HNG DN TH NGHIM

HA PHN TCH
-------***-------
Bin son: Trng Dc c
B mn Ha Phn Tch HBK.HN
Bi th nghim 1: Xc nh nng dung dch HCl bng Na
2
B
4
O
7
v xc nh nng
dung dch NaOH bng dung dch HCl...
Bi th nghim 2: Xc nh nng dung dch NaOH, Na
2
CO
3
trong hn hp bng dung
dch HCl
Bi th nghim 3: Xc nh nng dung dch NaOH bng dung dch Kali hydrophtalat v
xc nh nng HCl, H
3
PO
4
trong hn hp..
Bi th nghim 4: Xc nh nng KMnO
4
s dng H
2
C
2
O
7
. 2H
2
O v xc nh nng
FeSO
4
bng dung dch KMnO
4..
Bi th nghim 5: Xc nh nng dung dch FeSO
4
bng K
2
Cr
2
O
7
(kh Fe
3+
Fe
2+
).

Bi th nghim 6: Phng php Iot. Xc nh nng Na

2
S
2
O
3
bng K
2
Cr
2
O
7
. Xc nh
nng CuSO
4
bng Na
2
S
2
O
3
theo phng php iot...
Bi th nghim 7 :Chun dung dch Cl
-
bng dung dch AgNO
3
theo 2 phng php

Bi th nghim 8 :Chun EDTA. Xc nh nng EDTA bng ZnSO

4
. Xc nh
cng chung ca nc bng EDTA.
Bi th nghim 9: Phng php khi lng. Xc nh nng Fe
3+
vi thuc th NH
4
OH.
Xc nh nng SO
4
2-
vi thuc th BaCl
2
.
NI QUY TH NGHIM HA PHN TCH
1. Sinh vin i lm th nghim ng gi. n mun qu 15 pht khng c lm th
nghim.
2. Trc khi lm th nghim sinh vin phi np bi chun b, hiu r ni dung v mc
ch ca bi, sinh vin vi phm mt trong nhng iu trn khng c lm th
nghim.
3. Khi lm th nghim sinh vin phi cn thn, quan st t m, thao tc ng theo
hng dn ca cn b ph trch.
4. Khi s dng thit b, my mc sinh vin cn phi c s ng ca cn b ph
trch.
5. Ch lm vic phi c sp xp trt t, sch s ngn np, khng lm vic ring
trong phng th nghim.
6. Trc khi kt thc bui th nghim sinh vin phi thu dn ni lm vic, dng c
sch s, bn giao dng c v thit b y cho phng th nghim.
7. Sinh vin phi hon thnh tt c cc bi th nghim c trong ni dung mn hc v
np y bo co th nghim ng hn.
8. Sinh vin ch c lm b cc bi th nghim khi c s ng ca ging vin ph
trch.
9. Sinh vin vng trn 03 bui th nghim khng c tip tc hc mn Ha phn
tch II.
10. Sinh vin khng c php nh ngi lm h cng nh i lm th nghim h
ngi khc, nu vi phm s b x l theo quy ch.
Bi th nghim 1
Xc nh nng dung dch HCl bng Na
2
B
4
O
7
v xc nh nng dung dch
NaOH bng dung dch HCl
Mui natri tetraborat kt tinh (Na
2
B
4
O
7
.10H
2
O) c khi lng phn t ln (M=381,37) v
tinh khit c th dng lm cht gc trong chun axit-baz. N l mt cht rn kt tinh mu
trng, mm, nhiu cnh d dngha tantrongnc. Khi ra ngoi khng kh kh, n b mt
nc dn v tr thnhkhong cht tincalconit mu trng nh phn (Na
2
B
4
O
7
.5 H
2
O). Trong dn
gian, natri tetraborat c bit n vi tn gi hn the lm ph gia cho vo thc phm. Tuy
nhin, do c tnh v nh hng lu di ca n, hn the c cm s dng Vit Nam v
nhiu quc gia trn th gii.
Bi 1. Xc nh nng dung dch HCl bng Na
2
B
4
O
7
pha dung dch chun HCl trong phng th nghim ngi ta thng s dng dung dch c
axit HCl khong 37% khi lng. c im ca dung dch HCl c l bay hi v hp ph nc
mnh nn nng ca dung dch HCl c lun lun thay i theo thi gian. Do , ta khng th
pha chnh xc c dung dch chun HCl t dung dch HCl c, m sau khi pha ch cn xc nh
li nng ca dung dch pha c. xc nh li nng dung dch HCl pha, ta thng chn
cht gc l Na
2
B
4
O
7
.
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
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 axit HCl.
Khi tc dng vi HCl phn ng nh sau:
NaOH + HCl = NaCl + H
2
O
Phn ng tng cng:
B
4
O
7
2-
+2H
+
+5H
2
O =4H
3
BO
3
Trc im tng ng, trong dung dch cn d Na
2
B
4
O
7
, dung dch c tnh kim (pH>7). Ti
im tng ng trong dung dch c NaCl v H
3
BO
3
nn H
3
BO
3
s quyt nh pH ca dung
dch. Ta thy H
3
BO
3
l a axit c hng s phn ly K
a1
>>K
a2
, K
a3
(K
a1
=5,79.10
-10
; K
a2
=
1,82.10
-13
; K
a3
=1,58.10
-14
), do vy c th b qua s phn ly ra H
+
ca cc nc th hai v th ba.
Chng ta c th tnh pH ca dung dch a axit nh dung dch n axit vi K
a
=K
a1.
Xt cn bng:
Ta c :
B qua s phn ly H
+
ca nc ta c th xt gn ng: [H
+
] ~ [A
-
] v [HA] ~ Ca
Khi ,
a
a
C
H
K
2
] [
+
~
a a
C K H . ] [ =
+
T c th tnh pH theo cng thc gn ng sau :
pH = (pK
a1
logC
a
) (9,24 + 1) 5,12
Lu : pH =-log[H
+
], pK
a1
=-logK
a1
Trong Ca = 0,1 M (nng chun ca dung dch borat cn pha).
Cht ch th metyl (pT = 5) c coi l thch hp nht xc nh im tng ng. (im
nh phn pT cng gn pH ti im tng ng cng tt).
II. Cch tin hnh
1. Pha ch 250,0 ml dung dch chun natri tetraborat 0,10000N
Tnh ton lng Na
2
B
4
O
7
.10H
2
Ocn pha:
= x , (N)
Trong ,
Na2B4O7.10H2O
= 190,7 g/ lg
Vo =250,0 ml
m
a
lng Na
2
B
4
O
7
.10H
2
O cn cn.
T tnh c m
a
=
= = = 4,7675 g
Lu : vi lng cn ny th nng Na
2
B
4
O
7
pha c l 0,05M nn nng H
3
BO
3
l 0,2M,
nh vy so vi tnh ton l thuyt th ti im tng ng pH = (pK
a1
log Ca) = (9,24 +
0,7) =4,97 tc l khng khc nhiu so vi l thuyt.
Cch pha: Cn khong 4,6 4,8 gam Na
2
B
4
O
7
.10H
2
O trn cn phn tch vi chnh xc
0,0001 gam cho vo cc c m. Sau thm vo khong 40-50 ml nc ct, un nh trn bp
khuy bng a thy tin cho n tan hon ton ri chuyn nh lng vo bnh nh mc 250,0
ml, trng nc ct t nht 5 ln v chuyn nh lng vo bnh nh mc (trnh mt mt), nh
mc bng nc ct ti vch, lc u trc khi s dng.
Tnh li nng ca dung dch chun gc sau khi pha:
= x , (N)
Lc ny m
a
l lng cn thc t cn c.
2. Pha ch dung dch HCl 0,1N t dung dch HCl m c
pha 500 ml dung dch HCl c nng khong 0,1 N dng cho bi th nghim th th tch HCl
c (c d = 1,18g/ml cha 37% HCl nguyn cht ) (V
x
) phi ly:
V
x
=
=
Cch pha: Tin hnh trong t ht trnh khi HCl c hi. Dng ng ong ly khong 4,2 ml
dung dch axit HCl c, rt v cc c m 500ml cha sn khong 500 ml nc ct, khuy u
bng a thy tinh cho n khi dung dch ng nht. Nng chnh xc ca dung dch HCl va
pha s c xc nh li bng dung dch chun gc natri borat.
3. Chun .
Np dung dch HCl pha ch ln buret, ui ht bt kh, ch chnh vch 0 trc khi tin hnh
chun . Dng pipet ly chnh xc 10,00 ml dung dch chun Na
2
B
4
O
7
cho vo bnh nn, thm
vo 2 git ch th methyl , dung dch c mu vng. Chun cho n khi dung dch t mu
vng chuyn sang hng nht. Ghi th tch HCl tiu tn. Tin hnh th nghim t nht 3 ln, ly
gi tr trung bnh tnh ton.
III. Tnh ton
V
Na
2
B
4
O
7
ly chun : . . . .10,00 . . . . . . . ml
V
HCl
o c trong cc ln chun : Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh : . . . . . . . . . . . ml
Nng ca dung dch HCl :
- N
HCl
= , (N)
Trong : =10,00 ml
: l gi tr th tch HCl trung bnh ca 3 ln th nghim, ml

HCl
= 36,461 g/ng lng gam
- C
HCl
= N
HCl
.
HCl
, (g/l)
Bi 2. Xc nh nng dung dch NaOH bng dung dch HCl
Dung dch NaOH rt d hp th CO
2
trong khng kh, do trong dung dch NaOH lun
cha 1 lng nh Na
2
CO
3
, nng NaOH b gim dn theo thi gian bo qun. Ta cng khng
th pha c nng chnh xc dung dch NaOH t ha cht NaOH rn, do NaOH ht m rt
mnh nn khng th cn chnh xc c lng cn. V th, trc khi s dng NaOH ta phi xc
nh li nng ca n.
I. C s phng php
Khi tin hnh chun dung dch NaOH bng dung dch HCl th phn ng chun din ra nh
sau: NaOH +HCl =NaCl +H
2
O
y l trng hp chun mt baz mnh in hnh bng mt axit mnh in hnh. Ti im
tng ng dung dch c pH = 7. V l thuyt c th chn cht ch th sao cho im nh phn
cng gn pH ti im tng ng cng tt. Tuy nhin, vi yu cu v phn tch ta c th xc
nh im tng ng vi sai s 0,1% vn tha mn yu cu phn tch. Gi s chun 100,00
ml dung dch NaOH nng 0,1000N bng dung dch chun HCl 0,1000N th bc nhy pH ca
qu trnh chun vi sai s 0,1% s l 9,7 n 4,3. Do vy ta c th s dng cht ch th metyl
(pT = 5) hoc phenolphtalein (pT = 9) l cht ch th xc nh im cui ca qu trnh
chun .
II. Cch tin hnh
1. S dng cht ch th phenol phtalein
Np dung dch HCl pha ln buret, ui ht bt kh, chnh vch 0 trc khi chun . Dng
pipet ly chnh xc 10,00 ml dung dch NaOH t bnh mu kim tra cho vo bnh nn. Thm 7-8
git cht ch th phenol phtalein, dung dch c mu hng. Tin hnh chun cho n khi dung
dch chuyn t mu hng sang khng mu, ghi th tch HCl tiu tn. Lp li th nghim t nht 3
ln, ly gi tr trung bnh tnh ton.
2. S dng cht ch th metyl
Np dung dch HCl pha ln buret, ui ht bt kh, chnh vch 0 trc khi chun . Dng
pipet ly chnh xc 10,00 ml dung dch NaOH t bnh mu kim tra cho vo bnh nn. Thm 1-2
git cht ch th metyl , dung dch c mu vng. Tin hnh chun cho n khi dung dch
chuyn t mu vng sang mu hng. Ghi th tch HCl tiu tn. Lp li th nghim t nht 3 ln,
ly gi tr trung bnh tnh ton.
III. Tnh ton
Nng NaOH c tnh theo cng thc:
N
NaOH
= , (N)
C
NaOH
= N
NaOH
.
NaOH
, (g/l)
Trong , =10,00 ml
: l gi tr th tch HCl trung bnh ca 3 ln th nghim, ml

NaOH
= 39,997 g/ng lng gam
IV. Cu hi:
1. So snh th tch HCl tiu tn trong qu trnh chun vi 2 cht ch th trn. Nhn xt kt
qu thu c v gii thch?
Tr li: Th tch HCl tiu tn trong trng hp s dng cht ch th metyl cho kt qu ln hn
so vi trng hp s dng cht ch th phenol phtalein. Nguyn nhn ca s sai lch kt qu ny
l do trong dung dch NaOH bao gi cng ln 1 lng nh Na
2
CO
3
. Do vy phn ng xy ra
trong qu trnh chun :
NaOH +HCl =NaCl +H
2
O (1)
Na
2
CO
3
+HCl =NaHCO
3
+NaCl (2)
NaHCO
3
+HCl =H
2
CO
3
+NaCl (3)
Xut hin 2 im tng ng:
- im tng ng 1 ng vi phn ng (2) kt thc, pH ca dung dch c quyt nh
bi cht lng tnh NaHCO
3
. pH ca dung dch c th c tnh gn ng theo cng thc
sau:
pH = (pK
a1
+pK
a2
) = (6,35+10,33) =8,34
- im tng ng 2 ng vi phn ng (3) kt thc. Khi dung dch s cha 1 lng
nh H
2
CO
3
(hay CO
2
ha tan), pH ca dung dch s c quyt nh bi lng H
2
CO
3
ny. V
tan bo ha ca H
2
CO
3
l khong 10
-4
M nn c th tnh gn ng pH ca dung dch ti im
tng ng 2:
pH = (pK
a1
lgC
a
) = (6,35 +4) 5,18.
Do ta thy rng, khi s dng cht ch th phenol phtalein (pT =9) ta s nhn bit c im
tng ng 1, cn vi ch th metyl (pT = 5) th thc cht l nhn bit im tng ng 2.
Hai im tng ng ny khng trng nhau, chng lch nhau cng nhiu khi hm lng tp
Na
2
CO
3
ln trong dung dch cng ln.
2. Ngoi s dng HCl lm cht chun xc nh nng dung dch NaOH ngi ta cn hay
s dng phng php no khc?
Tr li: trong thc t, ngi ta hay s dng oxalic acid nh l cht gc xc nh nng dung
dch NaOH, cht ch th c s dng l phenol phtalein.
Bi th nghim 2
Xc nh nng dung dch NaOH, Na
2
CO
3
trong hn hp bng
dung dch HCl
Trong qu trnh bo qun NaOH, lun xy ra s hp th CO
2
trong khng kh :
2NaOH + CO
2
= Na
2
CO
3
+ H
2
O
Do dung dch NaOH lun lun cha Na
2
CO
3
. Khi bo qun trong mt thi gian di hm
lng Na
2
CO
3
c th chim tng i ln.Trng hp phi bit hm lng ring ca NaOH v
Na
2
CO
3
ngi ta c th s dng 2 phng php xc nh:
Phng php 1 l xc nh 2 im tng ng trn ng nh phn hn hp.
Phng php 2 l s dng Ba
2+
kt ta ht CO
3
2-
, sau nh phn xc nh ring NaOH.
Hm lng Na
2
CO
3
c th xc nh c sau khi xc nh hm lng tng NaOH v Na
2
CO
3
.
Trong bi th nghim ny chng ta s s dng c 2 phng php xc nh nng NaOH v
Na
2
CO
3
trong hn hp.
Bi 1. Phng php dng hai cht ch th
I. C s phng php:
Khi tin hnh dng dung dch chun HCl tc dng vi hn hp cn phn tch cha NaOH v
Na
2
CO
3
nh git t t, lc u th cc phng trnh phn ng xy ra ln lt nh sau:
NaOH +HCl =NaCl +H
2
O (1)
Na
2
CO
3
+HCl =NaHCO
3
+NaCl (2)
NaHCO
3
+HCl =H
2
CO
3
+NaCl (3)
R rng l khng th xc nh c im tng ng sau phn ng (1) do NaOH v Na
2
CO
3
u l 2 bazo mnh, cha kt thc phn ng (1) th phn ng (2) xy ra (do 2 baz c hng s
baz cch nhau cha ln 2 bc nhy r rt). Sau khi kt thc phn ng (1) v phn ng
(2) trong dung dch s cha NaCl v NaHCO
3
, pH ca dung dch s do NaHCO
3
quyt nh. Do
NaHCO
3
l mt cht lng tnh nn ta c th tnh pH ca dung dch nh sau:
Xt cn bng :
Dng axit : HCO
3
-
H
+
+CO
3
2-
(1) K
a
=K
a2
=4,69 . 10
-11
Dng bazo : HCO
3
-
+H
2
O H
2
CO
3
+OH
-
(2) K
b
=K
H2O
/K
a1
. Trong K
a1
=4,46 . 10
-7
Hoc biu din dng baz dng:
HCO
3
-
+H
+
H
2
CO
3
K =1/K
a1
(2)
H
2
O H
+
+OH
-
(3) K
w
=[OH
-
].[H
+
]
Ta c cc phng trnh sau:
- K
a2
=
] [
] ].[ [
3
2
3

+
HCO
CO H
[CO
3
2-
] =Ka
2
.
] [
] [
3
+

H
HCO
(*)
1
2
a
O H
K
K
=
] [
] ].[ [
3
3 2

HCO
CO H OH
hoc
1
1
a
K
=
] ].[ [
] [
3
3 2
+
H HCO
CO H
[H
2
CO
3
] =
1
3
] ].[ [
a
K
H HCO
+
(**)
Nhn xt H
+
trong dung dch l do phng trnh (1) v (3) to ra, cn phng trnh (2) hay (2) l
mt i. Nh vy,
[H
+
] =[H
+
]
(1)
+[H
+
]
(3)
[H
+
]
(2)
(***)
Mt khc,
- theo cn bng phng trnh (1) lun c [H
+
]
(1)
=[CO
3
2-
]
- theo cn bng phng trnh (3) lun c [H
+
]
(3)
=[OH
-
]
- theo cn bng phng trnh (2) lun c [H
+
]
(2)
=[H
2
CO
3
]
thay vo phng trnh (***) ta c:
[H
+
] =[CO
3
2-
] +[OH
-
] - [H
2
CO
3
]
Mt khc [OH
-
] =K
H2O
/ [H
+
] (****)
By gi t cc phng trnh (*), (**) v (****) ta thay vo phng trnh (***) c:
[H
+
] =Ka
2
.
] [
] [
3
+

H
HCO
+
] [
2
+
H
K
O H
-
1
3
] ].[ [
a
K
H HCO
+
Nhn c 2 v vi [H
+
] ri chuyn v ta c:
[H
+
]
2
+
1
2
3
] ].[ [
a
K
H HCO
+
=K
a2
.[HCO
3
-
] +K
H2O
t [H
+
]
2
lm tha s chung ta c :
[H
+
]
2
=
1
3
2 3 2
] [
1
] .[
a
O H a
K
HCO
K HCO K

+
+
=
] [
] .[
3 1
2 1 3 2 1

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

+
+
HCO K
K K HCO K K
a
O H a a a
Ta c th tnh ton gn ng nh sau:
Coi HCO
3
-
thamgia vo cc phn ng (1) v (2) l khng ng k, tc l [HCO
3
-
] =C
o
(khng
thay i).
V nu K
a1
rt nh hn < < [HCO
3
-
] th ta c th b qua K
a1
biu thc di mu s
V nu K
H2O
rt nh hn << K
a2
.[HCO
3
-
] th c th b qua K
a1
.K
H2O
biu thc trn t s
Khi ta c cng thc gn ng:
[H
+
] =
2 1
.
a a
K K
Suy ra :
pH = (pK
a1
+ pK
a2
) = (6,35+10,33) = 8,34
Ta chn cht ch th l phenol phtalein (pT =9) l ph hp trong trng hp ny, ti thi im
ny ch th s chuyn t mu hng sang khng mu.
Sau khi phn ng (3) kt thc, trong dung dch c H
2
CO
3
v NaCl. Nh vy, pH ca dung dch
s do H
2
CO
3
quyt nh (lu rng tan ti a ca H
2
CO
3
l khong 10
-4
M). Do H
2
CO
3
c
K
a1
>>K
a2
nn chng ta tnh pH ca dung dch n axit yu vi hng s phn ly K
a1
. B qua s
phn ly H
+
ca nc.
H
2
CO
3
HCO
3
-
+ H
+
B 0,0001 0 0
Ph ly x x x
Cb 0,0001-x x x
K
a1
= =4,46.10
-7
x =10
-5,18
M pH =5,18
Chn cht ch th l metyl c pT = 5 l ph hp xc nh im tng ng. Ti thi im
tng ng dung dch s i mu t vng sang mu hng.
Tuy nhin, trong bi th nghim ny chng ta s s dng ch th metyl da cam xc nh im
tng ng. Vy ch th metyl da cam c th s dng c trong trng hp ny ?
Ch th metyl da cam c khong i mu t pH 3,1 4,4. Vi sai s cho php ca php phn tch
l 0,1%, sau im tng ng d 1 git HCl 0,1N th pH ca dung dch vo khong 4,3 khi
dung dch s chuyn mu t mu vng sang mu da cam. Nh vy, s dng ch th metyl da cam
trong trng hp ny c th p dng c vi sai s cho php.
Lu : Theo mt s ti liu tham kho mi: tan ca CO
2
trong nc 25
o
C l khong 1,45
g/1kg nc ng vi nng khong 0,033M. Khi thc t pH ti T s l pH =3,91 (Tc l
cht ch th ph hp y s l metyl da cam)
Solubility of Carbon Dioxide - CO
2
- in Water
Source: http://www.engineeringtoolbox.com/gases-solubility-water-d_1148.html
II. Cch tin hnh.
Np dung dch HCl 0,1000 N vo buret, ui bt kh v chnh v vch 0 trc khi tin hnh
chun . Ly chnh xc 10,00 ml dung dch hn hp kim tra NaOH v Na
2
CO
3
vo bnh nn,
thm7-8 git ch th phenol phtalein, dung dch c mu hng. Chun cho ti khi dung dch
chuyn t mu hng sau khng mu, ghi th tch V
(1,2) HCl
tiu tn. Thm tip vo bnh nn 1-2
git ch th metyl da cam, dung dch chuyn mu vng, chun tip cho n khi dung dch
chuyn t mu vng sang mu da cam, ghi th tch V
(1,2,3) HCl
tiu tn. Lp li th nghim t nht 3
ln, ly gi tr trung bnh tnh ton.
Tnh ton
Phn ng dng CCT V
HCl
ln 1 V
HCl
ln 2 V
HCl
ln 3 V
HCl
TB
Phenolphtalein
Metyl da cam
Nng ca dung dch NaOH trong hn hp (N, g/l)
N
NaOH
= , (N)
C
NaOH
= N
NaOH
.
NaOH
, (g/l)
Trong : =10,00 ml
: l th tch HCl tiu tn cho phn ng (1) v (2) c tnh trung bnh t
ba ln th nghim (khi cht ch th phenolphatalein i mu hng sang khng
mu).
: l th tch HCl tiu tn cho phn ng (1), (2) v (3) c tnh trung
bnh t ba ln th nghim (khi cht ch th metyl da cam i mu t vng sang da
cam).
Nng ca dung dch Na
2
CO
3
(N, g/l) trong h hp
= , (N)
= . , (g/l)

NaOH
= 39,997 (g/lg) v
Na2CO3
= 52,999 (g/lg)
III. Cu hi:
1. Cn lu g khi xc nh im tng ng th nht khi ch th phenol phtalein i mu t
hng sang khng mu?
Tr li: Do H
2
CO
3
c t s gia hng s axit cc nc <10
4
, bc nhy T th nht (to
thnh NaHCO
3
) khng ln, bi vy vic i mu ca cht ch th im ny khng r rng
v do vic xc nh im tng ng km chnh xc.
Ngoi ra 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 chun cng l mt nguyn nhn gy ra sai s. Mt khc,
do tnh axit ca CO
2
mnh hn tnh axit ca phenol phtalein nn st im tng ng c th
mt phn CO
2
hp th c th gy ra s mt mu ca hng ca ch th.
Do vy, m bo tnh chnh xc ca php phn tch cn ch :
- Pha long dung dch cn phn tch bng nc khng cha CO
2
- Chun dung dch ngay khi ly hn hp.
- Khi gn kt thc chun (vi cht ch th phenolphtalein) thm HCl chm trnh to H
2
CO
3
t do ( y l sai s hay mc phi)
- Khng lc dung dch qu mnh nu khng s tng cng s hp th CO
2
- Dng mt lng phenolphtalein tng i ln (7-8 git) nu dng t th cht ch th c th mt
mu sm trc im tng ng do phenolphtalein nhy vi CO
2
Bi 2. Chun dung dch NaOH, Na
2
CO
3
trong hn hp dng BaCl
2
d
I. C s phng php
Kt ta Na
2
CO
3
bng BaCl
2
d:
BaCl
2
+Na
2
CO
3
=BaCO
3
+NaCl
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.
HCl +NaOH =NaCl +H
2
O
Ti im tng ng, dung dch cha NaCl, BaCl
2
d, pH =7. Bc nhy pH ng vi sai s
0,1% l t 9,7 n 4,3 nn chn phenol phtalein lm cht ch th l hp l.
xc nh nng Na
2
CO
3
, ly mt mu khc dng dung dch HCl 0,1000N nh phn hn
hp NaOH+Na
2
CO
3
, dng metyl da cam lmcht ch th. Ta bit c th tch dung dch HCl
tiu tn tc dng vi ton b NaOH v Na
2
CO
3
. T mi tng quan tnh ton c nng
ca Na
2
CO
3
.
NaOH +HCl =NaCl +H
2
O
Na
2
CO
3
+HCl =NaHCO
3
+NaCl
NaHCO
3
+HCl =H
2
CO
3
+NaCl
Ti im tng ng dung dch i mu t vng sang da cam.
II. Cch tin hnh
Np dung dch HCl 0,1000N vo buret, ui bt kh, chnh vch 0 trc khi chun . Ly chnh
xc 10,00 ml hn hp NaOH, Na
2
CO
3
vo bnh nn, thm1-2 git ch th metyl da cam, dung
dch c mu vng. Chun cho ti khi dung dch mu vng chuyn sang mu da cam, ghi th
tch V
(1,2,3) HCl
tiu tn. Lp li th nghim t nht 3 ln, ly kt qu trung bnh tnh ton.
Tip theo ly chnh xc 10,00 ml hn hp NaOH, Na
2
CO
3
vo bnh nn, kt ta hon ton bng
5-7ml dung dch BaCl
2
5%, khng lc kt ta thm7-8 git phenol phtalein, dung dch c ma
hng, chun n khi dung dch mt mu hng ch cn mu trng c ca kt ta BaCO
3
, ghi
th tch V
(1) HCl
tiu tn. Lp li th nghim t nht 3 ln, ly kt qu trung bnh tnh ton.
Tnh ton
- Khi dng vi ch th phenolphtalein: ( vi BaCl
2
d)
V
HCl
o c trong cc ln chun : Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh V
1
: . . . . . . . . . . . ml
- Khi dng ch th metyl da cam:
V
HCl
o c trong cc ln chun : Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh V
2
: . . . . . . . . . . . ml
V
HCl
o c khi chun c BaCl
2
d V
1
= . . . . . . . . . . ml
V
HCl
o c khi khng thm BaCl
2
vo V
2
= . . . . . . . . . . ml
V
HCl
cn thit chun NaOH trong hn hp V = . . . . . . . . . . ml
V
HCl
cn thit chun Na
2
CO
3
trong hn hp V = . . . . . . . . . . ml
Nng ca dung dch NaOH trong hn hp (N, g/l)
N
NaOH
= , (N)
C
NaOH
= N
NaOH
.
NaOH
, (g/l)
Nng ca dung dch Na
2
CO
3
(N, g/l) trong hn hp
= , (N)
= . , (g/l)
III. Cu hi
1. Chun dung dch hn hp NaOH + Na
2
CO
3
sau khi thm BaCl
2
d c th dng metyl da
cam xc nh im tng ng c khng? Ti sao?
Tr li: Khng th dng ch th metyl da cam xc nh im tng ng v:
Sau khi thmBaCl
2
vo bnh nn, xut hin kt ta BaCO
3
do phn ng
BaCl
2
+Na
2
CO
3
=BaCO
3
+NaCl
Khi tin hnh chun bng dung dch HCl, ti im tng ng dung dch c pH = 7. Bc
nhy pH ln cn im tng ng t 9,7 n 4,3, nu ta s dng ch th metyl da cam th im
kt thc ca qu trnh chun c mi trng axit ( do metyl da cam ch i mu khi pH ca
dung dch < 4,4) . Tuy nhin BaCO
3
d tan trong mi trng axit theo phn ng
BaCO
3
+2HCl =BaCl
2
+CO
2
+H
2
O
Kt ta b ha tan s dn ti sai s ln. S dng ch th phenol phtalein ph hp hn do phenol
phtalein mt mu pH cao khong 9, sai s mc phi thp hn. Nu sau khi thm BaCl
2
ta tin
hnh lc b kt ta v tip tc chun th c th s dng ch th metyl da cam xc nh im
tng ng. Tuy nhin thc hin cng nhiu cng on th kh nng mc sai s cng ln.
thy r c nh hng ca pH kt thc nh phn gy sai s ln cho php phn tch, ta s
tnh ton thc t s nh hng ca tan kt ta theo pH ca dung dch
Xt cn bng:
(1) BaCO
3
Ba
2+
+CO
3
2-
T
BaCO3
=8.10
-9
(2) CO
3
2-
+H
+
HCO
3
-
1/K
a2
Trong K
a1
=10
-6,36
(3) HCO
3
-
+H
+
H
2
CO
3
1/K
a1
K
a2
=10
-10,25
Thit lp mi quan h gia nhng cn bng trn ta c:
[CO
3
2-
] =
2 1 1
2
2 1
. ] [ ] [
.
a a a
a a
K K H K H
K K
+ +
+ +
(*)
Ti pH = 9 ta c [H
+
] =10
-9
, thay cc gi tr K
a1
, K
a2
vo (*) ta c:
[CO
3
2-
] =0,053 (M)
Khi tan ca BaCO
3
ti pH = 9 l
S =
] [
2
3
4

CO
T
BaO
=3,89 . 10
-4
(M).
Ti pH = 5 ta c [H
+
] =10
-5
, thay cc gi tr K
a1
, K
a2
vo (*) ta c:
[CO
3
2-
] = 2,35.10
-7
(M)
Khi tan ca BaCO
3
ti pH = 5 l
S =
] [
2
3
4

CO
T
BaO
=0,184(M).
Nh vy pH = 5, BaCO
3
tan gp khong 2000 ln so vi ti pH =9. Tc l ti pH = 9 ta c th
b qua tan ca BaCO
3
m sai s mc phi khng ng k, trong khi ti pH = 5 khng th b
qua c tan ca BaCO
3
.
Lu : mt s cu tr li cho rng khng th s dng metyl da cam xc nh T do im
nh phn ca metyl da cam pT = 4 nm ngoi bc nhy pH ln cn T vi sai s 0,1% l
khng hp l. V c th t cu hi logic ngc li l ti sao trong bi li s dng metyl da cam
xc nh T trong trng hp s dng 2 cht ch th?. y, nguyn nhn chnh quan trng
nht l axit d s ha tan kt ta dn n mc phi sai s ln.
2. Khi s dng BaCl
2
kt ta ht Na
2
CO
3,
qu trnh nh phn cn lu g?
Tr li: sau khi s dng BaCl
2
trong bnh nn s xut hin kt ta BaCO
3
, kt ta ny d tan
pH thp nn lu trong qu trnh nh phn phi lc u, tc nh git HCl va phi ( trnh
hin tng pH cc b do nh qu nhanh HCl c th lm tan kt ta dn ti sai s ln). Gn im
tng ng pH ca dung dch thay i rt ln nn phi nh tht chm, lc u trnh ha tan
BaCO
3
.
Bi th nghim 3: Xc nh nng dung dch NaOH bng dung dch Kali
hydrophtalat v xc nh nng HCl, H
3
PO
4
trong hn hp
Trong chun axit bazo, chut chun thng c chn l cc axit mnh (hoc bazo mnh)
v n d dng tc dng hon ton vi cht phn tch. Do , kh nng ng dng c m rng.
Trong in hnh l NaOH v HCl thng c s dng lmcht chun v l axit, bazo mnh,
d tm v r tin. Tuy nhin, thc t ta thng khng th pha c ngay nng chnh xc
bit ca dung dch NaOH v HCl do i t cht gc l NaOH rn (d ht m trong qu trnh cn)
v HCl c 37%(d bay hi). Do thng thng, ngi ta c th pha tng i bng cn k
thut, sau s dng mt chun gc bit chnh xc nng xc nh li nng ca cc
dung dch trn.
Bi 1: Xc nh nng NaOH bng Kali hydro Phthalat
1. C s phng php:
Phn ng chun :
OH
-
+HPh
-
=Ph
2-
+H
2
O K
cb
=
1
1
b
K
=
9
10 . 5641 , 2
1

=3,9.10
8
(kh ln)
Hng s cn bng ca phn ng kh ln nn phn ng c xem xy ra hon ton.
xc nh c nng NaOH chng ta pha chun gc Kali hydro Phthalat t cht gc
Kali hydro phthalat.
Yu cu ca 1 cht gc l:
+Phi tinh khit v mt ha hc, tp cht khng ln hn 0,05 - 0,1%, c th kt tinh li c
v sy kh mt nhit nht nh.
+Thnh phn ha hc phi ng ng vi cng thc ha hc. V d cc tinh th ngm nc
phi ng vi s phn t theo cng thc ha hc.
+Cht gc v dung dch chun phi bn trong thi gian gi gn v nng phi khng i
theo thi gian.
+ Mol ng lng ca cht gc cng ln cng tt tng chnh xc khi xc nh nng
ca dung dch.
Kali hydro phthalat, thng c gi n gin l KHPh, l mt hp cht mui axit. N c dng
bt trng, tinh th khng mu, v khi tan trong nc l dung dch khng mu. N c tnh axit v
thng c s dng nh l mt cht chun gc trong chun acid-baz v n l hp cht n
nh, bn trong khng kh, c khi lng mol ln (204,233g/mol), d cn chnh xc. Tuy nhin,
NaOH
KHPh
n c tnh ht m nh, nn thng c gi trong bnh ht m trc khi em s dng. Ngoi cc
tnh cht va nu trn, pH ca KHPh trong dung dch l rt n nh nn n cng c dng
nh mt cht gc chun ha thang pH.
Axit phthalic c K
a1
=1,12.10
-3
v K
a2
=3,9.10
-6
. Do vy, ta c th tnh c K
b1
v K
b2
tng
ng ca baz Phthalate l K
b1
=K
w
/K
a2
= 2,5641.10
-9
v K
b2
=K
w
/K
a1
=8,9.10
-12
. [v dng bazo
Ph
2-
(K
b1
) l bazo lin hp ca dng axit HPh
-
(K
a2
)].
Nu tnh gn ng pH ca dung dch mui kali hydrophatalat:
pH =(pKa
1
+pK
a2
) = (2,905+5,408) =4,18
Ti im tng ng: dung dch cha mui phatalat Ph
2-
(Na
2
Ph v K
2
Ph). L mt a bazo yu
2 nc tng ng vi hng s bazo l K
b1
=K
w
/K
a2
= 2,5641.10
-9
v K
b2
=K
w
/K
a1
=8,9.10
-12
. Do
K
b2
nh hn kh nhiu so vi K
b1
nn c th coi s phn ly ra OH
-
ca a baz phathalat do nc
th nht l ch yu. Gi s nng ca baz phathalat l 0,1M, khi
Ph
2-
+H
2
O HPh
-
+OH
-
K
b1
=2,5641.10
-9
B qua s phn ly ca nc, coi nng Ph
2-
ti T khng i = C
B
=0,1M.
[OH
-
] =
B b
C K .
1
-->pOH = ) log (
2
1
1 B b
C pK + -->pH =14-pOH
pH ~ 7 + ) log (
2
1
2 B a
C pK + =7 + ) 1 , 0 log 408 , 5 (
2
1
+ =9,20
Chng minh:
B
b
C
OH
Ph
HPh OH
K
2
2
1
] [
] [
] ][ [

= = -->[OH
-
] =
B b
C K .
1
[H
+
] =
B b
w
C K
K
.
1
-->pH =-log[H
+
] =-[logK
w
- ) log (log
2
1
1 B b
C K + ] = -logK
w
-
B b
C pK log
2
1
2
1
1
+ -->pH =14 -
B a
C pK log
2
1
) 14 (
2
1
2
+ =7 + ) log (
2
1
2 B a
C pK +
Trc im tng ng vi sai s -0,1%.:
Gi s chun 100,0 ml KHPh 0,1M bng dung dch NaOH 0,1M th V
e
=100,0ml
Thm 99,9 ml NaOH thmvo:
[HPh
-
]d =
99,9 100
(M) 0,1 . (ml) 0,1
+
=5,0.10
-5
(M)
[Ph
2-
] =
9 , 99 100
100
). ( 1 , 0 .
100
9 , 99
+
M =0,04997 (M)
Ta c dung dch m HPh
-
/Ph
2-
: p dng CT Henderson tnh pH cho dung dch m:
pH =pK
a2
+log
] [HPh
] [Ph
-
- 2
=5,408 +log
5 -
5.10
0,04997
=8,41
Sau im tng ng vi sai s +0,1%.:
Thm 100,1 ml NaOH thmvo:
[NaOH]d =
,1 100 100
(M) 0,1 . (ml) 0,1
+
=4,998.10
-5
(M)
[Ph
2-
] =
1 , 100 100
100
). ( 1 , 0 .
100
100
+
M =0,04998 (M)
Trong dung dch tn ti 2 bazo, Bazo NaOH l bazo mnh nn b qua s phn ly ca bazo
yu Ph
2-
. Nng NaOH ln (C
B
>10
-6
v bazo mnh) nn b qua s phn ly ca nc:
[OH
-
] = [NaOH]d = 4,998.10
-5
(M) -->pOH =4,30 -->pH =14-pOH =9,70
Vy bc nhy pH ca phn ng chun l 8,41 n 9,70 ( pH ti T l 9,20)
Bc nhy khng r rng. pH ti im tng ng l 9,20, cht ch th thch hp xc
nh im tng ng ca phn ng chun c th l phenolphthalein (khong pH i
mu 8,0 n 9,6), gi tr nh phn pT = 9.
(Bc nhy khng r rng yu cu chun chm trnh sai s. D on mu ca phenol
phtalein thay i chm, xut hin t t mu hng nht bn 30s khng c chun nhanh
trnh sai s qu xa, mu hng cng nht cng tt).
Nh vy ch ra c phn ng xy ra hon ton, nhanh, hp thc, tnh c bc nhy
pH v chn c CCT ph hp xc nh T.
2. Cch tin hnh
a. Pha ch 250,0 ml dung dch chun KHPh 0,1000N
Tnh ton lng cn cht gc cn ly:
m
a
= =
=5,1058g
Cch tin hnh: Cn KHPh trn cn phn tch mt lng khong m
a
(g) trn giy cn vi
chnh xc 0,0001g, cho vo cc c m 100ml sch. Sau thm khong 40-50ml nc ct,
khuy cho tan bng a thy tinh (lu : a thy tinh cho vo cc c m th lun lun c
gi trong cc, trnh a ra ngoi v c th lm mt mu ). Chuyn ton b lng dung dch
ha tan vo bnh nh mc (rt qua a thy tinh). Trng cc v a thy tinh 3-4 ln bng nc
ct ri chuyn ton b vo bnh nh mc. nh mc bng nc ct n vch mc. Lc tht u
dung dch trc khi s dng (tuyt i khng c qun thao tc lc u cho dung dch ng
nht).
T lng cn thc t trn cn phn tch, chng ta tnh li nng dung dch KHPh pha:
N
KHPh
= x = x
b. Chun xc nh nng NaOH
- Buret : np dung dch NaOH (phng th nghim pha sn). Trc khi np, buret v cc
c m 100 c ra sch, trng bng nc ct. Sau s dng khong 30ml dung dch
NaOH trng ton b buret v cc c m 100. Sau , tin hnh ly dung dch NaOH
np ln buret v ui bt kh ti mi buret.
- Bnh nn: bnh nn c ra sch v trng bng nc ct trc khi tin hnh. Dng pipet
ly chnh xc 10,00 ml KHPh cho vo bnh nn, thm 7-8 git cht ch th
phenolphtalein, dung dch khng mu.
- Chnh vch 0 trn buret bt u qu trnh chun . T t m kha van buret a dung
dch NaOH nh git xung bnh nn ng thi lc u bnh nn, mt quan st bnh nn.
Tc chun chm ( khi nh NaOH xung bnh nn c th quan st thy mu hng cc
b xut hin ri bin mt ngay ), ti gn im tng ng (khi m mu hng cc b
xut hin v bin mt chm hn) phi tin hnh chun rt chm. Ngay khi dung dch t
khng mu xut hin mu hng nht v bn mu trong khong 30s th kt thc qu trnh
chun . Ghi li th tch NaOH tiu tn. Lm th nghim 3 ln.
3. Tnh ton
p dng nh lut tc dng ng lng:
N
NaOH
= , (N)
Trong : =10,00 ml
: l th tch NaOH tiu tn c tnh trung bnh t ba ln th nghim (khi
cht ch th phenolphatalein i mu)
N
KHPh
l nng ca dung dch chun KHPh pha ch v c tnh li nng .
4. Nhng lu : nhng sai s c th mc phi?
- Sai s c th gp trong qu trnh cn pha chun gc. Do vic pha chun gc phi m
bo chnh xc, cn thn tun th mi th tc ca qu trnh cn pha.
- Sai s c th mc phi khi chun qu nhanh. Do bc nhy khng r rng (pH khng
thay i qu t ngt ti T) nn vic chun phi c tin hnh chm ln cn
T nu khng rt d chun qu T.
- Lng ch th phenol phtalein phi cho ln (7-8 git) v trnh lc qu mnh trnh
nh hng ca CO
2
trong khng kh hp th vo bnh chun gy sai s.
- Chun gc phi c pha bng nc ct mi c un si trc ( gim hm lng
CO
2
ha tan trong nc. Nu CO
2
tn ti trong nc n c th trung ha NaOH gy sai
s).
Bi 2. Xc nh nng HCl v H3PO4 trong hn hp bng dung dch chun NaOH
y l mt v d in hnh v chun mt hn hp axit. Trong thc t ta gp nhiu trng hp
phi xc nh tng axit hoc tng bazo trong hn hp ca chng. C rt nhiu hn hp axit, bazo
nhng khng c nhiu trng hp c th chun ln lt tng axit bng bazo mnh hoc
ngc li. i vi hn hp 2 axit HCl v H
3
PO
4
thot tin ta ngh c th chun ln lt chng
bng dung dch NaOH (v HCl l axit mnh Ka rt ln, H
3
PO
4
l 1 a axit yu c nc 1 K
a1
=
7,11.10
-3
) nhng thc t li khng phi nh vy v khi thm t t NaOH vo hn hp 2 axit
th thot tin HCl b trung ha trc, nhng H
3
PO
4
cng b trung ha ng thi vi HCl khi
lng HCl cn kh nhiu trong dung dch. H
3
PO
4
b trung ha 1 phn to H
2
PO
4
-
l 1 bazo yu
c K
b3
=K
w
/K
a1
=1,406.10
-12
. Do , trong dung dch s tn ti 1 h m H
3
PO
4
/ H
2
PO
4
-
lm
cho pH ca dung dch bin thin t t v do khng xut hin bc nhy pH ng vi chun
ring HCl. Thc t ch quan st thy bc nhy pH ng vi s chun tng cng ca 2 axit. Ta
s i vo kho st c th.
1. C s phng php
Gi s chun hn hp HCl 0,1N + H
3
PO
4
0,1N
Bit pK
a1
=2,15; pK
a2
=7,20; pK
a3
=12,38.
Chun mt hn hp hai axit bng mt baz mnh, cc phn ng xy ra ln lt l:
NaOH +HCl =NaCl +H
2
O (1)
NaOH +H
3
PO
4
=NaH
2
PO
4
+H
2
O (2)
NaOH +NaH
2
PO
4
=Na
2
HPO
4
+H
2
O (3)
NaOH +Na
2
HPO
4
=Na
3
PO
4
+H
2
O (4)
ng nh phn ca hn hp c dng nh sau:
NaOH
HCl+H
3
PO
4
Trn ng nh phn xut hin 2 bc nhy pH, bc nhy th nht ng vi T (2) {phn
ng (2) kt thc} v bc nhy th hai ng vi T (3) { phn ng (3) kt thc}. Phn ng th
(4) khng c bc nhy pH do pK
a3
=12,38 >>7. Trong 2 bc nhy ch c bc nhy pH ti
T (2) l r rng {K
a1
/K
a2
>10
4
}. Nguyn nhn v K
a2
<10
-7
nn bc nhy pH ti T (3)
khng r rng.
- Trc khi nh phn: trong dung dch cha hn hp 2 axit HCl v H
3
PO
4
v HCl l 1 axit
mnh nn pH ca dung dch s c quyt nh bi HCl (b qua nh hng ca H
3
PO
4
) -
->[H
+
] ~ 0,1M
pH =-log[H
+
] =-log0,1 =1
- Ti T (2): ton b H
3
PO
4
chuyn thnh H
2
PO
4
-
: Dung dch cha cht lng tnh
H
2
PO
4
-
. pH ca dung dch c tnh theo cng thc: (F: nng [H
2
PO
4
-
])
[H
+
] =
F K
K K F K K
a
w a a a
+
+
1
1 2 1
. . .
-->tnh gn ng: b qua s phn ly ca nc (K
a2
.F
>>K
w
) v F>>K
a1
. Khi [H
+
]~
2 1
.
a a
K K
C th tnh gn ng : pH = (pK
a1
+pK
a2
) = (2,15 +7,20) =4,68
Chn CCT ph hp l metyl da cam (khong pH i mu 3,1 n 4,4), gi tr nh phn pT = 4
xc nh im tng ng. C th bc nhy pH (4,12 5,21) ApH =5,21-4,12 = 1,09 n
v pH.
- Ti T (3): ton b H
2
PO
4
-
chuyn ha thnh HPO
4
2-
. Dung dch cha HPO
4
2-
l mt
cht lng tnh. pH ca dung dch c tnh theo cng thc:
[H
+
] =
'
2
2
'
3 2
. . .
F K
K K F K K
a
w a a a
+
+
tnh gn ng: b qua s phn ly ca nc (K
a2
.F >>K
w
) v F>>K
a1
. Khi [H
+
]~
2 1
.
a a
K K
pH =(pK
a2
+pK
a3
) = (7,20 +12,38) =9,79
Chn CCT ph hp l phenolphtalein (khong pH i mu 8,0 n 9,6), gi tr nh phn pT = 9
xc nh im tng ng. Lu : bc nhy pH ti T (3) khng r rng, s thay i gi
tr pH ln cn T khng qu t ngt nn cn phi chun chm trnh sai s. C th bc
nhy (9,21 10,36) ) ApH =10,36-9,21 =1,15 n v pH.
Nh vy, chng ta c th s dng cht ch th metyl da cam v phenolphtalein xc nh tng
thnh phn axit trong hn hp.
2. Cch tin hnh
- Buret : np dung dch NaOH
- Bnh nn: ra sch, trng nc ct. Dng pipet ly chnh xc 10,00 ml dung dch hn hp
mu kim tra (MKT) cha HCl v H
3
PO
4
cho vo bnh nn, thm 1-2 git cht ch th
metyl da cam, dung dch c mu hng da cam.
- Chnh vch 0 trn buret bt u qu trnh chun . T t m kha van buret a dung
dch NaOH nh git xung bnh nn ng thi lc u bnh nn, mt quan st bnh nn.
Chun cho ti khi dung dch chuyn mu t hng mu da cam sang mu vng, ghi th
tch NaOHtiu tn V
1,2 NaOH
.
- Thm tip 7-8 git cht ch th phenolphlein vo vo bnh nn (khi dung dch vn l
mu vng) ri chun tip ti khi dung dch chuyn sang mu hng tmnht bn 30s th
kt thc chun ghi th tch V
1,2,3 NaOH
.
Thc hin th nghim 3 ln.
3. Tnh ton:
N
HCl
= , (N)
= , (N)
Trong : V
hn hp
=10,00 ml
4. Lu : nhng nguyn nhn gy sai s?
- Trong qu trnh chun cn trnh khng lc bnh nn qu mnh to iu kin cho CO
2
ha tan vo trong dung dch trong bnh nn, lng CO
2
ny nu tn ti s tc dng vi
cht chun NaOH gy sai s.
- Khng nn tin hnh th nghim qu lu v CO
2
c th hp th vo dung dch chun
NaOH lm thay i nng dung dch chun NaOH.
Bi th nghim 4
Xc nh nng KMnO
4
s dng H
2
C
2
O
7
. 2H
2
O v xc nh nng FeSO
4
bng dung dch KMnO
4.
Trong cc bi th nghim trc chng ta lm quen vi phng php chun axit baz, trong
bi ny chng ta s tmhiu phng php chun da trn phn ng oxi ha kh.
Trong phng php chun oxi ha kh ngi ta thng tin hnh phn ng chun l phn
ng trao i electron gia dung dch chun cha cht oxi ha (hoc cht kh) vi dung dch
phn tch cha cht kh (hoc cht oxi ha). nhn bit im tng ng ca phn ng
chun , ngi ta thng dng cht ch th oxi ha kh.
Phn ng chun chung:
aOx1 +bKh2 = cKh1 +dOx2
Trong cht oxi ha 1 (Ox1) b kh thnh cht Kh 1 (Kh1) v cht Kh 2 (Kh2) b oxi ha
thnh cht Oxi ha 2 (Ox2) trong cht kh 1 v cht oxi ha 2 u c tnh kh v tnh oxi ha
yu hn so vi cht Kh 2 v cht oxi ha 1 ban u.
Phng trnh Nerst:
Th oxi ha kh ca mt cp oxi ha kh lin hp c tnh bng phng trnh Nerst.
i vi h n gin: Ox + ne = Kh
Ta c:
Trong : E l th oxi ha (Von), R l hng s kh (8,331 Jun),
T l nhit tuyt i, F l s Faraday (96500 c),
n l s electron trao i, E
o
l th oxi ha kh tiu chun, E
o
ch ph thuc vo bn cht ca h
oxi ha kh lin hp.
ln l logarit c s e (logarit t nhin)
a
Ox
, a
Kh
l hot ca dng oxi ha v dng kh.
- ng chun oxi ha kh:
Cng ging nh phn ng axit baz, phn ng oxi ha kh cng xut hin bc nhy in th
ln cn T. v c ng chun oxi ha kh ngi ta biu din trn mt phng ta
vi trc honh l th tch cht chun thm vo cn trc tung l th ca dung dch. S dng
phng trnh Nerst tnh th ca dung dch trc T, ti T v sau T.
ng chun oxi ha kh in hnh nh sau:
nhn bit im tng ng ngi ta thng s dng cht ch th oxi ha kh. l nhng
cht c kh nng chuyn mu khi b oxi ha hoc kh. Hay ni cch khc, cht ch th oxy ho
kh l nhng cht oxy ho kh m mu ca dng oxy ho (Ind
OX
) v dng kh (Ind
Kh
)l khc
nhau v i mu theo in th ca dung dch. S chuyn mu ca cc cht ch th oxi ha kh
ph thuc vo s bin i th in cc ca h xut hin do s tin trin ca php chun .
Nguyn tc chung chn cht ch th oxi ha kh l cht ch th oxi ha kh c E
o
nm trong
bc nhy th ca dung dch ln cn T.
C th vit na phn ng tng ng vi s chuyn mu ca mt cht ch th oxi ha kh thng
thng nh sau:
In
ox
+ne = In
kh
Theo phng trnh Nerst ta c:
Mt ta c th phn bit c mu ca mt dng no l tu thuc vo t s nng dng oxy
ho v dng kh trong dung dch. Thng th mt ngi c th nhn c mu ca dng oxy
ho hay dng kh khi t s hn km nhau 10 ln, ngha l:
Khi 10
] [
] [
>
Kh
Ox
Ind
Ind
th dung dch c mu ca dng Ind
Ox
ng vi dung dch c
n
E E
o
059 , 0
1
+ >
Khi
10
1
] [
] [
s
Kh
Ox
Ind
Ind
th dung dch c mu ca dng Ind
Kh
ng vi dung dch c
n
E E
o
059 , 0
2
s
Nh vy, mu ca cht ch th trong dung dch s bin i t mu ca dng Ind
Ox
sang dng
Ind
Kh
( mt nhn thy c) ng vi th ca E nm trong khong:
v khong gii hn ny gi l khong i mu ca cht ch th oxy ho kh. Tuy nhin, nhn
thy rng gi tr 0,059/n l rt nh nn trong thc t khong i mu gn trng vi gi tr th E
o
ca cht ch th oxy ho kh nn ngi ta ch quan tm n gi tr th E
o
ca cht ch th v gi l
th i mu.
Bi 1. Pha ch dung dch chun gc H
2
C
2
O
4
t H
2
C
2
O
4
.2H
2
O v xc nh nng dung
dch KMnO
4
Trong phng php chun oxi ha kh ta c th s dng cht kh hoc cht oxi ha bit
trc nng (cht chun) xc nh nng ca cht kh hoc cht oxi ha khc (cht phn
tch). Trong thc t phn tch, ngi ta thng s dng cc cht chun l cht c tnh oxi ha
hoc kh mnh nh KMnO
4
, K
2
Cr
2
O
7
do chng c th oxi ha c nhiu cht kh khc nhau
v phn ng oxi ha kh xy ra gn nh hon ton. Khi s dng KMnO
4
lm cht chun ta gi
l phng php permanganat. Do KMnO
4
rt nhy vi nh sng, nn ngoi nh sng mt thi
gian thng b bin i thnh MnO
2
mu en. 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 7-10 ngy nng mi
n nh. V nhng l do nn KMnO
4
khng c s dng lm chun gc, trc khi s dng
phi chun li nng ca KMnO
4
. Sau khi pha ch dung dch KMnO
4
thng c bo
qun trong cc l xm mu c np y kn.
I. C s phng php
KMnO
4
l cht oxi ha mnh, thng c dng xc nh nhiu loi cht kh khc nhau.
y l phng php chun oxy ho kh da trn phn ng oxy ho ca ion MnO
4
-
trong mi
trng axit:
2
5
MnO
4
-
+5e
-
+8H
+
=Mn
2+
+4H
2
O
C
2
O
4
2-
-2e
-
=2CO
2
2MnO
4
-
+5C
2
O
4
2-
+8H
+
=2Mn
2+
+10CO
2
+4H
2
O
2KMnO
4
+5H
2
C
2
O
4
+2H
2
SO
4
=2MnSO
4
+10CO
2
+K
2
SO
4
+8H
2
O
iu kin ca phn ng:
- Mi trng axit H
2
SO
4
d. Nu lng axit khng th xy ra phn ng : MnO
4
-
+3e
-
+4H
+
=MnO
2
+(en) +2H
2
O . Khi thmtip axit th: MnO
2
+2e
-
+4H
+
=Mn
2+
+
2H
2
O
- Ti nhit thng, vn tc ca phn ng l chm. Do vy, tng nhit phn ng nn
khong 70
o
C bng cch un nng dung dch di bnh nn H
2
C
2
O
4
tng tc phn
ng (theo nh lut Arhenius tc phn ng tng t 2-3 ln khi nhit tng 10
o
C).
Tuy nhit khng c un ti nhit qu cao v ti nhit ln hn 80
o
C c th xy
ra s phn hy nhit ca H
2
C
2
O
4
thnh CO
2
gy sai s.
- Sn phm ca phn ng cha mui Mn
2+
ng thi l xc tc dng lm tng tc
phn ng nn gp nhiu ln. Do , ta quan st thy tc ban u ca phn ng tng
i chm (mc d un nng), sau mt vi git u tc phn ng s tng mnh v
c th chun bnh thng.
- Sau im tng ng d KMnO
4
dung dch c mu hng nht (do dung dch KMnO
4
c mu tm), khng cn cht ch th (phn ng t ch th).
Mt vi lu :
- Ch nn chun trong mi trng axit H
2
SO
4
m khng nn tin hnh trong mi
trng axit HNO
3
v HNO
3
s oxy cht kh lm sai kt qu chun .
- Khng tin hnh trong mi trng axit HCl v:
trong mi trng c Cl
-
c phn ng ph xy ra
2MnO
4
-
+10 Cl
-
+16H
+
=2Mn
2+
+5Cl
2
+8H
2
O
S bay hi ca Cl
2
s gy sai s
- Nu ang tin hnh chun m thy xut hin kt ta mu en th ngay lp tc phi
thm mi trng axit th c th tip tc chun .
- Khng nn cho Mn
2+
vo bnh nn vi vai tr lm xc tc ngay t u v thao tc ny l
khng cn thit v Mn
2+
s c to thnh nh phn ng. Hn na, vic thm Mn
2+
c
th gy ra sai s do dung dch cha Mn
2+
c th ln tp cht.
II. Cch tin hnh
1. Pha dung dch chun gc H
2
C
2
O
4
t H
2
C
2
O
4
.2H
2
O
Tnh lng cn m
a
(g) H
2
C
2
O
4
.2H
2
O cn thit pha ch 250,0 ml dung dch H
2
C
4
O
4
0,05000N,
bit =126,065 g/mol.
Ta c
H2C2O4.2H2O
=
2
2 2 . 4 2 2 O H O C H
M
= 126,065/2 = 63,0325 (g/lg)
m
a
= = = =0,7875 g
T lng cn thc t trn cn phn tch, chng ta tnh li nng dung dch H
2
C
4
O
4
pha:
C
N
= x , (N)
Cch pha:
Cn khong 0,76 0,80 g axit H
2
C
2
O
4
. 2H
2
O trn cn phn tch vi chnh xc 0,0001g cho
vo cc c m 100ml. Cho nc ct khong 30-40 ml, un nh v khuy u bng a thy tinh
cho n tan hon ton. Chuyn ton b dung dch vo bnh nh mc 250,0 ml bng cch rt
nh lng qua a thy tinh. Trng cc c m 100ml v a thy tinh t nht 5 ln ri chuyn
hon ton vo bnh nh mc, nh mc ti vch bng nc ct, lc tht u trc khi s dng.
2. Chun dung dch KMnO
4
bng dung dch H
2
C
2
O
4
Np dung dch KMnO
4
vo buret, ui ht bt kh, ch chnh vch 0 trc khi tin hnh chun
. Dng pipet ly chnh xc 10,00 ml dung dch chun H
2
C
2
O
4
cho vo bnh nn, dng ng
ong thm 5-7 ml dung dch H
2
SO
4
6N lm mi trng ri un nng bnh nn ti nhit
khong 70
o
C (quan st bng mt hin tng ngng hi nc trn ming bnh nn, ko un n
si). Chun dung dch H
2
C
2
O
4
va ung nng, lc u nh 1 git KMnO
4
lc u cho n khi
mt mu hon ton. Sau chun vi tc thng cho n khi dung dch c mu pht hng
v bn trong khong 30s th ngng chun , ghi th tch KMnO
4
tiu tn. Lp li th nghim t
nht 3 ln, ly gi tr trung bnh tnh ton.
Lu :
- y l phng php chun lun sai, do ta dng chun khi c du hiu d KMnO
4
(dng sau im tng ng - tt nhin sai s l chp nhn c). Do , c gng dng li
dung dch mu cng pht hng cng chnh xc.
- Sau khong 30s m mu pht hng ca dung dch bin mt ta cng khng chun tip. V
rng KMnO
4
khng bn c th b phn hy di iu kin nh sng, nht l trong mi
trng axit n d dng tc dng vi cc cht kh c ln trong mi trng.
- Quan st qu trnh un nng nhn bit khi no bnh nn n nhit cn thit bng
cch quan st s ngng t ca hi nc quanh ming bnh nn, khi hi nc ngng t ng
thnh git v chy dc theo thnh bnh xung l c, trnh un si.
- Tin hnh chun tng bnh mt, trnh trng hp un nhiu bnh cng mt lc v trong
lc chun bnh th nht bnh th hai c th ngui hoc un nng lu c th lm phn
hy mt phn H
2
C
2
O
4
gy sai s.
III. Tnh ton:
V
H
2
C
2
O
4
ly chun : . . . .10,00 . . . . . . . ml
V
KMnO
4
o c trong cc ln chun : Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh : . . . . . . . . . . . ml
Nng ca dung dch KMnO
4
(N, g/l)
= , (N)
= . , (g/l)
Trong : =10,00 ml
: l th tch KMnO
4
tiu tn c tnh trung bnh t ba ln th nghim
l nng ng lng ca dung dch chun H
2
C
2
O
4
pha ch.
= = = 31,607 g/ng lng gam
IV. Cu hi
1. Gii thch vai tr ca xc tc dng Mn
2+
?
Tr li:
Phn ng: 2MnO
4
-
+5C
2
O
4
2-
+8H
+
=2Mn
2+
+10CO
2
+4H
2
O
Xy ra rt chm nu khng c s c mt ca xc tc l do phn ng ny cn s tng tc ca 2
ion u mang in tch m (y nhau). Chnh do s y nhau ca cc ion ny m xc sut va
chm ca chng gim i, phn ng kh khn.
Tuy nhin, khi c mt ca xc tc ng th Mn
2+
trong dung dch phn ng din ra nhanh hn.
Mn
2+
ng vai tr lm xc tc l do n c th d dng chuyn i cc trng thi Mn
2+
v Mn
3+
.
giai on 1: Mn
2+
s kh MnO
4
-
v to thnh Mn
3+
:
4 Mn
2+
+MnO
4
-
+ 8 H
+
5 Mn
3+
+4 H
2
O
giai on 2: Mn
3+
s oxi ha C
2
O
4
2-
to ra CO
2
v tr li Mn
2+
ban u
2 Mn
3+
+ C
2
O
4
2-
2 CO
2
+ 2 Mn
2+
R rng l cc qu trnh ny d dng hn do s tng tc gia cc ion tri du.
Phn ng trn c gi l phn ng t xc tc.
Bi 2. Xc nh nng dung dch FeSO
4
bng KMnO
4
Sau khi xc nh c nng dung dch KMnO
4
ta s s dng KMnO
4
lmdung dch chun
xc nh nng dung dch FeSO
4
t mu kim tra. Cc mu kim tra c pha ch t trc
vi cc nng khc nhau, c nh s v sinh vin khng bit trc.
I. C s phng php.
Fe
2+
l cht kh do c th xc nh nng bng cht oxi ha mnh KMnO
4
theo phn
ng oxi ha kh:
2
5
MnO
4
-
+5e
-
+8H
+
=Mn
2+
+4H
2
O
Fe
2+
-1e
-
=Fe
3+
MnO
4
-
+5 Fe
2+
+8H
+
=Mn
2+
+5 Fe
3+
+4H
2
O
2KMnO
4
+10FeSO
4
+8H
2
SO
4
=5Fe
2
(SO
4
)
3
+2MnSO
4
+K
2
SO
4
+8H
2
O
c im ca phn ng:
- Mi trng axit H
2
SO
4
d. Nu lng axit khng th xy ra phn ng :
MnO
4
-
+3e
-
+4H
+
=MnO
2
+(en) +2H
2
O .
Khi thm tip axit th: MnO
2
+2e
-
+4H
+
=Mn
2+
+2H
2
O
- Sau im tng ng d KMnO
4
dung dch c mu hng nht, khng cn cht ch th
(phn ng t ch th).
- y l phn ng oxi ha kh in hnh, phn ng din ra vi tc rt nhanh, ko cn un nng.
- Do sn phm ca phn ng c Fe
3+
c mu vng c th nh hng n vic quan st mu, nn
phi s dng H
3
PO
4
to phc khng mu [Fe(PO
4
)
2
]
3
nhm loi b mu vng ca ion Fe
3+
.
Lu :
- Ch nn chun trong mi trng axit H
2
SO
4
m khng nn tin hnh trong mi
trng axit HNO
3
v HNO
3
s oxy Fe
2+
thnh Fe
3+
lm sai kt qu chun .
- Khng tin hnh trong mi trng axit HCl v:
trong mi trng c Cl
-
c phn ng ph xy ra
2MnO
4
-
+10 Cl
-
+16H
+
=2Mn
2+
+5Cl
2
+8H
2
O (*)
phn ng ny bnh thng th xy ra rt chm nhng phn ng gia Fe
2+
v MnO
4
-
gy cm
ng n phn ng (*) v lm cho phn ng (*) xy ra nhanh hn.
Mc d to ra Cl
2
l mt cht oxy ha:
5Cl
2
+10Fe
2+
=10Fe
3+
+10Cl
-
(**)
Nh vy, Fe
2+
b oxy ha thnh Fe
3+
vi mt lng tng ng lng Fe
2+
b KMnO
4
oxy
ha thnh Fe
3+
. Tc l coi nh (*) khng nh hng n php phn tch. Tuy nhin, thc t Cl
2
sinh ra b bay i mt phn dn ti php chun mc sai s dng.
Phn ng (*) l phn ng cm ng. hn ch phn ng (*) ny ngi ta s dng hn
hp bo v Zimmecman (H
2
SO
4
, H
3
PO
4
, MnSO
4
) trong :
H
2
SO
4
: ngn nga cc sn phm thu phn ca mui st, ngn cn s oxi ho Fe
2+
bi O
2
khng
kh ng thi to mi trng phn ng.
H
3
PO
4
: Fe
3+
c hnh thnh c mu vng gy cn tr cho vic xc nh im cui
chun ( mu pht hng do d 1 git KMnO
4
), H
3
PO
4
to c vi Fe
3+
phc khng mu.
Mn
2+
( MnSO
4
): hn ch phn ng cm ng.
- Nu ang tin hnh chun m thy xut hin kt ta mu en th ngay lp tc phi
thm mi trng axit th c th tip tc chun .
- Phn ng xy ra nhanh iu kin nhit thng khng nn un nng, nu c un
nng c th gy ra sai s do iu kin nhit cao s thc y phn ng oxi ha Fe
2+
thnh Fe
3+
bi O
2
khng kh trong mi trng axit: 4Fe
2+
+4H
+
+O
2
=4Fe
3+
+2H
2
O
gy sai s m.
II. Cch tin hnh
Np dung dch KMnO
4
vo buret, ui bt kh, chnh vch 0 trc khi tin hnh chun . Dng
pipet ly chnh xc 10,00 ml dung dch FeSO
4
t mu kim tra cho vo bnh nn, dng ng ong
thm5-7 ml dung dch hn hp H
2
SO
4
+H
3
PO
4
6N. Chun cho ti khi dung dch xut hin
mu pht hng v bn trong khong 30s th kt thc chun , ghi th tch KMnO
4
tiu tn. Lp
li th nghim t nht 3 ln, ly gi tr trung bnh tnh ton.
III. Tnh ton:
V
FeSO
4
ly chun : . . . . 10,00. . . . . . . ml
V
KMnO
4
o c trong cc ln chun : Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh: . . . . . . . . . . . ml
Nng ca dung dch FeSO
4
= , (N)
= . (g/l)
Trong : =10,00 ml
: l th tch KMnO
4
tiu tn c tnh trung bnh t ba ln th nghim.
l nng ng lng ca dung dch chun KMnO
4
xc nh bi 1.
Tnh s gam Fe c trong lng mu ly phn tch:
1000
3
4 4
+

=
Fe
FeSO FeSO
V N
m , (g)
IV. Cu hi
1. to mi trng cho phn ng chun c th dng cc axit sau c khng? Vit cc
phng trnh phn ng gii thch? axit HNO3? axit HCl ?.
2.Khi trong dung dch c ion , chun c dung dch ngi ta phi dng hn hp
Zimecman. Hy vit thnh phn ca hn hp ny v gii thch vai tr ca tng phn trong
hn hp?
Bi th nghim 5
Xc nh nng dung dch FeSO
4
bng K
2
Cr
2
O
7
(kh Fe
3+
Fe
2+
)
Trong bi th nghim ny chng ta s cp n phng php oxi ha kh s dng cht oxi ha
K
2
Cr
2
O
7
lm cht chun xc nh nng ca cc cht kh, phng php ny thng c
gi l phng php bicromat.
Trong thc t phn tch, phng php bicromat thng c s dng nhiu hn phng php
permanganat do n nhiu u im:
- Do V E
o
Cr O Cr
36 , 1
3 2
7 2
/
=
+
< V E
o
Cl Cl
39 , 1
2 /
2
=

nn K
2
Cr
2
O
7
khng th oxi ha c Cl
-
trong dung
dch thnh Cl
2
. Do phng php ny khc phc c nhc im ca phng php
permanganat. Ta c th tin hnh phng php ny m ko s nh hng ca Cl
-
c mt trong
dung dch. Trong thc t phn tch, qu trnh ph mu thng s dng nc cng toan (hn hp
3 phn HCl v 1 phn HNO
3
) cng vi s nhim Cl
-
sn trong cc mu t l nguyn nhn
khin cho Cl
-
thng c mt trong mu phn tch. Chnh v vy, trong thc t phn tch ngi ta
thng u tin s dung phng php bicromat hn phng php permanganat.
- So vi KMnO
4
th K
2
Cr
2
O
7
bn hn, c th 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.
- 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
gn nh khng thay i trong thi gian bo
qun.
Tuy nhin, K
2
Cr
2
O
7
cng c nhc im so vi KMnO
4
.
- Do V E
o
Cr O Cr
36 , 1
3 2
7 2
/
=
+
< V E
o
Mn MnO
51 , 1
2
4
/
=
+
nn K
2
Cr
2
O
7
l cht oxi ha yu hn so vi KMnO
4
do kh nng p dng hn ch hn.
- Trong qu trnh chun ion Cr
3+
to ra c mu xanh gy kh khn cho vic nhn bit im
tng ng.
- So vi KMnO
4
c th t ch th th trong phng php bicromat cn phi s dng ch th
diphenylamin hoc axit phenylantranilic nhn bit im tng ng.
Trong thc t phn tch, mu cha Fe thng c ch ha v dng Fe
3+
, v vy trong bi th
nghim ny, mu kim tra c cho dng Fe
3+
. xc nh c nng ca mu kim tra
chng ta s tin hnh 2 giai on: kh Fe
3+
v Fe
2+
sau xc nh nng dung dch Fe
2+
sau
qu trnh kh bng dung dch chun K
2
Cr
2
O
7
0,05N.
I. Kh Fe
3+
v Fe
2+
bng Zn ht
Trc ht ta tin hnh qu trnh kh mu Fe
3+
v Fe
2+
bng cht kh Zn ht trong mi trng
HCl 1:1.
1. Phng trnh phn ng: 2Fe
3+
+Zn =2Fe
2+
+Zn
2+
( mi trng HCl 1:1 1 phn HCl c trn 1 phn nc ct)
c im phn ng:
- Mi trng HCl 1:1 d m bo vai tr:
+Zn s phn ng vi HCl to H
*
mi sinh, chnh H
*
mi sinh l tc nhn kh mnh s
kh nhanh Fe
3+
v Fe
2+
.
+To mi trng axit d m bo trnh qu trnh thy phn ca mui Fe
3+
, Fe
2+
, Zn
2+
thnh cc dang hydroxit kt ta.
+To mi trng axit d m bo Zn khng tc dng c vi Fe
2+
to thnh Fe bm
vo ht Zn lm mt mt Fe ( d H
+
th Zn lun phi tc dng vi H
+
m ko tc dng c
vi Fe
2+
do th E
o
ca cp 2H
+
/H
2
ln hn ca cp Fe
2+
/Fe).
+To phc vi Fe
3+
thnh [Fe(Cl)
4
]
-
c mu vng xm gip nhn bit s kt thc ca qu
trnh kh d dng hn.
- Zn ht d m bo qu trnh kh hon ton Fe
3+
v Fe
2+
.
- Nhit cao gip cho qu trnh kh nhanh hn, hon ton hn (nhng khng c
un si d lm hi nc li cun theo Fe
3+
gy sai s).
2. Cch tin hnh qu trnh kh:
Ly chnh xc 10,00 ml dung dch mu kim tra Fe
3+
cho vo bnh nn 100ml, thmvo bnh
nn khong 10 ht Zn. Chuyn bnh nn vo trong t ht v thm tip khong 5-7 ml dung dch
HCl 1:1 ri t ln bp un nng ti gn si, quan st thy dung dch c mu vng sm. Tin
hnh qu trnh kh cho n khi dung dch mt mu hon ton, lun phi m bo trnh un bnh
nn si, nu quan st thy kt ta trng xut hin (do thy phn mui Zn
2+
) th phi ngay lp tc
thmaxit HCl 1:1 cho tan ht. Cho n khi dung dch mt mu hon ton (hoc quan st thy
mu nh xanh) th ngay lp tc tia nc ct xung quanh thnh bnh nn vi vng lm ngui
ng thi pha long dung dch HCl d trnh bay hi HCl c hi trc khi mang bnh nn ra
khi t ht. Sau tin hnh lmngui nhanh bnh nn ti nhit mi trng bng nc ri
tin hnh qu trnh lc gn v ra gn 5-7 ln bng nc ct ( lc gn l qu trnh lc ch a
phn dung dch nn phu lc v gi li phn cn trng ra ), phn dung dch lc c hng
vo bnh nn 250ml dng cho qu trnh chun . Sau qu trnh lc, phn dung dch lc thu c
vo khong 120ml l c.
Lu :
- Trong qu trnh kh phi lun quan st thy hin tng si bt kh (H
2
) nu khng quan st
thy th nhiu kh nng l ht axit HCl, ngay lp tc phi thm HCl m bo trnh sai s
(v khi Zn c kh nng phn ng vi Fe
2+
).
- Khi c mt ca Zn trong dung dch ta khng s nh hng ca cht oxi ha O
2
trong khng
kh (v O
2
s tc dng vi Zn, H
+
trc khi tc dng vi Fe
2+
). Tuy nhin, sau khi lc b
Zn ra khi dung dch th Fe
2+
s d dng tc dng vi O
2
trong khng kh: 2Fe
2+
+ O
2
+
2H
+
=2Fe
3+
+H
2
O gy sai s nht l phn ng c tng tc khi nhit cao. Do trc
khi lc b Zn ra khi dung dch th phi tin hnh lmngui dung dch (khng lc Zn khi
dung dch cn nng).
II. Chun Fe
2+
bng dung dch K
2
Cr
2
O
7
.
1. C s phng php
Da trn phn ng oxi ho - kh gia Cr
2
O
7
2-
v Fe
2+
Trong mi trng axit mnh:
1
6
Cr
2
O
7
2-
+6e
-
+14H
+
=2Cr
3+
+7H
2
O
Fe
2+
-1e
-
=Fe
3+

Cr
2
O
7
2-
+6Fe
2+
+14H
+
=2Cr
3+
+6Fe
3+
+7H
2
O
c im phn ng:
- Phn ng din ra trong mi trng axit mnh H
2
SO
4
- H
3
PO
4
c thm vo to phc vi Fe
3+
to thnh phc khng mu gip d dng
quan st im tng ng. Fe
3+
+2HPO
4
2-
[Fe(HPO
4
)
2
]
-
- H
3
PO
4
cn c thm vo ko di bc nhy in th ln cn T do lm gim
nng ca ion Fe
3+
t do (v to phc) nn t s Fe
3+
/Fe
2+
gim cn khong 10
-1
. Do
vy bc nhy in th c ko di t khong [0,94 1,345] thnh [0,711 1,345] V
- Cht ch th oxi ha kh diphenylamin (E= 0,76V) s dng c trong trng hp
ny. Qua im tng ng, ch th i mu t khng mu sang xanh tm.
2. Cch tin hnh
Np dung dch chun K
2
Cr
2
O
7
0,05N vo buret, ui bt kh, chnh vch 0 trc khi tin
hnh chun . Thm vo bnh nn cha dung dch Fe
2+
lc Zn d t qu trnh kh
khong 5-7ml dung dch hn hp H
2
SO
4
+H
3
PO
4
6N. Thm tip 1-2 git ch th
diphenylamin, dung dch trong sut khng mu. Tin hnh chun , dung dch xut hin
mu xanh l m (ca ion Cr
3+
sinh ra), chun cho n khi dung dch chuyn t mu xanh
l m sang xanh tm, ghi th tch V
K2Cr2O7
tiu tn, lp li th nghim t nht 3 ln, ly gi tr
trung bnh tnh ton.
3. Tnh ton:
V
Fe
3+
ly chun : . . . 10,00. . . . . . . . . ml
V
K
2
Cr
2
O
7
c nng chun : . . .0,05 . . . . . N dng trong cc ln chun :
Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh: . . . . . . . . . ... . ml
Nng ca dung dch Fe
3+
:
= = , (N)
= . (g/l)
Trong : =10,00 ml
: l th tch K
2
Cr
2
O
7
tiu tn c tnh trung bnh t ba ln th nghim
(khi dung dch c mu xanh tm)
=0,05N l nng ng lng ca dung dch chun K
2
Cr
2
O
7
= 55,845 g/ng lng gam.
Tnh s gam Fe c trong lng mu ly phn tch:
m =(
Fe
3+
. V
Fe
3+
. N
Fe
3+
) / 1000
- Tnh (s gam st tc dng va vi 1,00 ml dung dch K
2
Cr
2
O
7
):
(vi =1,00 ml)
4. Cu hi
1. kh Fe
3+
v Fe
2+
ngi ta dng km ht trong mi trng HCl 1:1 v un nng. Sau
tin hnh chun bng dung dch KMnO
4
c c khng? Ti sao?
Tr li: trong qu trnh kh Fe
3+
v Fe
2+
dng km ht trong mi trng HCl 1:1 v un
nng do dung dch lc c cha ion Cl
-
. Nu chun bng dung dch KMnO
4
th ion Cl
-
c kh nng b oxi ha to thnh Cl
2
, mt phn bay hi s gy sai s. c th chun
c dng KMnO
4
th phi thm vo hn hp Zimecman. Hn hp ny cha:
+H
2
SO
4
to mi trng axit mnh cho phn ng chun :
MnO
4
-
+5Fe
2+
+8H
+
=Mn
2+
+5Fe
3+
+4H
2
O
+H
3
PO
4
to phc khng mu vi Fe
3+
kh mu vng ca ion ny gip nhn bit T d
dng.
Fe
3+
+2HPO
4
2-
[Fe(HPO
4
)
2
]
-
+MnSO
4
lm xc tc m ngn phn ng ph:
2MnO
4
-
+10Cl
-
+16H
+
=2Mn
2+
+5Cl
2
+8H
2
O (Cl
2
bay hi 1 phn gy sai s)
Thc t vi mu cha nhiu ion Cl
-
ngi ta trnh dng KMnO
4
.
Bi th nghim 6
Phng php Iot. Xc nh nng Na
2
S
2
O
3
bng K
2
Cr
2
O
7
. Xc nh nng
CuSO
4
bng Na
2
S
2
O
3
theo phng php iot
Phng php iot thng thng l phng php chun gin tip. xc nh cht oxi ha,
ngi ta cho mt lng xc nh chnh xc cht phn ng vi lng d KI to ra I
2
. Lng
I
2
sinh ra s i din cho lng cht oxi ha cn xc nh. Sau chun lng I
2
sinh ra bng
dung dch chun thiosunfat natri (Na
2
S
2
O
3
), t bit c nng ca cht oxi ho ban u.
V thng dng thiosunfat xc nh li lng I
2
sinh ra nn thng hay gi l phng php
iot-thiosunfat. Cng lu rng, y thng l phng php gin tip nn cng s dng nhiu
cng on th kh nng gy sai s cng ln.
Phng php iot cng c th dng chun trc tip xc nh nng cc cht kh khi
ngi ta s dng dung dch I
2
chun pha trong KI d (do I
2
l cht t tan, d thng hoa nhng c
kh nng to phc vi KI tan rt tt trong dung dch).
I. C s phng php
Phng php iot da trn phn ng oxi ha kh : I
2
+ 2e
-
= 2I
-
* Nh vy, I
2
l mt cht oxy ha tng i yu, yu hn nhiu so vi KMnO
4
v K
2
Cr
2
O
7
.
Nhng ngc li 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 oxy ha bng cch kh chng bi ion I
-
thnh
I
2
, sau xc nh li lng I
2
bng dung dch chun Na
2
S
3
O
3
. Do th Ox-Kh tiu chun ca cp
I
2
/2I
-
tng i nh, bng 0,54 V cho nn c th xem I
-
l mt cht kh rt tt xc nh nhiu
cht oxy ho nh K
2
Cr
2
O
7
, KMnO
4
, KClO
3
, Cl
2
, Br
2
, NO
2,
Fe
3+
, Cu
2+
....
* Lu rng phn t I
2
ch ha tan nh trong nc (1,3.10
-3
M 20C), nhng ha tan ca n
cao hn rt nhiu trong dung dch I
-
nh phn ng to phc vi I
-
I
2(dung dch)
+ I
-
I
3
-
(tri iotua) =7.10
2
phc ny ko qu bn, tc l d dng
nh I
2
i vo dung dch v thun li cho qu trnh chun . Phc cng c mu vng sm gip d
dng quan st phn on c lng hm lng I
2
tan trong dung dch. Trong trng hp cn pha
dung dch I
2
chun th ta hiu rng I
2
c pha trong dung dch I
-
d tng tan ca I
2
.
* Cht ch th h tinh bt: mc d bn thn dung dch I
2
c mu vng, tuy nhin mt ngi
khng th quan st c mu vng khi hm lng I
2
mc rt thp (do nu khng c bin
php h tr khc th c th gy sai s ln do quan st khng ng im tng ng). h tr
vic ny, ngi ta s dng h tinh bt lm cht ch th. H tinh bt c kh nng to phc mu
xanh tm c trng vi I
2
, nhy mu cao khi hm lng I
2
nh (nhit cng thp th nhy
mu cng cao). Yu t hot ng ca h tinh bt l amyloza, polyme ca ng -D glucose,
polyme ny tn ti dng cun xon c, ch c mt s t phn t c th chui qua c. Khi c
mt I
2
n to dng nhnh I
6
, xy ra trung tm amyloza dng xon c. Sn phm phc c mu
xanh en. S to phc ph thuc vo nhit , 50C mu ca phc nht bng 1/10 cng
mu 25C. V th nu yu cu cng mu cc i th c th lm lnh bng nc . Ta cn
lu rng, ch th h tinh bt khng phi l ch th oxy ha kh, tc l mu ca ch th khng
thay i do s thay i th oxi ha kh m thay i do s c mt ca I
2
. Nh vy, vi ch th h
tinh bt c mt iu thun li l ta khng cn quan tm n bc nhy in th ca dung dch
ln cn im tng ng, v trong mt s trng hp nu bc nhy in th qu nh th khi s
dng ch th oxi ha kh c th khng th xc nh c im tng ng hoc gp phi sai s
ln.
Bi 1. Xc nh nng dung dch Na
2
S
2
O
3
bng dung dch K
2
Cr
2
O
7
0,05N bng phng
php iot
Dng ph bin ca thiosunphat l Na
2
S
2
O
3
.5H
2
O l tinh th khng mu, 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
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

+2HI (1)
2S
2
O
3
2
+ I
2
= S
4
O
6
2
+ 2I

(2)
ng lng gam ca NaHSO
3
= M/2 (2e trao i) trong khi ng lng gam ca Na
2
S
2
O
3
=
M/1 (1e trao i).
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 lc nng Na
2
S
2
O
3
gn nh t thay i. ngn nga nh hng ca CO
2
ngi ta dng nc ct mi un si ngui pha (t hm lng CO
2
ha tan) 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
Trong mi trng axit dung dch thiosunphat khng n nh.
+H
+
+S

ngn nga dung dch b vi khun phn hy, ngi ta thm khong 10mg HgI
2
(hoc 1 git
CCl
4
) 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
.
Trong bi th nghim ny, trc tin ngi ta phi xc nh li nng ca Na
2
S
2
O
3
.
1. C s phng php: Dng mt lng xc nh dung dch chun K
2
Cr
2
O
7
oxi ho lng
d KI thnh I
2
v chun I
2
sinh ra bng dung dch Na
2
S
2
O
3
vi cht ch th h tinh bt. T
nng v th tch ca K
2
Cr
2
O
7
c th xc nh c nng ca dung dch thiosunfat.
Phn ng chun : K
2
Cr
2
O
7
+6KI +7H
2
SO
4
=Cr
2
(SO
4
)
3
+3 I
2
+4K
2
SO
4
+7H
2
O (*)
2Na
2
S
2
O
3
+I
2
=Na
2
S
4
O
6
+2NaI (**)
iu kin tin hnh phn ng:
- 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.
- Phn ng c tin hnh trong mi trng axit yu n kim yu. Mi trng axit yu
m bo lng axit cho phn ng (*).
+Nu mi trng qu axit (axit mnh): axit lm tng cng phn ng oxi ha gia O
2

khng kh v I

4I
-
+ O
2
+ 4H
+
= 2I
2
+ 2H
2
O to ra thm I
2
gy sai s phn tch
+Nu mi trng qu kim (kim mnh): I
2
sinh ra s tc dng vi kim
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
n Na
2
SO
4
nn lmsai lch
ng lng ca phn ng:
S
2
O
3
2
+ 4IO

+ H
2
O = 4I

+ 2SO
4
2
+ 2H
+
Do phn ng ph ny, kt qu phn tch s khng chnh xc. V vy phi gi pH < 9
- Chun ngui v iot l cht d bay hi, mt khc h tinh bt s km phn ng vi iot
khi un nng, iu dn n gim nhy.
- Cn dng kh d KI (V tan I
2
trong nc kh nh nn khi chun cc cht oxi ha
(to ra I
2
), KI d s ha tan I
2
to phc [KI
3
] ). Lu : s to thnh hp cht ny khng
nh hng g n qu trnh nh phn v phn ng to phc [KI
3
] thun nghch , [KI
3
] s
b phn hy dn gii phng I
2
vo dung dch. KI d cn c tc dng thc y cho phn
ng (*) xy ra hon ton ( m bo K
2
Cr
2
O
7
phn ng hon ton, I
2
sinh ra i din
cho ton b lng K
2
Cr
2
O
7
).
- 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.
- Trc khi chun cn dung dch trong bng ti hn ch phn ng ph:
4I
-
+ O
2
+ 4H
+
= 2I
2
+ 2H
2
O phn ng xy ra nhanh nu c nh sng kch
thch, to ra thm I
2
gy sai s phn tch
- 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. Do h tinh bt c cu trc dng xon nn
qu trnh gii hp I
2
chm, phn ng chm vi Na
2
S
2
O
3
do d nh phn qu im
tng ng.
2. Cch tin hnh:
- Buret: Np dung dch Na
2
S
2
O
3
vo buret, ui ht bt kh, chnh n vch 0 trc khi
bt u chun
- Bnh chun iot (Bnh nn 250mL ming loe, c nt nhm): ly chnh xc 10,00 mL
dung dch chun K
2
Cr
2
O
7
0,05N +khong 5-7ml dung dch H
2
SO
4
2N +khong 10ml
dung dch KI 20% ( tnh d). Khi rt dung dch KI hon ton vo bnh nn, nhanh
chng y np (trnh I
2
va to ra thng hoa), lc nh v tia nc ct ln np, ri nhanh
chng a bnh vo trong bng ti trong vng 5 pht (trnh nh sng).
- Sau 5 pht, ly bnh chun Iot ra, nh nhng m np, tia nc ct trng thnh bnh,
trng np v pha long dung dch ti khong 100ml (pha long lm gim mu xanh l
m ca mui Cr
3+
gip d dng quan st im tng ng). Dung dch c mu vng
sm.
- Tin hnh chun : em chun cho n khi dung dch t mu vng sm chuyn thnh
vng nht nh xanh ( khi lng I
2
trong bnh cn t c mu vng nht cng vi mu xanh
l m ca mui Cr
3+
). Thm vo bnh chun Iot khong 1ml ch th h tinh bt, dung
dch c mu xanh tm (nu cho sm qu ta s quan st thy dung dch c mu xanh en).
Tin hnh chun tip cho n khi mt hon ton mu xanh tmch cn mu xanh l
m. Lu : sau khi thm h tinh bt vo, lc ny sp n im tng ng, ng
thi s nh I
2
ra khi h tinh bt l chm. Do phi chun chm v lc u trnh
b chun qu im tng ng.
3. Tnh ton:
V
K
2
Cr
2
O
7
ly chun : . 10,00. ml
Nng dung dch chun K
2
Cr
2
O
7
: 0,05N
V
Na
2
S
2
O
3
o c trong cc ln chun : Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh: . . . . . . . . . . . ml
Nng ca dung dch Na
2
S
2
O
3
: = , (N)
= . (g/l)
Trong : : l th tch Na
2
S
2
O
3
tiu tn c tnh trung bnh t ba ln th nghim
l nng ng lng ca dung dch chun K
2
Cr
2
O
7
= 158,110 g/ng lng gam
Chng ta c th tnh nng Na
2
S
2
O
3
theo n v mol/l:
= , (M)
Trong : l nng mol/l ca dung dch chun K
2
Cr
2
O
7
4. Cu hi:
1. mi trng cho phn ng chun ?
Mi trng axit yu. Nu trong mi trng axit mnh s thc y phn ng ph
4I
-
+ O
2
+ 4H
+
= 2I
2
+ 2H
2
O to ra thm I
2
gy sai s phn tch
Nu mi trng kim: I
2
sinh ra s tc dng vi kim
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
n Na
2
SO
4
nn lmsai lch ng
lng ca phn ng:
S
2
O
3
2
+ 4IO

+ H
2
O = 4I

+ 2SO
4
2
+ 2H
+
Do phn ng ph ny, kt qu phn tch s khng chnh xc. V vy phi gi pH < 9
2. Gii thch vai tr ca KI?
- Cn dng kh d KI (V tan I
2
trong nc kh nh nn khi chun cc cht oxi ha
(to ra I
2
), KI d s ha tan I
2
to phc [KI
3
] ). Lu : s to thnh hp cht ny khng nh
hng g n qu trnh nh phn v phn ng to phc [KI
3
] thun nghch , [KI
3
] s b phn hy
dn gii phng I
2
vo dung dch.
- KI d cn c tc dng thc y cho phn ng (*) xy ra hon ton ( m bo K
2
Cr
2
O
7
phn ng hon ton, I
2
sinh ra i din cho ton b lng K
2
Cr
2
O
7
).
3. Ti sao ch cho cht ch th h tinh bt khi phn ng chun gn n im kt thc
chun ?
Nu cho h tinh bt vo qu sm lc lng I
2
trong dung dch ln, I
2
s to phc vi h tinh bt
v b hp ph su vo cu trc dng xon ca h tinh bt. Do , qu trnh gii hp tr li dung
dch s rt chm dn n php chun rt d b qu im tng ng.
4. Ring vi phng php ny, c th c cch kim tra xem chun qu im tng
ng bao xa? l cch no?
kim tra xem chun qu im tng ng bao xa, ta c th s dng lun dung dch
chun K
2
Cr
2
O
7
0,05N. V dung dch Na
2
S
2
O
3
trong th nghim ny c pha vi nng
khong 0,05N nn 1 ng lng Na
2
S
2
O
3
phn ng va vi 1 ng lng K
2
Cr
2
O
7
( lu
rng y ch l gi thuyt gn ng v nng ng lng cn ph thuc vo loi phn ng).
Khi ta nh git ngc dung dch K
2
Cr
2
O
7
vo bnh chun iot sau khi dng chun , lc
u, K
2
Cr
2
O
7
s phn ng vi Na
2
S
2
O
3
d trc (gi thuyt 1 git phn ng va vi 1 git).
Khi ht Na
2
S
2
O
3
, K
2
Cr
2
O
7
s phn ng vi I
-
to I
2
v lm h tinh bt xanh tr li. Nh vy, sai
s cho php trong th nghim ny l trong vng 1-2 git K
2
Cr
2
O
7
nh tr li ta quan st thy
dung dch xanh tm tr li th coi nh sai s ca php chun l cho php.
Bi 2. Xc nh nng Cu
2+
(CuSO
4
) bng dung dch chun Na
2
S
2
O
3
theo phng php
iot
Sau khi xc nh c nng Na
2
S
2
O
3
, chng ta s s dng Na
2
S
2
O
3
nh dung dch chun
xc nh nng ca Cu
2+
trong mu kim tra bng phng php iot. Mu Cu
2+
kim tra
c pha sn, nh s v thay i theo cc nhm th nghim khc nhau.
1. Nguyn tc: Cu
2+
phn ng vi I
-
gii phng I
2
mt cch nh lng, chun lng I
2
gii
phng ra bng dung dch chun Na
2
S
2
O
3
vi cht ch th h tinh bt.
Phn ng chun : Cu
2+
+4I
-
=2CuI

+I
2
(*)
2 Na
2
S
2
O
3
+I
2
=Na
2
S
4
O
6
+2NaI (**)
Phn ng (*) din ra hon ton nh s to thnh kt ta CuI. Chng ta c th thy r iu ny
khi xem xt cc th kh tiu chun di y:
Cu
2+
+e
-
=Cu
+
E =0,15V (a)
I
2
+2e
-
=2I
-
E=0,54V (b)
Cu
2+
+I
-
+e
-
=CuIE =0,86V (c) CuI kt ta trng nhng lun c xu hng hp I
2
trn b mt nn c mu vng nu nht.
Nu ch nhn vo th kh tiu chun (a) v (b), chng ta thy rng phn ng (*) s khng xy ra.
Tuy nhin, nh s to thnh cht t tan CuI (T
CuI
=10
12
) dn ti s gim nng t do ca Cu
+
v nu nh I
-
d t nht 4% th phn ng (*) xy ra hon ton.
iu kin tin hnh phn ng:
- To mi trng axit yu thch hp ngn nga phn ng thy phn mui Cu
2+
(axit axetic
c thm vo dung dch Cu
2+
).
- KI c dng d :
+ KI d m bo phn ng (*) din ra hon ton, d nhiu KI, nng I

cng ln
E
I2/2I
cng gim, E
Cu2+/Cu+
cng tng v phn ng cng hon ton.
+ ha tan ca I
2
trong nc nh, phi dng KI d to phc [KI
3
]ha tan tt trong
dung dch.
- D dng KI d, vn tc gia KI v cht oxy ha thng khng ln, v vy sau khi thm
cht oxy ha phi i mt thi gian v tin hnh trong bng ti trnh nh hng ca phn
ng ph
4I
-
+ O
2
+ 4H
+
= 2I
2
+ 2H
2
O phn ng xy ra nhanh nu c nh sng kch
thch, to ra thm I
2
gy sai s phn tch
- I
2
l cht bay hi nn phi tin hnh nhit thng. Mt khc khi tng nhit , nhy
ca h tinh bt gim.
- Kt ta CuI hp ph chn lc mt lng I
2
ng k, s nh hp ph I
2
ra khi b mt kt ta
l chm trong qu trnh chun , do kt qu chun c th b sai lch ln. trnh nh
hng ny, ta thm vo dung dch mt lng SCN
-
d thay th I
-
trong kt ta CuI (mu
trng) v kt ta CuSCN mu phn hng khng hp ph I
2
ln b mt. ng thi cn lm
tng th oxiho - kh ca cp Cu
2+
/Cu
+
do CuCNS c tch s tan nh hn (T
CuSCN
=
4,0.10
-14
). (CuI)
n
I
2
+n SCN
-
n CuSCN

(mu phn hng) +I

2
+nI
-
Phn ng ny xy ra c l do tch s tan ca CuSCN (T
CuSCN
=4,0.10
-14
) nh hn tch s
tan ca CuI (T
CuI
=1.10
-12
). Theo nhiu ti liu tham kho u cho rng phn ng ny din ra
hon ton, nhng bn thn ti ngh phn ng trn vn l thun nghch, do T
CuSCN
=4,0.10
-14
ch nh hn c vi trm ln T
CuI
=1.10
-12
. (tc l sai s <1%, c th b qua).
- i vi trng hp chun I
2
thot ra trong phn ng, ch c thmh tinh bt khi I
2
tc dng gn ht (dung dch c mu vng nht), nu I
2
cn nhiu, hp cht to bi I
2
v h tinh bt nhiu, I
2
phn ng chm vi Na
2
S
2
O
3
, do d chun qu im tng
ng.
2. Cch tin hnh:
- Buret: Np dung dch Na
2
S
2
O
3
vo buret, ui ht bt kh, chnh n vch 0 trc khi bt
u chun
- Bnh chun iot (Bnh nn 250mL ming loe, c nt nhm): ly chnh xc 10,00 ml dung
dch Cu
2+
t mu kim tra + khong 10 ml dung dch hn hp (KI+NH
4
SCN) 20% ( tnh
d). Khi rt dung dch KI hon ton vo bnh nn, nhanh chng y np (trnh I
2
va to ra
thng hoa), lc nh v tia nc ct ln np, ri nhanh chng a bnh vo trong bng ti
trong vng 5 pht (trnh nh sng).
- Sau 5 pht, ly bnh chun Iot ra, nh nhng m np, tia nc ct trng thnh bnh, trng
np bng mt cht nc ct ( ch khng pha long dung dch trong bnh chun ). Dung
dch c mu vng nu sa ging mu cafe sa.
- Tin hnh chun : em chun cho n khi dung dch t mu vng nu sa chuyn thnh
vng nht nh mu ve tng ( khi lng I
2
trong bnh cn t c mu vng nht cng vi mu
trng hng ca kt ta CuSCN). Thm vo bnh chun Iot khong 1ml ch th h tinh bt,
dung dch c mu xanh tm (nu cho sm qu ta s quan st thy dung dch c mu xanh
en). Tin hnh chun tip cho n khi mt hon ton mu xanh tm ch cn mu phn
hng. Lu : sau khi thm h tinh bt vo, lc ny sp n im tng ng, ng thi
s nh I
2
ra khi h tinh bt l chm. Do phi chun chm v lc u trnh b chun
qu im tng ng.
3. Tnh ton:
V
CuSO
4
ly chun : . 10,00. ml
V
Na
2
S
2
O
3
o c trong cc ln chun : Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh: . . . . . . .. . . . . ml
Nng ca dung dch CuSO
4
: = , (N)
= (g/l)
Tnh s gam CuSO
4
trong lng dung dch ly chun :
m = C
CuSO4
. V
CuSO4
. 10
-3
(g)
Tnh (s gam CuSO
4
tc dng va vi 1,00 ml dung dch Na
2
S
2
O
3
):
(vi =1,00 ml)
4. Cu hi
1. Mi trng chun ?
Mi trng axit yu CH
3
COOH pha sn vo mu kim tra Cu
2+
trnh s thy phn ca
mui Cu
2+
Nu trong mi trng axit mnh s thc y phn ng ph
4I
-
+ O
2
+ 4H
+
= 2I
2
+ 2H
2
O to ra thm I
2
gy sai s phn tch
Nu mi trng kim : I
2
sinh ra s tc dng vi kim
I
2
+ 2NaOH = NaIO + NaI + H
2
O
IO

l cht oxi ha mnh hn I

2
n oxi ha c Na
2
S
2
O
3
n Na
2
SO
4
nn lmsai lch ng
lng ca phn ng:
S
2
O
3
2
+ 4IO

+ H
2
O = 4I

+ 2SO
4
2
+ 2H
+
Do phn ng ph ny, kt qu phn tch s khng chnh xc.
2. Gii thch vai tr ca KI v vai tr ca NH
4
SCN?
- KI d thc y cho phn ng (*) xy ra hon ton. Hn na phi dng d KI (V
tan I
2
trong nc kh nh nn khi chun cc cht oxi ha (to ra I
2
), KI d s ha tan I
2
to phc [KI
3
] ). Lu : s to thnh hp cht ny khng nh hng g n qu trnh nh
phn v phn ng to phc [KI
3
] thun nghch , [KI
3
] s b phn hy dn gii phng I
2
vo
dung dch.
- To ra kt ta mi CuSCN thay th kt ta CuI. Kt ta ny khng hp ph chn lc I
2
trong dung dch nn trnh c sai s phn tch.
3. S i mu ca dung dch xy ra nh th no? Gii thch?
Trc khi chun dung dch c mu nu sa (do s kt hp ca mu vng sm ca phc [KI
3
]
v mu trng hng ca kt ta CuSCN). Sp ti im tng ng quan st thy mu vng nht
ging mu ve tng ( do mu vng nht ca lng I
2
cn t trong dung dch ha vi mu c
phn hng ca kt ta CuSCN). Khi cho ch th h tinh bt vo dung dch c mu xanh tm(do
s to phc ca h tinh bt vi I
2
nng thp). Khi ht I
2
dung dch c mu phn hng ca kt
ta CuSCN. Lu : trong dung dch cn c nh hng ca mu xanh l m ca mui Cr
3+
. (tuy
nhin chp nhn gii thch b qua nh hng ca mu ny).
4. C nn pha long dung dch trong bnh chun iot trc khi chun khng?
Khng nn. Khng c ti liu no ni v vic pha long nhm gim nh hng mu ca ion Cr
3+
trong dung dch. Vic pha long s gy sai s m (chun thiu Na
2
S
2
O
3
c th t 0,5-1,0 ml
so vi khng pha long). iu ny c th do nguyn nhn sau y: phn ng loi b kt ta CuI
l phn ng thun nghch
(CuI)
n
I
2
+n SCN
-
n CuSCN

+I
2
+nI
-
Khi tin hnh pha long dung dch th nng SCN
-
t do gim nhanh hn I
-
( do SCN
-

chuyn vo kt ta CuSCN) kt qu l cn bng dch chuyn sang tri (to ra nhiu CuI hn so
vi khng pha long). Lng CuI trong bnh chun iot cng nhiu th lng I
2
b gi cng
ln. Dn n kt qu chun b thiu.
5. Cc sai s chnh c th mc phi trong bi th nghim ny?
Cc sai s chnh c th l:
+ khng nhanh chng y np ngay v tia nc ct ln ming loe. Nh th, I
2
sinh ra rt d
thng hoa mt, chun s b sai s m (thiu ht)
+ Khng nhanh chng a bnh vo bng ti ngay. Ban u lng axit cn ln, vic phi
nh sng c th lm phn ng ph xy ra nhanh hn, O
2
trong khong khng gian trng trong
bnh chun c th oxi ha to thm1 phn I
2
gy sai s dng (tha).
+ Sai s do cho ch th h tinh bt vo qu sm v chun qu nhanh sau khi thmch
th h tinh bt. Vic cho ch th qu sm slm cho lng ln I
2
b gi do to phc vi h tinh
bt, s nh hp lng I
2
ny l chm do nu chun nhanh s mc phi sai s dng rt ln.
Bi th nghim 7
Chun dung dch Cl
-
bng dung dch AgNO
3
theo 2 phng php.
Trong bi th nghim ny, chng ta s lm quen vi phng php chun kt ta. Phng
php chun kt ta da trn phn ng to thnh cht kt ta trong qu trnh chun .
p dng phn ng to kt ta vo qu trnh chun th cc phn ng phi c tc
phn ng nhanh, xy ra tc thi, cc kt ta phi c thnh phn xc nh tng ng vi cht ch
th cho php. tha mn nhng yu cu trn th cho n nay ch c mui bc t tan thng
c s dng xc nh bc v nhng ion nh clorua, bromua, ioua v tioxianat. ng dng
nhng phng php chun kt ta trong cht chun khng phi l mui bc m l nhng
hp cht khc cn tng i hn ch.
ng chun kt ta: l ng biu din s ph thuc ca nng cation Ag
+
(thng biu
din di dng pAg = -log [Ag
+
] hoc nng anion cn xc nh theo th tch dung dch chun
AgNO
3
chun thm vo trong qu trnh chun . Cng ging nh cc phng php chun
khc, trong chun kt ta cng xut hin bc nhy pAg ln cn im tng ng. ng
chun c ch cho vic la chn ch th v c php tnh sai s trong chun . xy dng
ng chun da vo tch s tan ca kt ta to thnh. Dng ng chun kt ta thng
nh sau:
Bc nhy cng ln th kh nng chun chnh xc cng cao. Bc nhy pAg ph thuc
vo:
- Nng dung dch cn chun v dung dch chun cng ln th bc nhy cng ln
(khang nng 0,1M c nhy thch hp hn c).
- tan ca hp cht kt ta cng nh th bc nhy cng ln.
C s phng php:
Phn ng chun :
Ag
+
+Cl
-
=AgCl

T
AgCl
=1,82.10
-10
im tng ng c xc nh bng cht ch th K
2
CrO
4
(phng php Morh) hoc cht ch
th hp ph Fluorexin.
1. Phng php Mohr
1.1. C s phng php
Trong phng php Mohr, im tng ng c xc nh nh s to thnh kt ta th 2 c
mu khc vi mu ca kt ta chnh. Phng php Mohr c ng dng rng ri khi chun
clorua v bromua bng dung dch bc nitrat chun. Ion cromat c dng lm ch th, im
cui php chun xut hin kt ta bc cromat Ag
2
CrO
4
mu gch.
2 Ag
+
+CrO
4
2-
=Ag
2
CrO
4
( gch) T
Ag2CrO4
=1,2.10
-12
tan ca bc cromat cao hn nhiu tan ca bc halogenua. Do , khi chun theo
phng php Mohr, bc cromat cha c to thnh khi thc t tt c halogenua cha kt ta
ht. iu chnh nng cromat c th ngn nga s to thnh bc cromat cho ti khi nng
ion bc cha t ti nng tnh ton l thuyt i vi vng im tng ng khi chun
halogen.
V l thuyt c th tnh ton lng cromat a vo sao cho xut hin kt ta gch ng ti
T da vo phn ng. Ti thi im tng ng nng ca Ag
+
c tnh nh sau:
[Ag
+
] = = =1,35.10
-5
(M)
Khi nng ca ion cromat cn s dng kt ta cromat bc xut hin ng im tng
ng c tnh t tch s tan ca cromat bc:
= =6,6.10
-3
(M)
Nhng trong thc t nng ln hn 5.10
-3
M mu vng m ca ion cromat s cn tr mu
ca bc cromat. Ngi ta thng s dng nng cromat nh hn 0,005 M mt cht. Khng
th tnh ton lng ti thiu cromat cn phi c to thnh m mt c th nhn bit m ch xc
nh c bng thc nghim. V l do ny, ion cromat thng c s dng vi nng thp
hn. V vy, i hi mt lng d nitrat bc xut hin kt ta v lng d ny phi thy
c mu ca kt ta mu gch. Cc yu t ny to ra mt sai s h thng dng. Sai s
ny l ng k khi phng php Mohr c p dng trong phm vi nng nh hn khong
0,1M. Cng cn lu rng: theo tnh ton l thuyt th vi sai s 0,1% cho php th chun
chnh xc theo phng php Mohr, c th gi nng cht ch th trong mt khong kh
rng, gia 0,0008 v 0,05 M.
iu kin chun :
Phng php Mohr c tin hnh trong mi trng trung tnh hoc kim yu (pH = 7-10).
+nu pH < 6,5 nng ion cromat s gim do phn ng:
H
+
+
(Ion khng to c kt ta vi Ag
+
nn khng lm cht ch th c)
+Nu pH < 2 (mi trng qu axit) th cn bng :
2CrO
4
2-
+2H
+
Cr
2
O
7
2-
+H
2
O
S dch chuyn sang phi lm gim mnh nng ion cromat CrO
4
2-
, tan ca icromat bc
cao hn kh nhiu tan ca cromat bc (thc t Ag
2
Cr
2
O
7
tan trong mi trng axit) do i
vi phn ng ch th trong mi trng axit i hi nng ion bc ln ng k nu phn ng ni
chung c th xy ra, tc l sai s dng rt ln.
+Nu pH > 10 (mi trng kim) c th lng xung oxit bc:
2Ag
+
+ 2OH

= 2AgOH(rn) Ag
2
O(rn, en) + H
2
O
Ag
+
trong dung dch chun tc dng vi mi trng gy sai s rt ln, ng thi mu en ca
Ag
2
O thc t lm che hon ton kh nng quan st im tng ng.
1.2 Cch tin hnh:
Np dung dch chun AgNO
3
0,05N ln buret, ui ht bt kh, chnh vch 0 trc khi tin hnh
chun . Dng pipet ly chnh xc 10,00 ml dung dch mu NaCl cn xc nh nng vo
bnh nn, thmtip khong 0,5-1,0 ml dung dch ch th K
2
CrO
4
5% (bng pipet khng cn chnh
xc). Tin hnh chun , dung dch ban u c mu vng (mu ca ch th K
2
CrO
4
), trong qu
trnh chun xut hin kt ta trng, ng thi thy xut hin kt ta mu gch tc thi ri
tan ngay. Chun cho n khi xut hin kt ta gch khng tan. Ghi li th tch V
AgNO3
tiu
tn, lp li th nghim t nht 3 ln, ly gi tr trung bnh cho qu trnh tnh ton.
1.3. Tnh ton:
= , (N)
= (g/l)
Trong : =10,00 ml
: l th tch AgNO
3
tiu tn c tnh trung bnh t ba ln th nghim l nng
ng lng ca dung dch chun AgNO
3

NaCl
= 58,442 g/ng lng gam
1.4. Cu hi
1, Lng K
2
CrO
4
khi thiu hoc d nhiu nh hng nh th no n kt qu phn tch?
Tr li:
- Nu nng ca [CrO
4
2-
] qu thp s kh quan st thy mu gch, khi quan st r
mu gch th Ag
+
d nhiu gy ra sai s phn tch ln.
- Nu nng ca [CrO
4
2-
] d nhiu th mu vng cam ca K
2
CrO
4
s che lm mt kh
quan st mu gch ca kt ta Ag
2
CrO
4
cng gy sai s ln.
Do nng [CrO
4
2-
] c s dng trong khong gii hn hp hn khong nng tnh ton
l thuyt sai s vo khong 0,1% cho php.
2, Trong trng hp cn chun dung dch HCl bng phng php Mohr th lm th no?
Tr li: vi dung dch HCl ta khng th dng phng php Mohr trc tip c (v mi trng
rt axit). c th s dng phng php Mohr th mt bin php c th s dng l cho lng
mu chnh xc dung dch HCl tc dng d vi dung dch NaHCO
3
ta c dung dch cha NaCl
v NaHCO
3
d. Lc ny pH ca dung dch trong khong pH<10, nh c th s dng c.
(Lu AgHCO
3
l mt mui tan).
HCl +NaHCO
3
=NaCl +CO
2
+H
2
O
2.Phng php Fajans:
2.1 C s phng php
Fajans l phng php da trn s s dng cht ch th hp ph nhn bit im tng ng
ca qu trnh chun . Cht ch th hp ph l nhng cht axit hoc baz hu c yu b kt ta
hp ph hoc c gii hp t b mt kt ta c to thnh trong qu trnh chun , mu ca
cht ch th trng thi t do khc vi mu ca cht ch th khi b hp ph ln b mt kt ta..
Trong trng hp l tng, s hp ph hoc gii hp c quan st thy gn im tong
ng v km theo s bin i mu r rt do s to thnh hp cht mu trn b mt kt ta.
Fluorexin l mt axit hu c yu c K
a
10
-8
, 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 Fluorexin tn ti cn bng:
HFl H
+
+Fl
-
Ion Fl
-
t do trong dung dch gy ln mu hunh quang nh xanh.
Trc im tng ng dung dch d Cl
-
, ht keo kt ta AgCl u tin hp ph Cl
-
nn b mt
c in tch m, do nn khng hp anion c mu ca Fluorexin. Ta vn quan st thy mu nh
xanh hunh quang trong dung dch.
mAgCl +nCl
-
[mAgCl.nCl]
n-
ht keo kt ta mang in tch m
Sau im tng ng dung dch d Ag
+
, ht keo kt ta AgCl hp ph Ag
+
o chiu in tch
nn c in tch dng, lc ny ht keo dng s hp ph Fl
-
ln b mt dn n kt ta c mu
phn hng ng thi tt nh hunh quang (l tng l dung dch tt hon ton nh hunh quang
xanh do Fl
-
b hp ph ht). y l du hiu nhn bit im cui ca qu trnh chun . Nh
vy, chng ta s chun ti khi xut hin mu phn hng trn b mt kt ta (mc sai s
dng).
pAgCl +q Ag
+
[pAgCl.qAg]
q+
[pAgCl.qAg]
q+
+k Fl
-
[pAgCl.qAg.kFl]
(q-k)+
mu phn hng
- iu kin chun :
Phng php Fajans i hi mi trng chun trung tnh hoc kim yu pH = 6,5 10.
+Nu mi trng axit pH < 6,5 th cn bng HFl H
+
+Fl
-
s dch chuyn theo chiu nghch
lmgim nng ion ch th Fl
-
+Nu mi trng kim cao pH > 10 s gy kt ta AgNO
3
:
2Ag
+
+ 2OH

= 2AgOH(rn) Ag
2
O(rn, en) + H
2
O
Lu : Khi c s dng lm cht ch th Fluorexin ch c s dng hm lng nh
quan st r mu. Vic s dng qu nhiu ch th Fluorexin c th lm cho vic quan st im
tng ng khng thc hin c. ( mt phn do Fl
-
d khng b hp ph c mu hunh quang
che kh nng quan st mu phn hng ca dng hp ph trn b mt kt ta).
ng dng thnh cng cht ch th hp ph th cht kt ta v ch th cn c nhng tnh cht
sau:
- Nhng ht kt ta phi c c kch thc ca ht keo bi v b mt ca kt ta pht trin
mnh, hp ph c lng ln cht ch th.
- Kt ta phi hp ph bn cc ion ring bit, tnh cht l c trng i vi kt ta keo.
- Cht mu dng lm cht ch th cn phi c gi chc trong lp ion i bao quanh nhng
ion b hp ph u tin.
Php chun vi cht ch th hp ph nhanh, chnh xc, ng tin cy nhng ng dng ca n
tng i b hn ch bi s t phn ng kt ta c kt ta v nh hnh c to thnh nhanh
chng. Khi c mt cht in li nng cao, im cui ca php chun vi cht ch th hp
ph tr nn km r rng do s ng t kt ta lm gim b mt trn xy ra qu trnh hp ph.
Phn ln cc cht ch th hp ph l axit yu, do lnh vc ng dng ca chng b gii hn
trong cc dung dch trung tnh hoc axit yu v cht ch th ch yu tn ti dng anion.
Ngi ta bit mt s ch th hp ph cation chun trong cc dung dch axit mnh. Vi
nhng cht ch th , s hp ph cht mu v s nhum mu kt ta c quan st thy khi c
d anion kt ta, ngha l khi cc ht mang in tch m.
2.2 Cch tin hnh
Np dung dch chun AgNO
3
0,05N ln buret, ui ht bt kh, chnh vch 0 trc khi tin hnh
chun . Dng pipet ly chnh xc 10,00 ml dung dch mu NaCl cho vo bnh nn, thmvo
1 git cht ch th Fluorexin, dung dch xut hin hunh quanh nh xanh. Tin hnh chun
cho n khi kt ta nhum mu phn hng th dng li, ghi gi tr V
AgNO3
tiu tn, lp li th
nghim t nht 3 ln, ly gi tr trung bnh tnh ton.
Lu : m bo quan st r c im cui ca qu trnh chun , yu cu khi bt u tin
hnh chun phi lc u tay (khng lc mnh) v khng nn dng li m bo cc ht kt
ta keo khng b keo t li do gi c b mt ln, qu trnh hp ph Fl
-
s hon ton v mu
phn hng s quan st rt r.
2.3 Tnh ton
= , (N)
= (g/l)
Trong : =10,00 ml
: l th tch AgNO
3
tiu tn c tnh trung bnh t ba ln th nghim
l nng ng lng ca dung dch chun AgNO
3

NaCl
= 58,442 g/ng lng gam
2.4 Cu hi
Bi th nghim 8
Chun EDTA. Xc nh nng EDTA bng ZnSO
4
. Xc nh cng
chung ca nc bng EDTA
EDTA l tn vit tt ca ethylenediaminetetraacetic acid (cn gi l complexon II), n l mt
cht hu c c kh nng to phc bn t l hp phn 1:1 vi hu ht cc ion kim loi (t l lun
lun l 1:1 khng phn bit ha tr v in tch ca ion kim loi). Hai iu cc k quan trng:
l EDTA to phc bn nn n p ng c yu cu chun (phn ng to phc coi nh hon
ton) v t l hp phn lun l 1:1 nn cho php tnh c nng tng cc ion kim loi theo
nh lut tc dng ng lng m ko cn quan tm ha tr ca ion kim loi. Chnh v th n
c s dng rt rng ri trong ha phn tch. EDTA l mt amino axit a chc (4 nhm
cacboxyl, 2 nhm amin) cng thc phn t trng thi trung ha in tch l H
4
Y. Ty theo cc
iu kin pH khc nhau m n phn li trong dung dch cc khc nhau ( t H
6
Y
2+
, H
5
Y
+
.n
Y
4-
). Ngha l trong dung dch bt c pH no cng u tn ti tt c cc dng ny, nhng ty
theo pH no m dng no chim u th. EDTA l mt a axit c cc mc phn ly:
pK
1
=0,0
pK
2
=1,5
pK
3
=2,0
pK
4
=2,66
pK
5
=6,16
pK
6
=10,24
Lu rng: 4 nc u l do s phn ly H
+
ca cc nhm COOH, 2 nc cui l s phn ly ca
nhm NH
+
.
V EDTA dng axit tan rt km trong nc. tan ca n ch gii hn 0,5g/L nhit
phng v dung dch c pH = 2,7. Vic trung ha EDTA bng cc baz chng hn nh amoniac,
etylen diamin hay NaOH s to ra cc mui v ci thin tan ca EDTA trong nc. Do ,
tc nhn c s dng ph bin trong ha phn tch l dng mui hai natri Na
2
H
2
Y.2H
2
O
(cn gi l complexon III). Complexon III k hiu l Na
2
H
2
Y (372,25 g/mol). y l cht c
tinh khit lm dung dch chun. Tuy nhin, trong qu trnh pha chun c rt nhiu nguyn
nhn c th lm sai lch nng ca dung dch pha nn tt hn c l sau khi pha c dung dch
complexon III n nh ta c th chun li nng complexon III bng dung dch chun
ZnSO
4
.
Phn ng to phc ca EDTA vi ion kim loi:
Zn
2+
+Y
4-
ZnY
2-
Fe
3+
+Y
4-
FeY
-
Nh vy cn hiu l phn ng to phc thc s l phn ng gia ion kim loi v gc EDTA
4-
(Y
4-
). Do , nng ion Y
4-
cng ln th phc cng bn v phn ng cng hon ton. Ta bit
rng nng Y
4-
trong dung dch li ph thuc vo pH ca dung dch, pH ca dung dch cng
ln th s phn ly ca EDTA cng hon ton tc l phc cng bn.
- Hng s bn ca phc cht
Gi s c phn ng to phc :
Khi ta thy hng s bn ca phc chnh l t s gia nng cn bng ca phc [MY
n-4
] chia
cho tch nng ion kim loi t do [M
n+
] v nng anion EDTA t do [Y
4-
] ti v tr cn bng.
Hng s bn ny thng rt ln ~ 10
-20
nn nng kim loi t do [M
n+
] v nng anion
EDTA t do [Y
4-
] l rt nh so vi nng cn bng ca phc [MY
n-4
].
Tuy nhin, [Y
4-
] li ph thuc vo pH ca dung dch theo phng trnh :
Trong [EDTA] l tng nng ca cc dng ( t H
6
Y
2+
, H
5
Y
+
.n Y
4-
) t do trong dung
dch ti im cn bng (ch khng phi nng EDTA ban u).
[Y
4-
] nng dng Y
4-
t do ti im cn bng.
o
Y4-
l phn mol ca dng Y
4-
tnh theo cng thc sau:
Hoc n gin hn:
6 5 4 3 2 1 5 4 3 2 1 4 3 2 1
2
3 2 1
3
2 1
4
1
5 6
6 5 4 3 2 1
. . . . . . . . . ]. [ . . . . ] [ . . . ] [ . . ] [ . ] [ ] [
. . . . .
4
K K K K K K K K K K K H K K K K H K K K H K K H K H H
K K K K K K
Y
+ + + + + +
=
+ + + + + +

o
Nh vy, o
Y4-
l hng s ti 1 gi tr pH nht nh, thay tr li cng thc trn ta c:
Hng s K
f
gi l hng s cn bng c iu kin ca phc complexon, hng s cn bng c iu
kin ny ch ph thuc vo gi tr pH ca dung dch; ti 1 gi tr pH ca dung dch v ty thuc
vo bn cht ca ion kim loi to phc ta c hng s cn bng c iu kin tng ng. R
rng l khi pH ca dung dch cng ln th [H
+
] cng nh, tc l mu s cng nh, trong khi t s
l khng i. Do vy, pH cng ln th o
Y4-
cng ln, tc l K
f
cng ln, phc cng bn. Ti pH
=14 th o
Y4-
c coi nh bng 1 khi K
f
= K
f
. Tm li mun phc complexon bn th phi
to mi trng pH cng cao cng tt.
* Cht ch th trong phng php EDTA
xc nh c im tng ng trong phng php chun EDTA ngi ta s dng mt
s loi ch th trong c bit l cht ch th mu kim loi. Cht ch th mu kim loi l cc cht
mu hu c c kh nng to vi ion kim loi phc c mu, mu ca dng phc khc vi mu ca
dng t do ca cht ch th trong dung dch. Cht ch th mu kimloi thng l nhng axit hu
c yu hoc baz yu, phn t ca chng cha nhng nhm mang mu v tr mu, mu ca cht
ch th dng t do thay i theo pH ca dung dch.
Khi chn cht ch th mu kim loi cho chun EDTA th phi tun theo yu cu sau:
- Chn pH thch hp (bng cch s dng dung dch m ph hp) m bo phc
complexon l bn tc l phn ng to phc vi ion kim loi cn xc nh l hon ton.
- Cht ch th trng thi t do trong mi trng pH ny phi c mu khc vi mu ca
phc ca cht ch th vi ion kim loi . Mu sc phi d phn bit v s i mu ca cht ch
th phi xy ra rt gn im tng ng.
- Phc to bi cht ch th v ion kim loi phi km bn hn phc to bi EDTA v ion
kim loi tng ng.
Mt trong cc ch th mu kim loi in hnh l Eriocrom en T (ET-00) k hiu l H
3
Ind, l
mt a axit yu, anion Ind
3-
c mu da cam, c kh nng to phc vi kim loi to phc mu
hng tm (hay nho).
V d:
trng thi t do Ind
3-
phn ng vi H
+
to thnh cc dng axit c mu khc nhau:
pH >11,5 trong dung dch s tn ti ch yu dng Ind
3-
c mu da cam.
Nh vy, ty theo mi trng pH m dng axit no s chim u th v ta s quan st c mu
ca dng .
Bi 1. Xc nh nng complexon III bng dung dch chun ZnSO
4
I. C s phng php
Trc khi chun , mt lng nh cht ch th ET00 c thm vo dung dch khng mu Zn
2+
to ra mt lng nh phc mu . Khi complexon III c thm vo, u tin n phn ng
vi Zn
2+
t do. Khi ht Zn
2+
t do, complexon III thm vo thay th cht ch th HInd
2-
trong
phc mu ZnInd
-
. S thay i t mu ca phc ZnInd
-
sang mu xanh ca HInd
2-
trng
thi t do l du hiu kt thc chun .
Phng trnh phn ng chun : Na
2
H
2
Y =2Na
+
+H
2
Y
2-
Zn
2+
+H
2
Y
2-
ZnY
2-
+2H
+
Phn ng ch th: - ban u Zn
2+
+HInd
2-
ZnInd
-
+H
+
(xanh trong) (hng tm)
-ti T H
2
Y
2-
+ZnInd
-
ZnY
2-
+HInd
2-
+H
+
(hng tm) (khng mu) (xanh trong)
iu kin chun :
duy tr pH ca dung dch trong khong t 8-10 bng dung dch m NH
4
Cl +NH
4
OH :
+ m bo hng s bn c iu kin ca phc complexon l ln, nh phn ng xy ra hon
ton (m bo yu cu phn tch). Cn lu rng khong pH ny hng s bn c iu kin ca
phc complexon l ln nht, tc l phc complexon l phc bn nht trong cc phc nn
complexon III c th y c Ind
3-
to phc complexon bn hn.
+ m bo mi trng pH thch hp dng t do ca cht ch th l HInd
2-
mu xanh trong,
nh vy mt thng s quan st s i mu r rt ln cn im tng ng, dung dch i t
mu hng tm sang xanh trong.
( pH =7-11 )
( pH<6 )
+ khong pH 8-10, ion Zn
2+
rt d thy phn to hydroxit, hydroxit km th bn vng khng
to phc c vi complexon do vy s dn n sai s. ngn nga hin tng ny, ta phi s
dng dung dch m NH
4
Cl +NH
4
OH, NH
3
d trong dung dch m s to phc amiacat s b
vi Zn
2+
nh vy m trnh c kt ta Zn(OH)
2
.
Lu : trong qu trnh chun lun gii phng H
+
do mun gi c pH ca dung dch n
nh bt buc phi dng dung dch m.
II. Cch tin hnh:
Np dung dch Complexon III vo buret, ui bt kh v chnh v vch 0 trc khi tin hnh
chun. Dng pipet ly chnh xc 10,00 ml dung dch chun ZnSO
4
0,05N cho vo bnh nn,
thmtip khong 5-7 ml dung dch m NH
4
Cl +NH
4
OH (dng ng ong), lc nh v quan st
nu thy dung dch xut hin kt ta nhy th phi tip tc cho thm dung dch m cho n khi
trong sut, thm tip 1 git cht ch th ET-00, dung dch c mu hng tm. Tin hnh chun
cho n khi dung dch chuyn t mu hng tm sang xanh trong, ghi li th tch complexon III
tiu tn. Lp li th nghim t nht 3 ln.
III. Tnh ton
V
Zn
2+
ly chun : . 10,00 . ml c nng chun N
Zn
2+
=. .0,05N .
V
H
2
Y
2
dng sau cc ln chun :
Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh: . . . . . .. . . . . . ml
Nng ca dung dch H
2
Y
2-
(Lp cng thc tnh)
N
H
2
Y
2-
= =
IV. Cu hi:
1. Dung dch m l g? C ch n nh pH?
Dung dch m l dung dch c kh nng duy tr pH n nh (pH thay i khng ng k) khi
thmvo dung dch 1 lng nh dung dch axit hay baz mnh. Dung dch m c to
thnh khi pha mt hn hp gm 1 axit v 1 baz lin hp vi n ( v d dung dch hn hp
CH
3
COOH +CH
3
COONa) hay mt hn hp gm 1 baz v 1 axit lin hp vi n ( v d hn
hp NH
4
OH v NH
4
Cl). Dung dch m ch c hiu qu r rt khi t l hp phn gia 2 thnh
phn (t l axit/bazo lin hp) trong khong 1-10 ln.
C ch n nh pH ca dung dch m.
Ta xt cc cn bng trong dung dch m.
(1) K
a
(2) K
b
Ta nhn thy rng 2 cn bng trn l tng h, cn bng ny nh hng n cn bng kia v
ngc li.
Xt cn bng ca phn ng (1) ta c:
Phng trnh c thit lp gi l phng trnh Henderson-Hasselbalch
(*)
Nu xt cn bng ca phn ng (2) th ta li c (*), lu [OH
-
] =Kw/[H
+
] =10
-14
/[H
+
] v
K
a
.K
b
=Kw =10
-14
( v y l axit bazo lin hp)
T phng trnh (*) ta nhn thy rng pH ca dung dch ch ph thuc t s gia dng
baz/dng axit trong dung dch (do pK
a
l hng s ch ph thuc bn cht ca axit). Khi t s
ny thay i 10 ln th pH ca dung dch ch thay i 1 n v, khi t s ny thay i 100 ln
th pH ca dung dch thay i 2 n v. R rng ta phi thay i t s [A
-
]/[HA] rt nhiu nu
mun pH thay i ch vi n v. iu gii thch ti sao dung dch m c kh nng chng
li s thay i pH. Thc t, vi dung dch m cha cp axit bazo lin hp yu, bng vic
pha hn hp vi nng bng nhau ta c [A
-
] ~ [HA] nn pH s c duy tr pH ~ pK
a
.
Trong trng hp m NH
4
OH v NH
4
Cl c pK
a
=9,245. Ta s c dung dch m duy tr pH
khong 8-10 (pKa 1).
2. Ti sao phi gi n nh pH trong khong t 8-10 bng dung dch m NH
4
Cl/NH
4
OH?
m bo c th phn tch chnh xc ta phi m bo hng s bn c iu kin ca phc
kim loi (Zn
2+
) vi EDTA l ln nht, do phi duy tr pH cao. Mt khc, vic chn
pH cn ph thuc vo dng mu t do ca cht ch th mu sao cho mt quan st s thay i
mu r rt nht, trong trng hp ny vi ch th ET-00, ti im tng ng s thay i
mu t hng tm sang xanh trong l r rt nht trong khong pH t 7-11. Ngoi ra, i vi
ion kim loi, pH cao ca dung dch rt d dn ti s thy phn to hydroxit kim loi lm
ngn cn s to phc ca ion kim loi vi EDTA, do s c mt ca NH
3
gip ngn nga
qu trnh thy phn do s to phc s b [Zn(NH
3
)
4
]
2+
. Tm li, tha mn c cc yu
cu trn ta chn dung dch m NH
4
Cl/NH
4
OH.
Bi 2. Xc nh cng ca nc bng dung dch complexon III
cng ca nc l tng nng ion kim loi kim th (nhm II) trong nc. Bi v nng
ca ion Ca
2+
, Mg
2+
thng ln hn rt nhiu cc kim loi kim th khc, cng chung ca
nc c th nh ngha l s mili ng lng gam (mN) Ca
2+
v Mg
2+
trong mt lt nc.
Nc c cng nh hn 60 mg CaCO
3
/L c th coi l nc mm. Nu cng l hn 270
mg/L, nc c cho l cng. cng ring cp n nng ca mi ion kim loi kim th
trong nc. Nc cng khng c php dng trongni hi v khi un si nc cng th canxi
cacbonat (CaCO
3
) vmagie cacbonat (MgCO
3
) s kt ta bm vo pha trong thnh ni hi
supde (ni ct, m nc, bnh ng...) to thnh mt mng cn cch nhit, lm gim h s cp
nhit, c khi cn lm n ni hi. Nc cng cng khng dng pha ch thuc v c th gy kt
ta lm thay i thnh phn ca thuc. Khi dng nc cng nu lm rau, tht kh chn; lm mt
v ca nc ch. Git bng nc cng tn x phng do Ca
2+
lm kt ta gc axit trong x phng
v lm x phng khng ln bt. Nhiu cng ngh ho hc cng yu cu nc c cng nh.
Nu cng vt gii hn cho php (tu mc ch s dng) th phi lm mm ha nc cng
bng cch cho kt ta Mg
2+
v Ca
2+
vi soa (Na
2
CO
3
), photphat hoc tch chng bng nha
trao i ion hoc un si.
2.1. Xc nh cng chung ca nc
I. C s phng php:
Trc khi chun , mt lng nh cht ch th ET-00 c thm vo mu nc phn tch Ca
2+
v Mg
2+
to ra mt lng nh phc mu (CaInd
-
v MgInd
-
). Khi complexon III c thm
vo, u tin n phn ng vi Ca
2+
v Mg
2+
t do. Khi ht Ca
2+
v Mg
2+
t do, complexon III
thm vo thay th cht ch th HInd
2-
trong phc mu CaInd
-
v MgInd
-
. S thay i t
mu ca phc CaInd
-
v MgInd
-
sang mu xanh ca HInd
2-
trng thi t do l du hiu
kt thc chun .
Phng trnh phn ng chun : Na
2
H
2
Y =2Na
+
+H
2
Y
2-
Ca
2+
+H
2
Y
2-
CaY
2-
+2H
+
Mg
2+
+H
2
Y
2-
MgY
2-
+2H
+
Phn ng ch th pH =8-10: - ban u:
H
3
Ind 2H
+
+HInd
2-
Ca
2+
+HInd
2-
CaInd
-
+H
+
(xanh trong) (hng tm)
Mg
2+
+HInd
2-
MgInd
-
+H
+
(xanh trong) (hng tm)
-ti T H
2
Y
2-
+CaInd
-
CaY
2-
+HInd
2-
+H
+
(hng tm) (khng mu) (xanh trong)
H
2
Y
2-
+MgInd
-
MgY
2-
+HInd
2-
+H
+
(hng tm) (khng mu) (xanh trong)
iu kin chun : duy tr pH ca dung dch trong khong t 8-10 bng dung dch m NH
4
Cl
+NH
4
OH :
- m bo hng s bn c iu kin ca phc to bi ion kim loi v complexon III l ln
phn ng xy ra hon ton.
- m bo s i mu ca cht ch th r rt gip d dng quan st T. Vi ch th ET00,
min pH 8-10 m bo s i mu r rt t hng tm sang xanh trong.
Lu : Do hm lng ca ion Ca
2+
v Mg
2+
trong mu nc phn tch nh, do khong pH
ny s thy phn ca cc ion trn khng ng k. ( tc l v mt l thuyt cho php s dng 1
dung dch m khc ngoi NH
4
Cl +NH
4
OH tha mn duy tr pH khong 10 m vn t c
chnh xc yu cu).
II. Cch tin hnh:
Np dung dch complexon III vo buret, ui bt kh v chnh vch 0 trc khi tin hnh
chun .
Bnh nn 250ml, ly chnh xc 100,0 ml mu nc phn tch (s dng bnh nh mc 100ml)
thm vo 5-7 ml dung dch m NH
4
Cl +NH
4
OH, thm tip 4-5 git dung dch ch th ET-00,
lc u cho n khi dung dch xut hin mu hng tm. Tin hnh chun cho n khi dung
dch i mu hon ton t hng tm sang xanh trong. Ghi li th tch complexon III tiu tn. Lp
li th nghim t nht 3 ln, s dng kt qu trung bnh cho tnh ton.
V
Nc phn tch
ly chun : . . . .100,0 . . . . . . . . ml
V
H
2
Y
2
dng sau cc ln chun :
Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh : . . . . . . .. . . . . ml
- cng chung ca nc:
H = = 1000, (mN)
=100,0 ml
: l th tch complexon III tiu tn c tnh trung bnh t ba ln th nghim
l nng ng lng ca dung dch complexon III (xc nh bi 1)
2.2. Xc nh cng ring ca nc
I. Nguyn tc:
xc nh ring hm lng Ca
2+
v Mg
2+
trong nc, trc ht ta xc nh hm lng tng ca
chng trong nc ( cng chung), sau tin hnh xc nh hm lng ring Ca
2+
trong nc.
T tnh ton c ring hm lng Ca
2+
v Mg
2+
trong nc.
xc nh c ring hm lng Ca
2+
trong nc ta lp lun nh sau: do s khc bit v tch
s tan ca dng Ca(OH)
2
(T=10
-5.19
) v dng Mg(OH)
2
(T=10
-9.2
), do trong iu kin hm
lng thc t trong nc Ca
2+
v Mg
2+
ta c th a pH ca dung dch > 12 kt ta hon ton
dng Mg
2+
thnh Mg(OH)
2
trong khi dng Ca
2+
cha h b kt ta. Mg
2+
b kt ta khng cn
kh nng to phc vi EDTA na, vy ch cn Ca
2+
c kh nng to phc vi EDTA, bi ton
tr v xc nh hm lng Ca
2+
.
Chn cht ch th: do mi trng dung dch phn tch lun phi m bo pH > 12 trong sut qu
trnh phn tch Mg(OH)
2
khng tan tr li, nn ch th ET00 khng cn ph hp na. Trong
trng hp ny ta s dng ch th Murexit. Murexit l a axit c pK
a1
=0; pK
a2
=9,2; pK
a3
=
10,9; nn mu ca cht ch th ph thuc vo pH ca dung dch.
pH < 9,2 Murexit phn ly dng H
4
In
-
, c tm (red-violet)
pH =9,2-10,9 Murexit phn ly dng H
3
In
2-
, c mu tm hoa c (violet)
pH > 10,9 Murexit phn ly dng H
2
In
3-
, c mu xanh tm (blue)
Murexit to phc mu nho vi Ca
2+
H
3
In
2-
+ Ca
2+
CaIn
3-
+ 3H
+
( nho)
Thng thng murexit c chun b di dng ch th rn bng cch nghin trn hn hp t l
10mg murexit vi 5g NaCl. Khong 0.2g ch th c dng cho mi ln chun .
Trc khi chun , 5 ml NaOH 2N c thm vo mu nc phn tch (100ml) kt ta ht
Mg
2+
dng Mg(OH)
2
[theo tnh ton pH s t c khong 13]. Mg(OH)
2
kt ta v khng th
tip cn vi EDTA. Sau mt t cht ch th murexit c thm vo to ra mt lng nh
phc mu vi Ca
2+
. Khi complexon III c thm vo, u tin n phn ng vi Ca
2+
. Khi
ht Ca
2+
t do, complexon III thm vo thay th cht ch th murexit trong phc mu
CaIn
3-
. S thay i t mu ca phc CaInd
-
sang mu tm ha c trng thi t do ca cht
ch th l du hiu kt thc chun .
Phn ng chun : Mg
2+
+2OH
-
=Mg(OH)
2
+
Na
2
H
2
Y =2Na
+
+H
2
Y
2-
Ca
2+
+H
2
Y
2-
CaY
2-
+2H
+
Phn ng ch th: - ban u: H
3
In
2-
+ Ca
2+
CaIn
3-
+ 3H
+
( nho)
- ti T: H
2
Y
2-
+CaIn
3-
+H
+
CaY
2-
+H
3
In
2-
(tmhoa c)
II. Cch tin hnh
Np dung dch complexon III vo buret, ui bt kh v chnh vch 0 trc khi tin hnh
chun .
Bnh nn 250ml, ly chnh xc 100,0 ml mu nc phn tch (s dng bnh nh mc 100ml)
thm vo 5-7 ml dung dch NaOH 2N (pH >12), thm tip 1 t ch th Murexit v lc u,
dung dch c mu nho. Tin hnh chun cho n khi mu nho chuyn thnh mu tm
hoa c. Ghi th thch complexon III tiu tn, lm t nht 3 ln, ly gi tr trung bnh tnh ton.
III. Tnh ton:
V
Nc phn tch
ly chun : . . . .100,0 . . . . . . . . ml
V
H
2
Y
2
dng sau cc ln chun xc nh Ca
2+
:
Ln 1: . . . . . . . . . . . ml
Ln 2: . . . . . . . . . . . ml
Ln 3: . . . . . . . . . . . ml
Trung bnh : . . . . . . . . . . . ml
N
Ca
2+
=1000 . (nN)
Trong : =100,0 ml
: l th tch complexon III tiu tn c tnh trung bnh t ba ln th
nghim ( to phc ring vi Ca
2+
).
l nng ng lng ca dung dch complexon III (tnh ton
bi 1).
V
H
2
Y
2
dng sau cc ln chun xc nh Mg
2+
:
Vcomplexon III (Mg
2+
) =Vcomplexon III (Ca
2+
, Mg
2+
) Vcomplexon III (Ca
2+
)
N
Mg
2+
=H - N
Ca
2+
(nN)
III. Cu hi
1. Phng php chun EDTA c th dng xc nh Al
3+
, Fe
3+
c khng?
Tr li: v mt l thuyt th EDTA c th to phc vi nhng kim loi ny gn nh hon ton,
tc l tha mn iu kin chun . Tuy nhin, y l nhng kim loi thy phn mnh in hnh
(c bit pH cao), nu tin hnh iu kin pH thp th phn ng to phc din ra qu chm
v khng hon ton. Do , phng php chun EDTA khng th p dng c. Trong
trng hp xc nh Al
3+
bng chun EDTA ngi ta dng phng php nh phn ngc.
Bi th nghim 9
Phng php khi lng. Xc nh nng Fe
3+
vi thuc th NH
4
OH. Xc
nh nng SO
4
2-
vi thuc th BaCl
2
.
I. C s chung
Phn tch khi lng da trn php o khi lng ca hp cht c thnh phn bit, lin quan
v mt ha hc vi cu t cn xc nh. Hp cht c th c tch ra dng tinh khit ha
hc hoc tch ra dng hp cht bn c thnh phn bit trc. Trong phng php phn tch
khi lng, c rt nhiu bin php khc nhau phn tch mt cu t ban u, v d nh tch
cu t ra khi hn hp dng tinh khit ( VD: xc nh hm lng vng trong qung,
ngi ta ph 1 lng chnh xc mu tan hon ton bng nc cng toan 3 phn HCl v 1 phn
HNO
3
, ch ha dung dch bng thuc th thch hp, ri kh chn lc Au ra di dng tinh khit.
em cn v xc nh c %Au trong qung ban u), tch cu t dng kt ta (VD bi ny: 1
lng chnh xc mu Fe
3+
sc chuyn vo dng kt ta Fe(OH)
3
sau em nung hon ton
thnh dng c thnh phn bit trc Fe
2
O
3.
Cn v xc nh c nng Fe
3+
ban u), tch
cu t dng kh (VD 1 lng chnh xc mu hu c c t chy hon ton, s dng bin
php thch hp tch ring c CO
2
bng hp ph kim chng hn, cn khi lng kim trc v
sau hp ph xc nh c CO
2
. T lng cn tnh c %C trong hp cht hu c ban
u)Nh vy c rt nhiu phng php, c s chung l chuyn cu t cn xc nh v dng
bn, tch ra c, c th cn c, tn hiu khi lng s l thng tin cn cho php phn tch.
C s su xa ca phng php phn tch khi lng l da trn nh lut thnh phn khng i
v nh lut tc dng ng lng. Trong nh lut thnh phn khng i, t s khi lng ca
cc nguyn t trong thnh phn 1 cht lun lun nh nhau khng ph thuc vo con ng to
nn cht (V d d nc c tng hp bng phng php no th t s khi lng H:O lun
l 1:8). iu c ngha l khng cn quan tm n vic to ra dng cn bng phng php no
ta lun c th tnh c khi lng ca cu t trong dng cn v khi lng chnh l khi
lng ca cu t trong hp cht ban u. nh lut tc dng ng lng ni rng: khi lng
cc nguyn t tham gia phn ng lun lun khng i v t s gia chng khng thay i. iu
c ngha l ta c th tnh ton c cc dng khc nhau tng ng theo t lng phn ng ca
chng.
Cn lu rng: Ngi ta chia thnh hai nhm cc phng php phn tch khi lng l nhm
cc phng php kt ta v nhm cc phng php chng ct. Trong nhm cc phng php kt
ta, cu t cn xc nh tham gia vo phn ng ha hc vi thuc th to thnh sn phm t tan;
sau lc v thc hin nhng ng tc cn thit khc v cui cng cn kt ta rn c thnh phn
ha hc bit. Trong nhm cc phng php chng ct, cu t cn xc nh c tch ra khi
mu dng kh: trong trng hp ny, php phn tch hoc l da trn php xc nh trng
lng cht c ct ra, hoc l da trn php xc nh trng lng cht cn li.
Trong nhm phn tch khi lng phng php kt ta cn phn bit 2 khi nim l : dng
kt ta v dng cn. Dng kt ta l dng t tan thu c sau khi s dng thuc th, cn dng
cn l dng thu c sau khi nung sn phm t tan . Vy thng thng dng kt ta s khc vi
dng cn (i khi c th dng kt ta trng vi dng cn). Vn cn phi tin hnh qu trnh nung
th mi o c chnh xc bi v thc t dng kt ta thng cha tp cht khng bn v nc (
qu trnh nung s loi b hon ton cc tp cht khng bn v nc ln trong dng kt ta).
Phng php phn tch khi lng l phng php tim cn n chnh xc tuyt i?
ng vy, khi tin hnh phng php phn tch th tch ta lun phi s dng dung dch chun c
nng bit trc xc nh dung dch khc. Mt cu hi nghi vn t ra: dung dch chun
ny chun cha? T li phi xc nh li nng dung dch chun bng mt dung dch
chun khc. Cu hi nghi vn na: chun chun cha? Nh vy th chun l ty thuc
vo kh nng to c 1 dung dch chun chnh xc. So vi phng php phn tch th tch th
phn thch khi lng li khng cn cht chun m ch da trn vic o tn hiu khi lng nh
cn phn tch, cho n nay cng vi s pht trin vt bc ca khoa hc cng ngh th k thut
cn t n chnh xc rt cao. Chnh v vy, phng php phn tch khi lng cho n
nay thng cho kt qu chnh xc cao nht so vi cc phng php phn tch khc, v do n
thng c coi l phng php trng ti phn x trong trng hp c sai lch ln gia cc
phng php khc nhau cng nh gi 1 vn .
Cn lu : phng php phn tch khi lng l phng php v lng (s dng lng ln)
nn dng lng mu cng ln th cng chnh xc. Tuy vy nu dng nhiu mu qu thng gy
kh khn cho qu trnh thao tc (lc, tch, nung), ty theo cc trng hp c th ngi ta a
ra lng mu ti u (lng mu ph hp vi sai s nh):
- i vi dng kt ta tinh th th lng mu c tnh theo cng thc thc nghim:
M
A
: khi lng mol ca cht cn xc nh m,n: cc h s cn bng ca phng trnh
phn ng
M
B
: khi lng mol ca dng cn 0,5: h s thc nghim vi kt ta tinh th
Th d: tnh lng mu CaCO
3
cn ly phn tch hm lng Ca bng phng php khi
lng, to kt ta tinh th CaC
2
O
4,
dng cn CaO.?
- i vi dng kt ta v nh hnh th khi lng mu cn ly tnh theo cng thc thc nghim:
M
A
: khi lng mol ca cht cn xc nh m,n: cc h s cn bng ca phng trnh
phn ng
M
B
: khi lng mol ca dng cn 0,1: h s thc nghim vi kt ta v nh
hnh
Th d : tnh lng mu Fe(NO
3
)
3
.9H
2
O cn ly phn tch hm lng Fe bng phng php
kt ta, to kt ta v nh hnh Fe(OH)
3
vi dng cn Fe
2
O
3
?
Tha s chuyn F:
M
A:
khi lng mol ca cht cn xc nh, M
B:
khi lng mol ca dng cn
m,n: cc h s tng ng
Tha s chuyn F l t s gia khi lng mol ca cht cn xc nh (nhn vi h s tng ng)
v khi lng mol ca dng cn. N cho bit 1 gamdng cn cha F gam cht cn xc nh.
Tha s chuyn cho php ta chuyn khi lng mol ca dng cn sang khi lng cht ta cn
xc nh mt cch nhanh chng.
Th d: tnh khi lng Fe trong 2,56g Fe
2
O
3
? Ta c: tha s chuyn F =(2*56)/160 =0,65.
Khi lng Fe =m dng cn * F =2,56*0,65 =1,664 (g)
II. Cc yu cu ca phng php phn tch khi lng
Cng ging nh cc phng php phn tch khc, phng php phn tch khi lng yu cu
phn ng to kt ta phi hon ton (hoc coi nh hon ton). Tc l nguyn t cn phn tch
phi c chuyn hon ton vo dng kt ta. Nh vy, vic chn thuc th no cho phn tch
nguyn t no phi c nghin cu kho st mt cch t m c tnh ton t c cc yu cu
c th di y:
Yu cu chung cho dng kt ta:
- Kt ta phi c tan nh ta c hon ton ( tan l lng cht c th tan ti a trong 1
th tch xc nh dung dch 1 iu kin c th. Nh th tan nh th lng kt ta mt mt l
t, sai s nh). Mun vy khi tin hnh to kt ta phi chn cc iu kin thch hp nh pH ti
u, nng thuc th ph hp v phi dng d thuc th m bo kt ta hon ton. Thng
thng mt kt ta c chn phn tch khi lng phi c tan < 10
-8
M.
- Kt ta c tinh khit cao, t b hp ph hay ln tp bn. Ch c nh vy th dng cn mi c
thnh phn xc nh ng vi ng cng thc ha hc ca n. Khi kt ta hnh thnh b mt kt
ta thng khng n nh do cha bo ha lin kt nn c xu hng hp ph v ko theo cc tp
bn trn b mt v trong lng kt ta (cha tp trong cc l xp). Hin tng ny gi l s cng
kt. S cng kt rt phc tp s c bn c th sau.
- Kt ta cn c kch thc ln d lc, khng b mt mt trong qu trnh lc, ra. Thng
thng kch thc ht < 1 m thng d dng chui qua c giy lc, do phi m bo kch
thc ht kt ta c vi m tr ln.
- Kt ta phi c th c chuyn sang dng cn 1 cch d dng v hon ton.
Yu cu chung ca dng cn:
- Dng cn phi bn vi mi trng, khng b ht m, khng b ph hy. c th tin hnh
cn c chnh xc khi lng dng cn trong iu kin thc t yu cu dng cn phi bn trong
gii hn cho php.
- Dng cn phi c cng thc xc nh, c thnh phn khng i v tnh c chnh xc tha s
chuyn. Mun vy dng kt ta phi tinh khit v phi chn c iu kin nung ph hp to
ra dng cn mong mun (c thnh phn xc nh v tinh khit cao),
- Tha s chuyn F ng vi dng cn cng nh th cng tt. Khi tha s chuyn F cng nh th sai
s ca phng php cng nh (tc l chnh xc cng cao). Do ta phi chn dng cn u tin
c F nh nht.
Yu cu chung vi thuc th:
- L tng nht thuc th cn tc dng chn lc vi cht cn phn tch. iu ny rt kh thc hin
c, trong trng hp thuc th c th to kt ta vi nhiu ion trong dung dch th phi c
bin php che ph hp. Ni chung thuc th c chn sao cho to ra sn phm c tan b,
u tin to ra kt ta tinh th (do d lc ra, t ln tp), kt ta tr vi mi trng (VD: kh tan
trong axit, kim), kt ta d to ra dng cn ph hp sau khi nung.
- m bo kt ta hon ton thng thuc th phi dng d 10-15% tr ln. i vi thuc th
d bay hi (VD: dung dch NH
3
) th phi dng d 2-3 so vi l thuyt.
- S nhim bn kt ta:
Trong thc t khi tin hnh phn ng kt ta, kt ta thng tch ra khi dung dch khng hon
ton tinh khit m thng ln tp cht. S ln tp cht ny c chia thnh 2 loi: s cng kt v
s kt ta theo.
S cng kt l hin tng cc tp cht ng thi b kt ta cng vi kt ta chnh v ln vo kt
ta chnh. S cng kt c chia lm nhiu loi : s cng kt b mt, s cng kt trong, s cng
kt c hc v hin tng ni hp.
+ S cng kt b mt: l s hp ph cc tp cht trn b mt ca kt ta. Nguyn nhn l do b
mt kt ta cha bo ha lin kt nn c xu hng hp ph cc cht trn b mt tr ln bn
vng. Hin tng hp ph b mt ny a phn l hp ph vt l (ta nhit v c nng lng lin
kt yu, thun nghch). Do , loi b hin tng ny ngi ta c th tin hnh un nng
dung dch ngn cn qu trnh hp ph (do nhit tng xu hng hp ph gim); c th ha
long dung dch gim nng cc tp cht trn b mt kt ta; gim din tch b mt ca ht
kt ta bng cch tng kch thc ht (lu rng kch thc ht ca kt ta cng ln v ht cng
c t l xp th din tch b mt cng nh); s hp ph ny cn ph thuc bn cht ca cc ion
trong dung dch, thng thng u tin hp ph cc ion c cng bn cht vi thnh phn cu to
ca kt ta.
+S cng kt trong: c 2 loi cng kt trong l cng kt do phn ng gia thuc th d vi cht
cn phn tch v cng kt ng hnh (do kt ta v tp cht l nhng cht ng hnh vi nhau c
kh nng cng kt tinh trong cng mt mng li tinh th).
+S cng kt c hc: trong kt ta thng c cc l xp (mao qun) l ni cha rt nhiu ion l
i vo t dung dch. Sau qu trnh nung cc ion ny s nm trong kt ta dng rn. loi b
cng kt c hc phi tm iu kin to ra kt ta c, t xp (i vi kt ta v nh hnh)
hoc kt ta tinh th hon thin (t b khuyt tt bn trong).
+S ni hp: l hin tng cc tp cht b hp ph su vo bn trong tinh th trong qu trnh cc
tinh th ln ln. V d: nu nh t t BaCl
2
vo dung dch CuSO
4
th kt ta tinh th BaSO
4
c hnh thnh vi nhng mm rt nh. Ban u dung dch s c BaSO
4
, Cl
-
, SO
4
2-
d, Cu
2+
kt
ta s u tin hp ph SO
4
2-
ln trn b mt, SO
4
2-
s hp ph 1 phn Cu
2+
, cc tp cht mi b
hp ph ny s b ln vo kt qu l tinh th BaSO
4
s b ln CuSO
4
. Cn trng hp lm ngc
li, s dn ti Cl
-
s b ln vo tinh th BaSO
4
di dng BaCl
2
.
S kt ta theo: l hin tng kt ta tp cht hnh thnh trn b mt kt ta chnh sau khi lu
kt ta chnh trong dung dch. Nguyn nhn l do: trong iu kin bnh thng cc kt ta tp
cht khng th hnh thnh c do nng ca chng trong dung dch cha t n trng thi
qu bo qu bo ha (cha tha mn iu kin kt ta). Tuy nhin, khi c kt ta trong dung
dch cc ion s b hp ph trn b mt kt ta, kt qu l nng ca chng trn b mt tng v
chng d dng b kt ta. V d cc kt ta hydroxit kim loi, kt ta cacbonat kim loi d dng
b kt ta theo. Cng c th gp l trng hp kt ta Cu
2+
bng S
2-
nu lu CuS trong dung
dch th xut hin thm tp ZnS ln vo. gim nh hng ca kt ta theo, ta phi nhanh
chng lc ra kt ta thu c hoc phi s dng cht ph kt ta theo (v d nh s dng mi
trng axit gim nh hng ca kt ta theo hydroxit v cacbonat kim loi).
- Lc v ra kt ta:
y l cng on quan trng trong phng php phn tch khi lng v kh nng gy sai s ln.
Nhim v ca lc v ra kt ta tch kt ta ra khi dung dch v lm sch kt ta. Ty theo
bn cht kt ta v ln ca ht kt ta chn giy lc ph hp. iu quan trng l khng
kt ta bm qu 1/3 chiu cao giy lc ta c ra hon ton. i vi lng kt ta ln c
th tin hnh lc gn (ch dung dch trong vo giy lc, gi kt ta trong bnh cha). Ra kt
ta l lm sch kt ta, loi b cng kt b mt nn phi chn c dung mi ra thch hp
ty vo tng trng hp. C th chia lm 4 loi dung mi ra:
- Ra bng dung dch ca cht to kt ta: mc d kt ta rt t tan nhng thc ra l c tan vi
tan nh, nu ra bng nc ct th mi ln ra s mt mt mt t kt ta (do tan) do vy ra
nhiu ln s b sai s ln. gim sai s, ngn nga kt ta tan ngi ta chn dung mi ra l
dung dch long ca chnh cht to kt ta. V d: ra 0,1g kt ta CaC
2
O
4
bng 200 ml nc ct
th b mt 1,3% khi lng, nhng nu ra bng 200 ml dung dch long (NH
4
)
2
C
2
O
4
th b mt
khong 0,0067%. (Lu : khng c php ra bng dung dch c Ca
2+
v ta ang phn tch hm
lng Ca). Ngi ta thng chn dung dch c kh nng bay hi khng li tp cht sau khi
nung. Trong trng hp ny (NH
4
)
2
C
2
O
4
s b phn hy hon ton v khng gy sai s cho php
phn tch.
- Ra kt ta bng dung dch cht in ly: nhiu kt ta v nh hnh c kh nng b peptit ha tr
thnh dng keo chui qua c giy lc khi ra bng nc ct, do trnh to keo ngi ta
phi ra bng dung dch cht in ly mnh, thng chn dung dch ca cht in ly c kh nng
bay hi hoc phn hy hon ton sau khi nung nh HNO
3
, NH
4
NO
3

- Ra bng dung dch c kh nng ngn cn s thy phn: mt vi dng kt ta c kh nng thy
phn khi ra bng nc, iu ny dn ti mt mt kt ta hoc lm cho dng cn cui cng
khng cn ng thnh phn xc nh na. trnh hin tng ny ngi ta chn dung dch ra
c kh nng trnh c s thy phn (v cng thng chn cht c kh nng bay hi, phn hy
sau nung). V d: kt ta MgNH
4
PO
4
d b thy phn trong mi trng trung tnh hoc axit,
ra kt ta ny c th dng dung dch NH
4
OH long, cn bng s dch chuyn sang bn tri,
trnh thy phn.
- Ra bng nc ct n thun: loi b cc ion tp th nc ct l dung mi tt nht (v nng
cc ion l trong nc ct rt thp), i vi nhng kt ta c tan rt thp m qu trnh ra
mt mt khng ng k th c th chn nc ct l dung mi ra, hn ch kt ta tan ngi ta
c th dng nc ct lnh.
- Sy v nung:
Sy loi b dung mi, nc v cc tp cht c th bay hi khi kt ta. Vi trng hp ch
cn sy ti khi lng khng i l c th em cn v tnh ton xc nh lng mu ban u.
Tuy nhin, qu trnh sy thng khng loi b nc hp ph su, cc tp cht trn b mt
kt ta, khi cn phi tin hnh nung nhit cao ti khi lng khng i chuyn thnh
dng cn c thnh phn xc nh (phi m bo chc chn rng qu trnh nung ti khi lng
khng i chuyn hon ton dng kt ta v dng cn).
---***---
Bi 1. Xc nh Fe
3+
bng phng php kt ta.
1. C s phng php: Fe
3+
c kt ta t dung dch vi mt lng d NH
4
OH
Fe
3+
+3NH
4
OH =Fe(OH)
3
+3
Fe(OH)
3
=Fe
2
O
3
+3H
2
O
Lc ra kt ta thu c kt ta Fe(OH)
3
sch, sy kh v nung 800C n khi lng khng
i. T khi lng ca dng cn Fe
2
O
3
suy ra nng ca Fe
3+
.
Lu : Fe(OH)
3
l kt ta v nh hnh in hnh,do cc iu kin tin hnh kt ta tun theo
cc iu kin ti u ca kt ta v nh hnh:
Yu cu to kt ta:
- To kt ta c chc nht nh
- t nhim bn
- Trnh to keo (tch s tan ca Fe(OH)
3
b d to keo) kch thc ca ht keo nh d chui qua
giy lc lc lc ra. (Kch thc ca ht keo trong khong 1-100 nm, thng thng th giy lc
gi li nhng ht c kch thc khong t 10 m ).
iu kin tin hnh to kt ta:
- Dung dch phn tch v dung dch thuc th phi c v nng (tuy nhin trong bi TN ny khng
un nng dung dch NH
4
OH trnh b phn hy lm gim nng ). Dung dch phn ng c
kt ta to ra chc v khng b xp. Dung dch nng hn ch qu trnh hp ph tp cht v
hn ch qu trnh to ht keo. Khi un nng dung dch Fe
3+
rt d b thy phn to kt ta keo
nhy bm vo thnh cc lm cho qu trnh lc v ra kh khn nn trc khi tin hnh un nng
phi thm dung dch HNO
3
hn ch qu trnh thy phn.
Hn na HNO
3
c sn trong dung dch vi nng tng i ban u s phn ng vi thuc th
NH
3
to thnh cht in ly mnh NH
4
NO
3
l cht ng t keo ngn nga qu trnh keo ha.
- Qu trnh thm thuc th nhanh, khuy u ( kt ta hon ton v chc, khng b xp). Ngay
sau khi kt ta hon ton (khong vi giy sau khi rt ht dung dch NH
4
OH) phi tin hnh pha
long dung dch ngay trnh nhim bn kt ta. Qa trnh pha long lm gim nng cc
tp cht trong dung dch nh th s hn ch c s cng kt trn b mt kt ta.
- Phi thm vo dung dch cht in ly mnh, trong iu dung dch nng trnh qu trnh to ht
keo (keo ha). Nh tc dng ca cht in ly mnh, ht keo s ng t li v lng xung y.
Cht in ly mnh c s dng trong bi l NH
4
NO
3
vi nng 2%.
- Ngay sau khi kt ta lng phi nhanh chng lc v ra kt ta ngay trnh ngm lu kt ta
trong dung dch trnh hin tng kt ta theo. Tin hnh qu trnh lc gn gi li kt ta trong
cc ch chuyn phn dung dch ln giy lc sau tin hnh ra nhiu ln (khng nn chuyn
phn kt ta ln giy lc trnh ht kt ta bt lm tc l giy lc). Tin hnh ra kt ta bng
dung dch cht in ly mnh NH
4
NO
3
2% loi b cc tp cht ra khi kt ta m vn ngn
nga c hin tng to keo. (lu rng NH
4
NO
3
ln li trong kt ta s b phn hy hon ton
khi nung).
Lu :
- S dng thuc th l dung dch NH
3
d kt ta hon ton Fe
3+
m khng dng NaOH trnh
cng kt ln kt ta l. Trong trng hp ny NH
3
d to phc amiacat lm tan kt ta l v d
(Ag(NH
3
)
2
)OH, Cu(NH
3
)
4
(OH)
2
...
- Phi ra ht Cl
-
ra khi kt ta. Nu Cl
-
cn li trong kt ta n s to vi st FeCl
3
. Qu trnh
nung ti 600
o
C s dime ha thnh Fe
2
Cl
6
v bay hi. Kt qu l gy sai s m (thiu ht Fe).
2. Cch tin hnh:
Dng pipet ly chnh xc 10,00 ml dung dch FeCl
3
cn xc nh nng vo cc c m sch
250 ml thm tip khong 5-7 ml dung dch HNO
3
2N ri tin hnh un nng dung dch ti
khong 80
o
C. Trong t ht, dng ng ong ly khong 20 ml dung dch NH
4
OH 10%, rt t t
(khng qu chm) vo dung dch Fe
3+
un nng, khuy nh bng a thy tinh phn ng
hon ton (trnh khuy qu mnh s to iu kin ht keo kh ng t). Ngay sau khi rt hon
ton lng NH
4
OH lp tc pha long dung dch ti khong 100 ml bng dung dch NH
4
NO
3
2%
un nng. t ln trn bp un nng nh, ch cho kt ta ( nu, l lng, xp) lng xung y.
Sau khong vi pht kt ta lng, tin hnh lc gn ngay, chuyn ton b dung dch trong ln
giy lc, gi li kt ta trong cc. Sau tin hnh qu trnh ra kt ta trong cc, mi ln ly
khong 30 ml dung dch NH
4
NO
3
2% nng, ch kt ta lng ri li lc gn. Lp li qu trnh ra
t nht 5 ln ri tin hnh th Cl
-
, dng 1-2 git dung dch AgNO
3
0,05N cho vo cc c m
100ml, nh 4-5 git dung dch lc t cung phu vo v quan st nu khng thy kt ta keo
trng xut hin th qu trnh ra hon thnh. Dng khong 10 ml dung dch NH
4
NO
3
2% nng
trng v chuyn ton b kt ta ln giy lc. ly hon ton lng kt ta dnh li thnh
cc c m 250 ml, ta s dng mnh giy lc nh, trc tin lau sch a thy tinh, sau dng
a thy tinh iu khin mnh giy lc lau sch thnh cc v chuyn vo chn nung (lp li
qu trnh cho n khi khng quan st thy mu nu bm ln mnh giy lc dng lau).
Chuyn ton b lng kt ta ro nc trn phu lc vo chn nung ( cn trc gi tr m
o
) nh
nhng dng a thy tinh p giy lc v kt ta gn gng nm st y chn ( trnh b ri vi
trong qu trnh thao tc v sau). a ln bp in tro ha giy lc trc khi tin hnh nung
800
o
C. Nung nhit 800C khong 30 pht, ly ra bnh ht m, ngui, cn ghi khi lng
Fe
2
O
3
. Thc hin li thao tc cho ti khi lng khng i m
1
.
3. Tnh ton:
V
FeCl
3
ly xc nh: . 10,00. ml
- Khi lng ca chn s khi cha c kt ta: m
0
=. . . . . . . . . . . . . . . gam
- Khi lng ca chn s c kt ta sau khi nung: m
1
=. . . . . . . . . . . . . . . gam
- Khi lng ca dng cn thu c: m = . . . . . . . . . . . . . . . gam
Nng ca dung dch FeCl
3
:
CM
FeCl
3
=
Cg/l
FeCl
3
=CM
FeCl
3
* D
FeCl3
Tnh s gam Fe c trong lng mu ly phn tch:
m =CM
FeCl
3
* (V
Fe
3+/1000)* M
Fe
Cu hi b xung:
1. Cch nhn bit ion Fe
3+
kt ta hon ton?
m bo phn tch chnh xc ta phi chc chn Fe
3+
c kt ta hon ton. nhn bit
Fe
3+
kt ta hon ton hay cha ta c th da vo du hiu mi khai ca NH
3
bay ra khi tin
hnh un nng ch lng kt ta, v khi rt dung dch thuc th NH
4
OH vo Fe
3+
th qu trnh
phn ng s ln lt nh sau:
HNO
3
+NH
4
OH =NH
4
NO
3
+H
2
O
FeCl
3
+3NH
4
OH =Fe(OH)
3
+ 3NH
4
Cl
NH
4
OH =NH
3
+H
2
O (phn ng phn hy khi un nng).
Nh vy c du hiu NH
3
bay ra c ngha l phn ng kt ta Fe
3+
din ra hon ton.
Bin php an ton hn c th tin hnh nh sau, i cho kt ta lng 1 phn, nh t t theo thnh
dung dch NH
4
OH 10% v quan st phn dung dch trong, nu thy kt ta nu xut hin
ngha l cha kt ta hon ton st, phi tip tc cho thm thuc th, v lp li qu trnh th.
2. Vai tr ca axit HNO
3
?
- HNO
3
c a vo trc khi un nng dung dch Fe
3+
hn ch qu trnh thy phn dung
dch ny khi un nng. Qu trnh thy phn s to kt ta keo bm rt chc vo cc, kh ra
sch.
- HNO
3
c sn trong dung dch vi nng tng i ban u s phn ng vi thuc th NH
3

to thnh cht in ly mnh NH
4
NO
3
l cht ng t keo ngn nga qu trnh keo ha.
HNO
3
+NH
4
OH =NH
4
NO
3
+H
2
O
3. Ti sao phi ra sch Cl
-
ra khi kt ta?
i vi 1 trng hp phn tch c th, ty theo bn cht mu ngi ta chn ra mt hoc mt vi
ion trong dung dch c nh hng ln gy sai s kt qu phn tch tin hnh ra hon ton
chng ra khi kt ta, trong trng hp c th ny l Cl
-
. Ra sch Cl
-
rt quan trng v nu Cl
-
ln trong kt ta ( tt nhin chng b ln do b hp ph trn b mt kt ta hoc b gi trong cc
lp in tch ht keo) khi nung s to FeCl
3
, khong 600
o
C qu trnh ime ha s to Fe
2
Cl
6
v
bay hi. Kt qu l mc sai s m do lm mt Fe.
4. Ti sao khng nung kt ta nhit cao hn 800
o
C?
Khi nung nhit qu cao (thng > 900
o
C) v qu lu th mt phn tng i Fe
2
O
3
chuyn
thnh Fe
3
O
4
lm sai lch dng cn. Do vy khi tnh ton s b mc phi sai s ln. Cn lu l
khng nung nhit qu thp s khng m bo c Fe(OH)
3
chuyn thnh Fe
2
O
3
v phn
hy ht c tp cht ln bn. Nhit 800
o
C c chn l nhit ph hp tha mn 2 yu
cu trn.
5. Th no l nung ti khi lng khng i?
chc chn Fe(OH)
3
chuyn ha hon ton thnh Fe
2
O
3
ta phi tin hnh nung ti khi
lng khng i, tc l nung nhit 800C khong 30 pht, ly ra bnh ht m, ngui, cn
ghi khi lng Fe
2
O
3
. Thc hin li thao tc cho ti khi khi lng 2 ln cn lin tip l bng
nhau hoc sp x bng nhau (vi sai s cho php).
6. D c gng ra kt ta, nhng cc tp cht b hp ph su trong cc mao
qun, l xp ca kt ta v nh hnh hu nh khng th ra sch c, lm cch no tng
chnh xc php phn tch?
Khi lc kt ta ngi ta ra bng dung dch long cht in li bay hi. Nhng ion b hp ph
trc t b tch ra khi ra bi v chng lin kt cht vi cht kt ta rn. Nhng gia nhng ion
i trong kt ta v mt trong nhng ion ca cht lng ra c th trao i. Khi k ti tt c
nhng iu , kh m hy vng rng kt ta khng b bn n mc no thm ch c ngay
sau khi ra tch cc. Sai s phn tch do nguyn nhn c th dao ng t (1 2).10
4
% (v d
nh bc nitrat cng kt trn bc clorua) n nhng i lng khng th chp nhn c (v d
nh hiroxit cc kim loi nng cng kt trn oxit hirat ha st ha tr ba hoc nhm). Kt ta li
l bin php hiu qu nht lm gim hp ph. Trong trng hp ny ngi ta ho tan kt ta
c lc v kt ta li mt ln na. Nh thng l, kt ta thu c ngay t u ch cha mt
phn nh lng cht bn tng qut tn ti ban u. Do , nng hn hp bn trong dung dch
thu c khi ho tan kt ta s nh hn rt r rt so vi nng cht bn trong dung dch ban
u. Khi lp li ng tc kt ta c th b qua sai s do s hp ph thp. Kt ta li lm ko di
ng k ng tc phn tch, nhng mc d vy, ng tc y thng yu cu bt buc i vi
nhng kt ta nh hiroxit st (III) v nhm do chng c khuynh hng hp ph c bit ln cc
hiroxit cc kim loi nng nh km, cadimi v mangan.
7. Ti sao phi ra kt ta bng dung dch cht in ly mnh?
Kt ta v nh hnh lun c xu hng to cc ht keo, nh n mc khng gi c khi lc m
d dng lt qua li lc. Keo l cc ht tiu phn c kch thch t 10
-10
n 10
-7
m, vi kch
thc ny ht keo tr nn rt kh lng thng trng thi huyn ph trong dung dch. Cc ht
keo c th mang in tch m hoc dng l ph thuc vo s hp ph cc cation hay anion trn
b mt ca n (s hp ph ny thng chn lc lp s cp). Cu to ca ht keo bao gm:
Lp s cp s quyt nh in tch ca ht keo, cc ht keo smang cng in tch (cng du vi
in tch lp s cp) v y nhau. Lp ion s cp gi l lp ion hp ph lp ny lin kt cht ch
vi nhn keo, cn lp ion th cp gi l lp ion i, lin kt vi nhn lng lo hn v linh ng
hn. Qu trnh ph v h keo, lm cho cc ht ln ln v lng xung gi l qu trnh ng t
keo. ng t ht keo c th tin hnh un nng (S nng nhit lm gim s hp ph v do
lm gim in tch chung ca ht; ngoi ra cc ht c c nng lng ng hc vt
qua hng ro ngn cn chng tin gn li nhau), khuy v thmcht in li. S lm tng nng
cht in li trong dung dch bng cch thmhp cht c c tnh ion thch hp l phng php
ng t hiu qu hn. Bi v, s thmvo cht in ly gy nn s mo m lp ion i v kt qu
l in tch ht nhn c trung ha hon ton hn, dn ti cc ht xch li gn nhau hn.
S peptit ha keo. Peptit ha l qu trnh lm cho keo ng t li c chuyn thnh trng
thi khuch tn ban u. S peptit ha thng xy ra khi ra kt ta v nh hnh bng nc,
nguyn nhn l do qu trnh ra lm gim nng cc cht in ly mnh (cc cht gy ng t
keo) kt qu l ht keo li tch in tr li, y nhau v phn tn tr li dung dch. Chnh v
nguyn nhn ny, phi tin hnh ra kt ta bng dung dch cht in ly mnh trnh s peptit
ha keo.
---***---
Bi 2. Xc nh SO
4
2-
bng phng php phn tch khi lng
1. C s phng php:
c kt ta t dung dch vi mt lng d BaCl
2
:
+Ba
2+
=BaSO
4
Lc ra kt ta thu c kt ta BaSO
4
sch, sy kh v nung n khi lng khng i. T
khi lng ca BaSO
4
suy ra nng ca
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
.
Lu : BaSO
4
l kt ta tinh th in hnh, cc iu kin tin hnh kt ta tun theo cc iu kin
ti u ca kt ta tinh th.
Yu cu:
- To tinh th ht ln, hon chnh v t b khuyt tt d lc ra, t b nhim bn trn b mt v
trong lng kt ta.
iu kin tin hnh to kt ta:
- Dung dch phn tch v dung dch thuc th phi long v nng Dng dung dch long, thm
cht kt ta chm v khuy mnh ngi ta c th lm gim s qu bo ha tng ni trong dung
dch. Nhit cao cng gip lm tng tan ca kt ta. Kt qu l trnh c s qu bo ha
cc b, s trnh c vic to ra qu nhiu mm m bo tt cho vic to cc tinh th ln v
hon chnh v sau.
- Mi trng pH thch hp. Mi trng pH thng chn l mi trng axit c tc dng lm tng
tan ca kt ta (cng trnh bo ha cc b). V d c th chn mui trng axit pH =2
lm tng tan ca kt ta BaSO
4
do H
+
to vi SO
4
2-
thnh HSO
4
-
. Sau khi lm kt ta xong,
tan ca BaSO
4
s c lm gim bng cch cho d thuc th BaCl
2
. Ngoi ra, mi trng
axit ph hp cn trnh s kt ta theo (v d Fe(OH)
3
, Al(OH)
3
hay cc mui cacbonat kim
loi nng rt d dng bm vo kt ta khi ngm lu) nhng y khng phi l do chnh, trong bi
thmHCl cn gip trnh c hp ph BaCO
3
v gim cng kt Ba(OH)
2
. Lu rng: vi
phng php xc nh SO
4
2-
trc khi tin hnh kt ta cn phi tch cc ion cn tr nh SiO
3
2-
,
SnO
3
2-
(v chng d to kt ta theo H
2
SiO
3
), cng cn tch hoc che cc ion d cng kt
nh Fe
3+
, Al
3+
(v chng d cng kt theo di dng ta hydroxit).
- Qu trnh thmthuc th vo dung dch phn tch phi rt chm, v khuy u trnh hin
tng bo ha cc b. Qu trnh to kt ta tinh th chia lm 2 giai on: giai on to mm v
giai on ln ln ca mm thnh tinh th hon chnh. Giai on to mm xy ra khi dung dch
trong iu kin bo ha hoc qu bo ha sau s bi p ca cc lp kt ta mi s lm cho
tinh th ln dn ln. Nu dung dch bo ha cc b n s to ra qu nhiu mm kt qu l thu
c phn ln cc tinh th rt nh.
- Kt ta c ngm trong dung dch cha ion d ca thuc th v tin hnh qu trnh mui kt
ta (cn gi l qu trnh gi ha). C th tin hnh nhit cao (un cch thy, khng khuy)
trong thi gian ph hp hoc nhit phng trong thi gian tng i di. Mc ch l lm
tan cc kt ta nh v pht trin cc kt ta ln. Nguyn nhn l vi cng 1 lng cht nh nhau
th cc tinh th nh s c tng din tch b mt ln hn tng din tch b mt ca cc tinh th ln,
qu trnh ha tan v kt ta li xy ra trn b mt l 1 qu trnh cn bng ng v ph thuc vo
din tch b mt. Nh vy tinh th nh c tan ln hn tinh th ln cng iu kin. Khi ngm
lu trong dung dch cn bng c dch chuyn kt qu l tinh th nh dn tan ra cn tinh th ln
ngy cng ln hn. Mi trng axit cng h tr cho qu trnh ny do lm tng tan. Qu trnh
mui kt ta cn c tc dng lm sch kt ta, nguyn do l n sp xp li tinh th, ha tan cc
tinh th nh do loi b c tp cht hp lu (hp lu l qu trnh xm nhp ca tp su vo
bn trong kt ta do qu trnh mi hnh thnh kt ta chng hp tp ln b mt, lp bi p tip
theo s gi cht cc tp trong lng kt ta).
2. Tin hnh:
Cc c m 250ml, ly chnh xc 10,00 ml dung dch SO
4
2-
cn xc nh nng , thm khong 5-
7ml dung dch HCl 2N lm mi trng bng ng ong, thm tip khong 1 ml dung dch axit
picric 1% bng pipet. (axit picric c tc dng hn ch qu trnh to qu nhiu mm). Pha long
dung dch bng nc ct n khong 120 ml, cui cng em un nng trn bp n gn si.
Cc c m 100 ml, ly khong 5-7 ml dung dch BaCl
2
5% bng ng ong, thm nc ct pha
long ti khong 50 ml, cui cng em un nng trn bp n gn si.
Sau khi 2 dung dch nng gi, tin hnh rt t t rt chm dung dch BaCl
2
vo dung dch
SO
4
2-
v khuy u, gi li khong 2 ml dung dch BaCl
2
th kt ta hon ton. Dung dch t
trong sut s dn dn c hn v sau kt ta lng xung y hon ton (t lc bt u hnh
thnh n khi kt ta lng khong t 15-30 pht). Sau khi kt ta lng hon ton, rt theo thnh
dung dch BaCl
2
cn li quan st dung dch, nu khng thy xut hin kt ta trng vn c th
qu trnh kt ta hon ton.
Tin hnh un cch thy dung dch trong khong 60 pht. em lc v ra ht ion Cl
-
, th ht Cl
-
bng dung dch AgNO
3
0,05N nh bi 1. Nu khng ra ht Cl
-
ra khi kt ta, qu trnh nung s
thu c BaCl
2
t bay hi nm li dng cn dn n sai s dng.
Chuyn ton b kt ta vo chn nung, tro ha v tin hnh nung 800
o
C ti khi lng khng
i. Khi nung BaSO
4
c th b kh 1 phn bi C ca giy lc:
BaSO
4
+4C =BaS +4CO
Qu trnh kh ny c th trnh c nu khi tro ha giy lc khng c ngn la, sau
cacbon chy chm nhit thp vi lng d khng kh v khi c khng kh thi BaS
chuyn ha thnh BaSO
4
. Cng lu : BaSO
4
s b phn hy khi nhit t ti 1400C
BaSO
4
=BaO +SO
3
3. Tnh ton
=m
o
m
1
m
o
: khi lng ca chn trc khi nung, g
m
1
: khi lng ca chn v kt ta sau khi nung, g
= , mol/l
: th tch ca ly dung dch cn phn tch em kt ta, ml
Cu hi b xung:
1. Vai tr ca axit HCl?
HCl c tc dng lm tng tan ca kt ta, nh trong qu trnh mui kt ta cc tinh th nh
tan ra cn cc tinh th ln ngy cng ln hn. Kt qu l thu c tinh th ln v hon thin, t b
nhim tp bn v d lc ra thu hi.
Ngoi ra HCl cn ngn nga s cng kt Ba(OH)
2
v hu ta BaCO
3
/
2. Ti sao tin hnh kt ta BaSO
4
li lu hn kt ta Fe(OH)
3
?
BaSO
4
l kt ta tinh th in hnh, qu trnh to kt ta phi tin hnh lu thu c tinh th
ln, hon thin khng b khuyt tt, t nhim tp bn v nh d lc ra v cho chnh xc
cao.
Fe(OH)
3
l kt ta v nh hnh in hnh, qu trnh to kt ta phi tin hnh trong iu kin
dung dch c, kt ta nhanh v lc ra nhanh kt ta d ng t, ht ln, chc, t xp, t to
keo v t nhim bn.
3. Quan st kt ta BaSO
4
v so snh vi kt ta Fe(OH)
3
?
Kt ta BaSO
4
hnh thnh chm, mu trng c, lng nhanh. Trong khi kt ta Fe(OH)
3
mu nu
xut hin tc thi, l lng, xp v kh lng.
4. Trong thc t phn tch ngi ta mong mun kt ta loi no hn, tinh th hay v
nh hnh?
R rng kt ta tinh th c nhiu u im hn: d dng lc, ra, t nhim tp bn nn thng cho
kt qu phn tch chnh xc hn. Trong khi kt ta v nh hnh kh lc ra, d b nhim tp bn
v thng gp sai s ln hn. Khu lc v ra kt ta l 2 khu gy sai s ln nht do c nhiu
nguyn nhn lm mt mt kt ta v ra khng sch kt ta. Do loi kt ta no d lc ra
hn s c mong mun hn trong php phn tch khi lng.