calomen v in cc bcbc clorua

118
Bi 44
XC NH NNG HCl BNG NaOH (IN CC QUINHYDRON BO HA)

I. C s phng php
Phn ng chun :
HCl + NaOH = NaCl + H
2
O (1)
H
+
+ OH
_
= H
2
O
Trong qu trnh chun pH ca dung dch lin tc thay i. Dng in cc
quinhydron bo ha lm in cc ch th v o th ca n vi in cc calomen bo ha.
Xy dng th E V
NaOH
(E l th o c trong qu trnh chun ) hoc E/
V
V xc
nh im tng ng trn th.
Phn ng in cc quinhydron l:
X + 2H
+
+ 2e = H
2
X (2)

K hiu: X l quinon
O O

OH HO
H
2
X l hydroquinon

(Quinhydron l hp cht ng phn t ca quinon v hydroquinon, km ha tan trong nc)
T (2) p dng h thc Nerst, nhn c:
E
quinhydron
= E
0
0,059pH ( 20
0
C) vi E
0
= 0,6990 V
II. Cch tin hnh
Ly chnh xc 10,0ml dung dch HCl cn xc nh nng cho vo cc thy tinh
100ml, thm vo 1 tha quinhydron v khong 20ml nc ct. Khuy u dung dch trn my
khuy t. Ni in cc platin vi mt cc ca my o ri nhng in cc vo dung dch
trong cc. Ni cu mui KCl gia dung dch cn o vi in cc calomen bo ha. Ni in
cc calomen bo ha vo cc th hai ca my o. Np dung dch NaOH c nng chnh
xc 0,1M ln trn buret. Nh tng lng th tch xc nh dung dch NaOH 0,1M vo dung
dch phn tch.
1. Ln chun th 1: (Chun s b)
Nh 1,0ml dung dch NaOH trn buret vo dung dch phn tch lun c khuy u
bng my khuy t. Sau mi ln nh nh th i cho gi tr in th trn my pH met n
nh t 35 giy th ghi gi tr li. Nhn xt gi tr in th ng vi th tch NaOH cho
vo xem u l qung nhy vt in th.

119
2. Ln chun th 2: (Chun chnh xc)
Lc u nh 1,0 hoc 2,0ml dung dch NaOH 0,1M vo dung dch phn tch, nhng ti
bc nhy vt in th th nh 0,2ml dung dch NaOH 0,1M mi ln chun, sau bc nhy
in th li nh 1,0ml NaOH 0,1M ny thm 3, 4 gi tr na. Ghi li cc gi tr E thu c.
T kt qu thu c xy dng th EV
NaOH
v th E/
V
NaOH
V
NaOH
trn giy
milimet, xc nh im tng ng v tnh nng ca dung dch HCl.
III. Ha cht v dng c
- My o pH, in cc platin, in cc calomen bo ho
- Bt quinhydron
- Dung dch NaOH c nng chun 0,1M

Bi 45
XC NH NNG NaOH V Na
2
CO
3
BNG HCl (IN CC THY TINH)

I. C s phng php
Phn ng chun NaOH bng HCl:
2
O
Phn ng chun Na
2
CO
3
bng HCl
Na
2
CO
3
+ HCl = NaHCO
3
+ NaCl
NaHCO
3
+ HCl = NaCl + H
2
CO
3
o s bin thin pH trong sut qu trnh chun dng in cc mng thy
tinh (l loi in cc phn hi chn lc i vi ion H
+
trong dung dch) lm in cc
ch th v in cc Ag/AgCl lm in cc so snh.

Hnh 35: in cc thy tinh dng trong php o pH

120
Trn thc t bi th nghim c thc hin trn in cc kp kt hp c in cc ch th
(in cc thy tinh) v in cc so snh (in cc Ag/AgCl) trn mt thn in cc.

Hnh 36: in cc thy tinh dng kp (t hp)
in th ca mng tun theo phng trnh:
1 2, 303.
ln
X X
H
RT RT
E K K pH
F a F
+
= =
K l th ca in cc so snh, in th bt i xng ca mng thy tinh v in th
sinh ra do cc dung dch tip xc vi nhau trong mt h pin in ha. K khng phi l mt
hng s dng cho mi in cc v n nh trong mt thi gian di do vy cn nh k hiu
chnh li in cc bng cc dung dch pH chun (thng l cc pH=7 v pH=4).
Khi th ca pin (iu kin chun) s bng:
2, 303.
s s
RT
E K pH
F
=
pH
s
chnh l pH ca dung dch chun, kt hp c hai phng trnh ta c pH ca mt
dung dch cha bit s tun theo phng trnh:
( )
2, 303.
X s
X s
. E E F
pH pH
RT
=

121

Hnh 37: V d v mt thit b chun t ng s dng trong cc phng phn tch

II. Cch tin hnh
Ly chnh xc mt lng NaOH hoc Na
2
CO
3
cho vo cc c m loi 100ml thm
khong 30ml nc ct. t cc ln my khuy t, nhng t hp in cc v autoburet vo
dung dch phn tch.
Thit lp cc thng s cn thit trn my chun t ng KEMAT 500N nh:
phng php (Method); iu kin chun (Titration); iu khin (Control); tnh ton v
bo co kt qu (Result), thng s v mu (Sample)
n nt START bt u tin hnh chun . Kt qu cui cng s hin ra trn mn
hnh con v in ra thnh bng.
Cn lu vi tng mu khc nhau cn t cc ch chun ph hp mi cho kt
qu phn tch chnh xc c.

122
Bi 46
XC NH Cl
, I
TRONG DUNG DCH HN HP BNG AgNO

3
0,1N

I. C s phng php
Vic xc nh da trn phn ng to thnh hp cht khng tan AgI v AgCl.
Ag
+
+ I
= AgI
Ag
+
+ Cl
= AgCl
Do AgI c ha tan nh hn so vi AgCl kh nhiu nn kt ta AgI c tch ra
trc cn AgCl tch ra sau. Nu trong dung dch cng tn ti hai ion Iodua v Clorua c
cng nng , khi cho ion bc vo hn hp ny th AgCl bt u kt ta th AgI kt ta
hon ton. (T
AgI
= 8,5.10
17
, T
AgCl

= 1,78.10
10
)
Vic xc nh im tng ng trong trng hp ny c th s dng phng php o
in th. Trn ng cong in th s c hai bc nhy in th ng vi hai giai on: to
thnh kt ta AgI v AgCl.
Trong php o ny in cc ch th c s dng l in cc bc, in cc so snh l
in cc Calomen bo ha.
II. Cch tin hnh th nghim
Dng pipet ly chnh xc 10,00ml hn hp dung dch I
v Cl
cho vo cc dung tch

100ml cho thm khong 20ml nc ct. Nhng in cc Bc vo dung dch v ni cu mui
KCl (tt hn th dng cu mui KNO
3
) vi in cc calomen bo ha. in cc bc v in
cc calomen c ni vi hai cc ca my o. Dung dch chun AgNO
3
c np vo buret
25,0ml. Nh tng lng th tch xc nh dung dch AgNO
3
vo dung dch phn tch.
1. Ln chun th 1: (chun th)
Nh chnh xc 1,0ml dung dch AgNO
3
c nng 0,1N xung dung dch phn tch
lun c khuy u bi my khuy t. Sau mi ln nh nh th tin hnh ghi li gi tr in
th E ca dung dch bng my o (i cho gi tr E n nh t 35 giy). Nhn xt gi tr
in th E thu c.
2. Ln chun th 2: (chun tinh)
Trc bc nhy th th 1 v th 2 nh 1,0ml dung dch AgNO
3
0,1N vo dung dch
phn tch, khi n gn im tng ng th 1 v th 2 (ti bc nhy th) th nh mi ln
0,2ml dung dch AgNO
3
mi ln chun, sau bc nhy th th 2 cho 1,0ml dung dch
AgNO
3
0,1N thm 3-4 ln na ghi li cc gi tr in th E thu c. Qu trnh tin hnh v
cc thao tc th nghim nh trn.
T s liu thu c xy dng th EV
AgNO
3
v th E/
V
V
AgNO
3
trn giy
milimet

123
T th xc nh hai im tng ng ng vi vic to thnh kt ta AgI v AgCl.
Tnh hm lng v nng Cl
v I
trong dung dch hn hp.

II. Ha cht v dng c
- My o in th
- in cc Bc
- in cc Calomen bo ha
- Dung dch AgNO
3
0,1N
- Dung dch hn hp NaCl v KI (MKT)

Bi 47
CHUN Fe
3+
BNG K
2
Cr
2
O
7

I. C s phng php
Dng SnCl
2
d kh Fe
3+
Fe
2+
, sau chun dung dch .
Nhn xt rng E
0
Sn
4+
/Sn
2+ = 0,15V; E
0
Fe
3+
/Fe
2+

= 0,77V
E
0
Cr
2
O
7
2
/2Cr
3+ = 1,36V cho nn ngoi phn ng kh Fe
3+
Fe
2+
khi dng SnCl
2
d
xy ra hai phn ng chun l:
3Sn
2+
+ Cr
2
O
7
2
+ 14H
+
3Sn
4+
+ 2Cr
3+
+ 7H
2
O (1)
6Fe
2+
+ Cr
2
O
7
2
+ 14H
+
6Fe
3+
+ 2Cr
3+
+ 7H
2
O (2)
Phn ng (1) xy ra i vi lng Sn
2+
d sau khi kh Fe
3+
v qu trnh ny xy ra
trc qu trnh (2). Do trn th nh phn quan st c 2 im tng ng; im
tng ng th nht ng vi s chun Sn
2+
im tng ng th 2 ng vi qu trnh (2).
Th tch dung dch K
2
Cr
2
O
7
cn thit cho vic chun Fe
3+
c suy ra t th chun .
III. Cch tin hnh
Ly chnh xc 10,00ml dung dch Fe
3+
cho vo cc thy tinh thm 10ml dung dch HCl
1:1 un dung dch trn bp ti gn si. Cho vo tng git dung dch SnCl
2
n dung dch
mu vng v thm tip 12 git dung dch d na. Thm 50ml HCl 1:1 vo cc un nng
dung dch n 6070
o
C. Nhng in cc Pt vo dung dch ni du in ly vi in cc
calomen. Ni 2 u in cc vo my o.
Chun bng K
2
Cr
2
O
7
0,1N, lc u cho cho tng git. Sau khi lng Sn
2+
chun
ht (c bc nhy in th th nht), th cho dung dch K
2
Cr
2
O
7
vi lng nh i vi qu
trnh chun th v chun tinh ca bi trn.

124
III. Dng c v ha cht
- in cc ch th: in cc bch kim
- in cc so snh: in cc calomen bo ha
- SnCl
2
dung dch 5% 50g SnCl
2
.2H
2
O pha trong 200ml HCl 1:1 ri pha bng nc
ct thnh 1lt
- HCl 1:1
- K
2
Cr
2
O
7
dung dch 0,1N
- My o in th.

125
CHNG 5: PHNG PHP SC K TRAO I ION

Sc k trao i ion l mt trong cc phng php sc k dng tch dung dch hn
hp nhiu cht thnh tng cht ring bit. Cng nh cc phng php sc k khc, trong
phng php trao i ion, qu trnh dung dch hn hp tch thnh cc cht ring bit c
thc hin khi c hai pha rn lng tip xc vi nhau. Pha rn gi l cht hp th. Qu trnh
tip xc ny lin tc v c lp mi nhiu ln. iu ny c thc hin bng cch cho
dung dch hn hp (pha lng) i qua mt lp pha rn ca cht hp th c t trong mt
ng thy tinh. ng ny c gi l ct trao i ion hay ct sc k.
Khi dung dch hn hp i qua ct trao i ion, do i lc tng tc khc nhau gia cc
thnh phn ca hn hp vi cht hp th, cc cht b tch dn v phn b dc theo ct thnh
tng min. Nhng min ny c gi l ph sc k hay ph s cp. Nu dung dch i t trn
xung di th cc cht c kh nng hp th mnh s phn b phn trn ca ct; cng
xung di ct l nhng min ca cc cht hp th yu. Cht no khng b hp th s i ra
khi ct. Nu cho dung mi tinh khit hoc dung dch cc cht in gii thch hp i qua ct,
th cc ph chuyn dch ln lt xung di ct, do c th tch c cc cht ring bit.
Qu trnh cho dung mi tinh khit hoc dung dch cc cht in gii thch hp i qua ct
tip tc tch cc cht gi l qu trnh ra ct.
Trong phng php trao i ion c ch tng tc gia cc cht hp th v cc cht
trong dung dch l s trao i ion gia cc ion linh ng ca cc nhm chc trong phn t
cht hp th vi cc ion cng du in tch trong dung dch. Cc cht hp th trong phng
php trao i ion gi l ionit, nhng ionit trao i ion linh ng mang in tch dng ca
n vi cc cation trong dung dch gi l cationit, v nhng ionit trao i ion linh ng mang
in tch m ca n vi anion trong dung dch gi l anionit.
Qu trnh trao i ion gia cht hp th vi dung dch l qu trnh thun nghch v
tun theo quy tc t lng v c trng cn bng:
RZ + X RX + Z
R l gc phn t ca ionit; Z l ion linh ng ca ionit; X l ion trong dung dch cng
du in tch vi Z.
C hai loi ionit: ionit v c v ionit hu c.
Ionit v c thng dng nh oxyt nhm, silicagel, cc loi aluminosilicat v.v
Ionit hu c l nhng loi nha iu ch bng phng php polyme ha hay trng
ngng nh phenol focmandehit, polystyrol Ty theo bn cht ca cc nhm chc trong

126
nha m nha ionit l cationit hay anionit. V d cc loi nha cationit thng cha cc
nhm chc SO
3
H, COOH, PO(OH)
2
ion linh ng l ion hydro hoc bng cch trao
i ion c th thay ion H
+
bng ion Na
+
, NH
4
+
Cc nha anionit thng cha cc nhm
chc: NH
2
R
+
, NHR
2
+
Ion linh ng ca cc anionit thng l Cl
, OH
.

Bi 48
PHNG PHP TRAO I ION TRN NHA CATIONIT TCH NIKEN V COBAN

I. C s phng php
Khi cho dung dch hn hp CoCl
2
+NiCl
2
i qua nha cationit dng NH
4
+
c hai ion
trn du b hp th trn nha. Kh nng hp th ca coban trn nha mnh hn Niken. Do
c th ra tch niken bng axit HCl long sau tch coban bng axit HCl nng cao
hn.
II. Phn thc hnh
Qui trnh tch:
1. Pha dung dch hn hp CoCl
2
+NiCl
2
Dng pipet ly mi loi 2ml cho vo cc pha long bng nc ct ti khong 20ml
2. Chun b nha dng trao i ion
Ly 60ml dung dch HCl (1:1) cho vo cc cho axit ny qua nha vi tc
35ml/pht. Ra nha bng nc ct cho ti khi dung dch hng c c mi trng trung
tnh. Tip theo ra nha bng dung dch NH
4
Cl 5M cho ti khi dung dch hng ra c pH=5
(kim tra bng metyl da cam) Giai on ny tn khong 50ml NH
4
Cl 5M. Ra nha bng
100ml nc ct.
3. Giai on tch
Cho dung dch ca hn hp CoCl
2
+NiCl
2
i qua nha vi tc 25ml/pht. Nhn xt
s phn b min hp th ca hai loi ion trn nha. Ra nha vi ln bng nc ct.
Tch Niken khi nha:

127
Ly 150ml dung dch HCl 1,5N cho vo cc ln, thm nc ct ti khong 450ml ri
chuyn dung dch ny ln bnh cha xiphng v cho dung dch i qua nha vi tc 3-
5ml/pht. Hng dung dch vo cc b khong 100ml u. Khi Niken bt du xut hin (th
bng imetylglioxin c pha vi git NH
4
OH trn bn s. Thay cc hng bng bnh nh mc
250ml Hng dung dch NiCl
2
n th tch khong 200ml mi c th kt thc giai on tch
Niken bt u hng thu CoCl
2
vo bnh nh mc 100ml . nh mc dung dch NiCl
2
bng
nc ct ti vch lc u.
Tch Coban ra khi nha:
Sau khi tch Ni tip tc ra nha bng 50ml HCl 1:1 vi tc 3-5ml/pht. hng vo
bnh nh mc 100ml. Ra nha bng nc ct vi ln ri nh mc bng nc ct ti vch
lc u.
Xc nh Coban & Niken
1. Xc nh Coban
Dng pipet ly 10ml dung dch CoCl
2
10ml dung dch complexon III cho vo bnh nn
lc u. Thm vi git dung dch NH
4
OH 10% sau thm mt t ch th ETOO Nu dung
dch cha c mu xanh th cho tip vi git NH
4
OH cho ti khi no xut hin mu xanh r
(pH=910) Chun dung dch bng dung dch ZnCl
2
n khi chuyn sang mu hng mn.
Ghi th tch ZnCl
2
tiu tn. Tnh nng g/l ca coban trong dung dch ban u ly
pha trn.
2. Xc nh Niken
Ly chnh xc 100,00ml dung dch NiCl
2
cho vo bnh nn thm dung dch NH
4
OH
10% cho ti pH=79 mt t ch th Murexit chun dung dch ny bng dung dch
complexon III ti khi xut hin mu ta. Tnh nng g/l ca niken trong dung dch ban
u ly pha trn.

128
Bi 49
TCH V XC NH Fe
3+
, Zn
2+
TRONG DUNG DCH HN HP

I. C s phng php
Dung dch hn hp Fe
3+
v Zn
2+
cho qua ct nha cationit dng H
+
, c hai ion u b
hp th trn nha:
RH + Fe
3+
R(Fe
3+
) + H
+
RH + Zn
2+
R(Zn
2+
) + H
+
Sau ra ct nha bng dung dch NaOH 10%, Zn
2+
b tch ra di dng ZnO
2
2

vo dung dch cn Fe
3+
vn cn li trn ct nha.
R(Zn
2+
) + NaOH R(Na
+
) + ZnO
2
2
Sau khi tch ht Zn
2+
, ra ct nha bng dung dch HCl 2N, lc ny Fe
3+
s tch ra
khi nha v tan ln trong dung dch.
R(Fe
3+
) + HCl R(H
+
) + FeCl
3
Cc dung dch ZnO
2
2
v Fe
3+
thu c em xc nh nng ca chng bng
phng php thch hp nh phng php chun in th, phng php cc ph, phng
php trc quang v.v
Trong bi ny yu cu tch c hon ton Zn
2+
v xc nh Fe
3+
bng phng php
trc quang bng thuc th axit sunfoxalixilic.
II. Cch tin hnh
1. Chun b ct nha cationit dng H
+
Np nha cationit vo ct trao i c ng knh bng 1cm, chiu cao khong
10cm (Nha lm vic trong iu kin trng n v vy trong bt c giai on no
cng khng c lm cho cc ht nha trao i tip xc vi khng kh). Ra ct nha
bng khong 30ml dung dch HCl 2N vi tc dung dch ra khi ct l 10ml/pht.
Ra ct nha bng nc ct cho ti khi dung dch ra khi ct ht Cl
(th bng phn

ng vi AgNO
3
trong mt trng HNO
3
)
Ly chnh xc 2,0ml dung dch hn hp Zn
2+
v Fe
3+
bng pipet cho vo cc thy tinh
loi 100ml sau d pha long bng nc ct n khong 20ml
2. Cc giai on tch
Cho dung dch hn hp Zn
2+
v Fe
3+
qua ct nha vi tc chy ra khi ct l
57ml/pht. Hng dung dch chy ra khi ct nha vo cc ng nc thi ri b i.
Sau khi cho ht dung dch hn hp qua ct nha, trng cc bng nc ct nhiu ln
ri tip tc cho qua ct nha.

129
Sau ra ct nha bng dung dch NaOH 2N vi tc chy gi nh trn, cho ti
khi khng cn Zn
2+
trong dung dch ra khi ct nha. Cch th: hng vi mililit dung dch
chy ra khi ct nha, axit ha bng dung dch HCl ri th bng K
4
[Fe(CN)
6
], nu vn cn
Zn
2+
th s xut hin kt ta mu trng xanh l K
2
Zn
3
[Fe(CN)
6
]
2
. Giai on ra ny tn
khong 2030ml dung dch NaOH 2N.
Sau khi tch ht Zn
2+
, ra ct bng HCl 2N vi tc nh trn, Fe
3+
b tch ra khi ct
nha, i vo dung dch. Qu trnh ra ny yu cu hng dung dch i ra khi ct vo bnh
nh mc c dung tch 100ml. Qu trnh ra ct nha bng HCl thc hin cho ti khi kim
tra khng cn Fe
3+
trong dung dch ra khi ct nha. Cch th: nh 1 git NH
4
CNS vo bn
s ri hng 1 git dung dch chy ra khi ct nha, nu cn Fe
3+
th s xut hin kt ta
mu mu [Fe(CNS)
6
]
3
. Giai on ny tn khong 3040ml HCl 2N (ra khong 34
ln).
3. Xc nh nng Fe
3+
Dung dch thu c trn em nh mc va ti vch.
Sau dng pipt ly 2,0ml dung dch Fe
3+
thu c cho vo bnh nh mc 25,0ml,
thm 2,5ml dung dch axit sunfosalixilic 10%, 2,53ml dung dch NH
4
OH 10% ri nh mc
bng nc ct ti vch. o hp th quang ca dung dch trn my trc quang 722 bc
sng 420nm . T ng chun cho trc xc nh nng Fe
3+
thu c.
Ch : Nng Fe
3+
xc nh trn l nng Fe
3+
trong bnh nh mc 100ml, yu
cu phi tnh nng ca Fe
3+
trong dung dch hn hp ban u.

130
CHNG 6: PHNG PHP CHIT O QUANG

Chit l phng php tch, chuyn mt cht t dung mi ny sang dung mi khc da
vo tnh tan khc nhau ca cc cht trong cc dung mi . Hai dung mi khng tan ln vo
nhau, thng th mt dung mi l nc v mt dung mi l cht hu c.
Cc cht c th chit c bng dung mi hu c l nhng cht trung ho in ( l
cc phn t hoc tp hp ion) t a nc, a dung mi.
C 2 loi h thng chit:
H thng chit cc hp cht ni phc.
Me
n+
+ nR
-
= MeR
n
R
l cc anion hu c: 8-oxyquinolin, dithizon, cuperon

H thng chit tp hp ion.
Me
n+
+ (n + a)X
=
( )
a
n a
MeX

+

+
+ +
+
a a
( n a) ( n a)
MeX a.Y MeX .aY
+
I. Cn bng ca h chit
1. nh lut phn b
nh lut phn b ch ra kh nng phn b ca cht tan X vo 2 dung mi khng trn
ln (dung mi hu c v dung mi nc):

[ ]
[ ]
hc
pb
nc
X
K
X
=

K
pb
: hng s phn b
[X]
nc
, [X]
hc
: nng cht tan X trong pha nc v pha hu c
K
pb
ph thuc: - Bn cht ca cht tan v dung mi.
- Nhit v p sut.
Thc t hay dng i lng D (h s phn b).

S lng cc dng ca X trong pha hu c
D=
S lng cc dng ca X trong pha nc

D thng tm c bng thc nghim.
- Trong iu kin l tng, cht tan khng tham gia bt k phn ng no ti hai pha th
D = K.
- Trong thc t hay dng D, tin hnh th nghim theo D tm iu kin ph hp cho
vic chit.
2. chit hay phn trm chit
Phn trm chit R(%): s % cht tan b tch ra khi pha nc sau mt ln chit.

131
Quan h gia R v D:
Gi x l lng cht tan c tch ra khi pha nc sau 1 ln chit.
1 - x l lng cht tan cn li trong pha nc.
V
hc
, V
nc
l th tch ca pha hu c v pha nc.
R = 100 . x

= = =
+
hc nc hc
hc hc nc
nc
x
V x V D.V
D . x
1 x
1 x V DV V
V

Hay = =
+ +
nc nc
hc hc
D 100.D
x R
V V
D D
V V

Nu V
nc
= V
hc
=
+
100.D
R
D 1

R ph thuc vo D v t s th tch
nc
hc
V
V

3. Cn bng trong h chit
V d chit mt ion Me
n+
to phc vi thuc th hu c HR l mt axit yu, c cc cn
bng sau:
a. Cn bng phn ly ca HR trong pha nc
HR = H
+
+ R
-

[ ]
+
=

nc
nc
HR
nc
H R
K
HR
(1)
b. Cn bng to hp cht ni phc trong pha nc
Me
n+
+ R
-
= MeR
n

[ ]
+
=

n
nc
n
n
nc nc
MeR
Me . R
(2)
c. Cn bng phn b ca thuc th gia hai pha
[HR]
hc
= [HR]
nc

[ ]
[ ]
=
hc
pb
nc
HR
K (HR)
HR
(3)
d. Cn bng phn b ca hp cht ni phc gia hai pha

[ ] [ ]
[ ]
[ ]
= =
n
hc
n n pb n
hc nc
n
nc
MeR
MeR MeR K (MeR )
MeR
(4)
Gi thit qu trnh chit c tin hnh trong pha nc vi nng axit ln qu
trnh to phc hydrxo ca ion kim loi Me
n+
c th b qua.

132
H s phn b ca KL Me
n+
l D.

[ ]
+
=

n
hc
n
nc
MeR
D
Me

T (1) v (3) ta c:
[ ]
[ ]
[ ] [ ]
+ +
= =

nc nc nc nc nc
HR
pb
nc hc hc
-
H R H R
HR
1
K . .
K (HR) HR HR HR

[ ]
+
=

HR hc
nc
pb
nc
HR
K
R .
K (HR) H
(5)
T (2) v (4) ta c:
[ ] [ ]
[ ]
[ ]
+

+
=

n
nc
pb
n n n
nc hc hc
n n
n
n
n
nc
nc
nc nc
MeR MeR MeR
1
. K (MeR ) = . .
MeR Me
R
Me . R

[ ] n
n
hc
pb n
n
nc
nc
MeR
R . .K (MeR
Me

+
=

)
T (5)
[ ] [ ]
n
n
n
hc HR hc
pb n
n
pb
nc nc
MeR HR
K
. .K (MeR ). D
K (HR)
Me H
+ +

=

=
(6)
T h thc (6) ta thy kh nng chit tt (D ln) khi:
- (HR)
hc
ln (d thuc th).
- K
HR
ln (thuc th l axit mnh).
- ln (phc bn).
- K
pb
(HR) b (thuc th t tan trong dung mi hu c).
i vi [H
+
] th phi chn nng thch hp (cn ngn s to phc hydroxo m
khng lm gim s phn ly ca HR).
II. Mt s vn trong k thut chit
1. Cc phng php chit
a. Chit gin on: Cho mt th tch xc nh dung mi hu c tip xc vi th tch
xc nh dung dch nc c cha cht cn chit mt bc hoc nhiu bc.
b. Chit lin tc: i vi h chit c h s phn b D b th phi s dng phng php
chit lin tc. Cho hai pha tip xc lin tc vi nhau bng cch chuyn ng ngc chiu
hoc xui dng mt bc hoc nhiu bc.
2. Chn dung mi
Chn dung mi m c h s phn b D ln, chn dung mi thun li cho qu trnh gii
chit sau ny.

133
3. Cht tr chit
Thng l cht in ly mnh tng h s hot ca cc ion tham gia chit v lm
gim cc phn t nc bao quanh hp cht chit (gim bn knh hydrat ho).
4. Ra phn chit
Ra pha hu c loi b tp cht bng cch lc pha hu c vi dung dch c pH
thch hp v cht tr chit.
5. Gii chit
L qu trnh ngc li ca qu trnh chit, chuyn cht tan t pha hu c vo pha nc
v tin hnh cc qu trnh phn tch tip theo.
- Lc pha hu c vi dung dch axit mnh c nng pH thch hp.
- Lc pha hu c vi dung dch cha cht to phc.
- em un bay hi, c cn pha hu c, sau ho tan b bng nc.
V d: Khi chit Cu
2+
, Pb
2+
, Fe
2+
, Zn
2+
di dng phc vi DDTK (dietyl dithio
cacbamat natri). Chit pH = 4 11, dung mi chit l CCl
4
hoc CH
3
Cl.
Gii chit bng dung dch HCl 0,4M Zn
2+
b gii chit.
HCl 4M Pb
2+
v Fe
2
b gii chit.
Pha hu c ch cn li Cu
2+
.

III. ng dng
* Chit, tch cc ion cn tr qu trnh phn tch.
* Phng php chit kt hp vi 1 phng php xc nh c 1 phng php xc
nh.
- Phng php chit - trc quang.
- Phng php chit - cc ph
- Phng php chit - quang ph.
* Chit - lm giu.

134
Bi 50
XC NH VI LNG NG(II)
KHI C NIKEN(II) LNG LN BNG PHNG PHP CHIT-O QUANG

I. Nguyn tc xc nh
S xc nh vi lng Cu(II) trong dung dch cha mt lng ln Ni(II) da vo phn
ng chit trao i ion Cu(II) trong pha nc vi phc cht ca Pb(II) ietylditiocarmabat
trong pha hu c clorofoc:

(Hu c) (Hu c)
+ +
+ +
2
) O H ( 2 2
2
) O H (
2 2
Pb ) DDC ( Cu ) DDC ( Pb Cu
Cu(II) to vi dietylditiocarmabat thnh mt phc bn hn phc ca Ni(II) vi thuc
th trn. V vy phn ng chit trao i xy ra: Cu(II) chuyn vo pha hu c dng phc
Cu(DDC)
2
c mu vng ta. dung dch ca phc ny hp th cc i bc sng =
436nm; cn Pb(II) s chuyn vo pha nc. Trong phn ng chit trao i trn Ni(II) li
trong pha nc nu hm lng nh hn 10g/lt. Do vy khng cn tr vic xc nh Cu.
III. Cch tin hnh
Cho vo phu chit dung tch 100ml: 10ml nc ct, ly chnh xc 10,00ml NiSO
4
c
cha ti a 25g Cu thm 10ml hn hp m CH
3
COOH+CH
3
COONa iu chnh pH ca
dung dch ti 4,55 . Dng chnh xc 10,00ml dung dch thuc th Pb(DDC)
2
trong clorofoc
chit. Lc mnh 45 pht. Sau khi phn lp ly pha hu c o hp th quang ca dung
dch Cu(DDC)
2
thu c =436nm, cuvet 1,00cm. Dng dung dch trng l clorofoc.
xy dng th chun, ngi ta phi pha cc dung dch mu c cha 5, 10, 15, 20,
25g Cu v tin hnh chit o quang nh lm vi dung dch nghin cu. T xy dng
th chun AC. T th chun ny s xc nh c hm lng Cu c trong mu phn tch.
III. Cc thuc th v dung dch
1. Dung mi hu c clorofoc CHCl
3
tinh khit.
2. Dung dch phc Pbdietylditiocarbamat trong clorofoc c chun b nh sau:
Cho vo phu chit 50ml dung dch cha 0,1g ch axetac v 25ml dung dch cha
0,1g dietylitiocarbamat. Dng mi ln 50ml dung mi CHCl
3
. Lc vi pha nc cho ti khi
kt ta trngLc pha hu c qua giy lc vo bnh nh mc 250ml cui cng cho ti
vch bng CHCl
3
.
Dung dch thuc th ny cn c gi trong bnh nu, trnh nh sng v bn c 34
tun l.
3. Ha tan chnh xc 0,1gam ng kim loi tinh khit bng 35ml dung dch HNO
3

1:1. Sau khi mu tan cho vo bnh nh mc 1lt ri nh mc bng nc ct ti vch. Dung
dch ny cha 100 gCu/ml.

135
Ngay trc khi lm th nghim, ly chnh xc 10,00ml dung dch ny cho vo bnh
nh mc 100ml, cho nc ct ti vch nh mc. Ta c dung dch chun c nng Cu
10g/l.
4. Dung dch m hn hp CH
3
COOH+CH
3
COONa.
Ha tan 16,4gam CH
3
COONa trong 1 lt dung dch CH
3
COOH 2M

136

T T I I L LI I U U T TH HA AM M K KH H O O

1. G.Saclo, Cc phng php ha phn tch- tp 1 v tp 2, o Hu Vinh, T Vng
Nghi (dch), NXB i hc v trung hc chuyn nghip, H Ni 1976.
2. A.P.Creskov, C s ha hc phn tch- tp 1 v tp 2, T Vng Nghi, Trn T Hiu
(dch), NXB i hc v trung hc chuyn nghip, H Ni 1989-1992.
3. Douglas A. Skoog, Donal M.West, F.James Holler, Fundamentals of analytical
chemistry, 7
th
Edition, Saunders college publishing.
4. J.Mendham, R.C.Denney, J.D.Barnes, M.Thomas, Vogels textbook of quantitative
chemical analysis, 6
th
Edition, Prentice Hall, 2000.
5. Daniel C.Harris, Quantitative Chemical Analysis, 5
th
edition, W.H.Freeman and
Company, NewYork, 1999.
6. T Vn Mc, Phn tch ha l, NXB Khoa hc v k thut, H Ni, 1995.
7. T Vn Mc, Cc phng php phn tch dng cng c, NXB i hc quc gia H
Ni, 2005.
8. Nguyn Xun Dng, Phm Lun, Sch tra cu pha ch dung dch, NXB Khoa hc v
k thut, H Ni, 1987.
9. P. P. Koroxtelev, Chun b dung dch cho phn tch ha hc, Nguyn Trng Biu, Mai
Hu ua, Nguyn Vit Hu, L Ngc Khnh, Trn Thanh Sn, Mai Vn Thanh (dch) ,
NXB Khoa hc v k thut, H Ni, 1974.
10. Bi Long Bin, Ha hc phn tch nh lng, NXB Khoa hc v k thut, 2001.

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TRNG I HC BCH KHOA H NI

Chng 2: Phng php in phn ............................................................. 100

th thi (dng dung dch AgNO

kt ta trc khi nung, khng nung nhit qu cao).

] hoc ngc li. Tc l:

khi b kh chuyn thnh ion Mn

(xem phn phn ng lin hp).

ngi ta thm hn hp Zimecman

= +1,36V. Tuy nhin nu nng HCl>2N cng nh khi un si, s oxy ha c th

trc khi chun Cr

Th oxy ha- kh tiu chun ca cp I

li l cht kh mnh hn cc ion Cr

l cht oxi ha mnh hn I

), phc ny d dng b oxy ha bng iot.

BNG DUNG DCH CHUN AgNO

c thm Fluorexein trc im tng ng khi Cl

c in tch m nn khng hp th Fluorexein (ng ra l khng hp

BNG DUNG DCH CHUN Hg(NO

l ion ca Murexit, th im tng ng

cng b hp th mt phn. Ion MnO

BNG THY NGN THYOXYANATE

2,5 mg/ml 0 0,5 1,0 1,5 2,0

trong dung dch.

chun 2,5mg/ml: Sy kh tinh th NaCl (tkpt) 180

0,01M pha ch ra cc dung dch c nng thch hp (mi nng

Khi in phn sinh ra H

TRONG DUNG DCH HN HP BNG AgNO

cho vo cc dung tch

trong dung dch hn hp.

(th bng phn

l cc anion hu c: 8-oxyquinolin, dithizon, cuperon

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