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1

BI GING PHN TCH NH LNG


Ging vin: Nguyn Thi Hng





2
Chng 1: M U

1.1. i tng, nhim v ca phn tch nh lng
1.1.1. V tr, chc nng
1.1.2. Qu trinh phn tch u bao gm cc giai on c bn sau
-Chn mu i din (chn mt phn nh mu i din cho ton b i tng
cn phn tch), cng vic ny cn phi c quy hoch trc.
-Chuyn cht phn tch v dng dung dch: ha tan hon ton mu trong dung
mi thch hp, tin hnh phn tch theo phng php chn. Nu phn tch bng
mt s phng php vt l th c th khng cn ha tan mu nhng cn phi x l
ha hc trc.
-Tch hoc che cc cu t cn tr cu t chnh (dng phng php ha hc,
ha l, vt l). V d: xc nh Ni
2+
c mt Fe
2+
bng dimetylglioxim th cn
chuyn Fe
2+
thnh Fe
3+
sau che Fe
3+
bng F
-
dng FeF
6
3-
.
-Tin hnh phn tch theo phng php chn.
-Tnh kt qu (nh gi kt qu v chnh xc phn tch).
1.1.3. Phn loi cc phng php phn tch
1.1.3.1. Cc phng php phn tch ha hc
-Phng php phn tch khi lng: da vo vic cn sn phm to thnh sau
qu trnh thc hin phn ng to kt ta t xc nh hm lng cu t cn phn
tch.
-Phng php phn tch th tch: Da vo vic o chnh xc th tch dung
dch thuc th c nng chnh xc tnh hm lng cu t cn phn tch.
1.1.3.2. Cc phng php phn tch cng c
-Cc phng php vt l: da trn vic o mt tnh cht vt l no ( hp
th nh sng, dn in, in th, cng dng, cng bc x in t,...) m
tnh cht ny l hm lng ca khi lng hoc ca nng ca cu t cn phn
3
tch. V d: xc nh hm lng Bi
3+
c th o hp thu nh sng BiI
3
bc
sng 450nm v cng mu ca dung dch ny t l thun vi nng ca n.
- Cc phng php ha l: trong nhiu trng hp, phn ng ha hc ng
vai tr rt quan trng chuyn cu t phn tch thnh dng c tnh cht vt l c
th o c. V d: nh lng Fe3
+
: dng thuc th axit sunfosalixilic trong mi
trng amoniac chuyn v dng phc Fe(Ssal)
3
3-
mu vng, o hp th t
xc nh c nng ca Fe
3+
.
Hai yu t quan trng phn loi cc phng php phn tch l: kch thc
mu th v hm lng phn trm ca cu t cn phn tch.
-Mu bn vi: 0,01-0,1g; mu vi lng: 0,001-0,01g; mu siu vi lng
<0,001g.
-Cu t ln: 1-100%; b: 0,01-1% v vt<0,01%.
1.2. Biu din kt qu trong PTL
1.2.1. Cch biu din kt qu phn tch: biu din ha hc, s hc
1.2.1.1. Biu din ha hc
Biu din cu t phn tch theo dng tn ti ca n trong cht phn tch. V
d: Cr
3+
, Cr
2
0
7
2-
, CrO
4
2-
,.
Biu din cu t phn tch di dng nguyn t hoc di dng oxit thng
p dng i vi cc hp cht cha bit chnh xc thnh phn hoc khi khng cn
xc nh trc tip thnh phn. V d: i vi mu v c phc tp cha oxi ngi ta
thng biu din cc ngguyn t di dng oxit: Fe Fe
3
O
4
, Si SiO
2
,
1.2.1.2. Biu din s hc
Hm lng cu t c trong mu phn tch thng c biu din theo phn
trm khi lng cu t trong mu:
q% = % 100
au khoiluongm
ch autuphanti khoiluongc

q% = % 100
Q
a

Nu hm lng cu t trong mu qu b th biu din theo phn triu (ppm):
4
q% =
6
10
Q
a

Trong nhiu trng hp, chng ta khng th xc nh trc tip cu t trong
mu m phi thng qua khi lng ca mt hp cht thch hp. Lc cn phi
nhn thm tha s chuyn khi K, chuyn khi lng hp cht xc nh sang
khi lng ca cht phn tch.
1.2.2. Biu din nng trong PTL
1.2.2.1. Nng phn trm(%)
1.2.2.2. Nng mol ( M, mol/lt )
1.2.2.3. Nng ng lng(N) v chun

Quan h gia C%, C
M
v C
N
: C
N
= n.C
M
;
D
C d
C
N
% . . 10
=
chun l s gam (hoc miligam) cht tan trong 1 ml dung dch. chun
c dng biu din nng cc dung dch chun.
Cng thc tnh :
) (ml V
a
T = (a: s gam cht tan, V: th tch dung dch ml)
1.3. Sai s trong PTL
1.3.1. ng v lp ( chnh xc)
ng phn nh s ph hp gia kt qu thc nghim thu c vi gi tr
thc ca php o.
Tham s nh gi ng l sai s tuyt i d v sai s tng i %:
d = Xi % 100
d
%

= A
Sai s tuyt i d phn nh s sai lch gia kt qu o Xi v gi tr thc .
Sai s tng i phn nh lch tng i ca kt qu o vi gi tr thc.
lp phn nh s ph hp gia cc kt qu thu c trong cc th nghim
lp li trong cng mt iu kin thc nghim ging nhau. Kt qu phn tch c th
c lp cao nhng khng ng v ngc li.
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1.3.2. Sai s h thng
Sai s h thng (sai s xc nh) l cc sai s do cc nguyn nhn c nh
gy ra, n lp i lp li trong mi th nghim. N phn nh s sai lch gia cc gi
tr trung bnh vi gi tr thc nn sai s ny ni ln ng ca quy trnh phn tch.
Nguyn nhn sai s h thng l xc nh v v nguyn tc c th bit c.
Mi loi sai s h thng lm cho kt qu phn tch dch chuyn theo mt chiu nht
nh ( tng hoc gim) (cc gi tr thc nghim u nm v mt pha ca gi tr
thc), n lun c du + hay -.
Sai s h thng c th khng i hay thay i ty theo iu kin.
Mt s loi sai s h thng trong phn tch ha hc:
-Sai s do mu o: gy ra khi mu phn tch khng i din
-Sai s do dng c: d t hay nhiu cc dng c o lng lun c sai s h
thng. Sai s dng c thng d pht hin v hiu chnh c bng cch nh k
chun ha cc dng c trong ptn.
-Sai s do phng php o: phng php o lng cng gy sai s h thng.
V vy khi p dng mt phng php mi phn tch lun phi xy dng v thm
nh quy trnh chng minh mt cch khoa hc rng sai s ca phng php l rt
thp v c th chp nhn c. Sai s do phng php thng kh pht hin v l
nguyn nhn chnh gy ra sai s h thng.
-Sai s do ngi lm cng tc phn tch : i hi c k nng ngh v kinh
nghim phn tch. Sai s do c nhn l iu khng trnh khi, v d: mi c nhn c
mt kh nng quan st mu ring, c vch buret, c tn hiu trn my o,... u
dn n sai s. Sai s do c nhn c th khc phc c khi thao tc ng theo quy
nh v nhiu ngi phn tch cng thc hin trn mt mu th.
1.3.3. Sai s ngu nhin
Sai s ngu nhin do nhng nguyn nhn ngu nhin, khng xc nh v bin
thin theo cc chiu khc nhau (lc tng lc gim).
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Sai s ngu nhin lun xut hin d php phn tch c thc hin ht sc
cn thn v cc iu kin th nghim c gi nghim ngt
Sai s ngu nhin khng b trit tiu m ch c th gim bng cch o lp li
nhiu ln trong nhng iu kin thc nghim c gi c nh nghim ngt v c
x l bng ton hc thng k.
1.3.4. nh gi sai s ca php o trc tip
Php o trc tip c thc hin khi so snh vt o vi vt chun nh cn,
o th tch. Mi php o trc tip u mc sai s ngu nhin. Khi tin hnh phn
tch ta thng tin hnh mt s php o c lp trong cng mt iu kin ging
nhau sau tin hnh x l thng k nh gi chnh xc ca php o. Cc i
lng c trng thng k quan trng nht l gi tr trung bnh cng v phng sai.
1.3.4.1. Gi tr trung bnh cng ( X )
L gi tr gn vi gi tr thc ca i lng cn o vi xc sut cao nht
trong s cc gi tr o c ca ai lng cn o.
Gi s ta tin hnh n php c lp i lng X vi cc kt qu: X1,
X2,....Xn:

n
Xi
X
n
i

=
1

1.3.4.2. Phng sai (s
2
)
Phng sai phn nh phn tn ca cc gi tr o c, l gi tr trung bnh
cng ca cc bnh phng hiu gia cc gi tr ring l o c v gi tr trung bnh,
biu din theo cng thc:

k
i
n
i
X
X
s

=
=
1
2
2
) (
_

k: s bc t do, nu ch c mt i lng cn o th k = n 1.
lch chun ca php o:
2
s s =
7
lch chun ca i lng trung bnh cng:
n
s
n
s
s
x
= =

2

Trong thc t tin tnh ton cc i lng

x
s s X , ,
2
, ngi ta thng chn
trong dy gi tr n gi tr o c X1, X2,,Xn mt gi tr C sao cho C

X . Sau
tnh

X v s
2
theo cc cng thc sau:

n
y
C X
n
i
i
=

+ =
1
v
1
1
2
2

=
n
x
s
n
i
i

y:
n
y
y x i
n
i
i n
i
i
n
i
i


=
= =
= =
1
2 2
1
2
1
2
) (
v C X y
i i
=
V d: Tnh gi tr trung bnh cng, lch chun, phng sai ca php xc
nh pht pho trong cht dit trng theo cc s liu sau: P%:
16,2;15,4;17,5;15,9;16,3.
Chn C = 16,3
stt Xi% y
i
.10 y
i
2
.100
1 16,2 -1 1
2 15,4 -9 81
3 17,5 12 144
4 15,9 -4 16
5 16,3 0 0
------------------------------------
2 , 0
5
1
=

= i
i
y 42 , 2
5
1
2
=

= i
i y
Ta c: 26 , 16
5
2 , 0
3 , 16 =

+ =

X
412 , 2
5
) 2 , 0 (
42 , 2
2 5
1
2
=

= i
i
X
8
603 , 0
4
412 , 2
2
= = s
7765 , 0
2
= = s s 347 , 0
5
7765 , 0
= =

X
s
1.3.4.3. H s bin ng(v)
Gi s tin hnh n th nghim c cc gi tr X1, X2,,Xn, t cc biu thc
ton hc ta tnh c

X , s. H s bin ng v ca phng php phn tch trng


cho lp li hay phn tn ca cc kt qu th nghim:

%
100 .

=
X
s
v

T ta c th tnh h s bin ng theo lch chun v ngc li.
Bin gii tin cy ():L gi tr tuyt i ca hiu gia gi tr trung bnh cng

X v gi tr thc ca i lng phi o: =

X
Trong thc t s lng th nghim n thng l nh nn tnh thng dng
chun Student (t) :

n
ts
X n
s
X
s
X
t
X
=


V c nh gi ng vi mt tin cy cho. V d: = 0,95; =
0,99,.
c tnh theo cng thc: k
X
t s
,


=

vi t
,k
: h s student ng vi s bc t do k ca php o v tin cy
cho trong bng 1.1.
Khong tin cy ca gi tr o l khong ti c kh nng tn ti gi tr thc
ca php o vi xc sut cho:

+ s s

X X
Cc gi tr h s Student ng vi = 0,95; 0,99
9

k
0,95 0,99
k
0,95 0,99
1 12,706 63,657 14 2,145 2,977
2 4,303 9,925 15 2,131 2,947
3 3,182 5,814 16 2,120 2,921
4 2,776 4,604 17 2,110 2,898
5 2,571 4,032 18 2,103 2,878
6 2,447 3,707 19 2,093 2,861
7 2,365 3,499 20 2,086 2,845
8 2,306 3,355 25 2,060 2,707
9 2,262 3,250 30 2,042 2,750
10 2,228 3,169 40 2,021 2,704
11 2,201 3,106 60 2,000 2,600
12 2,179 3,055 120 1,980 2,671
13 2,160 3,012

V d: nh gi chnh xc ca kt qu xc nh hm lng pht pho trong
cht dit trng trong v d trn vi tin cy = 0,95
26 , 12 =

X 347 , 0 =

X
s
Tra bng t = 2,776 ( = 0,95; k = 4)
Vy k
X
t s
,


=
=0,347.2,776= 0,96
96 , 0 26 , 16
95 , 0
= =

X hay 22 , 17 30 , 15 s s
Sai s tng i, tnh theo %(%) ca php xc nh c tnh:
% 100 %

= A
X

v v d ny % 059 , 0 % 100
26 , 16
96 , 0
% = = A
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1.3.5. Ch s c ngha v cch ghi kt qu phn tch
1.3.5.1. Ch s c ngha
Kt qu ca mt php o trc tip cng nh ca mt thao tc phn tch phi
c ghi chp sao cho ngi s dng s liu hiu c mc chnh xc ca php
o. V vy ngi ta quy nh vic biu din kt qu ca php o theo ng quy c
v ch s c ngha.
Ch s c ngha bao gm cc ch s tin cy cng vi ch s bt nh u
tin. V nguyn tc, s liu phi c ghi sao cho ch s cui cng l bt nh.
VD: 1, 2 3 4 5 : 5 ch s c ngha, 4 ch s tin cy (1,2,3,4), 1 ch s bt nh
(5)
i vi kt qu o trc tip ta da vo thng s k thut ca thit b o
ghi ch s tin cy v ch s bt nh.
Nu cn trn cn phn tch vi nhy 0,1mg th kt qu phi c ghi n
ch s ch phn mi mg.
V d: 1,8925 gam m khng ghi l 1,89 gam hay 1,892 gam, trong cc
ch s 1, 8, 9, 2 l cc ch s hon ton tin cy v ta c c t qu cn, cn ch
s 5 l bt nh v c ghi c tnh trn thang chia. Trong kt qu cn ny, ta c 5
ch s c ngha gm 4 ch s tin cy (cc ch s 1, 8, 9, 2) v 1 ch s bt nh
(ch s 5).
Khi c th tch ghi trn buret c chia n 0,1ml th kt qu phi c
ghi n ch s ch phn trm ml v phn mi ml l s chc chn (tin cy), cn phn
trm ml l s ghi ng (bt nh).
V d: phi ghi V= 12,85ml m khng ghi 12,8ml hay 12,854ml
i vi kt qu phn tch, ta da vo gi tr , s biu din cc ch s tin
cy v ch s bt nh.
V d: ta tnh c

X =3,86712 v = 0,005, nh vy ch s th ba sau du


phy l bt nh v ghi kt qu phn tch phi lm trn n con s th ba sau du
phy tc l

X =3,867 ( = 3,8670,005). y c 4 ch s c ngha (bao gm cc


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ch s tin cy cng vi ch s bt nh u tin) (cc ch s 3, 8, 6 tin cy v
ch s 7 l bt nh).
1 ch s bt nh (7)

= 3,8670,005 4 ch s c ngha (3,8,6,7)

3 ch s tin cy

Trong trng hp khng c thng tin b sung th ngm hiu rng ch s cui
cng c bt nh 1. V d: nu ghi pH = 6,77 c ngha l gi tr pH c th dao
ng trong khong pH= 6,77-6,79 v nh vy my o pH c chnh xc 0,01 v
pH.
i vi ch s 0: khng c tnh l s c ngha khi n c dng thit
lp im thp phn, cn ch s 0 ng gia hoc ng sau cc ch s khc th c
tnh vo s c ngha. V d: s 0,02030 th hai ch s 0 ng trc s 2 khng c
tnh l s c ngha, hai ch s 0 cn li l s c ngha, s ny c 4 ch s c ngha
(2, 0, 3, 0) trong 2, 0, 3 l s tin cy v 0 (ch s cui cng) l s bt nh.

S khng c ngha 4 ch s c ngha (2,0,3,0)

0,02030

3 ch s tin cy(2,0,3) 1ch s bt nh (0)
i vi cc s phc tp ngi ta thng chuyn sang dng s ly tha thp
phn th cc s phn nguyn c tnh vo ch s c ngha, cn bc ly tha
khng c coi l ch s c ngha.
V d: 1705 = 1,705.10
3
c 4 ch s c ngha; 0,000840 = 8,40.10
-4
c 3 ch
s c ngha; 2,4 gam c 2 ch s c ngha v nu quy ra mg th phi vit 2,4.10
3
mg
( c 2 ch s ngha) m khng c vit l 2400mg (c 4 ch s c ngha).
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i vi cc s logarit th cc ch s bn tri im thp phn (phn nguyn)
khng c coi l s c ngha. V d: lgx = 3,45 c 2 ch s c ngha (ch s 4 v
5) cn ch s 3 l bc ca ly tha.
1.3.5.2. Quy tc lm trn s
trnh lm gim chnh xc ca kt qu o vic lm trn s cc giai
on trung gian, trong cc php tnh ch c c php lm trn kt qu cui
cng.
-Php cng v php tr: ch gi li kt qu cui cng mt s thp phn
bng ng s thp phn ca s hng c s thp phn t nht.
Y = 1,526 + 10,45 + 58,1 = 70,076 Kt qu lm trn Y = 70,1
Y = 1158,451 415,28 = 743,171 Kt qu lm trn Y = 734,17
-Php nhn v chia: cn gi li kt qu cui cng mt s ch s c ngha
bng ng s ch s c ngha ca tha s c s ch s c ngha t nht.
3
10 . 3589 , 1
1497 , 35
0279 , 0 . 7120 , 1

= = Y kt qu lm trn Y = 1,36.10
-3
-Php tnh logarit
VD: tnh logarit ca Y = 6,19.10
-8
Log Y = -8+0,7917 = -7,208 (c 3 ch s c ngha l 2, 0, 8 tng t
trong Y c 3 ch s c ngha.
VD: cho pH = -lg| |
+
H = 11,15. Tnh | |
+
H
| |
+
H = 10
-11,15
= 7,0795.10
-12
lm trn | |
+
H

= 7,1.10
-12
( c 2 ch s c
ngha tng t gi tr pH c 2 ch s c ngha).
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2. Chng 2: PHN TCH KHI LNG V I CNG
V CC PHNG PHP PHN TCH TH TCH

2.1. Phn tch khi lng
2.1.1. Nguyn tc chung. Dng kt ta v dng cn
Phn tch khi lng l phng php phn tch nh lng da vo vic cn
khi lng sn phm to thnh sau phn ng kt ta bng phng php ho hc hay
phng php vt l. Do cht phn tch chim mt t l xc nh trong sn phm em
cn nn t khi lng sn phm d dng tnh c lng cht phn tch trong i
tong phn tch.
2.1.2. Phn loi
Bao gm: phng php tch, phng php ct v phng php kt ta
2.1.2.1. Phng php tch
2.1.2.2. Phng php ct (lm bay hi)
2.1.2.3. Phng php lm kt ta

Dng kt ta l hp cht to thnh khi cho thuc th lm kt ta phn ng
vi cu t cn phn tch.
Dng cn l sn phm cui cng sau khi nung n khi lng khng i,
em cn tnh hm lng cht phn tch.
Dng kt ta c th hoc khng phi dng cn.
V d: BaSO
4
: dng kt ta, dng cn.
Fe(OH)
3
:dng kt ta ; Fe
2
O
3
: dng cn
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2.1.3. iu kin tin hnh phn tch theo phng php kt ta
2.1.3.1. Thuc kt ta
2.1.3.2. Lng cht phn tch
2.1.3.3. Nng thuc th
2.1.4. Lc v ra kt ta
Lc kt ta: Kt ta c lc bng giy lc khng tn, c dy mng khc
nhau ph thuc vo kch thc ca cc phn t kt ta cn lc.
Ra kt ta: ui ht cht bn, k c nc ci ra khi kt ta, c th dng
cc loi nc ra sau:
K thut ra kt ta:
Trc ht cn lng sau mi ln ra kt ta trong cc v ch khi gn sch ta
mi chuyn ton b kt ta ln giy lc v ra trn giy lc.
2.1.5. Chuyn dng kt ta thnh dng cn
2.1.6. S ht m ca kt ta
2.1.7. Phm vi ng dng ca phng php phn tch khi lng
Phng php phn tch khi lng cho kt qu kh tin cy v chnh xc khi
xc nh cc cu t lng ln v trung bnh vi sai s thng t 0,2-0,4%.
2.2. i cng v phn tch th tch
2.2.1. i cng
Phng php phn tch th tch l phng php phn tch nh lng da vo
vic o chnh xc th tch ca dung dch thuc th (B) bit trc nng chnh
xc (dung dch chun) tc dng va vi mt th tch nht nh ca cht cn phn
tch (A).
Ngi t c s cho php phn tch th tch l nh bc hc J.L.Gay Lussac.
2.2.2. Mt s nh ngha v khi nim c bn
A + B C
(cht xc nh) (dung dch chun B)
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Qu trnh nh phn l qu trnh thm t t dung dch chun B ( bit nng
) t buret vo dung dch cht xc nh A tin hnh phn ng phn tch.
im tng ng l im m cht B thm vo va tc dng ht vi
cht A theo phng trnh phn ng.
nhn bit im tng ng thng ngi ta dng ch th. Cht ch th
cho tn hiu nht nh (i mu, kt ta,...) ti im tng ng trong qa trnh
nh phn. Thi im m cht ch th cho tn hiu thay i r rt da vo ta
kt thc qu trnh nh phn gi l im kt thc nh phn hay im cui.
Trong thc t, im tng ng v im cui khng trng nhau v gy ra
sai s ca php chun .
Dung dch chun gc l dung dch cht B bit nng chnh xc. C 2
phng php pha dung dch chun
iu kin ca cht gc:
2.3. Phn loi cc phng php phn tch th tch
+Phng php chun axit baz
+ Phng php chun to phc
+ Phng php chun kt ta
+ Phng php chun oxi ha-kh
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2.4. Cc cch chun
2.4.1.1. Chun trc tip
2.4.1.2. Chun ngc
2.4.1.3. Chun thay th
2.4.1.4. Chun gin tip
2.4.1.5. Chun phn on
2.5. Tnh kt qu trong phn tch th tch
2.5.1.1. Trng hp chun trc tip
2.5.1.2. Trng hp chun ngc
2.5.1.3. Trng hp chun gin tip


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3. Chng 3: PHNG PHP CHUN AXIT-BAZ

3.1. Nguyn tc ca chun axit baz
Phng php chun axit baz l phng php phn tch th tch da vo
phn ng trung ho : A
1
+ B
2
B
1
+ A
2
(A, B l axit, baz tng ng).
Phng php ny dng xc nh ch yu cc axit, baz ( hoc cc cht c
tnh axit, tnh baz ).
3.2. Cht ch th trong chun axit baz
3.2.1. Khi nim
Cc yu cu i vi cht ch th axit baz l:
3.2.1.1. L thuyt v cht ch th axit baz
1)Thuyt ion:
2)Thuyt nhm mang mu:
3) Thuyt ion-nhm mang mu:
3.2.1.2. Khong i mu ca cht ch th
Khong i mu ca cht ch th axit baz l khong gi tr pH trong khi
pH ca dung dch thay i th mu ca cht ch th cng thay i theo m mt ta
nhn thy c.

| |
| |

=
Ind
HInd
pK pH
ct
0
lg (2)
pK
ct
= - lgK
ct
: gi l ch s cng ca cht ch th.
(2) l phng trnh c bn biu din s ph thuc mu ca cht ch th vi
pH ca dung dch .
Theo (2), khi thay i pH ca dung dch , t s |HInd
0
| / |Ind
-
| cng thay i.
Trong thc t, ngi ta nhn thy rng khng phi mi s bin i ga tr pH ca
dung dch u a n s i mu ca cht ch th m mt ta c th nhn thy c.
Mt ta ch nhn thy c cht ch th c mu ca mt dng h bin khi nng ca
dng ny ln hn nng ca dng kia mt s ln nht nh ( tu theo mi loi cht
ch th)
18
V d: i vi metyl da cam ta nhn thy mu thay i nh sau:
Mu khi |HInd
0
| / |Ind
-
| > 4,5; pH s 3,1
Mu vng khi |HInd
0
| / |Ind
-
| s 4,5; pH > 4,4
Khi pH s 3,1 mt ta thy metyl da cam mu
Khi pH > 4,4 mt ta thy metyl da cam mu vng
Khi thay i dn gi tr pH t 3,1 n 4,4, mu ca metyl da cam thay i
dn t n vng v ngc li. Khong gi tr pH t 3,1 n 4,4 hay 4,4 n 3,1
ng vi s i mu gi l khong i mu ca cht ch th axit baz.
V d : i vi ch th phenolphtalein, t s |HInd
0
| / |Ind
-
| =10, K
ct
= 10
-9
;
pH = pK
ct
1 nn khong i mu t 8-10.
Vy khong i mu ca cht ch th axit baz l khong ga tr pH trong
khi pH ca dung dch thay i th mu ca cht ch th cng thay i theo m mt ta
nhn thy c.
3.2.1.3. Ch s nh phn pT ca cht ch th
Ngi ta nhn thy rng trong khong i mu ca cht ch th axit baz c
mt gi tr pH m ti mu ca cht ch th thay i r nht. Gi tr pH gi l
ch s nh phn ca cht ch th (pT). Vy ch s nh phn ca cht ch th axit
baz l gi tr pH nm trong khong i mu m ti gi tr pH ny mu ca cht
ch th bin i r nht.
3.2.1.4. Cc yu t nh hng n khong i mu ca cht ch th
1)Hiu ng mui ca cc cht in li:
2)nh hng ca nhit :
3)nh hng ca dung mi:.
4)Th t nh phn
3.2.2. Sai s ch th ca php chun
Trong phn tch th tch ni chung, ngoi sai s do dng c v s dng n
(pipet, buret, bnh nh mc,...) gy nn cn sai s do pT ca cht ch th khng
19
trng vi pH im tng ng. Sai s ch th l sai s do im cui c nhn ra
bng cht ch th c pT khng trng vi im tng ng.
3.3. Cch xc nh im tng ng trong phng php trung ha vi dung
mi nc
3.3.1. Khi nim ng nh phn (ng cong logarit)
Qu trnh chun axit baz khng km theo hin tng bn ngoi m mt
ta quan st c (khng thay i mu sc, khng to kt ta) nn xc nh im
tng ng phi dng cht ch th. Nu biu din s bin i trn mt h trc to
gm: trc tung biu din s thay i ca pH, trc honh biu din lng thuc
th thm vo (% hay Vml) ta s c mt ng cong lin tc: ng cong logarit
hay ng cong nh phn.
Vy ng nh phn l th biu din s bin i tnh cht no ca
dung dch cht nghin cu theo lng thuc th thm vo trong qu trnh nh phn.
C th, ng nh phn axit baz l mt ng cong logarit biu din s
thay i ca pH (trc tung) ca dung dch cht nghin cu (axit hay baz) vo lng
thuc th (baz hay axit ) (% hay Vml) thm vo trong qu trnh nh phn.
Bng tnh ton v thc nghim u thy rng pH ca dung dch trong qa
trnh chun thay i t ngt khi ch thm mt lng nh th tch dung dch
chun. Khong pH ny gi l bc nhy ca qu trnh chun v da vo
chn cht ch th thch hp.
3.3.2. Nguyn tc xy dng ng nh phn axit baz
Ni cc gi tr pH ti cc thi im trn ta c ng nh phn







p
Bc nhy
F
20

3.4. Chun axit mnh v baz mnh
3.4.1. Chun axit mnh bng baz mnh


ng chun dung dch axit HCl 0,1 N bng dung dch NaOH 0,1M


Bc nhy
pH
100
4,3
9,7
7
V
NaOH


21
3.4.2. Chun baz mnh bng axit mnh
3.5. Chun n axit yu v n baz yu
3.5.1. Chun n axit yu CH3COOH bng baz mnh NaOH


3.5.2. Chun n baz yu NH3 bng axit mnh HCl

ng chun dung dch NH
4
OH 0,1 N bng dung dch HCl 0,1 N

Bc nhy
5,28
pH
100
4,3
6,26
V
HCl
(ml)
2
1
8,8
6,8
10,6
Bc nhy
pH
100
V
NaOH

22
3.6. Chun a axit v a baz
3.6.1. Chun a axit bng n baz mnh
Kho st qu trnh chun 100 ml dung dch H
3
PO
4
0,1M bng dung dch
NaOH 0,1M.
H
3
PO
4
H
+
+ H
2
PO
4
-
K
1
=7,51.10
-3
; pK
1
=2,15
H
2
PO
4
-
H
+
+ HPO
4
2-
K
1
=6,23.10
-8
; pK
2
=7,20
HPO
4
2-
H
+
+ PO
4
3-
K
1
=2,2.10
-13
; pK
3
=12,38
Theo cc nc phn ly trn, dung dch H
3
PO
4
coi nh hn hp ca 3 axit:
H
3
PO
4
, H
2
PO
4
-
, HPO
4
2-
vi cc nng C1, C2, C3 v K
1
>> K
2
>> K
3
v vy khi
dng NaOH chun th H
3
PO
4
s c trung ha ln lt tng nc 1:
H
3
PO
4
+ NaOH NaH
2
PO
4
+ H
2
O im tng ng 1
H
2
PO
4
-
+ NaOH Na
2
HPO
4
+ H
2
O im tng ng 2
HPO
4
2-
+ NaOH Na
3
PO
4
+ H
2
O im tng ng 3
*Tnh pH ca dung dch ti cc thi im:











*Nhn xt:
-ng nh phn c 3 im tng ng. Tuy nhin ch c im tng
ng th 1 v 2 l c bc nhy.
3 2 1
13
S mol NaOH
pH
4
5
9
H
3
PO
4

NaH
2
PO
4

Na
2
HPO
4

23
c c bc nhy, tc l c th xc nh c im tng ng ng
vi mi nc th hng s K
i
ca mi nc phi cch nhau t nht 10
4
ln.
Trong thc t c th nh phn n nc th 3 bng cch gin tip nh sau:
Cho tc dng vi CaCl
2
, lng HCl gii phng c xc nh bng NaOH:
2H
3
PO
4
+ 3Ca
2+
= Ca
3
(PO
4
)
2
+ 6H
+

6H
+
+ 6OH
-
= 6H
2
O
-Chn ch th: xc nh im tng ng th nht 1 dng metyl da cam,
im tng ng th 2 dng phenolphtalein.


3.6.2. Chun a baz bng n axit mnh
Xt c th: Lp phng trnh ng nh phn 100 ml dung dch Na
2
CO
3

0,1M bng dung dch chun HCl 0,1M vi K
1
= 4,3.10
-7
, K
2
= 4,8.10
-11
(pK
1
=6,36, pK
2
=10,3)
CO
3
2-
+ H
+
HCO
3
-
(1)
HCO
3
-
+ H
+
H
2
CO
3
(2)
24
4. Chng 4: PHNG PHP CHUN TO PHC
4.1. Gii thiu cc complexon
1)Complexon I l axit nitriltriaxetic (NTA), k hiu:H
3
Y, cn gi l trilon A.
CH
2
COOH
N CH
2
COOH
CH
2
COOH
Complexon I to phc km bn vi ion kim loi nn t dng.
2)Complexon II l axit etylen diamin tetraaxetic (EDTA), k hiu : H
4
Y, t
tan trong nc.
HOOC-CH
2
CH
2
-COOH
N-CH
2
-CH
2
-N
HOOC-CH
2
CH
2
-COOH
3) Complexon III (trilon B) : mui dinatri ca axit etylen diaminotetra axetic
(mui dinatri ca EDTA), k hiu : NaH
2
Y
2-
, trong phng th nghim vn hay quen
gi l EDTA.
NaOOC-CH
2
CH
2
-COOH
N-CH
2
-CH
2
-N
HOOC-CH
2
CH
2
-COONa
4.2. S to phc ca EDTA vi cc ion kim loi
4.2.1. Phn ng to phc
Mt trong cc axit amino polycaboxilic c ng dng rng ri v sm nht
trong phn tch th tch l axit etylen diamin tetra axetic (EDTA):
HOOC-CH
2
CH
2
-COOH
N-CH
2
-CH
2
-N
HOOC-CH
2
CH
2
-COOH
EDTA l axit 4 nc H
4
Y: K
1
= 10
-2
, K
2
= 10
-2,76
, K
3
= 10
-6,16
, K
4
= 10
-10,26
.
EDTA t tan trong nc, v vy hay dng di dng mui dinatri Na
2
H
2
Y
2
,
thng gi l complexon III (thi quen vn gi l EDTA)
25
EDTA to phc bn vi cc ion kim loi v trong hu ht trng hp phn
ng to phc xy ra theo t l ion kim loi : thuc th = 1: 1:
M
n+
+ Y
4-
MY
(n-4)+

Vi hng s bn kh cao.
Thng th cc php chun complexon c tin hnh khi c mt cc cht
to phc ph duy tr pH xc nh nhm ngn nga s xut hin kt ta hydroxit
kim loi.
S phn ly ca thuc th:
H
4
Y H
+
+ H
3
Y
-
K
1

(1)
H
3
Y
-
H
+
+ H
2
Y
2-
K
2

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

(3)
HY
3-
H
+
+ HY
4-
K
4

(4)
S to phc hodroxo ca ion kim loi:
M
n+
+ H
2
O MOH
(n-1)+
+ H
+

1

(5)
M
n+
+ 2H
2
O MOH
(n-2)+
+ 2H
+

2

(6)
...
M
n+
+ jH
2
O MOH
(n-j)+
+ jH
+

j

(7)
(j = 1 N vi N: s phn t nc m ion kim loi c kh
nng to phc hidroxo ti a).
S to phc ph ca ion kim loi:
M
n+
+ X MX
1

(8)
26
M
n+
+ 2X MX
2

2

(9)

M
n+
+ nX MX
n

n

(10)
(n = 1 N vi N: s phn t X m ion kim loi c kh nng to phc ph ti
a).
Phn ng to phc chnh gia EDTA vi ion kim loi:
M
n+
+ Y
4-
MY
(n-4)+

MY

(11)
S to phc cha proton hoc to phc hydroxo ca phc to thnh:
MY + H
+
MHY K
MHY

(12)
MY + OH
-
MOHY K
MOHY

(13)
( n gin khng ghi in tch ca cc phn t)


4.2.1.1. *S to thnh cc complexonat

N
OOCCH
2
CH
2
CH
2
N
CH-CHOO
CH
2
-COONa Ca
NaOOC-CH
2

Phn ng gia complexon III v ion kim loi Me
n+
nh sau:
Me
2+
+ H
2
Y
2-
MeY
2-
+ 2H
+

Me
3+
+ H
2
Y
2-
MeY
-
+ 2H
+

Me
4+
+ H
2
Y
2-
MeY + 2H
+

4.2.2. bn phc cht, hng s bn iu kin
n gin v d dng khi tnh ng chun chng ta dng phng php
gn ng da trn vic s dng hng s bn iu kin:
27

| |
| | | |
, ,
,
.
'
Y M
MY
= (14)
Trong :
[MY]

= tng nng cc dng tn ti ca phc gia ion kim loi v EDTA


[MY]

= [MY] + [MHY] + [MOHY] (15)


T hp (15) vi nh lut tc dng khi lng p dng cho (12) v (13) ta c:
[MY]

= [MY](1 + K
MHY
[H
+
] + K
MOHY
[OH
-
] (16)
[M]

= tng nng cc dng tn ti ca ion kim loi tr cc dng to phc


vi EDTA, tc l nng ion kim loi cha b chun
[M]

= [M] + | | | |

= =
+
N
n
N
j
j
MX MOH
1
'
1
) ( (17)
T hp (17) vi nh lut tc dng khi lng p dng cho (5-10) ta c:
[M]

= [M] (1 + | | | |

= =

+
+
N
n
n
n
N
j
j
j
X H
1
'
1
(18)
[Y] = tng nng cc dng tn ti ca EDTA tr cc dng to phc vi ion
kim loi
[Y] = [Y] + [HY] + [H
2
Y] + [H
3
Y] + [H
4
Y] (19)
T hp cc biu thc nh lut tc dng khi lng p dng cho (1-4) ta c:
[Y] = [Y](
4 3 2 1
4 3 2 1 3 2 1
2
2 1
3
1
4
K K K K
K K K K h K K K h K K h K h + + + +
) (20)
(h = [H
+
])
T hp (14, 16, 18, 20) ta c:

MY
Y M


= ' (21)
Trong :

MY
= (1 + K
MHY
h + K
MOHY
[OH
-
])
-1
(22)

M
= (1 +

'
1
*
N
j
j
j h + | |

=
N
n
n
n
X
1
)
-1
(23)
28

Y
=
4 3 2 1 3 2 1
2
2 1
3
1
4
4 3 2 1
K K K K h K K K h K K h K h
K K K K
+ + + +
(24)
(*: hng s to phc hydroxo, : hng s to phc MX
n
)
Nh vy hng s bn iu kin ph thuc vo pH ca dung dch v nng
cht to phc ph X. Trong trng hp khng c hoc b qua cht to phc ph th
ch ph thuc pH ( mt gi tr pH cho c mt gi tr tng ng).
4.3. Tnh nng ion kim loi trong qu trnh chun . Sai s chun
4.3.1. Tnh nng ion kim loi trong qu trnh chun
Ta hy thit lp phng trnh tng qut ca qu trnh chun dung dch
mui kim loi M (C
o
, V
o
) bng EDTA (C, V).
p dng nh lut bo ton nng u ta c:

| | | |' ' MY M
V V
V C
C
O
O O
M
+ =
+
=
(25)

| | | |' ' MY Y
V V
CV
C
O
Y
+ =
+
=
(26)
(25) tr (26) ta c:
| | | |
V V
CV V C
Y M
O
O O
+

= ' '
(27)
Chia c hai v cho C
o
V
o
, bin i ta c:

| | | | 0 1 ) ' ' ( = +
+
F
V C
V V
Y M
O O
O
(28)
T (14) ta c:
| |
| |
| |
,
,
,
'
1
M
MY
Y

=
(29)

| | | |
,
' ( M
V V
V C
MY
O
O O

+
=
(30)
Phng trnh tng qat c t hp t (28), (29), (30):
(
| |
,
1
'
1
M V V
V C
O
O O
+
-
'
1

- [M])
V V
V C
O
O O
+
+ 1 F = 0 (31)
Khi > 10
8
ta c th coi s phn li ca phc MY l khng ng k, khi :

| |
V V
V C
MY
O
O O
+
= ' (
(32)

29
Tnh ton mt s im trong qu trnh chun :
-Trc im tng ng: [Y] << [M] nn t (27) ta c:

| |
V V
CV V C
M
O
O O
+

= '
(33)
-Ti im tng ng: F = 1, nn t (28) ta c:

| | | | 0 ) ' ' ( =
+

O O
O
V C
V V
Y M

(34)
T (29) ,(32), (34) ta c:
| |
V V
V C
M
O
O O
+
= .
1
'
,
2

(35)
T CV = C
o
V
o
ta c:
C C
CC
V V
V C
O
O
O
O O
+
=
+
(36) thay vo (35):

| |
C C
CC
M
O
O
T
+
=
,
,
1

(37)
-Sau im tng ng: [M] << [Y]nn t (27) ta c:

| |
V V
V C CV
Y
O
O O
+

= '
(38)
T (29) ,(32), (38) ta c:
| |
O O
O O
V C CV
V C
M

= .
1
'
,

(39)
[M] = [M].
M
hay pM = pM - lg
M
(40)
vi pM = -lg[M] v pM = -lg[M]
V d: Chun 25,00 ml ZnSO
4
0,001M bng EDTA cng nng pH =
9,00 c thit lp bng h m NH
3
+NH
4
Cl trong [NH
3
] = 0,100M. Tnh pZn
khi thm : a) 24,00 ml b)25,00 ml c)26,00 ml Cho
ZnY
= 10
16,5

(khng k n s to phc hydroxo m ch tnh n s to phc ca Zn
2+
v
NH
3
)
Phn ng chun : Zn
2+
+ Y
4-
ZnY
2-
= 3,16.10
16

(41)
Hoc Zn
2+
+ H
2
Y
2-
ZnY
2-
+ 2H
+

V C
Zn2+
= C
EDTA
nn V
T
= 25,00ml
p dng (23) v (24) ta c:
30
| | | | | | | |
5
4 4
3 4
3
3 3
2
3 2 3 1
2
10 . 4775 , 1
10 . 7681 , 6
1
1
1

+
= =
+ + + +
=
NH NH NH NH
Zn

Y
=
4 3 2 1 3 2 1
2
2 1
3
1
4
4 3 2 1
K K K K h K K K h K K h K h
K K K K
+ + + +

V h = 10
-9
<< K
3
<< K
2
, K
1
nn:

Y
0521 , 0
10 10
10
26 , 10 9
26 , 10
4
4
=
+
=
+

K h
K

ZnY
=
ZnY
.
Zn2+
.
Y4-
= 10
16,5
.1,4775.10
-5
.5,21.10
-2
= 2,34.10
10
= 10
10,39

a)Khi thm 24,00 ml (trc im tng ng), p dng (33) c:
| |
5
10 . 4483 , 3
00 , 24 00 , 25
00 , 24 . 001 , 0 00 , 25 . 001 , 0
'

=
+

=
+

=
V V
CV V C
Zn
O
O O

pZn = pZn - lg
Zn
= -lg3,4483.10
-5
lg1,4775.10
-5
= 9,29
b)Khi thm 25,00 ml( im tng ng), p dng (37) c;
| |
845 , 6
39 , 10 ,
,
10
001 , 0 001 , 0
001 , 0 . 001 , 0
.
10
1 1

=
+
=
+
=
C C
CC
Zn
O
O
T


pZn
T
= pZn
T
- lg
Zn
= - lg10
-6,845
lg1,4775.10
-5
= 11,68
c)Khi thm 26,00ml (sau im tng ng), p dng (39) c:

| |
9921 , 8
39 , 10 ,
10
00 , 25 . 001 , 0 00 , 26 . 001 , 0
00 , 25 . 001 , 0
10
1
.
1
'

=

=
O O
O O
V C CV
V C
Zn


pZn = pZn - lg
Zn
= -lg10
-8,9921
lg1,4775.10
-5
=13,82








F
pZn
31

ng chun 25,00 ml dung dch Zn
2+
bng EDTA 10
-10
M trong m
NH
3
+NH
4
Cl trong [NH
3
] = 0,100M
Nhn xt:
+ng chun cng c dng tng t cc ng chun theo pp khc.
+ gn im tng ng c bc nhy chun . Trong v d trn, bc
nhy pZn l 11,10 12,25 (1,15 n v pZn) nu coi sai s l 0,1%; bc nhy
pZn l 10,13 13,22 (3,1 n v pZn) nu coi sai s l 1%.
4.3.2. Sai s chun
Gi S l sai s chun v S = F-1, t (28) ta c:
S =
| | | |
O O
O
V C
V V
M Y
+
) ' ' (
(42)
gn im tng ng coi CV~C
O
V
O

nn
C C
CC
V V
V C
O
O
O
O O
+
=
+
(43)
T (29,30,42,43) ta c phng trnh tng qut tnh sai s l:
S =
| |
| |
O
O
O
O
CC
C C
M
C C
CC
M
+

+
)
1 1
.
1
(
,
, , ,


Hay S =
| |
| |
O
O
CC
C C
M
M
+
+ )
1
(
1
.
1
,
, , ,

(44)
Khi > 10
8
(phc bn) c th coi [M] >>
,
1

lc ny pt sai s nh sau:
S =
| |
| |
O
O
CC
C C
M
M
+

,
, ,
1
.
1

(45)
V d: Tnh sai s khi chun 25,00 ml Zn
2+
0,001M bng EDTA 0,001M
pH = 9 c thit lp bng h m NH
3
+ NH
4
Cl trong [NH
3
] = 0,100 M, nu
php chun kt thc pZn = 11,00 (khng k n s to phc hydroxo ca km).
pH = 9 theo v d trn ta c:
5
2
10 . 4775 , 1

+
=
Zn
;
Y
0521 , 0 ;
ZnY
=10
10,39
> 10
8

Nn [Zn2+] =
17 , 6
5
11
10
10 . 4775 , 1
10

=
32
Thay cc gi tr vo (45) ta c:
S= % 13 , 0
001 , 0 . 001 , 0
001 , 0 001 , 0
. 10
10
1
10
1
17 , 6
17 , 6 39 , 10
=
+




V d: Chun 25 ml CaCl2 0,001M bng EDTA cng nng . Tnh pCa
sau khi thm 24,5 ml EDTA. a) pH 6, b) pH 10
V d: Xy dng ng cong chun 50 ml Ca2+ 0,01M bng EDTA cng
nng trong dung dch m pH 10.


4.4. Cc cht ch th trong phng php complexon
4.4.1. Yu cu
4.4.2. Mt s ch th kim loi ph bin
4.4.2.1. Eriocrom en T (ETOO)
L ch th thuc nhm phm mu azo, c s dng nhiu nht.
Mu khi tn ti trong dung dch c pH < 7

N
OH
HO
3
S
O
2
N
N
OH

K hiu : H
2
In
-
(pK
2
= 6,3; pK
1
= 11,6) mang in tch m v trong phn t
c nhm sunfo ha nh n c kh nng tan c trong nc. hai nguyn t
hydro trong k hiu l proton ca cc nhm hydroxit chng b tch ra khi kim ha
trong dung dch
H
2
In
-

pK1 = 6,3


HIn
2-

pK2 = 11,5
In
3-

xanh da cam
Nu chun ion kim loi M
2+
pH = 7-11 bng EDTA dng ch th
ETOO ti im dng chun : MIn
-
+ HY
3-
HIn
2-
+ MY
2-

33
Mu chuyn t nho ca MIn
-
sang xanh ca HIn
2-
.
Nu chun EDTA bng M
2+
ti im dng chun :
HIn
-
+ M
2-
MIn
-
+ H
+

Mu chuyn t xanh ca HIn
2-
sang nho ca MIn
-
.
4.4.2.2. Murexit
Thuc nhm phm mu azo v cng hay c s dng.
Anion murexit c mu tm.
K hiu : H
4
In
-
. Bn nguyn t hydro trong k hiu l proton ca cc nhm
amino.
H
4
In
-
H
3
In
2-
+ H
+
K
2
= 10
-9,2

tm tm
H
3
In
2-
H
2
In
3-
+ H
+
K
3
= 10
-10,9
Tm xanh tm
Mu Ca H
2
In : ; CuH
2
In, NiH
2
In, CoH
2
In : vng.
Khi chun vi ch th murexit thng dung mi trng pH = 10-11 ch
th gii phng c mu tm H
3
In
2-
l s chuyn mu r nht.
4.4.3. S chuyn mu v nhy ca cht ch th kim loi
Hu ht cc cht ch th kim loi l nhng axit v baz m cc dng phn li
c mu khc nhau thay i theo pH v s i mu ca cht ch th khi chun (i
mu t mu ca phc gia kim loi v ch th sang mu ca cht ch th trng thi
t do hay ngc li) ph thuc vo pH.
c trng nh lng cho s i mu ca cht ch th kim loi ngi ta
dng hng s bn iu kin ca phc ch th kim loi.
M + In MIn
MIn
=
| |
| | | |
, ,
,
. In M
MIn
(46)
( n gin khng ghi in tch cc phn t)
[MIn]: tng nng cc dng tn ti ca phc gia ch th v kim loi
[MIn]= [MIn] + [MIn
2
] +...
34
[M]: tng nng cc dng tn ti ca ion kim loi khng to phc vi ch
th v vi EDTA
[M] = [M] + | | | |

= =
+
N
n
N
j
j
MX MOH
1
'
1
) ( X: cht to phc ph
[In]: tng nng cc dng tn ti ca ch th khng to phc vi ion kim
loi
[In] = [In] + [HIn] + [H
2
In] + ...
T (46) ta c:
MIn
=
MIn
.
MIn
In M


(47)
Trong :
M
= (1 +

'
1
*
N
j
j
j h + | |

=
N
n
n
n
X
1
)
-1
(48)

In
=
3 2 1 2 1
2
1
3
3 2 1
K K K h K K h K h
K K K
+ + +
(49)
(*: hng s to phc hydroxo, : hng s to phc MX
n
)
T s
| |
| |
,
,
In
MIn
l t s gia nng cht ch th tn ti di dng phc kim loi
vi nng cc dng ch th t do (khng to phc). T ny quyt nh s chuyn
mu ca cht ch th. T (46) ta tnh c nng kim loi t do [M] ng vi thi
im chuyn mu:
[M]= .
1
,

| |
| |
,
,
In
MIn
(50)
Gi thit rng
| |
| |
,
,
In
MIn
= p c s chuyn mu r th
[M]=
MIn
p
,

(51)
Hay pM = lg
MIn
- lgp (52)
Nu chp nhn quy c thng thng mu chuyn r khi p > 10 (mu ca
MIn chim u th) hoc khi p s 10
-1
(mu ca In chim u th) th khong chuyn
mu ca cht ch th s l : pM = lg
MIn
1
35
V d: p =1 ngha l s chuyn mu xy ra khi 50% nng cht ch th tn
ti dng phc vi kim loi v 50% dng t do th: p[M] = lg
MIn
. Tnh c
hng s to thnh iu kin
MIn
ta c th nh gi pM ti im chuyn mu v
nh gi c sai s chun .
V d: Chun Ca
2+
1,00.10
-3
M bng EDTA 1,00.10
-3
M pH = 10,0 c
thit lp bng h m NH
3
+NH
4
Cl trong [NH
3
] = 0,1M, dng ETOO lm ch th.
Hy nh gi sai s ca php chun khi kt thc:
a)50% lng ch th tn ti trng thi t do
b)90% lng ch th tn ti trng thi t do
Phn ng gia kim loi v ch th:
Ca
2+
+ In
3-
CaIn
-

CaIn
= 10
5,4

Phn ng chun :
Ca
2+
+ Y
4-
CaY
2-

CaY
= 10
10,7

im cui chun :
CaIn
-
+ Y
4-
CaY
2-
+ In
3-

Cc phn ng ph:
Ca
2+
+ H2O CaOH
+
+ H
+
*
CaOH+
= 10
-12,6

H
2
In
-
H
+
+ HIn
2-
K
2
= 10
-6,3

HIn
2-
H
+
+ In
3-
K
3
= 10
-11,6

Do *
CaOH+
= 10
-12,6
<< [H
+
] = 10
-10
nn
Ca2+
= 1
p dng (24) tnh
Y
:
V [H
+
] = 10
-10
<< K
3
<< K
2
<< K
1
nn:
Y
= 447 , 0
10 10
10
26 , 10 10
26 , 10
4
4
=
+
=
+

K h
K

p dng (49) cho ch th phn ly 2 nc tnh
In
:

In
=
41
1
10 10 . 10 10
10
9 , 17 10 3 , 6 20
9 , 17
=
+ +


thay cc gi tr
Ca2+
,
In
va tnh c vo (47) v
Y
vo (21) c:

CaIn
=
CaIn
.
79 , 3 4 , 5
CaIn
10
41
1
. 10 . = = =
In CaIn
In Ca



36
tng t ta c:

CaY
=
CaY
.
35 , 10
CaIY
10 . = =
Y CaY
Y Ca



a)Khi dng chun ti thi im 50% lng ch th tn ti trng thi t
do:
T (50, 52) c: pM = lg
CaIn
= 3,79
V
CaY
= 10
10,35
> 10
8
, nn p dng (45) tnh sai s:
S = % 4 , 32
10 . 10
10 10
. 10
10
1
.
10
1
3 3
3 3
79 , 3
79 , 3 35 , 10
=
+


b)Khi dng chun ti thi im 50% lng ch th tn ti trng thi t
do:
T (50) c: [Ca] =
| |
| | 9
1
.
1
.
1
, ,
,
,
CaIn CaIn
In
CaIn

= nn [Ca]= 1,8.10
-5

S = % 6 , 3
10 . 10
10 10
. 10 . 8 , 1
10 . 8 , 1
1
.
10
1
3 3
3 3
5
5 35 , 10
=
+


4.5. Cc phng php chun complexon
4.5.1. Chun trc tip
4.5.2. Chun ngc
4.5.3. Chun thay th
4.5.4. Chun gin tip
4.6. Cc phng php chun phc cht khc
4.6.1. Chun thy ngn
Phng php ny da vo phn ng to phc gia Hg
2+
vi cc anion
haloganua, CN
-
, SCN
-
,... vi ch th l diphenylcacbazit, diphenylcacbazon trong
mi trng pH thch hp.
V d : Hg
+
+ Cl
-
HgCl
-
K
1
= 5,5.10
6

HgCl
+
+ Cl
-
HgCl
2
K
2
= 3,0.10
6

HgCl
2
+ Cl
-
HgCl
3
-
K
3
= 7
HgCl
3
-
+ Cl
-
HgCl
4
K
4
= 10
37
Hai phn ng sau khng c gi tr nh lng v vy trong thc t ch da
vo 2 phn ng u.
4.6.2. Phng php xyanua
Phng php ny da vo phn ng to phc gia Ag
+
(dung dch AgNO
3
) v
ion xyanua CN
-
to phc [Ag(CN)
2
]
-
:
Ag
+
+ 2CN
-
|Ag(CN)
2
|
-

Nu tha Ag
+
th li to ra kt ta:
|Ag(CN)
2
|
-
+ Ag
+
Ag[Ag(CN)
2
] + (T
Ag[Ag(CN)2]
= 10
-
12
)
kt thc nh phn khi bt u thy dung dch vn c do to kt ta
Ag[Ag(CN)
2
] .
Phng php ny dng nh phn gin tip mt s ion kim loi nh : Ni
2+
,
Co
2+
, Cu
2+
, Zn
2+
v chng to c vi CN
-
nhng phc cht bn hn |Ag(CN)
2
|
-

v phn ng xy ra theo mt h s t lng xc nh.
V d : nu cho lng d chnh xc CN
-
vo dung dch Ni
2+
trong amoniac
th ton b Ni
2+
s dng phc |Ni(CN)
4
|
2-
bn hn phc |Ag(CN)
2
|
-
, do c th
nh phn lng tha CN
-
bng phng php trn.
4.7. Cc cht ch th khc
4.7.1. Ch th axit baz
4.7.2. Ch th oxy ho kh
4.7.3. Ch th c bit




38
5. Chng 5: CHUN OXY HA KH

5.1. Cht ch th trong chun oxy ha kh
5.1.1. Trng hp khng dng cht ch th t ngoi vo
5.1.2. Dng cht ch th a t ngoi vo
5.1.2.1. Ch th c bit
5.1.2.2. Cht ch th bt thun nghch
Loi ch th ny c c tnh l mu ca dng oxy ho v dng kh khc
nhau v khng bin i thun nghch c.
V d : nh phn dung dch Sb
3+
bng dung dch KBrO
3

trong mi trng
axit vi ch th metyl da cam hay metly :
3Sb
2+
+ BrO
3
-
+ 6H
+
3Sb
3+
+ Br
-
+ 3H
2
O
dung dch s c mu . Nu cho tha 1,2 git dung dch KBrO
3
th s c
phn ng : BrO
3
-
+ 5Br
-
+ 6H
+
3Br
2
+ 3H
2
O
Br
2
sinh ra s oxy ho metyl da cam hay metyl to thnh 1 hp cht khng
mu, ta kt thc nh phn.
5.1.2.3. Cht ch th oxy ho kh
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,
tn ti trong dung dch theo cn bng:
Ind
OX
+ ne Ind
Kh

Th oxy ho ca h oxy ho kh lin hp ny tnh bng phng trnh Nerst:

| |
| |
Kh
OX 0
Ind
Ind
lg
n
059 , 0
E E + =
Tng t cc cht ch th axit baz, mu sc ca dung dch c quyt nh
bi t s:
| |
| |
Kh
OX
Ind
Ind
.
39
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
| |
| |
Kh
OX
Ind
Ind
> 10 : dung dch c mu dng Ind
OX
,
ng vi dung dch c E
1
>
n
059 , 0
E
0
+
Khi
| |
| |
Kh
OX
Ind
Ind
s
10
1
: dung dch c mu dng Ind
Kh
,
ng vi dung dch c E
2
s
n
059 , 0
E
0

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:

n
059 , 0
E
0
s E
d.d
s
n
059 , 0
E
0
+
v khong gii hn ny gi l khong i mu ca cht ch th oxy ho kh .
Vy khong i mu ca cht ch th oxy ho kh l khong gi tr in th
E m trong khong khi E ca dung dch thay i th mu ca cht ch th oxy ho
kh thay i (mt ngi nhn thy c).
Lu : do 0,059/n l qu nh, trong thc t khong i mu gn trng vi gi
tr th E
0
ca cht ch th oxy ho kh nn ngi ta ch quan tm n gi tr th E
0

ca cht ch th v dng th i mu.
Mt s cht ch th oxy ho kh hay dng:
Ch th
Mu dng
oxy ho
Mu
dng kh
E
0

khi[H
+
]=1
Diphenylamin Xanh tm khng mu +0,76V
Axit diphenylazosulphonic tm khng mu +0,84V
Axit phenylantranilic tm khng mu +1,08V
40
Pheroin Xanh nht +1,06V
Axio,o-
diphenylamindicacbonic
Xanh tm khng mu +1,26V
5.2. ng chun oxy ha kh
5.2.1. Trng hp khi s electron trao i trong cc na phn ng oxy ha kh l
bng nhau









5.2.2. Trng hp khi s electron trao i trong cc na phn ng oxi ha kh l
khc nhau
*C th xt trng hp chun Fe
2+
0,1M bng MnO
4
-
0,1M (pH = 0) :
Fe
2+
Fe
3+
+ e E
2
= 0,68V
MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O E
1
= 1,51V
Ti im tng ng : ) ( 371 , 1
5 1
51 , 1 . 5 68 , 0 . 1
V E
t
=
+
+
=
Bc nhy vi sai s S = 0,1% l :
857 , 0
001 , 0
001 , 0 1
lg
1
059 , 0
68 , 0 =

+ =

E
474 , 1 001 , 0 lg
5
059 , 0
51 , 1 = + =
c
E
E(V) 0,620 0,680 0,736 0,797 0,857 1,371 1,474 1,486 1,498
F 0,09 0,50 0,90 0,99 0,999 1,00 1,001 1,010 1,10
Nhn xt :
F
E
1,3
0,8
Bc nhy th
41
5.2.3. Trng hp khi h s hp thc ca 2 dng ca t nht 1 cp trong 2 cp oxi
ha kh l khc nhau
Cr
2
O
7
2-
+ 6Fe
2+
+ 14H
+
= 2Cr
3+
+ 6Fe
3+
+ 7H
2
O

Hay
| | | |
td td
td
Fe
E E
Cr
E E
E
+ +
+
+
= +
+
=
3
1 2
3
1 2
2
3
lg
7
059 , 0
7
6
2
1
lg
7
059 , 0
7
6

Nh vy th ti im tng ng ph thuc nng cc cht phn ng.

Nh vy sau im tng ng th ph thuc nng cc cht phn ng.
5.3. Mt s phng php oxy ha kh hay dng
5.3.1. Phng php pemanganat
5.3.1.1. Nguyn tc
y l phng php chun oxy ho kh da trn phn ng oxy ho ca
ion MnO
4
-
trong mi trng axit :
MnO
4
-
+ 5e
-
+ 8H
+
Mn
2+
+ 4H
2
O vi E
0
MnO4-/Mn2+
=
1,51V
5.3.1.2. Mt s c im ca phng php chun ny l:
a)Cht ch th:
b)KMnO
4
khng phi l cht gc
c)Ch nn chun trong mi trng axit H2SO4
Tuy nhin, qu trnh chun cn lu :
+Khng 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:
10Cl
-
+ 2MnO
4
-
+ 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.
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 :
42
H
2
SO
4
: ngn nga cc sn phm thu phn ca mui st, ngn cn s oxi ho
Fe
2+
bng O
2
trong khng kh, to mi trng axit mnh.
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 |FeHPO
4
|
+
.
Mn
2+
( MnSO
4
): hn ch phn ng cm ng.
5.3.1.3. u im ca phng php permanganat
5.3.1.4. ng dng ca phng php permanganat
5.3.2. Phng php dicromat
5.3.2.1. Nguyn tc
y l phng php chun oxi ho kh da trn phn ng oxy ho ca
ion cromat Cr
2
O
7
2-
trong mi trng axit.
Cr
2
O
7
2-
+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O E
0
Cr2O72-/2Cr3+
=1,33V
5.3.2.2. Mt s c im ca phng php chun ny l:
a)Cht ch th :
b)K
2
Cr
2
O
7
l cht gc rt bn v n
c)Phng php ny c th chun trong mi trng axit H
2
SO
4
, H
3
PO
4
v
HCl (v E
0
Cr2O72-/2Cr3+
=1,33V; E
0
Cl2/2Cl-
=1,33V). Tuy nhin, khng tin hnh trong
mi trng HCl c nng ln hn 2M v lc ny nng Cl
-
rt ln s lam gim
th ca cp Cl
2
/2Cl
-
v Cr
2
O
7
2-
s oxy ho c 1 phn Cl
-
thnh Cl
2.

5.3.2.3. ng dng ca phng php bicromat
5.3.3. Phng php iot
5.3.3.1. Nguyn tc
Phng php ny da trn phn ng oxy ho ca I
2
v phn ng kh ca I
-
:
I
2
(rn) + 2e 2I
-
E
0
I2/2I-
=0,54V
T gi tr E
0
I2/2I-
ta thy I
2
l cht oxy ho yu hn KMnO
4
, K
2
Cr
2
O
7
nhng I
-

l cht kh mnh. Nhiu cht kh c th b oxy, v nhiu cht oxy ho c th b
kh. Trong phn tch, ngi ta thng dng c 2 tnh cht oxy ho (ca I
2
) v
kh(ca I
-
) xc nh cht kh v cht oxy ho. Phng php ny, ngi ta
43
thng dng phn ng ca thiosunfat (S
2
O
3
2-
) vi iot nn phng php ny c tn l
phng php iot-thiosunfat, phn ng nh sau:
I
2
+ 2e 2I
-

2S
2
O
3
2-
- 2e S
4
O
6
2-

2S
2
O
3
2-
+ I
2
S
4
O
6
2-
+ 2I
-
E
0
S2O32-/S4O62-
=0,1V
5.3.3.2. Mt s c im ca phng php :
a)Cht ch th :
b)Natrithiosunfat Na
2
S
2
O
3
c th kt tinh tinh khit ng ng vi cng thc
Na
2
S
2
O
3
.5H
2
O nhng n khng phi l cht gc v dung dch Na
2
S
2
O
3
khng bn,
d b tc ng bi CO
2
, O
2
v vi sinh vt trong khng kh ( hn ch s phn hu
ny, ngi ta thm vo 10mgHgI
2
/1 lt dung dch Na
2
S
2
O
3
):
Na
2
S
2
O
3
+ CO
2
+ H
2
O NaHCO
3
+ NaHSO
3
+ S+
Na
2
S
2
O
3
+ O
2
Na
2
SO
4
+ S+
c)Qa trnh chun theo phng php iot-thiosunfat cn phi tin hnh
trong mi trng kim yu (pH <9) v nu mi trng kim mnh th phn ng sau
s xy ra: I
2
+ 2OH
-
IO
-
+ I
-
+ H
2
O
IO
-
to thnh c tnh oxy ho mnh, n s oxy ho 1 phn S
2
O
3
2-
thnh
SO
4
2-
:
S
2
O
3
2-
+ 4IO
-
+ 2OH
-
2SO
4
2-
+ 4I
-
+ H
2
O
Trong trng hp sn phm c sinh ra H
+
lm pH ca dung dch gim, khng
m bo mi trng kim yu th phi dng NaHCO
3
ly bt H
+
trong dung dch:
HCO
3
-
+ H
+
= CO
2
| + H
2
O
I
2
l cht thng hoa v kh nng hp ph I
2
ca h tinh bt gim khi
nhit tng nn khng un nng khi tin hnh php chun ny.
I
2
t tan trong nc, tan nhiu trong dung dch KI : I
-
+ I
2
I
3
-
(*)
44
khi s dng php chun ny phi cho KI d. Phn ng (*) to I
3
-
l phn ng
thun nghch v ion I
3
-
rt km bn nn khi dng Na
2
S
2
O
3
chun I
2
, cn bng
(*) b ph v v chuyn dch hon ton sang tri, lng I
2
thot ra c chun
bng dung dch Na
2
S
2
O
3
.
Phn ng gia I
2
vi cc cht kh v I
-
vi cc cht oxy ho thng xy ra
chm, do sau khi thm I
2
hay I
-
vo dung dch cn ch 1 thi gian, phi y kn
dung dch v t vo ch ti (v nh sng lm tng phn ng oxy ho I
-
thnh I
2
bi
O
2
trong khng kh) ri mi tin hnh chun :
4I
-
+ 4H
+
+ O
2
2I
2
+ 2H
2
O
5.3.3.3. ng dng ca phng php chun iot-thiosunfat
a)Xc nh cht kh
V d : SO
3
2-
+ I
2
+H
2
O SO
4
2-
+ 2I
-
+ 2H
+

Sn
2+
+ I
2
Sn
2+
+ 2I
-

b)Xc nh cht oxy ho :bng phng php chun thay th phng php
ny tin hnh theo nguyn tc: thm vo dung dch cht oxy ho 1 lng KI d, ri
to iu kin thch hp phn ng gia I
-
v cht oxy ho xy ra hon ton. I
-
b
oxy ho thnh I
2
(tan nhiu trong KI nn phi dng d KI), chun lng I
2
thot ra
( dng KI
3
-
) bng dung dch chun Na
2
S
2
O
3
.
V d : Cc cht oxy ho nh : Br
2
, MnO
4
-
, Cr
2
O
7
2-
, Fe
3+
,...
Br
2
+ 4I
-
2Br
-
+ I
2

2MnO
4
-
+ 10I
-
+16H
+
2Mn
2+
+ 5I
2
+ 8H
2
O
Cr2O72- + 10I
-
+16H
+
2Cr3+ + 3I
2
+ 7H
2
O
2Fe
3+
+ 4I
-
2Fe
2+
+ I
2

c)Xc nh axit : cch ny dng xc nh nng ion H
+
ca mi trng
v y ngi ta cn c vo phn ng : 5I
-
+ IO
3
-
+ 6H
+
3I
2
+ 3H
2
O
45
T phng trnh ta thy lng ion H
+
tham gia phn ng tng ng lng
I
2
gii phng ra. Do , sau khi phn ng hon ton, ta chun lng I
2
thot ra
bng dung dch chun Na
2
S
2
O
3
. T tnh c lng ion H
+
trong dung dch.







46
6. Chng 6: PHNG PHP CHUN KT TA

6.1. c im ca phng php
Trong thc t c 1 s phn ng kt ta c dng l:
1)Phng php bc: da vo phn ng gia ion Ag
+
(AgNO
3
) vi cc
halogenua (Cl
-
, Br
-
, I
-
) v SCN
-
. Phng php ny c s dng ph bin hn.
Ag+ + X- AgX+
2)Phng php thu ngn :dng nh phn SCN- bng cch to kt ta
Hg
2
X
2
. Hg
2
2+
+ 2X
-
Hg
2
X
2
+
3)Phng php feroxianua : dng xc nh Zn
2+
bng feroxianua kali vi
ch th diphenylamin theo phn ng sau:
2K
4
|Fe(CN)
6
| + 3Zn
2+
K
2
Zn
3
|Fe(CN)
6
|
2
+ 6K
+

4)Chun ion Ba
2+
bng sunfat : Ba
2+
+ SO
4
2-
BaSO
4
+
vi ch th l rodizoonat natri lm ch th. Khi c mt Ba
2+
th dung dch
nhum mu , gn im tng ng mu bin mt.
5)Chun Pb
2+
bng cromat vi ch th Ag
+
, gn im tng ng s xut
hin mu gch do : CrO
4
2-
+ Ag
+
Ag
2
CrO
4
+
6.2. ng chun kt ta
6.2.1. ng chun
Kho st qu trnh nh phn dung dch cha anion halogenua X (C
0
,V
0
)
bng dung dch chun AgNO
3
(C,V) bit T
AgCl
= 10
-10
, pAg + pCl = 10
Phn ng chun : Ag
+
+ X
-
AgX
Khi thm Vml dung dch chun phn ng xy ra th: [Ag
+
].[X
-
] = T
AgX

(1)
Theo nh lut bo ton nng ta c:
[X-] + m
AgX
=
V V
V C
o
o o
+
(2)
v [Ag
+
] + m
AgX
=
V V
CV
+
(3)
47
(m
AgX
: s mol kt ta ng vi 1 lt dung dch)
(3) tr (2) c: [Ag
+
] - [X
-
]=
V V
V C CV
o
o o
+

v chia 2 v ca ptr ny cho


V V
V C
o
o o
+
ta c: | |
| |
o o
o
AgX
o o
o o
V C
V V
Ag
T
Ag
V C
V C CV +
=

+
+
) (
| |
| |
o o
o
AgX
V C
V V
Ag
T
Ag F
+
=
+
+
) ( 1 (4)
t st im tng ng ta khng th b qua [Ag
+
] v [X
-
] nn phi gii (4).
V d: Kho st ng nh phn dung dch NaCl 0,1M hoc NaI 0,1M bng
dung dch AgNO
3
0,1M, cho T
AgCl
= 10
-10
, T
AgI
= 10
-16

Ta tnh pAg hoc pCl. pI theo F:
Khi F = 0,999 p dng (5) ta tnh pAg, pCl, pI
Khi F = 1,001 p dng (7) ta tnh pAg, pCl, pI
st im tng ng dng (4) tnh.
Tnh ton vi tng t khi thay i nng dung dch NaCl ta c bng s
liu sau:









6.2.2. Sai s chun
Tnh sai s chun ta da vo (4).
pAg
V
AgNO3

6,7
4,3
BN
48
Nu dng chun trc im tng ng th(4) s c n gin l:

| |
o o
o
c
AgX
c
V C
V V
Ag
T
F S
+
= =
+
1
(8)
Nu dng chun sau im tng ng th(4) s c n gin l:

| |
o o
o
c
V C
V V
Ag F S
+
= =
+
1
(9)
Nu dng chun st im tng ng th gii(4).
6.3. Cc phng php xc nh im cui trong chun o bc
6.3.1. Phng php Mohr
Ag
+
+ Cl
-
AgCl+ K
2
CrO
4
ch th
Ti gn im tng ng hay ti im tng ng khi d 1 git AgNO
3
,
xut hin kt ta gch Ag
2
CrO
4
ta s dng chun :
Ag
+
+ CrO
4
2-
Ag
2
CrO
4
+ T
Ag2CrO4
= 1,1.10
-12

Vn t ra l: phi chn c nng K
2
CrO
4
l bao nhiu kt ta xut
hin ti im tng ng, tc l khi: pAg = pCl = 5 (T
AgCl
= 10
-10
)
c kt ta Ag
2
CrO
4
th |Ag
+
|
2
. |CrO
4
2-
| > 2.10
-12

|CrO
4
2-
| >
| |
2
2 5
12
2
12
10 . 2
) 10 (
10 . 2 10 . 2

= =
Ag
M
Vy th mun kt thc gn im tng ng cn dng lng K
2
CrO
4
tha
mn: 2.10
-4
MsC
K2CrO4 s
2M.
Tuy nhin, vi nng ny mu vng m ca ion cromat s cn tr vic
nhn ra mu nu ca kt ta Ag
2
CrO
4
nn thc t thng dng dung dch
K
2
CrO
4
5.10
-3
M (tng ng khong 5%).
iu kin chun trong phng php Mohr:
-Trong mi trng baz mnh xy ra phn ng ca Ag
+
vi OH
-
to Ag
2
O:
-Cn phi loi cc ion cn tr nh :Ba
2+
, Pb
2+
, Bi
3+
(v chng to kt ta vi
CrO
4
2-
); S
2-
, SO
4
2-
, PO
4
3-
, C
2
O
4
2-
(v chng to kt ta vi Ag
+
).
-Dung dch chun AgNO
3
bao gi cng cha buret.
49
- nhy ca cht ch th gim khi nhit tng do tan ca Ag
2
CrO
4
tng
nn phi chun nhit thp.
6.3.2. Phng php Volhard
Phng php Volhard dng nh phn dung dch AgNO
3
bng dung dch
NH
4
SCN chun vi ch th l Fe
3+
dng phn FeNH
4
(SO
4
)
2
.12H
2
O 1M (dng 1 -2
ml dung dch phn st trn 100 ml hn hp chun ).
Cl
-
) theo nguyn tc: dung dch cha halogen cn chun tc dng vi
lng d chnh xc dung dch chun AgNO
3
:X
-
+ Ag
+
(d) AgX+ + Ag
+
(cn
li)
Sau nh phn lng Ag
+
cn li bng dung dch chun NH
4
SCN theo
phng php Volhard trc tip. T tnh c lng Ag
+
phn ng vi X
-
v
tnh c lng halogen X
-
.
Lu : trong s cc halogen th nh phn ngc Br
-
, I
-
thun li v chnh
xc hn so vi nh phn ngc Cl
-
v kt ta AgCl c T
AgCl
= 10
-10
, kt ta AgSCN
c T
AgSCN
= 10
-12
nn khi nh phn lng Ag
+
cn li, ng l gn hay ti im
tng ng, mt git dung dch cui cng NH
4
SCN lm dung dch nh phn phi
nhum hng ngay nhng li thy xut hin kt ta AgSCN do SCN
-
kt hp vi Ag
+

ca kt ta AgCl tan phn li ra. Do kt qu phn tch s b sai:
AgCl Ag
+
+ Cl
-

Ag
+
+ SCN
-
Ag SCN
Mun nh phn ngc Cl
-
theo phng php trn t kt qa tt c th dng
2 bin php sau y: lc kt ta AgCl tch ra khi dung dch trc khi dng
NH
4
SCN nh phn lng Ag
+
cn li hoc cho thm mt t dung mi hu c
nh: nitrobenzen C
6
H
5
NO
2
lm chm qu trnh phn li ca AgCl v ngn cn
AgCl tip xc vi SCN
-
.
u im ca phng php ny l c th nh phn trong mi trng axit do
AgSCN khng tan trong axit nn ta c th dng nh phn bc trong hp kim
c ph mu bng axit mnh. Cc ion Ba
2+
, Pb
2+
khng gy cn tr trong phng
50
php ny. Cc ion cn tr : mui thu ngn (I) to kt ta vi SCN
-
, cc cht oxy
ho s oxy ho SCN
-
, cht c kh nng to phc bn vi Fe
3+
nh PO
4
3-
, F
-
.
6.3.3. Phng php Fajans
6.3.3.1. Hin tng hp ph trong qu trnh nh phn
Trong qu trnh nh phn, cc kt ta c xu hng ho keo, nht l cc
halogenua bc. Kt ta keo hp ph chn lc, c bit hp ph mnh ion to ra kt
ta c trong dung dch nn s to ra nhng ht keo tch in cng du y nhau.
V d :nh phn dung dch KI bng dung dch AgNO
3
ta thy rng:
Trc im tng ng : trong dung dch tha I
-
, kt ta AgI s hp ph I
-

to thnh ht keo tch in m : AgI + mI
-
nAgI.mI
-

Sau im tng ng : dung dch tha Ag
+
, ta li c ht keo tch in
dng: pAgI + qAg
+
pAgI.qAg
+

Trng thi kt ta AgI t tch in m sang tch in dng s c lc khng
tch in, lc gi l im trung ho in (im ng in). im trung ho in
c th trng hoc khng trng im tng ng tu thuc vo bn cht ca kt ta.
6.3.3.2. Cht ch th hp ph
Cht ch th hp ph l nhng cht mu hu c in li yu. Theo Fajians, cc
anion ca ch th hp ph khi b hp ph ln b mt kt ta tch in dng s b
bin dng v thay i mu. Li dng tnh cht ny xc nh im tng ng.
Cc cht ch th thng dng l fluoretxein v cc dn xut ca n nh eozin.
V d : Cht ch th eozin l mt axit hu c yu k hiu l HE. Trong
dung dch tn ti theo cn bng : HE H
+
+ E
-

E
-
trng thi t do c mu hng, khi b kt ta hp ph c mu tm hoa c.
Nu dung eozin xc nh im tng ng khi nh phn dung dch KI bng
dung dch AgNO
3
th :
Trc im tng ng: nAgI.mI
-
khng hp ph E
-
v cng du (-), E
-
vn
trng thi t do, dung dch c mu hng.
Sau im tng ng : pAgI.qAg
+
s hp ph E
-
, kt ta s nhum mu tm
hoa c.
51
6.3.3.3. chnh xc ca php chun dng cht ch th hp ph ph thuc vo
cc yu t sau
a)Tnh hp ph chn lc ca cht ch th :Trng hp l tng nht l cht
ch th thay i mu ngay sau im tng ng khi in tch kt ta va i du.
iu ny cn tu thuc vo lc ion ca cht mu v ion li. S hp ph khng
nhng ph thuc vo tng tc tnh in m cn ph thuc vo tnh cht phn cc
ca cc cht, v vy anion ca cht mu c th hp ph chy ua vi anion li.
V d : Eozin c th y Cl
-
v chim v tr ion to th:
AgCl, Cl
-
Na
+
+ flBr
-
AgCl, flBr
-
Na
+
+ Cl
-

b)nh hng ca pH : Cht mu b hp ph ch yu dng anion m nng
ca n ph thuc pH v vy khi chun phi duy tr pH thch hp sao cho nng
anion mu ln bo m cn bng hp ph v s i mu r.
V d: Fluoretxein l axit rt yu (K
A
= 10
-7
) do khng th chun pH
<7 v khi y cht ch th tn ti ch yu dng khng phn li v kh nng hp ph
b hn ch. Mt khc, cn lu : dng axit ca fluoretxein t tan trong nc. i vi
ch th diclofluoretxein l axit mnh hn (K
A
= 10
-4
) v kh nng hp ph ca anion
ny mnh hn nn c th chun pH thp.
c)Tnh cht b mt ca kt ta: S hp ph ph thuc nhiu vo b mt ca
pha rn. Nu cht kt ta b ng t th cht ch th hp ph km tc dng. Cn trnh
s c mt ca cc ion kim loi a ho tr (nh Al
3+
, Fe
3+
) c tc dng lm ng t
mnh kt ta. trnh ng t c th cho vo hn hp chun mt cht keo bo
v, v d khi chun Cl
-
c th cho dextrin, gelatin. Khng c chun cc
dung dch qu c v s ng t d xy ra hn (nng chun khng c qu
0,025 M). Ngoi cc cht ch th anion, ngi ta cng dng c cc cht ch th cation
nh metyl tm, rozamin 6G, metyl vng,...




52

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