3

1. CHNG 1
DUNG DCH CHT IN LY CN BNG HO HC

1.1. CHT IN LY MNH V CHT IN LY YU
Cht in li mnh trong dung dch thc t phn li hon ton, a s cc mui tan,
kim v axit mnh u thuc nhm ny.
Trong dung dch, cht in li yu phn li khng hon ton. Cc axit yu, baz
yu v phc cht l cc cht in li yu.
c trng cho kh nng phn li ca cc cht trong dung dch, ngi ta dng
hai i lng : in li v hng s in li K ( hng s cn bng). in li ca
mt cht ph thuc vo nhit , bn cht ( th hin qua hng s in li K) v nng
ca cht in li trong dung dch. in li v hng s in li K lin h vi nhau qua
h thc Ostwald nh sau:

=
1
2
C
K (C: nng ban u ca cht tan)

1.2. CN BNG HO HC V HOT
1.2.1. Nhc li mt s kin thc cn dng
1.2.1.1. Nng gc (C
0
)
1.2.1.2. Nng ban u (C):
1.2.1.3. Nng cn bng [ ]
1.2.1.4. nh lut bo ton nng
Pht biu: nng ban u ca mt cu t no bng tng nng cn bng
cc dng tn ti ca cu t trong dung dch thi im cn bng.
1.2.1.5. nh lut bo ton in tch
m bo tnh trung ho in ca dung dch cht in li, tng in tch m ca
cc anion bng tng in tch dng ca cc cation c mt trong dung dch.
1.2.2. Cn bng v hng s cn bng
Nng cn bng c tnh trn hng s cn bng.
mA + nB + .... pC + qD +.... (a)
4
trong A, B, C, D,... l nhng cu t tham gia cn bng (a) m chng khng
tch in. p dng nh lut tc dng khi lng ta c:

[ ] [ ]
[ ] [ ]
K
n B A
D C
m
q p
= (1.1)
trong [A], [B], [C],.... l nng cn bng K ca cc cht A, B, C,...Nu A,
B, C, ... l nhng ion th trong biu thc (1.1) ta phi thay nng bng hot do
phi tnh n tng tc tnh in ca chng. Nh vy, hot l nng thc ca ion
trong dung dch.
Mi lin h gia hot (a) v nng (C):
a = f.C (1.2)
f: h s hot ; n ph thuc vo lc ion ca dung dch. Lc ion biu th
tng tc tnh in gia cc ion trong dung dch:

) . (
2
1
2
1
i
n
i
i
Z C

=
=

C
i
: nng ca ion i; Z: in tch ca ion i.
Tu thuc vo m f c cc gi tr khc nhau.

5
2. CHNG 2
I CNG V PHN TCH KHI LNG
V PHN TCH TH TCH

2.1. NGUYN TC CHUNG CA PHNG PHP PHN TCH KHI
LNG
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
tng phn tch.
2.2. CC PHNG PHP PHN TCH KHI LNG
Phng php phn tch khi lng c th c tin hnh theo cc phng php
sau: phng php y, phng php in phn, phng php chng ct, phng php
kt ta.
2.2.1. Phng php y:
2.2.2. Phng php in phn
2.2.3. Phng php chng ct
2.2.4. Phng php kt ta
2.3. Phng php kt ta
2.3.1. Ni dung v yu cu ca kt ta trong phng php kt ta
Cn phn bit dng kt ta v dng cn.
6
2.3.2. iu kin tin hnh phn tch theo phng php kt ta
2.3.2.1. Thuc kt ta
2.3.2.2. Lng cht phn tch
2.3.2.3. Nng thuc th
2.3.2.4. Lc kt ta
2.3.2.5. Ra kt ta
2.3.2.6. Lm kh v nung kt ta
2.4. PHNG PHP PHN TCH TH TCH
2.4.1. i cng v phn tch th tch
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) v da vo nh lut ng lng hoc nh lut hp thc xc nh :
A + B = C + D

A
B B
A
V
N V
N
.
=
Mt s nh ngha v khi nim cn nm: Qu trnh nh phn, im tng
ng, im cui chun .
2.4.1.1. Cht ch th
Cht ch th l cht c kh nng cho tn hiu nht nh (i mu, kt ta,...) ti
im tng ng. Vic dng qa trnh chun l da vo hiu ng ca cht ch th.
Do vic hiu bn cht ca cht ch th cho php ta tnh c sai s ca php phn
tch.
2.4.1.2. Dung dch chun gc (dung dch tiu chun)
Dung dch chun gc v cch pha.
2.4.2. Cc phn ng dng trong phn tch th tch
2.4.3. Phn loi cc phng php phn tch th tch
1)Phng php chun axit baz (chun trung ho): da trn phn ng axit
baz.
2)Phng php chun oxy ho kh: da trn phn ng oxy ho kh.
3)Phng php chun to phc: da trn cc phn ng to phc bn (thuc
th dng nhiu nht l cc complexon).
7
4)Phng php chun kt ta: da vo phn ng to kt ta.
2.4.4. Cc cch chun
2.4.4.1. Chun trc tip
2.4.4.2. Chun ngc
2.4.4.3. Chun thay th
2.4.4.4. Chun gin tip
2.4.4.5. Chun phn on
2.4.5. Cch biu din nng trong phn tch th tch
2.4.5.1. Nng th tch
2.4.5.2. Nng phn trm khi lng:
2.4.5.3. Nng mol
2.4.5.4. Nng ng lng
2.4.5.5. chun
2.4.5.6. Nng phn triu v phn t
i vi cc dung dch rt long hoc c hm lng cht xc nh rt nh, ngi
ta dng nng ny.
2.4.6. Cch tnh kt qu trong phn tch th tch
Trong phn tch th tch, vic tnh ton kt qu ph thuc vo cch biu din
nng v cch phn tch. Nguyn tc chung l da vo nng , phng trnh phn
ng v c th tnh theo nh lut hp thc hoc theo nh lut ng lng.
nh lut hp thc: Khi phn ng hon ton th to cc i ca mi cht phn
ng phi bng nhau. To cc i bng s mol ban u chia cho h s hp thc ca
mi cht.
Gi s c phn ng aA + bB = cC + dD
a, b, c, d : h s hp thc ca A, B, C, D.
nh lut hp thc biu din nh sau:
b
V C
a
V C
B B A A
. .
=
nh lut ng lng : s ng lng mol ca dung dch chun bng s
ng lng mol cht xc nh phn ng vi nhau:
V
A
.N
A
= V
B
.N
B
= a
B
/
B
8
2.4.6.1. Trng hp chun trc tip
2.4.6.2. Trng hp chun ngc
2.4.6.3. Trng hp chun gin tip

3. CHNG 3
CN BNG AXIT BAZ. CHUN AXIT BAZ

3.1. CC QUAN NIM V AXIT, BAZ
3.1.1. Thuyt axit, baz ca Arhenius
Trong dung dch nc, axit l nhng cht phn ly cho ion hydro (H
+
), baz l
nhng cht phn ly cho ion hydroxit (OH
-
).
3.1.2. Thuyt axit, baz ca Brnsted Lowry
3.1.2.1. Ni dung
Axit (c th l phn t : HCl, H
2
SO
4
, hoc ion: Al
3+
, NH
4
+
,) l nhng cht
c kh nng cho proton.
Baz (c th l phn t: NaOH, KOH hoc ion: CO
3
2-
, Cl
-
,) l nhng cht c
kh nng nhn proton.
Phn ng axit l phn ng m trong c s cho v nhn proton. Ta c th biu
din nh sau:
HA H
+
+ A
-

(axit)
B + H
+
BH
+
(baz)
HA + B A
-
+ BH
+
A
-
l baz lin hp ca axit HA: HA/A
-
, BH
+
l axit lin hp ca baz B:B/BH
+
Khi ho tan mt axit hay mt baz vo dung mi th s c tng tc gia axit v
baz vi dung mi, to ra cc cp axit /baz lin hp :
axit + S (dung mi) baz + SH
+

baz+ S (dung mi) axit + S
-

Theo thuyt ny th cc axit, baz c th l phn t, anion, cation.

Ngoi ra cn c cc cht lng tnh, v d nh nc:
9
H
2
O (axit) H
+
+ OH
-
(baz)
H
2
O (baz) + H
+
H
3
O
+
(axit )
3.1.2.2. Dung mi
Theo thuyt axit,baz ca Brosted Lowry, dung mi ng vai tr quan trng
quyt nh mnh yu ca axit, baz. Da vo kh nng cho v nhn proton ca
dung mi, ta chia dung mi thnh hai nhm: dung mi khng cha proton v dung mi
c cha proton.
3.1.2.3. Phn ng axit, baz
Theo Brosted Lowry, phn ng axit baz c biu din nh sau:
Axit (1) + Baz (2) Axit (2) + Baz (1)
3.1.2.4. Cng axit, cng baz. Hng s axit K
A
, hng s baz K
B

Cng axit, cng baz ni ln kh nng cho hoc nhn proton ca cc
axit, baz. Kh nng cho nhn proton ny c nh gi qua hng s axit K
A
, hng s
baz K
B
. Xt axit HA trong nc, ta c cn bng:
HA + H
2
O H
3
O
+
+ A
-

[ ] [ ]
[ ] HA
A O H
K
A
+
=
*
3
(2)
K
A
: v bn cht l hng s cn bng nn n khng i v ph thuc vo nhit .
K
A
l i lng c trng cho cng ca axit. K
A
cng ln, axit cng mnh v
ngc li.
Tng t c hng s baz K
B
: B + H
2
O BH
+
+ OH
-
[ ] [ ]
[ ]
+
+
=
B
OH BH
K
B
*
(3)
K
B
v bn cht l hng s cn bng nn n khng i v ph thuc nhit . K
B

l i lng c trng cho cng baz. K
B
cng ln tnh baz cng mnh.
3.2. CN BNG AXTI BAZ TRONG MI TRNG NC
3.2.1. Tch s ion ca nc, ch s hydrogen:
pH = -lga
H+
; pOH = -lga
OH-

Trong phn tch thng dng cc dung dch long nn c th xem h s hot
bng 1, lc pH=-lg[H
+
] ; pOH=-lg[OH
-
]. Ta lun c : pH + pOH = 14
3.2.2. Quan h gia K
A
, K
B
ca mt cp axit, baz lin hp
K
A
.K
B
= K
H2O
(25
0
C) = 10
-14

10
K
H2O
(25
0
C) : tch s ion ca nc 25
0
C.
n gin ngi ta dng i lng ch s cng axit pK
A
v ch s cng
baz pK
B
vi: pK
A
= -lgK
A
; pK
B
= -lgK
B
Lc : pK
A
+ pK
B
= 14
3.2.3. Tnh pH ca mt axit, baz, mui trong nc
3.2.3.1. Cng thc tng qut tnh pH ca dung dch hn hp axit v baz lin hp
Bi ton: Xt dung dch cha hn hp gm axit HA c nng C
A
, K
A
v baz
lin hp A
-
di dng NaA c nng C
B
.
[ ]
[ ] [ ]
[ ] [ ]
+
+
+
+
+
=
OH H C
OH H C
. K H
B
A
A
(6)
(6) l cng thc tng qut tnh pH ca dung dch cha cp axit/baz lin hp.
3.2.3.2. Tnh pH ca dung dch axit mnh n chc
Cc axit mnh thng gp l nhng axit n chc nh: HCl, HNO
3
, HBr,...tr
H
2
SO
4
l a axit c K
1
= , K
2
= 10
-2
. Axit mnh trong nc phn li hon ton:
HA H
+
+ A
-
[H
+
]
2
- C
A
. [H
+
] - K
H2O
= 0 (8)
Phng trnh (8) dng tnh chnh xc pH ca dung dch axit mnh.
3.2.3.3. Tnh pH ca dung dch baz mnh n chc
[H
+
]
2
+ C
B.
[H
+
] - K
H2O
= 0 (11)
Phng trnh (11) dng tnh chnh xc pH ca dung dch baz mnh.
3.2.3.4. Tnh pH ca dung dch axit yu n chc
V trong dung dch ch c axit yu nn coi nh C
B
= 0 v lc cng thc tng
qut tnh pH ca dung dch axit yu ni chung l:
[ ]
[ ] [ ]
[ ] [ ]
+
+
+

+
=
OH H
OH H C
K H
A
A
* (13)
3.2.3.5. Tnh pH ca dung dch baz yu n chc
[ ]
[ ] [ ]
[ ] [ ]
+
+
+
+
+
=
OH H C
OH H
K H
B
A
*
3.2.3.6. Tnh pH ca dung dch cha axit v baz lin hp (HA / A
-
)
Nu thm vo nc axit HA v baz lin hp A
-
( dng NaA) th lng ion
hydro c th tng hoc gim, dung dch s tr nn axit hay baz.
Tu theo mi trng ca dung dch l axit hay baz m c th chia cc trng
hp xem xt.
11
3.2.3.7. Tnh pH ca dung dch a axit
Theo Brosted Lowry, a axit l nhng axit m phn t hay ion ca n c th
cho 2 proton tr ln v s tng ng vi cc hng s axit K
1
,K
2
,...K
n
.
1)Nu axit khng qa yu (K
1
10
-4
, pK
1
4), p dng cng thc :
[ ]
[ ]
[ ]
+
+
+

=
H
H C
. K H
A
1

2)Nu axit qu yu (K
1
< 10
-4
, pK
1
> 4), p dng cng thc :
[ ]
A A
C . K H =
+
; pH =
2
1
(pK
A
lgC
A
)
3.2.3.8. Tnh pH ca dung dch a baz
Theo Brosted Lowry, baz a chc l nhng baz m phn t hay ion ca n
c kh nng nhn 2 proton tr ln.V d: Na
2
CO
3
, Ca(OH)
2
, Na
3
PO
4
,...


1)Nu a baz khng qu yu ( K
B1
10
-4
, pK
B1
4), cng thc tng qut (6)
c n gin li v ta tnh pH theo cng thc:
C
B
[H
+
]
2
- K
H2O
.[H
+
] - K
H2O
.K
cuicng
= 0
2)Nu a baz qu yu (K
B1
< 10
-4
, pK
B1
> 4), cng thc tng qut (6) c n
gin li v ta tnh pH theo :

pH = 14 -
2
1
(pK
B1
lgC
B
) = 7 +
2
1
(pK
cuicng
+ lgC
B
)
3.2.3.9. Tnh pH ca dung dch cht lng tnh
Cc cht nh NaHCO
3
, Na
2
HPO
4
,trong dung dch phn ly thnh cc ion
HCO
3
-

, HPO
4
-
, Cc ion ny u l cc cht lng tnh.
Nu C
0
>> K
1
v C
0
.K
1
>> K
H2O
ta c cng thc rt gn thng dng:
[ ]
2 1
.K K H =
+
; pH = ) (
2
1
2 1
pK pK +
Cng thc ny cho thy pH ca dung dch mui axit khng ph thuc vo nng
ca n m ch ph thuc vo cc gi tr hng s phn ly axit.
3.3. DUNG DCH M
3.3.1. Khi nim dung dch m
Dung dch m l dung dch hn hp ca axit yu v baz lin hp ca n (hoc
baz yu v axit lin hp), dung dch ny c kh nng gi c pH gn nh khng i
12
khi ta thm vo dung dch 1 lng nh axit hoc baz mnh hoc pha long 1 s ln
nht nh.
Cng thc tnh:
B
A
A
C
C
pK pH lg = hay
B
A
A
C
C
pK pH lg = (25)
3.3.2. m dung
m dung l s mol axit mnh hay baz mnh thm vo 1 lt dung dch m
pH ca dung dch thay i 1 n v.
Cng thc tnh :
C
Cb Ca *
* 303 , 2 = : mol
C
A
: nng axit, C
B
: nng baz lin hp, C = C
A
+ C
B


ma x
khi C
A
= C
B
= C/2 hay
ma x
= 2,303.C/4= 0,575.C
ngha l
ma x
khi pH = pK
A
.
3.3.3. ng dng dung dch m trong phn tch ( lm mi trng)
1)Trong phn tch nh tnh : dung dch m dng lm mi trng tch cc ion ra
khi nhau hoc pht hin ion bng phn ng c trng.
2)Trong phn tch nh lng : dung dch m dng lm mi trng chun
xc nh nng cc cht.
3.4. PHNG PHP CHUN AXIT BAZ
3.4.1. Bn cht ca phng php
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 ).
Dung dch chun trong phng php ny l axit mnh hoc baz mnh (HCl,
H
2
SO
4
, NaOH, KOH,).Cc cht ny khng p ng cc yu cu ca cht gc nn
khng phi l cht gc. V vy, cc dung dich ny ch c chun b vi nng gn
ng. Sau nng cc dung dch ny s c chun ho bng dung dch chun
gc khc.
13
3.4.2. Cht ch th trong phng php trung ho
3.4.2.1. Khi nim
Cht ch th trong phng php trung ho l nhng axit (HInd), baz (IndOH)
hu c yu m mu ca dng axit v baz lin hp l khc nhau, v c kh nng thay
i cng vi s thay i pH ca dung dch . Dung dch mu ca cht ch th thay i
trong mt khong pH hp, khong pH ny ch ph thuc vo bn cht ca cht ch th,
khng ph thuc vo cc cht phn ng vi nhau trong dung dch.
3.4.2.2. L thuyt v cht ch th axit baz
1) Thuyt ion:
2)Thuyt nhm mang mu :
3) Thuyt ion-nhm mang mu: Thuyt ny kt hp hai thuyt trn v gii thch
c hu ht hin tng i mu ca cht ch th axit baz. Theo thuyt ny, cht ch
th axit baz l nhng cht hu c, trong dung dch chng tn ti 2 dng h bin (to
ng phn c th chuyn ho ln nhau) hoc nhn prton th cu trc ca n ng thi
thay i theo v dn n s i mu. Mt trong 2 dng h bin ca cht ch th c th
l axit hu c yu hay baz hu c yu ( c khi l cht lng tnh). Gi s mt trong
hai dng h bin l mt axit yu, trong dung dch s tn ti mt h 2 cn bng sau:
HInd
0
I HInd II H
+
+ Ind
-
(a)
I : cn bng h bin; II; cn bng baz
Mu ca dung dch do t s nng 2 dng h bin quyt nh. Nh vy, khi pH
thay th cn bng I v II s chuyn dch sang tri hay sang phi v mu ca cht ch
th thay i theo.
3.4.2.3. 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 .
3.4.2.4. Ch s nh phn pT ca cht ch th
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.
14
3.4.2.5. 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
3.5. XC NH IM TNG NG TRONG PHNG PHP
TRUNG HO VI DUNG MI NC
Khi nh phn mt dung dch axit bng mt dung dch baz hay ngc lai ta s
c phn ng : A
1
+ B
2
= B
1
+ A
2
Trong trng hp l tng, khi kt thc nh phn, cht ch th phi i mu
ngay im tng ng ngha l pT ca cht ch th trng vi pH ca dung dch
im tng ng. Nhng trong thc t, pT c sai khc ( thiu hoc tha) so vi pH
ca dung dch im tng ng nn gy ra sai s.
3.5.1. Khi nim ng nh phn (ng cong logarit)
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.
3.5.2. Nguyn tc xy dng ng nh phn axit baz
Tnh pH ca dung dch ng vi cc thi im nh phn:
1)Trc khi chun : cha thm thuc th
2)Trc im tng ng : gi s ti cc thi im 50%, 90%, 99% lng
thuc th cn a vo t im tng ng.
3)Ti im tng ng: khi thm ng 100% lng thuc th t im
tng ng .
4)Sau im tng ng: gi s ti cc thi im tha 0,1%; 1%; 10%,...thuc
th.
Ni cc gi tr pH ti cc thi im trn ta c ng nh phn
15

3.6. CC TRNG HP CHUN
3.6.1. Chun axit mnh bng baz mnh:
Kho st qu trnh chun 100ml dung dch HCl 0,1M bng dung dch NaOH
0,1M ta c ng nh phn:
Phn ng chun : NaOH + HCl = NaCl + H
2
O (1)

ng chun dung dch axit HCl 0,1 N bng dung dch NaOH 0,1M
Bc nhy pH cn ph thuc nng cc dung dch.
Bc nhy
pH
100
4,3
9,7
7
9,7
Bc nhy
pH
100
4,3
V
NaOH

7
V
NaOH

16
3.6.2. Chun axit yu bng baz mnh hoc baz yu bng axit mnh
3.6.2.1. Chun dung dch axit CH
3
COOH bng dung dch NaOH
Kho st qu trnh chun 100 ml dung dch axit CH
3
COOH 0,1M (C
0
, V
0
)
bng dung dch NaOH 0,1M (C,V). Bit pK
CH3COOH
= 4,75.
Phn ng chun : CH
3
COOH + NaOH = CH
3
COONa + H
2
O


ng nh phn dung dch CH
3
COOH 0,1N (ng 1) v dung dch HCl 0,1N
(ng 2) bng dung dch NaOH 0,1N

2
1
8,87
6,8
10,6
Bc nhy
pH
100
V
NaOH

3.6.2.2. Chun dung dch NH
3
bng dung dch axit HCl
Kho st qu trnh chun 100 ml dung dch NH
3
0,1M (C
0
, V
0
) bng dung
dch HCl 0,1M (C,V), bit pK
NH3
= 4,75.
Phn ng chun : NH
3
+ HCl = NH
4
Cl
17

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
V
HCl
(ml)
6,26
18
4. CHNG 4
CN BNG OXY HO KH.CHUN OXY HO KH

4.1. CN BNG OXI HO KH
4.1.1. Phn ng oxy ho kh
Phn ng oxy ho kh l phn ng xy ra c km theo s trao i electron gia
cc cht tham gia phn ng . Mt phn ng oxy ho kh bao gi cng gm 2 qu
trnh: cho v nhn electron.
Tu thuc vo iu kin phn ng, mt cht c th va l cht oxy ho , va l
cht kh ( H
2
O
2
, H
2
SO
4
, HNO
3
, S,).
4.1.2. Cch thnh lp phng trnh oxy ho kh theo phng php ion-electron
Phng php ion-electron da trn s cn bng khi lng v cn bng in tch
cc cu t tham gia phn ng trng thi tn ti ch yu ca chng trong dung dch.
Cc cht in li mnh vit di dng ion.
Cc cht in li yu, cht kh vit di dng phn t
Cht rn vit di dng phn t hay nguyn t
C s tham gia ca mi trng th phi c H
+
, OH
-
trong phng trnh
4.1.3. Cng cht oxy ho. Th in cc
Th in cc l i lng o cng ca cht oxy ho v cht kh ca cc cp
oxy ho kh.Th cng cao, cht oxy ho ca cp cng mnh v cht kh ca cp oxy
ho kh lin hp cng yu. Mun so snh th ca cc cp oxy ho kh lin hp th
phi o th ca chng trong nhng iu kin nh nhau.
Th ca cp oxy ho kh lin hp Ox/Kh (gi tt l th oxy ho kh):
Ox + ne Kh
c xc nh bng cng thc Nerst:

Kh
O
O
a
a
nF
RT
E E
X 0
X/Kh
ln + = (1)
Trong : E : th oxy ho kh ca cp Ox/Kh
E
0
:l mt hng s v c gi l th tiu chun, n ch ph thuc vo bn cht
ca cp oxy ho kh.
R : hng s kh (8,315 Jun/mol.)
T : nhit tuyt i
19
F : s Faraday ( 96500 Culomb)
n : s electron trao i (cho hay nhn)
a
OX
, a
Kh
: hot ca cht oxy ho v cht kh trong dung dch.
Mt cch tng qut hn : nu cht oxy ho, cht kh tham gia vo cc phn ng
kt ta, to phc th cng thc Nerst c dng:
aA + bB +cC + ne mM + nN + ...
th :
n
N
n
M
c
C
O
a a
a a
nF
RT
E E
.
.
ln
a
A 0
X/Kh
+ =

vi a
A
, a
B
, a
M
, a
N
l hot ca cc cht tham gia v sn phm ca phn ng.
Nu thay cc gi tr R, F v i logarit t nhin sang logarit thp phn th 25
0
C,
phng trnh Nerst c vit li l:

n
N
m
M
c
C
O
a a
a a
n
E E
.
.
lg
059 , 0
a
A 0
X/Kh
+ =
Biu din hot qua nng ta c:

[ ] [ ]
[ ] [ ]
n m
c a
O
N M
C A
n
E E
.
.
lg
059 , 0
0
X/Kh
+ = +
N M
C A
f f
f f
n .
.
lg
059 , 0
(2)
Phng trnh (2) cho thy rng th in cc khng nhng ph thuc vo nng
cc dng oxy ho v dng kh m cn ph thuc vo lc ion ca cc ion trong dung
dch. Trong phn tch thng dng dung dch long nn c th coi f
ox
: f
kh
= 1, ta c
phng trnh n gin hn l:
[ ] [ ]
[ ] [ ]
n m
c a
O
N M
C A
n
E E
.
.
lg
059 , 0
0
X/Kh
+ = (3)
E
0
l th thc ch dng c trong mi trng c th.
Trong thc t, khng th xc nh c gi tr tuyt i th oxy ho ca 1 cp
oxy ho kh lin hp m ch xc nh c gi tr tng i ca n so vi th ca 1
cp khc. so snh th ca cc cp oxy ho kh lin hp vi nhau th cn xc nh
gi tr tng i th ca cc cp y so vi th ca 1 cp oxy ho kh lin hp c
quy c bng 0 khi a
Ox
= a
Kh

v trong thc t thng so snh vi th tiu chun ca
cp hydro 2H
+
/H
2
vi quy c th cp hydro bng 0.

20
4.1.4. Chiu ca phn ng oxy ho kh v cc yu t nh hng
4.1.4.1. Chiu ca phn ng oxy ho kh
Nu bit c gi tr E
0
ca cp oxy ho kh ta c th on c chiu ca phn
ng oxy ho kh .
4.1.4.2. Cc yu t nh hng n chiu phn ng oxy ho kh
1)nh hng ca nng
Theo phng trnh Nerst :
[ ]
[ ] Kh
Ox
n
E E
O
lg
059 , 0
0
X/Kh
+ =
Gi tr in th oxy ho kh ca mi cp ph thuc t s ca dng oxy ho v
dng kh. Do khi thay i t s nng ny th in th s thay i dn n thay
i chi ca phn ng oxy ho kh .
2)nh hng ca mi trng
Khi xc nh chiu ca cc phn ng oxy ho kh c s tham gia ca ion H
+
,


ngi ta thng da vo cc gi tr ca cc cp oxy ho kh tng ng trong iu kin
[H
+
] = 1M. Nu trong phn ng c s tham gia ca ion H
+
, khi nng ion H
+
thay i
th dn n cc gi tr th oxy ho kh cng thay i v chiu ca phn ng cng thay
i theo.
4.1.5. Hng s cn bng v vn tc ca phn ng oxy ho kh
4.1.5.1. Hng s cn bng ca phn ng oxy ho kh
Phng trnh oxy ho kh:
pOx1 + qKh2 pKh1 + qOx2
Hng s cn bng ca phn ng l:
[ ] [ ]
[ ] [ ]
q p
q p
2 Kh . 1 Ox
2 Ox . 1 Kh
K =
Khi phn ng t cn bng, ta c th tnh hng s ny theo in th oxy ho kh
ca hai cp oxy ho kh lin hp trong phn ng :
+ Tnh theo cp th 1:
[ ]
[ ]
p
p
1
0
X1/Kh1 O 1
1 Kh
1 Ox
lg
n . p
059 , 0
E E + =
+ Tnh theo cp th 2 :
[ ]
[ ]
q
q
2
0
X2/Kh2 O 2
2 Kh
2 Ox
lg
n . q
059 , 0
E E + =


[ ]
[ ]
p
p
1
0
1
1 Kh
1 Ox
lg
n . p
059 , 0
E +
[ ]
[ ]
q
q
2
0
2
2 Kh
2 Ox
lg
n . q
059 , 0
E + =
(t p.n
1
= q.n
2
= n)
21
- =
0
1
E
0
2
E
[ ] [ ]
[ ] [ ]
p q
p q
1 Ox . 2 Kh
1 Kh . 2 Ox
lg
n
059 , 0

K lg
n
059 , 0
E
0
= vi
[ ] [ ]
[ ] [ ]
p q
p q
1 Ox . 2 Kh
1 Kh . 2 Ox
lg K =


059 , 0
E n
K lg
0

=

059 , 0
E n
0
10 K

=
4.1.5.2. Vn tc phn ng oxy ho kh
Cc yu t nh hng n vn tc phn ng:
1)Tng nhit
2)Tng nng cht phn ng v pH ca mi trng:
3)Cht xc tc
4)Phn ng cm ng : L nhng phn ng m khi mt mnh n th xy ra chm
nhng khi c phn ng no trong h xy ra th vn tc ca n tng. Phn ng ny
c th lm sai lch, nh hng n qu trnh phn tch.
4.2. PHUNG PHP CHUN OXI HO KH
4.2.1. Ch th dng trong phng php oxy ho kh
4.2.1.1. Trng hp khng dng cht ch th t ngoi vo
Trong trng hp ny, thuc th l mt cht c mu r rt v ta kt thc nh
phn khi dung dch i mu.
4.2.1.2. Dng cht ch th a t ngoi vo
1)Ch th c bit : Loi ch th ny dng nhn ra lng thuc th tha ra (1,2
git) trong qu trnh nh phn. S cht ch th thuc loi ny khng nhiu.
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.
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 + =
22
Tng t cc cht ch th axit baz, mu sc ca dung dch c quyt nh bi t
s:
[ ]
[ ]
Kh
OX
Ind
Ind
.
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
E
d.d

n
059 , 0
E
0
+
v khong gii hn ny gi l khong i mu ca cht ch th oxy ho kh .
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.
4.2.2. ng nh phn trong phng php oxy ho kh
4.2.2.1. Tnh th oxy ho kh ca dung dch E
dd
trong qu trnh chun
Biu din mi quan h gia in th ca dung dch (E
dd
)v lng thuc th thm
vo trong qu trnh chun ln trc to ta c ng nh phn oxy ho kh.
Ta xt trng hp sau y:
Tnh th oxy ho kh ca dung dch E
dd
trong qu trnh nh phn V
0

ml dung
dch Fe
2+
C
0
M bng dung dch Ce
4+
CM trong mi trng axit H
2
SO
4
c [H
+
] = 1M
cho E
0
Fe3+/Fe2+
= 0,77V; E
0
Ce4+/Ce2+
= 1,45V.
Phng trnh phn ng : Ce
4+
+ Fe
2+
Ce
3+
+ Fe
3+
(1)
K
CB
= 10
1.(1,45 - 0,77)/0,059
= 10
11,52
K
CB
ln nn (1) xy ra hon ton. mi thi im nh phn, phn ng s t
mt trng thi cn bng mi, ta c : E
Fe3+/Fe2+
= E
Ce4+/Ce2+
v chnh l in
th ca dung dch ngay ti thi im :
E
dd
= E
Fe3+/Fe2+
= E
Ce4+/Ce2+

Hay E
dd
= E
Ce4+/Ce2+
=
[ ]
[ ]
+
+
+ +
+
2
4
0
2 Ce / 4 Ce
Ce
Ce
lg 059 , 0 E (2)
E
dd
= E
Fe3+/Fe2+
=
[ ]
[ ]
+
+
+ +
+
2
3
0
/Fe2 Fe3
Fe
Fe
lg 059 , 0 E (3)
Do , mun tnh th ca dung dch E
dd
trong qu trnh chun ta c th tnh
theo th ca 1 trong 2 cp. thun li, trc im tng ng ta tnh in th dung
dch theo cp Fe
3+
/Fe
2+
, sau im tng ng ta tnh in th dung dch theo cp
Ce
4+
/Ce
2+
.
23
Tnh th ti cc thi im trong qu trnh chun :
1)Trc lc chun (V<V
t
), trong dung dich c Fe
2+
:
[ ]
[ ]
+
+
+ =
2
3
d d
Fe
Fe
lg 059 , 0 77 , 0 E
trong : [ ]
V V
V . C
Fe
0
3
+
=
+
;
[Fe
2+
] = C
Fe2+
- [Fe
3+
] =
V V
V . C V . C
V V
V . C
V V
V . C
0
0 0
0 0
0 0
+

=
+

+

[ ]
[ ] V . C V C
V . C
Fe
Fe
0 0
2
3

=
+
+

do : E
dd
= 0,77 + 0,059lg
V . C V . C
V . C
0 0
+
(a)
2)Ti im tng ng (V=V
t
) khi cho 100ml dung dch Ce
4+
th ton b Fe
2+

thnh Fe
3+
v Ce
4+
thnh Ce
3+
, theo phn ng chun ta c:
[Fe
2+
] = [Ce
4+
] ; [Fe
3+
] = [Ce
3+
] lc :
[ ]
[ ]
[ ]
[ ]
1
Ce
Ce
.
Fe
Fe
3
4
2
3
=
+
+
+
+

Th ca dung dch c tnh nh sau:

[ ]
[ ]
+
+
+ =
2
3
dd
Fe
Fe
lg 059 , 0 77 , 0 E

[ ]
[ ]
+
+
+ =
3
4
dd
Ce
Ce
lg 059 , 0 45 , 1 E

[ ][ ]
[ ][ ]
+ +
+ +
+ + =
3 2
4 3
dd
Ce . Fe
Ce . Fe
lg 059 , 0 45 , 1 77 , 0 E 2
3)Sau im tng ng (V>V
t
), tnh th da vo cp Ce
4+
/Ce
3+
(coi nh Fe
2+

phn ng ht).

[ ]
[ ]
+
+
+ =
3
4
dd
Ce
Ce
lg 059 , 0 45 , 1 E
24
4.2.2.2. V ng nh phn

ng nh phn dung dch Fe
2+
0,1 N bng dung dch Ce
4+
0,1 N
Lu : c th ko di bc nhy th thun li trong qu trnh chun .
1,11
Bc nhy
E (V)
100
0,95
1,27
V
Ce4+
(ml)
4.2.3. Mt s phng php oxy ho kh hay s dng
4.2.3.1. Phng php permanganat
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
4.2.3.2. Phng php bicromat
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
4.2.3.3. Phng php iot-thiosunfat
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 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:
25
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
26
5. CHNG 5
PHC CHT V THUC TH HU C TRONG HO
PHN TCH. CHUN COMPLEXON

5.1. PHC CHT
5.1.1. nh ngha
Phc cht l loi cht sinh ra do ion n (thng l ion kim loi) kt hp vi
phn t hoc ion khc, c kh nng tn ti trong dung dch v phn li ti mc
sn phm ca s phn li c th ho hp vi nhng cht khc.
Cn phn bit phc cht v mui kp. Tri vi phc cht, mui kp tn ti
trong dung dch v chng phn li thnh cc ion n gin.
5.1.2. Phn loi phc cht
5.1.2.1. Phc cht cng
Trong dung dch, phc cht cng phn li thnh cc ion n gin v ion phc (tc
l ngoi cu v ni cu) c in tch ngc du nhau, ni cu c vit trong du [ ].
Trong ni cu (ion phc) gm ion kim loi lm nhn trung tm kt hp vi cc
phi t (cc phi t c th l phn t, ion v c, hu c hoc phn t hu c) theo lin
kt phi tr khng to vng.
5.1.2.2. Ni phc
Ni phc l nhng phc cht m nhn trung tm gm nhng ion kim loi kt hp
vi phi t l nhng phn t cht hu c bng lin kt phi tr hoc va bng lin kt
phi tr va bng lin kt ho tr to thnh 1 hay nhiu vng.
Ni phc c mt s c im nh sau: phn ln t tan trong nc, tan nhiu
trong dung mi hu c, c bn ln, c mu khc vi mu ca ion trung tm v
m.
5.1.3. bn ca phc cht
5.1.3.1. Hng s bn v hng s khng bn ca phc cht
Trong dung dch, phc cht A
c
B
d
c cn bng sau :
phn li
A
c
B
d
cA + dB (1)
to thnh
27
Hng s cn bng i vi qu trnh phn ly phc: hng s khng bn (K) trong
cn bng (1) l:
[ ] [ ]
[ ]
d c
d c
kb
B A
B . A
K = (a)
Hng s cn bng i vi qu trnh to thnhphc: hng s bn (), trong cn
bng (1) l:
[ ]
[ ] [ ]
d c
d c
B . A
B A
= (b)
So snh (a), (b) ta thy:hng s bn () l nghch o ca hng s khng bn
(K
kb
) :
kb
K
1
= (c)
Hng s khng bn cng nh th hng s bn cng ln, phc cng bn ngha l
phc phn ly cng t.
Da vo hng s khng bn ta c th tnh c nng cn bng ca cc ion
hoc phn t do phc cht phn li ra tm cch tng hay gim cc nng n mc
cn thit phc v cho qu trnh phn tch.
5.1.3.2. S phn hu phc cht
1)Phn hu phc cht bng cc phn ng axit baz
Ni cu do ion kim loi lm ion trung tm v cc phi t l phn t hay ion to
thnh
2)Phn hu phc cht do cu t ca ni cu kt hp vi 1 cht khc to thnh
hp cht t tan.
Nu 1 cht (vi mt lng ln) c th kt hp vi ion trung tm hay vi cc
phi t to thnh mt cht t tan th phc cht c th b phn hu.
3)Phn hu phc cht do cu t ca ni cu kt hp vi cht khc to thnh mt
phc khc bn hn
Nu cho mt cht vi lng ln c th kt hp vi ion trung tm hay vi cc
phi t to thnh mt phc mi bn hn th phc cht trc c th b phn hu.
5.2. THUC TH HU C
Thuc th hu c l cc cht hu c ng dng trong ho phn tch nh tnh,
nh lng tm hay xc nh, phn chia hay lm giu cc nguyn t.
28
5.2.1. Cc phn ng ca thuc th hu c
5.2.1.1. Phn ng to cc hydroxyt hoc cc mui kh tan
V d : cc baz hu c nh piridin C
5
H
5
N, - picolin C
6
H
7
N trong nc c
phn ng baz : C
5
H
5
N + H
2
O C
5
H
5
NH
+
+ OH
-

Do khi tc dng vi mt s ion kim loi th to kt ta hydroxyt
Cc ion ca mt s axit hu c (oxalat, tatrat) to c mui t tan vi mt s ion
kim loi : C
2
O
4
2-
+ Ca
2+
CaC
2
O
4
5.2.1.2. Cc phn ng to thnh sn phm oxy ho kh
V d: Ion Fe
3+
oxy ho benzidin (baz hu c) to thnh diphenylbenzidin tm,
c th dng phn ng ny nhn ra Fe
3+
.
5.2.1.3. Phn ng to phc
Cc phn ng to phc ca thuc th hu c c th chia lm 2 loi sau: phn ng
to phc thng v phn ng to thnh ni phc. Trong phn ng to thnh ni
phc c nhiu ng dng nht trong ho phn tch.
V d : Tm Ni
2+
bng dimetlyglioxim to mui ni phc dimetlyglioximat niken
(phn ng Sugaep):
C NO H
3
C
C N
OH
H
3
C
Ni
C
NOH
H
3
C
C
NOH
H
3
C
NiCl
2
+ 2NH
3
+
2 2NH
4
Cl +
2

5.2.2. c tnh ca thuc th hu c
5.2.2.1. Tnh ring bit ca thuc th hu c
Nhiu thuc th hu c khi tc dng vi cc ion v c trong iu kin nh nhau
u cho phn ng gn nh nhau. Loi thuc th ny khng c tnh ring bit.V d:
piridin (cc ion Zn
2+
, Cu
2+
, Cd
2+
, Ni
2+
,...tc dng vi piridin khi c mt SCN
-
v mt
s anion khc to mui kh tan).
Tri li, mt s thuc th c kh nng cho phn ng c trng vi mt hay mt
s t nguyn t khi c mt cc nguyn t khc. Loi thuc th ny c tnh ring bit
cao v kh him. V d: dng h tinh bt pht hin iot (cho mu xanh c trng).
5.2.2.2. nhy
nhy ca thuc th hu c th hin hiu qu phn tch ca thuc th hu c.
Trong cng mt iu kin tin hnh phn ng, thuc th hu c c nhy cao hn
29
hn so vi cc thuc th khc. V vy mc d mt thuc th hu c no c chn
lc km nhng nhy cao hn, n cng c s dng tt cho mc ch phn tch.
c trng cho nhy ca thuc th, ngi ta dng khi nim pha long
gii hn (nng gii hn) v nng ti thiu (lng nh nht tm thy).
5.2.3. C ch tng tc ca thuc th hu c
Chng ta cp ch yu c ch tng tc ca nhm thuc th hu c to cc ni
phc, c bit i vi thuc th hu c to mui ni phc.
Khi nghin cu ngi ta thy rng : mt thuc th hu c phn ng c vi
mt s ion nht nh to mui ni phc l do cu to phn t ca thuc th hu c
v iu kin tin hnh phn ng
5.2.3.1. Cu to phn t ca thuc th hu c
Kt qu tng tc ca thuc th hu c vi cc ion c quyt nh bi 2 phn
trong phn t thuc th hu c :
Mt phn ca phn t quyt nh s tng tc vi ion ny hay vi ion khc gi l
nhm chc phn tch (nhm nguyn t c trng).
Mt phn khc ca phn t c nh hng n sn phm phn ng gi l phn
gy hiu ng phn tch (nhm hot phn tch).
5.2.3.2. nh hng ca iu kin to kt ta
Trong cc iu kin tin hnh phn ng c nh hng ln n tnh chn lc,
quan trng nht l iu kin pH ca mi trng.
C nhng thuc th hu c c kh nng tc dng c vi rt nhiu ion to
thnh mui ni phc, nhng khi thay i pH ca mi trng th thuc th hu c to
mui ni phc vi mt s ion t hn . Do , c th chn pH ca mi trng thch hp
tng tnh chn lc ca thuc th.
5.2.4. Mt vi loi thuc th hu c hay dng trong ho phn tch
Cc thuc th hu c l dn xut ca amoniac c dng lm cht che, iu
Axit etylendiamin tetraaxetic (EDTA thng gi l complexon) l mt axit 4
chc:
N
HOOCCH
2
CH
2
CH
2
N
CH
2
COOH
HOOCCH
2
CH
2
COOH

Dimetylglioxim cha 2 nhm oxim:
30
C
NOH
H
3
C
C
NOH
H
3
C


Alizarin S to vi nhm mui ni phc c mu :
O
O O
Al
OH OH
OH
SO
3
Na


5.3. NG DNG CA PHC CHT V THUC TH HU C TRONG
HO PHN TCH
5.3.1. Pht hin v xc nh ion
Dng phc cht pht hin cc ion trong phn tch nh tnh h thng cc
cation, thuc th s kt hp vi cc cation to phc c mu c trng. V d : tm Al
3+

bng alizarin S trong mi trng kim dng mui ni phc c mu son son
nhm, tm Ni
2+
bng dimetylglioxim trong mi trng NH
3
dng mui ni phc c
mu ti,...
Dng pha ch dung dch m. V d: hn hp m formiat biphtalat.
Nhiu ion n gin khng c tnh c trng r rt nn t c ng dng trong phn
tch nhng khi chuyn thnh phc cht chng li rt c trng v c th s dng
nhn ra ion . V d : ion Cu
2+
nng long c mu xanh nht, khng th nhn ra
c nhng khi chuyn thnh phc amminacat ng [Cu(NH
3
)
4
]
2+
th c mu xanh
m rt c trng gip vic pht hin Cu
2+
d dng.
Trong phn tch nh lng, thuc th hu c c dng lm cht kt ta trong
phn tch khi lng (V d: xc nh Ni
2+
bng dimetylglioxim), dng lm cht gc
trong phn tch th tch (V d : H
2
C
2
O
4
.2H
2
O c dng lm cht gc cho phng
php trung ho v oxy ho kh ), dng pha ch dung dch chun (V d : dung dch
chun trilon B).
31
5.3.2. Che du
Trong thc t rt t thuc th ch tc dng vi mt ion nht nh m thng cho
phn ng vi ng thi vi mt s ion no . Ta ni cc ion ny cn tr ln nhau. V
vy, khi nhn bit mt ion no trong dung dch c cc ion khc cn tr ta cn phi
che chng li dui dng phc bn, khng mu. Cht a vo trong mi trng phn
ng nhm trit tiu hoc km hm mt phn ng khc c gi l cht che. Cht che
a vo s dng phi to c vi ion cn tr phc c bn ln cc ion
khng cn tc dng c vi thuc th s dng cho ion cn xc nh v bn ca
phc gia ion cn xc nh vi cht che (nu c) phi b ion ny c kh nng
phn ng c trng vi thuc th s dng.
5.3.3. Thay i cng cc cht
S to phc c nh hng n tnh axit baz v tnh oxy ho kh ca hp cht.
Nu anion ca mt axit yu no m to phc vi cation khc th s lin kt
gia n v ion H
+
s yu i, ta s c mt axit mnh hn axit u.
5.3.4. Ho tan v tch
S to phc c th c s dng chuyn kt ta vo trong dung dch hay tch
mt cht ra khi dung dch dng kt ta.
5.4. CHUN TO PHC
5.4.1. Phng php thu 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
Hai phn ng sau khng c gi tr nh lng v vy trong thc t ch da vo 2
phn ng u.
5.4.2. 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
]
-
:
32
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
] .
5.4.3. Phng php chun complexon
5.4.3.1. Cu to ca cc loi complexon
Complexon l dn xut ca axit amino polycacboxylic, c 3 complexon quan
trng hay dng l:
1)Complexon I l axit nitriltriaxetic (NTA), k hiu H
3
Y, 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 : Na
2
H
2
Y, 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

N
OOCCH
2
CH
2
CH
2
N
CH-CHOO
CH
2
-COO
-
Ca
-
OOC-CH
2

5.4.3.2. S to thnh cc complexonat
Phn ng gia complexon III v ion kim loi Me
n+
nh sau:
33
Mg
2+
+ H
2
Y
2-
= MgY
2-
+ 2H
+
Al
3+
+ H
2
Y
2-
= AlY
-
+ 2H
+
5.4.3.3. Cht ch th kim loi trong chun complexon
Ch th kim loi l nhng cht hu c, c mu. Chng c th kt hp vi ion kim
loi to mui ni phc kh bn, tan trong nc. Mui ni phc ny c mu khc vi
mu ca ch th trng thi t do.
Qu trnh nh phn Me
2+
bng H
2
Y
2-
dng ch th kim loi Ind
-
(mu A) xy ra
nh sau:
-Trc nh phn, ta cho 1 lng nh cht ch th th s c phn ng gia
ion kim loi v cht ch th : Me
2+
+ Ind
-
[MeInd]
+
(mu B)
Lc ny dung dch c mu B (mu ca phc gia ion kim loi v ch th) v Me
2+

phn ln tn ti trng thi t do (v lng ch th a vo rt t).
-Khi nh phn : Me
2+
t do kt hp vi thuc th H
2
Y
2-
:
Me
2+
(t do) + H
2
Y
2-
= MeY
2-
+ 2H
+
-Kt thc nh phn: khi tha 1git dung dch thuc th H
2
Y
2-
th n s
phn hu [MeInd]
+
gii phng ra ch th trng thi t do Ind
-
(mu A):
[MeInd]
+
+ H
2
Y
2-
= MeY
2-
+ 2H
+
+ Ind
-
(mu A)
(phc MeY
2-
bn hn phc [MeInd]
+
).
Mt s ch th kim loi trong chun complexon:
-Ericromen T (ET.OO) c th xc nh trc tip phn ln cc cation v
mt s anion. y l cht mu azo, l mui natri ca axit H
3
Ind, trong dung dch tn
ti dng ion k hiu l H
2
Ind
-
N
OH
HO
3
S
O
2
N
N
OH


ET.OO c tnh cht ca mt cht ch th axit baz 3 mu, theo s :
H
2
Ind
-

pK1 = 6,3


HInd
2-

pK2 = 11,5
Ind
3-

xanh da cam
34
pH = 6 : ch th c mu ca dng H
2
Ind
-

pH = 7-11: ch th c mu xanh ca dng HInd
2-

pH >11,5 : ch th c mu da cam ca dng Ind
3-

mi trng kim yu, ET.OO c th kt hp vi Mg
2+
v mt s cation khc
to phc c mu mn : Mg
2+
+ HInd
2-
MgInd
-
+ H
+
-Murexit : l mui amoni ca axit pupuric C
8
H
5
O
6
N
5
, k hiu : H
4
Ind
-
:
pH = 0-9 : ch th c mu tm ca dng H
3
Ind
2-

pH > 11 : ch th c mu xanh ca dng H
2
Ind
3-
. Trong mi trng kim
mnh (pH 12), murexit kt hp vi Ca
2+
to phc mu theo s :
Ca
2+
+ murexit [Ca- murexit]
5.4.3.4. Cc cch chun complexon
1)Chun trc tip: dng khi phc complexonat bn, phc ca ch th vi ion
kim loi km bn v c ch th thch hp.
H
2
Y
2-
+ Mg
2+
= MgY
2-
+ 2H
+
2)Chun ngc: Cho mt lng d chnh xc complexon ( bit nng
chnh xc) vo dung dch cht phn tch pH thch hp ri nh phn lng
complexon d theo cch nh phn trc tip. Da vo lng complexon d ta d
dng tnh c lng ion kim loi cn xc nh theo s :
Me
n+
+ H
2
Y
2-
MeY
n-4
+ H
2
Y
2-
(d)
Lng complexon d c nh phn trc tip bng dung dch chun MgSO
4

hay ZnSO
4
vi ch th ET.OO trong mi trng m amoni.
3) Chun thay th: Cch chun ny da vo tnh cht km bn ca
complexonat magie Na
2
MgY. Na
2
MgY km bn so vi complexonat khc v kt qu
l ion Mg
2+
b y ra khi Na
2
MgY mt lng tng ng theo phn ng :
Me
n+
+ MgY
2-
= MeY
n-4
+ Mg
2+
Sau nh phn trc tip Mg
2+
c gii phng bng complexon vi ch th
ET.OO pH= 9-10.
5.4.3.5. Cc cht ch th khc
1)Ch th axit baz: trong phn ng to complexonat lun gii phng ra mt
lng ion H
+
xc nh. Nu nh lng lng H
+
theo phng php trung ho s
tnh c lng ion kim loi tng ng.
V d : Xc nh lng CaCl
2
: CaCl
2
+ H
2
Y
2-
CaY
2-
+ HCl
35
nh phn lng HCl thot ra bng NaOH vi ch th metyl da cam hay metyl
, t ta tnh c lng CaCl
2
.
Cch nh phn ny c nhc im l trc khi chun phi trung ho mi
trng tht chnh xc.
2)Ch th oxy ho kh:Phng php ny da vo s bin i in th ca mt
h oxy ho kh. S bin i c thc hin bng cch lm thay i nng cc
dng oxy ho v dng kh khi cho tc dng vi complexon.
V d: Trong h feri/fero : [Fe(CN)
6
]
3-
/[Fe(CN)
6
]
4-
v ch th oxy ho kh : 3,3-
imetylnaptidin, nu c mt Zn
2+
th s to kt ta Zn
3
K
2
[Fe(CN)
6
]
2
lm gim nng
ion [Fe(CN)
6
]
4-
do in th ca dung dch s tng ln v cht ch th s i t
khng mu sang tm. Sau nu thm H
2
Y
2-
vo th H
2
Y
2-
s tc dng vi Zn
2+
v
gii phng [Fe(CN)
6
]
4-
ra khi kt ta, in th ca dung dch li gim, ch th tr li
khng mu, ta kt thc nh phn.
3)Ch th c bit: l nhng ch th phn ng chn lc vi mt s ion nht
nh to thnh hp cht c mu c trng.
V d : Axit sunfosalisilic pH = 2 to thnh phc mu tm vi Fe
3+
. Do ,
xc nh lng Fe
3+
ta cho vo dung dch Fe
3+
mt t axit sunfosalisilic pH=2 ,
sau dng H
2
Y
2-
nh phn, phc cht mu tm b H
2
Y
2-
phn hu nn dung dch
dn dn mt mu tm chuyn sang mu vng nht, ta kt thc nh phn.


36
6. CHNG 6
CN BNG TRONG DUNG DCH CHA HP CHT T
TAN. CHUN KT TA

6.1. CN BNG TRONG DUNG DCH CHA HP CHT T TAN
6.1.1. iu kin to kt ta v qui tc tch s tan
Khi cho dung dch NaCl tc dng vi dung dch AgNO
3
, Ag
+
v Cl
-
kt hp vi
nhau to thnh kt ta AgCl tch ra khi dung dch. AgCl s ngng kt ta khi phn
ng t n cn bng : Ag
+
+ Cl
-
AgCl
Khi t n cn bng th : V
ht
= V
kt

Hay a
Ag+
.a
Cl-
= T
AgCl
: ta gi l tch s tan ca AgCl.
Tng qut, i vi cc cht t tan c cng thc B
m
A
n
:
B
m
A
n
mB
n+
+ nA
m-
T
BmAn
= a
B
m
. a
A
n

Nu ngoi ion do cht rn tan ra khng c ion no khc th lc ion ca dung
dch s nh, h s hot gn bng khng nn c th coi hot bng nng . Lc
, tch s tan l: T
BmAn
= [B
n+
]
m
. [A
m-
]
n
(1)
(1) l ni dung ca qui lut tch s tan.
Theo qui lut tch s tan th:
-Khi T
BmAn
> [B
n+
]
m
. [A
m-
]
n
: tc phn ng ho tan ln hn tc
phn ng to kt ta, A v B khng kt hp c vi nhau to kt ta : dung dch
cha bo ho i vi B
m
A
n
v nu thm B
m
A
n
vo dung dch ny th n c th tan
thm n khi t cn bng, lc T
BmAn
= [B
n+
]
m
. [A
m-
]
n
.
-Khi T
BmAn
= [B
n+
]
m
. [A
m-
]
n
: tc phn ng ho tan bng tc phn ng to
kt ta, kt ta cng khng tan i v cng khng to thm: dung dch bo ho.
-Khi T
BmAn
< [B
n+
]
m
. [A
m-
]
n
: tc phn ng ho tan b hn tc phn ng
to kt ta, A v B kt hp c vi nhau to kt ta B
m
A
n
lm gim nng ca
A v B n khi T
BmAn
= [B
n+
]
m
. [A
m-
]
n
(phn ng t cn bng): dung dch qu bo
ho.
37
6.1.2. Quan h gia tan v tch s tan. Cc yu t nh hng n tan
6.1.2.1. tan v tch s tan
tan (S) ca mt cht l nng mol / lit ca cht trong dung dch bo ho
(c th tnh bng nng gam/lt hoc mg/lt).
Tch s tan (T) ca cht l tch s hot ion ca cc ion trong dung dch bo
ho.
Xt cn bng trong dung dch bo ho B
m
A
n
. B
m
A
n
nm cn bng vi cc ion ca
n: B
m
A
n
mB
n+
+ nA
m-
S l tan ca B
m
A
n
c ngha l trong 1 lt dung dch bo ho c S mol B
m
A
n

tan, do : [A
m-
] = nS ; [B
n+
] = mS
T
BmAn
= [B
n+
]
m
. [A
m-
]
n
= (nS)
n
.(mS)
m
= n
n
.m
m
.S
n+m

m n
m n
BmAn
m . n
T
S
+
= (2)
(2) l h thc biu din mi quan h gia tan S v tch s tan T.
6.1.2.2. Cc yu t nh hng n tan S
1)nh hng ca ion chung (ion cng tn): Ion chung l ion c trong thnh phn
ca kt ta : B
m
A
n
mB
n+
+ nA
m-
Nu thm ion chung vo dung dch bo ho ca kt ta , tch s nng ion
s ln hn tch s tan lm cn bng chuyn dch v pha to thm kt ta c ngha l
tan gim xung.
2)nh hng ca ion khc ion ca kt ta (ion l): Cc ion l s lm tng tan
ca kt ta. Khi c mt cc ion l, chng lm tng lc ion ca dung dch, ngha l lm
gim h s hot f trong biu thc tch s tan, do nng ion ca kt ta s tng
v lm tng tan ca kt ta. nh hng ny cn gi l hiu ng mui.
3)nh hng ca nhit :Tch s tan T ch l mt hng s mt nhit nht
nh v vy nu nhit thay i th tch s tan cng thay i. i vi cc cht khi ho
tan thu nhit th tan tng khi tng nhit , i vi cc cht khi ho tan to nhit th
tan gim khi tng nhit .
4)nh hng ca dung mi: Phn ln cc cht v c t tan trong dung mi hu
c hn trong nc do phn cc ca dung mi hu c nh hn phn cc ca
nc. Trong nhng trng hp nu kt ta c to ra dung dch nc c tan ln,
khi cn thit ta tin hnh kt ta trong dung mi hu c thch hp.
38
5)nh hng ca nng H
+
:
6)nh hng ca kch thc ht kt ta: i vi cng mt lng cht, kt ta
ht nh tan nhiu hn kt ta ht ln ngha l tch s tan ca kt ta ht nh ln hn
tch s tan ca kt ta ht ln. Trn tinh th ht nh c nhiu gc cnh, cc ion cc v
tr gc cnh d tan hn nhng ion v tr pha trong, v vy nhng v tr pha trong
cc ion b gi cht hn. Do , trong thc t mun c kt ta c tch hon ton ra
khi dung dch ngi ta tm mi cch c tinh th ht to.
Khi tin hnh tch mt ion di dng kt ta, ion c coi l kt ta hon
ton nu lng ca n cn li sau khi lm kt ta khng cn gy cn tr n phn ng
ca cc ion khc c trong dung dch. Khi tin hnh nh lng, mt ion c coi l kt
ta hon ton nu lng cn li ca n trong dung dch ch nm trong gii hn
chnh xc ca php cn (0,1-0,2mg). i vi cc mc ch phn tch thng thng th
php kt ta c coi l hon ton khi nng ca ion cn tch nm trong khong 10
-
5
-10
-6
M.
7)nh hng ca cht to phc: Nu M ca kt ta MA to phc vi X ln lt
theo cc phng trnh sau:
MA M + A T
MA
= [M]. [A] (*)
M + X MX
[ ]
[ ][ ] X . M
MX
K
1
=
MX + X MX
2

[ ]
[ ][ ]
[ ]
[ ][ ]
2
1
2 2
2
X . M . K
MX
X MX
MX
K = =
MX
n-1
+ X MX
n

[ ]
[ ][ ] X . MX
MX
K
1 n
n
n

=
[ ]
[ ][ ]
n
1 n 2 1
n
X M K ... K K
MX

=
M, A c th mang 1, 2, 3,...in tch, cn X c th dng phn t hay ion. K
1
,
K
2
, ...., K
n
l nhng hng s to phc ca cc nc. Gi S l tan ca MA th c th
vit: S = [M] + [MX] + ...+ [MX
n
]
S = [M] ( 1 + K
1
[X] + K
1
K
2
[X]
2
+....+ K
1
.K
2
.....K
n
.[X]
n
)
Mt phc dng MX
n
vi cc hng s phn li tng nc K
1
, K
2
,...., K
n
c hng s
chung c gi tr l : K
1
.K
2
.....K
n
, nu ta thay tch ca cc hng s tng nc bng hng
s chung K
i
(i : ch phc ca mt phi t), ngha l c i nc phn li s c :
S = [M] vi K [ ]
i
n i
0 i
i
X K

=
=
0
= 1
39
Hay [ ]
[ ]
i
n i
0 i
i
X K
S
M

=
=
=
Thay gi tr ca [M] v [A] = S (MA c tan l S) vo (*), ta c:

[ ]
[ ]
i
n i
0 i
i
X K
S
M

=
=
=
.S = T hay
[ ]

=
=
=
n i
0 i
i
i
X . K . T S

8)nh hng ca s to phc gia kt ta v anion ca n:
Gi s M v A kt ta theo t l 1:1 theo phn ng:
M + A MA
[ ][ ] T
1
Cl . Ag
1
K
1
= =
+

MA
tan
ho tentn1 hp vi A d ln lt to thnh:
MA
tan
+ A MA
2

[ ]
[ ][ ] A . MA
MA
K
tan
2
2
=
MA
2
+ A MA
3

[ ]
[ ][ ] A . MA
MA
K
2
3
3
=
MA
n-1
+ A MA
n

[ ]
[ ][ ] A . MA
MA
K
1 n
n
n

=
MA
tan
l mt hng s, [MA] = S.
K
1
, K
2
,....,K
n
l cc hng s to phc theo cc nc, ta c:

[ ]
[ ][ ] [ ][ ] T
S
A . M
S
A . M
MA
K
tan
1
= = =
m S = [M] + [MA] + [MA
2
] +... + [MA
n
]
Thay cc gi tr tng ng rt ra t cc cn bng trn, ta c:
S= tan ca kt ta =
[ ]

A
T
+K
1
.T + K
1
K
2
T[A
-
] + K
1
K
2
K
3
T[A
-
]
2
+..+ K
1
K
2
..

K
n
T[A
-
]
n-1
[ ]

=
n
0 i
1 i
i
A . K . T S vi K
0
= 1
6.1.3. Kt ta phn on
6.1.3.1. Bn cht ca kt ta phn on
Gi s c 2 ion A v B trong dung dch c nng C
A
v C
B
cng kt ta c
vi ion X ca thuc th tng ng to ra kt ta AX v BX. Nu cho dn thuc th
cha ion X vo dung dch cha c 2 ion A v B, ta xt xem:
-AX hay BX kt ta trc?
40
-Khi no th AX v BX cng kt ta?
-Khi AX v BX cng kt ta, iu kin no cht kt ta trc s kt ta hon
ton?
1)AX hay BX kt ta trc?
Theo qui tc tch s tan : khi tch s nng cc ion to ra kt ta vt qu gi
tr tch s tan th bt u xut hin kt ta, ngha l khi thm dn thuc th, nu
[A].[X] > T
AX
th AX kt ta hay [B].[X] > T
BX
th BX kt ta.
Gi s AX kt ta trc th lng thuc th thm vo phi t gi tr sau:
[A].[X] > T
AX
[X] >
[ ] A
T
AX

Trong khi BX cha kt ta th : [B].[X] < T
BX
[X] <
[ ] B
T
BX

Nh vy, lng thuc th cho dn vo dung dch AX kt ta trc cn BX
cha kt ta phi tho mn iu kin:
[ ] A
T
AX
< [X] <
[ ] B
T
BX
(*)
Theo bt ng thc ny, khi nh dn thuc th mun bit xem hp cht no kt
ta trc ta ch vic so snh hai t s:
A
AX
C
T
v
B
BX
C
T
.
H qu: Trong trng hp n gin, nu AX, BX c cng thc tng t v C
A

= C
B
th hp cht no c tch s tan nh hn hay tan nh hn s kt ta trc.
2)Khi no th AX v BX cng kt ta?
Khi AX kt ta th [A] gim dn, do
[ ] A
T
AX
tng dn, mun AX tip tc kt ta
th cn phi thm X vn tho mn bt ng thc (*), qu trnh ny tip tc n mt
lc th: [X] >
[ ] A
T
AX
=
[ ] B
T
BX
. Lc ny c A v B u cng kt ta.
Vy A v B cng kt ta khi :
[ ] A
T
AX
=
[ ] B
T
BX
hay
[ ]
[ ] B
A
=
BX
AX
T
T
(**)
3)Khi AX v BX cng kt ta, iu kin no cht kt ta trc s kt ta hon
ton?
Gi s AX kt ta trc v kt ta hon ton th trong dung dch [A] cn li
s : [A]
cn li
10
-6
.
41
T (**) ta rt ra iu kin kt ta AX kt ta trc v kt ta hon ton l:
[ ] [ ]
6
BX
AX
10 B
T
T
A

=
Hin tng cc kt ta c to thnh ln lt trong dung dch tch hon
ton cht A ra khi cht B gi l kt ta phn on.
6.1.3.2. ng dng ca kt ta phn on
Pht hin Ba
2+
trong dung dch gm Ba
2+
, Sr
2+
bng dung dch SrSO
4
bo ho v
T
BaSO4
= 1,1.10
-10
< T
SrSO4
= 2,2.10
-7
.
Pht hin Sr
2+
trong dung dch gm Sr
2+
, Ca
2+
bng dung dch CaSO
4
bo ho v
T
SrSO4
= 2,2.10
-7
< T
CaSO4
= 10
-4
.
Trong phn tch nh lng c th dng dung dch AgNO
3
nh phn lin tc
dung dch hn hp I
-
, Cl
-
da vo kt ta phn on I
-
, Cl
-
.
Trong phng php chun kt ta dng phng php Mo, da vo s kt ta
phn on ca Cl
-
v CrO
4
2-
c th nh phn dung dch Cl
-
bng dung dch AgNO
3
.
6.1.4. Chuyn mt hp cht kh tan ny sang mt hp cht kh tan khc
6.1.4.1. Bn cht ca vn
Gi s khi cho mt dung dch thuc th B vo mt cht kh tan AX lm cho kt
ta ny chuyn thnh mt cht kh tan khc : AX
dung dch B
BX
Khi , trong dung dch tn ti cc cn bng:

AX A + X
B
BX
1
2
+

Khi ta cho lng B ln, cn bng (2) s chuyn dch t trn xung di, ko
theo cn bng (1) chuyn dich t tri sang phi v r rng s chuyn kt ta ph
thuc vo tch s tan ca AX, BX v lng thuc th thm vo.
gii quyt cu hi : trong iu kin no AX chuyn hon ton sang BX ta gi
thit rng: cn bng (1) v cn bng (2) chuyn dch t tri sang phi v t trn xung
di, ngha l AX ang tan ra v kt ta c BX to thnh, ta c th vit c:
[B].[X] > T
BX
[X] >
[ ] B
T
BX

42
[A].[X] < T
AX
[X] <
[ ] A
T
AX


[ ] B
T
BX
< [X] <
[ ] A
T
AX
hay
[ ]
[ ] A
B
>
AX
BX
T
T

Vy mun kt ta AX chuyn hon ton sang kt ta BX th phi cho mt
lng thuc th B sao cho bt ng thc trn lun c tho mn.
Qu trnh chuyn kt ta ny c th xy ra 1 trong 3 trng hp sau:
1)Trng hp 1: Nu T
BX
< T
AX
tc l chuyn t hp cht d tan sang mt hp
cht kh tan hn th qu trnh chuyn ny c thc hin d dng v khi t s
AX
BX
T
T
<
1.
2)Trng hp 2 : Nu T
BX
= T
AX
th qu trnh chuyn cng thc hin d dng v
lc ch cn tho mn iu kin :
[ ]
[ ] A
B
> 1.
3)Trng hp 3 : Nu T
BX
> T
AX
tc l chuyn t hp cht kh tan sang mt
hp cht d tan th qu trnh chuyn ny c thc hin kh khn hn v khi
AX
BX
T
T
>1 v nu t s ny ln hn 1 rt nhiu th khng th thc hin c.
6.1.4.2. ng dng ca s chuyn kt ta
1)Ho tan kt ta: Trong nhng trng hp khng th ho tan kt ta mt cch
d dng ngay trong mi trng axit. ho tan c kt ta ngi ta chuyn n
sang mt kt ta khc d tan hn.
V d: BaSO
4
khng tan ngay c trong mi trng axit mnh nh HCl, HNO
3

nhng nu chuyn n sang kt ta BaCO
3
th axit yu CH
3
COOH cng ho tan c
BaCO
3
d dng.
2)Tch ion:
V d : Tch S
2-
ra khi hn hp S
2-
, SO
3
2-
dng bt CdCO
3
nh sau: Do tan
S
CdS
< S
CdCO3
< S
CdSO3
nn kt ta CdCO
3
d dng chuyn sang kt ta CdS. Kt qu l
trong dung dch ta thu c hn hp kt ta gm CdS, CdCO
3
(d). Lc kt ta. Mun
tch CdS ta ch cn nh vo hn hp kt ta mt t axit CH
3
COOH, CdCO
3
tan ht,
ta c kt ta CdS. Kt ta ny em ra sch sau dng HCl c ho tan ta s thu
c dung dch c cha S
2-
dng H
2
S.
43
6.1.5. Ho tan kt ta
Qu trnh ho tan kt ta l qa trnh ngc vi qu trnh to kt ta. i vi hp
cht mui loi M
m
A
n
: M
m
A
n
mM
n+
+ nA
m-
iu kin ho tan kt ta l tch s hot ca cc ion trong dung dch phi
nh hn tch s tan : < T
n
- An
m
Mn
a . a
+ MmAn
tho mn iu kin ny cn phi gim nng ca cc ion trong dung dch
bo ho. Nh vy, nguyn tc chung ho tan kt ta l : gim nng ca t nht
mt trong cc ion do kt ta phn li ra trong dung dch.
Trong thc t c th dng cc bin php sau ho tan kt ta :
6.1.5.1. Ho tan kt ta bng cch to vi ion ca kt ta thnh mt hp cht t phn
li.
Trong trng hp ny cc hp cht t phn li c to thnh c th l axit yu,
baz yu, nc v phc cht.
Ta xt trng hp n gin sau: gi s dng thuc th l cht in li mnh XY
ho tan kt ta MeA to ra mui tan MeY v cht t phn li XA theo phn ng:
MeA + XY MeY + XA (1)
V MeA Me
+
+ A
-
(2)
+
XY = Y
-
+ X
+

XA (3)

MeA + X
+
Me
+
+ XA (4)
Qua cc cn bng (2), (3), (4) ta thy: ho tan kt ta MeA , cn bng (4) phi
lun chuyn dch t tri sang phi. Mun c nh vy, cn bng (3) phi chuyn dch
t trn xung di v cn bng (2) chuyn dch t tri sang phi.
Nh vy, qu trnh ho tan kt ta hon ton nu:
-Tng nng [X
+
] bng cch cho lng thuc th ln.
-K
XA
cng nh tc l hp cht XA c to ra cng t phn li th s kt hp
gia X
+
v A
-
cng tt.
-T
MeA
khng qu nh tc l MeA tan kh tt.
Tnh tan ca kt ta MeA : S
MeA
(mol/lt) :
44
T (4), c 1 mol MeA tan ra s cho 1 mol Me
+
v 1 mol XA, nn:
S
MeA
= [Me
+
] = [XA] (5)

[ ][ ]
[ ]
+
+
=
X
XA . Me
K
ht
K
ht
: hng s ho tan ca cn bng (4) (6)
[X
+
] : nng thuc th lc cn bng.
T (5), (6) ta rt ra c : S
MeA
= [ ]
+
X . K
ht
(7)
T (2) ta c : [Me
+
] .[A
-
] = T
MeA
(8)
T (3) ta c :
[ ][ ]
[ ]
XA
K
XA
X . A
=
+
(9)
Chia (8) cho (9) ta c :
[ ][ ]
[ ]
XA
MeA
K
T
X
XA . Me
=
+
+
v y cng l K
ht
.
Hay
XA
MeA
ht
K
T
K = (10)
Thay (10) vo (7) ta c : S
MeA
=
tt
XA
MeA
C .
K
T
(11)
Nhn xt : t (11) thy rng: tan S tng khi:
-T
MeA
cng ln v K
XA
cng nh.
-Nng thuc th cng ln cng tt (gii hn n nng bo ho).
Lu : Khi T
MeA
nh th S
MeA
s gim nhng nu kt ta XA to thnh c tch
ra khi mi trng phn ng (bay hi hay tan nhiu trong dung mi hu c) th S
MeA

s tng.
V d : AgCl + 2NH
3
[Ag(NH
3
)
2
Cl]
CaC
2
O
4
+ 2H
+
Ca
2+
+ H
2
C
2
O
4
6.1.5.2. Ho tan kt ta bng phn ng oxy ho kh
Nu mt trong cc ion ca kt ta c tnh oxy hay tnh kh th ngi ta thng
dng cc dung mi c tnh oxy hay tnh kh ho tan n.
V d: CuS khng tan trong axit HCl v T
CuS
=10
-45
(rt nh) v H
2
S c to ra
c K
H2S
= 6,9.10
-23
nn ngi ta dng HNO
3
c nng ho tan theo phn ng:
3CuS + 8HNO
3
3Cu(NO
3
)
2
+ 3S + 4H
2
O +NO
do tc dng oxy ho ca HNO
3
nn S
2-
chuyn thnh S
0
lm cho S
2-
gim i rt
nhiu.
45
6.1.5.3. Ho tan kt ta bng cch phi hp c hai phng php trn
Khi kt ta rt t tan, T
MeA
qu nh, nu ta ch dng bin php thay i ho tr ion
th cha gim nng ion n mc cn thit kt ta tan ra hon ton.
V d: HgS c T
HgS
= 10
-53
, bi vy mun ho tan kt ta ny ta cn kt hp c
hai bin php trn bng cch dng nc cng toan:
3HgS + 4HNO
3
+ 2HCl 3[HgCl
4
]
2-
+ 3S + 4H
2
O + 2NO Theo phn
ng ny Hg
2+
kt hp vi Cl
-
to thnh cht t phn li [HgCl
4
]
2-
v S
2-
b oxy ho
thnh S
0
do nng ca c Hg
2+
v S
2-
u gim nn kt ta tan c.
6.1.6. L thuyt v cu to kt ta
6.1.6.1. Kt ta tinh th v kt ta v nh hnh
Kt ta tinh th l loi kt ta m cc ion to ra kt ta sp xp theo mng li
tinh th v theo mt chiu hng xc nh lm cho kt ta c hnh dng nht nh. V
d : kt ta PbCl
2
trng, hnh kim; kt ta PbI
2
vng, hnh vy,...
Kt ta v nh hnh l loi kt ta khng c cu trc mng li tinh th, kt ta
khng c hnh th nht nh. V d : kt ta Al(OH)
3
trng , NiS en,...
Kt ta v nh hnh d bin thnh dung dch keo, b mt tng cng ln, kh
lng, kh lc, kh ra v d nhim bn.
6.1.6.2. Hai giai on ca mt qu trnh kt ta
Qua trnh kt ta l mt qu trnh kh phc tp. Ta xt xem qu trnh to kt ta
BaSO
4
: Ba
2+
+ SO
4
2-
BaSO
4

Nu ch c 1ion Ba
2+
v 1 ion SO
4
2-
th khi gp nhau chng to thnh phn t
BaSO
4
v cha th c cu trc tinh th. to nn cu trc tinh th cn phi c nhiu
ion Ba
2+
v SO
4
2-
tp hp li thnh nhng tp hp nh nhng vn cha gi l kt ta
m ch gi l mm tinh th hay trung tm kt tinh. Giai on ny ca qu trnh kt ta
ng vi s to nn trng thi keo ca vt cht. t cc trung tm kt tinh ny, cc phn
t tip tc tp hp thm v ln dn ln n mc c th thnh ht kt ta lng
xung. Nh vy, qu trnh kt ta gm 2 giai on: giai on to mm tinh th v giai
on mm tinh th ln ln. Trong giai on mm tinh th ln ln, tu thuc vo bn
cht v iu kin kt ta m c th gy ra mt trong hai hng khc nhau to thnh kt
ta tinh th hay kt ta v nh hnh.
1)To kt ta tinh th: Nhng trung tm kt tinh mi c to thnh s ln dn
ln thnh nhng ht tinh th ln ri sau to thnh kt ta tinh th. Qu trnh ny xy
46
ra khi qu bo ho ca dung dch nh. T dung dch ny sinh ra ra chm v t cc
trung tm tinh th kt tinh, tc l tc kt ta nh hn tc nh hng, do to
iu kin cho cc phn t c thi gian phn b ln cc trung tm kt tinh theo v tr
khng gian xc nh hnh thnh nn nhng tinh th ln. Do to tinh th ht
ln phi tin hnh kt ta trong dung dch qu bo ho cng nh cng tt.
2)To kt ta v nh hnh: Nhng trung tm kt tinh s lin kt yu vi nhau to
thnh nhng tp hp nh. Cc tp hp nh ny kt hp vi nhau thnh nhng tp hp
ln hn v cui cng to kt ta v nh hnh. Qu trnh ny c th xy ra trong 2
trng hp sau:
-Do bn cht ca kt ta l v nh hnh: Loi kt ta ny thng thy cc
cht c tan kh nh, nh cc sunfua, hydroxyt kim loi,...V tnh kh tan ca chng
nn khi thm thuc th vo dung dch th dung dch tc thi t trng thi qu bo
ho.
-Do iu kin kt ta: Nu khi tin hnh kt ta t dung dch qu bo ho ln
th s sinh ng thi nhanh v nhiu trung tm kt tinh, do khng to iu kin
nhng trung tm ln ln nn s to ra kt ta v nh hnh.
to ra kt ta l tinh th hay v nh hnh ta cn tm nhng iu kin thun li
nht tin hnh.
6.1.7. Cng kt v kt ta sau. Nguyn nhn lm cho kt ta khng tinh khit
Thng th kt ta tch ra khng th dng tinh khit m c km theo tp cht.
Khi tp cht kt ta ng thi vi kt ta chnh th gi l cng kt. Khi tp cht kt ta
sau khi kt ta chnh kt ta ht th gi l kt ta sau.
6.1.7.1. Cng kt b mt
Cng kt b mt l s hp ph cc tp cht trn b mt ca kt ta.
Nguyn nhn ca s hp ph l nhng ion hay phn t b mt ca kt ta cn
c kh nng ht thm nhng ion hay nhng phn t trong dung dch. Khc vi
nhng ion v phn t trong kt ta, nhng ion v phn t b mt kt ta c nhng
lc ho tr t do nn c th lin kt tip c vi cc tiu phn khc trong dung dch.
Hp ph l mt hin tng thun nghch v nhng ion hay phn t b hp ph c
th tan tr li trong dung dch hay cn gi l gii hp.
47
Khi tc hp ph bng tc gii hp, cn bng hp ph c thnh lp, lng
tp cht b hp ph khng thay i na. Mt s yu t sau y nh hng n cn
bng ny l:
-nh hng ca din tch b mt :lng cht hp ph t l vi din tch b mt
kt ta nn tinh th cng ln th lng cht b hp ph cng nh.
-nh hng ca nng : qu trnh hp ph l mt qu trnh thun nghch nn
n s t mt cn bng ng. V d : Kt ta AgCl trong dung dch KCl th kt ta s
hp ph ion Cl
-
:
nAgCl + mCl
-
nAgCl.mCl
-
Theo cn bng ny : nu tng [Cl
-
] th s hp ph s tng ngha l nng cng
ln th lng cht b hp ph cng nhiu nhng n mt lc no s tng ny s
chm hn khi tng nng .Ngi ta chng minh c rng:
n
1
C . K a = (*)
vi a : lng ion b hp ph; C: nng ca ion b hp ph trong dung dch; K,n
: h s i vi mt h cho. T (*) thy rng : qu trnh gii hp gim chm khi
gim nng C. y l c s cho vic ra kt ta nhng khng lm sch tuyt i
c.








-nh hng ca nhit : qu trnh hp ph l mt qu trnh to nhit:
nAgCl + mCl
-
nAgCl.mCl
-
+ Q
nn nhit cng thp hp ph cng mnh v nhit cng cao th gii hp cng
mnh.
-nh hng ca bn cht kt ta v ion b hp ph: cng trong mt iu kin
vi cng mt kt ta, cc ion b hp ph khc nhau tu theo bn cht ca chng.
L

n
g

i
o
n

b

p

Nng ion b hp ph
48
Thng th ion b hp ph theo qui lut sau: ion to vi ion ca kt ta hp cht cng
t tan b hp ph cng nhiu, do ion ca kt ta b hp ph nhiu hn.
V d : AgI s hp ph mnh I
-
hn Br
-
, Cl
-
, cn i vi NO
3
-
th hp ph rt
yu v : S
AgI
< S
AgBr
< S
AgCl
, cn AgNO
3
tan hon ton trong dung dch. BaSO
4
hp
ph trc ht ion Ba
2+
hay SO
4
2-
trong dung dch, BaSO
4
hp ph mnh SO
4
2-
hn
CO
3
2-
v S
BaSO4
< S
BaCO3
.
-nh hng ca iu kin kt ta : Vi kt ta l v nh hnh nh Fe(OH)
3
,
Al(OH)
3
khi kt ta t dung dch c t hp ph hn khi kt ta t dung dch long, do
lng tp cht b hp ph cng t i. Vi kt ta l tinh th th khi kt ta t dung
dch long tinh th s ln hn khi kt ta t dung dch c, do cng t hp ph tp
cht hn. lu kt ta trong dung dch, kt ta s ln hn v c dng tinh th hon
chnh hn gi l hin tng lm mui kt ta, lng tp cht b hp ph cng gim i.
6.1.7.2. Cng kt trong
Cng kt trong thng xy ra i vi kt ta tinh th. Da vo c im ca
cng kt trong, c th chia lm 2 loi:
1) Cng kt do phn ng gia kt ta v thuc th d:
V d : Khi cho Zn
2+
phn ng vi K
4
[Fe(CN)
6
] th khng sinh ra kt ta
Zn
2
[Fe(CN)
6
] m sinh ra kt ta K
2
Zn
3
[Fe(CN)
6
]
2
. Kh nng ion kim loi kim i vo
trong phc cht ph thuc vo kch thc v mc hydrat ho ca ion . Ion cng
nh cng d vo mng li ca kt ta v cng t tan. Ion hydrat ho cng yu vo
mng li cng d. Mc hydrat ho ca ion kim loi kim tng theo chiu : Cs
+
<
K
+
< Na
+
< Li
+
, nh vy Cs
+
d b cng kt nht.
2)Cng kt ng hnh:
Nguyn nhn ca loi cng kt ny l kt ta v tp cht l nhng cht ng
hnh, tc l nhng cht c kh nng kt tinh trong cng mt mng li tinh th. V d:
phn nhm KAl(SO
4
)
2
.12H
2
O khng mu ng hnh vi phn crm KCr(SO
4
)
2
.12H
2
O
mu tm v khi chng cng kt tinh vi nhau s cho tinh th c mu tm m hay nht
tu theo nng tng i ca chng trong mng li tinh th.
Thng th nhng ion kim loi c s phi tr v bn knh bng nhau th d thay
th nhau trong mng li tinh th m khng lm gim bn ca mng li. V d :
Ra
2+
(1,52A
0
) c bn knh gn bng Ba
2+
(1,43A
0
) nn nu trong dung dch Ba
2+
c rt
t Ra
2+
ta cho SO
4
2-
vo th RaSO
4
v BaSO
4
kt ta trong cng mng li. Ca
2+

49
(1,05A
0
) c bn knh nh hn bn knh ca Ba
2+
nn Ba
2+
v Ca
2+
khng th kt tinh
trong cng mt mng li.
6.1.7.3. Cng kt c hc
Nhng tinh th thng c mng li khng hon ton nn c nhng khe h hoc
nhng ch trng ng y nc ci cha tp cht. Nhng tinh th nh khi kt hp vi
nhau cng c th gi tp cht gia mng li.
6.1.7.4. Ni hp
Trong qu trnh ln ln, tinh th mang theo tp cht trc b hp ph, th t
cho cc thuc th v dung dch tc dng vi nhau rt nh hng n cht b hp ph.
V d: Nu thm dn dung dch H
2
SO
4
vo dung dch BaCl
2
th tinh th BaSO
4

ln dn trong dung dch c d Ba
2+
nn hp ph nhiu Ba
2+
ko theo ion Cl
-
. Ion SO
4
2-

s y dn mt phn ion Cl
-
v ch cn li mt t ion Cl
-
trn kt ta. Ngc li, nu
thm dn dung dch BaCl
2
v dung dch H
2
SO
4
th tinh th BaSO
4
ln dn trong dung
dch c d SO
4
2-
nn hp ph nhiu SO
4
2-
ko theo cc cation khc trong dung dch.
Tc thm thuc th cng nh hng n lng tp cht b hp ph. Nu thm
ngay mt lc thuc th n d th kt ta s hp ph tp cht nhiu. Nu thm t t
thuc th th kt ta ln hn, tinh khit hn, hp ph tp cht t hn v tp cht cng
d b thay th bi ion ca kt ta hn.
6.1.7.5. Kt ta sau
Cc loi cng kt trn ch xy ra trong khi to thnh kt ta. Loi cng kt xy
ra sau khi hon thnh kt ta mt thi gian gi l cng kt sau.
V d : Nu lc ngay kt ta CuS sau khi kt tabng H
2
S trong mi trng axit
c ion Zn
2+
, ta thu c kt ta khng c ZnS. Nhng nu kt ta trong dung dch
mt thi gian, khi lc ta s thu c kt ta c cha c ZnS do : kt ta CuS tip xc
lu vi dung dch bo ho H
2
S s hp ph H
2
S ln b mt kt ta lm cho nng ca
H
2
S tng ln to kt ta ZnS mc d nng axit trong dung dch kh ln.

6.2. PHNG PHP CHUN KT TA
6.2.1. 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.
50
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

6.2.2. ng nh phn trong phng php bc
Trong qu trnh nh phn dung dch cc cht to kt ta, nng ca ion to kt
ta s thay i. Nu ta biu din ch s nng ion to kt ta pIon = -lg[Ion] (Ion c
th l cation hay anion) (trc tung) theo lng thuc th thm vo (trc honh) ta s
c ng cong nh phn Ion.
Kho st qu trnh nh phn 100 ml dung dch NaCl 0,1N (C
0
,V
0
) bng dung
dch AgNO
3
0,1N (C,V) gi thit th tch ca dung dch phn tch trong qu trnh nh
phn khng i bit T
AgCl
= 10
-10
, pAg + pCl = 10:
AgNO
3
+ NaCl AgCl + Na
+
+ NO
3
-
T
AgCl
=[Ag
+
].[Cl
-
]
Trong qu trnh nh phn, nng [Cl
-
] s gim. Biu din s bin thin ca
pCl = -lg[Cl
-
] v pAg = -lg[Ag
+
] (trc tung) theo lng dung dch chun AgNO
3
(trc
honh) ta s c ng nh phn.
6.2.2.1. Tnh pCl v pAg trong qu trnh nh phn
1)Trc im tng ng:
-Khi cha thm dung dch AgNO
3
, trong dung dch ch c Cl
-
:
[Cl
-
] = 0,1; pCl = 1
-Khi thm dung dch AgNO
3
nhng cha n im tng ng, giai on ny
Cl
-
nm 1 phn dng kt ta AgCl, nng Cl
-
cn li trong dung dch l:
[ ]
100
CV V C
Cl
0 0

=

(gi thit th tch dung dch khng i trong qu trnh chun ).

51
2)Ti im tng ng khi cho thm 100ml dung dch AgNO
3
th ton b Cl
-

c kt ta thnh AgCl : [Ag
+
] = [Cl
-
] = 10
-5
; pAg = pCl = 5.
3)Sau im tng ng, AgNO
3
d: [ ]
100
V C CV
Ag
0 0

=
+


6.2.2.2. V ng nh phn v nhn xt

ng nh phn dung dch NaCl 0,1 N bng AgNO
3
0,1 N

5
Bc nhy
pAg
100
4
V
AgNO3
(ml)
6
6.2.3. Cch xc nh im cui
6.2.3.1. Phng php Mo (Mohr)
Trong phng php Mo, K
2
CrO
4
c dng lm ch th xc nh ch yu ion
Cl
-
bng dung dch AgNO
3
da trn hin tng kt ta phn on:
Ag
+
+ Cl
-
= AgCl
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-
] 1,1.10
-12
[CrO
4
2-
]
[ ]
2
2 5
12
2
12
10 . 1 , 1
) 10 (
10 . 1 , 1
Ag
10 . 1 , 1

= = M
52
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:
-Phng php Mohr cn c tin hnh trong mi trng trung tnh hoc kim
yu :pH = 6,5 -10 nhng bo m chnh xc cn tin hnh pH = 8 -10. Trong
mi trng axit mnh, kt ta Ag
2
CrO
4
tan do K
2
CrO
4
mt vai tr ch th. Do vy,
nu mi trng axit cn phi trung ho bng NaHCO
3
hay borac. Nu trong dung dch
c ion NH
4
+
th phi chun pH = 6,5 -7,2 v pH 7,2 c s hnh thnh r rt
NH

3
lm tan mt phn kt ta Ag
2
CrO
4
v gy sai s.
-Trong mi trng baz mnh xy ra phn ng ca Ag
+
vi OH
-
to Ag
2
O:
Ag
+
+ OH
-
= AgOH
2AgOH = Ag
2
O + H
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.
- nhy ca cht ch th gim khi nhit tng do tan ca Ag
2
CrO
4
tng nn
phi chun nhit thp.
6.2.3.2. Phng php Vonha (Volhard)
Phng php Vonha 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 ).
Tin hnh : Nh dn dn dung dch NH
4
SCN chun vo dung dch AgNO
3
, phn
ng nh sau : Ag
+
+ SCN
-
AgSCN
gn im tng ng hay ti im tng ng, git dung dch NH
4
SCN
cui cng lm dung dch nh phn nhum mu hng ta kt thc nh phn v lc
to ra Fe(SCN)
3
(): Fe
3+
+3SCN
-
Fe(SCN)
3

ng dng ca phng php Vonha: nh phn ngc cc halogenua X
-
(I
-
, Br
-
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)
53
Sau nh phn lng Ag
+
cn li bng dung dch chun NH
4
SCN theo phng
php Vonha 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
-
AgSCN
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 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
-
.
6.2.3.3. Phng php dng ch th hp ph : phng php Pha Gian (Fajians)
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.
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.
54
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.
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
-
M Na
+
+ flBr
-
AgCl, flBr
-
M 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
55
cht ch th anion, ngi ta cng dng c cc cht ch th cation nh metyl tm,
rozamin 6G, metyl vng,...
6.2.3.4. Chun Zn
2+
bng K
4
[Fe(CN)
6
]
Trong phng php chun kt ta, ngoi vic chun cc halogenua bng
AgNO
3
, ngi ta cn chun Zn
2+
bng dung dch K
4
[Fe(CN)
6
]. Trong mi trng
trung tnh hay axit yu, ion Zn
2+
tc dng vi K
4
[Fe(CN)
6
] cho kt ta kh tan:
3ZnSO
4
+ 2K
4
[Fe(CN)
6
] K
2
Zn
3
[Fe(CN)
6
]
2
+ 3K
2
SO
4
xc nh im cui ca phng php ny, ngi ta dng ch th oxy ho kh
l diphenylamin v trong dung dch chun c pha thm mt t K
3
[Fe(CN)
6
]. Khi Zn
2+
kt ta ht vi K
4
[Fe(CN)
6
] th 1 git dung dch chun d s to 1 cp oxy ho kh
lin hp [Fe(CN)
6
]
3-
/ [Fe(CN)
6
]
4-
trong dung dch nn trong dung dch xut hin mt
th oxy ho v s oxy ho diphenylamin lm cho n i mu, ta dng chun ti
y.
56