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PHN NG TO THNH CC HP CHT T TAN

I/ Quy tc tch s tan
Khi cho dung dch Ag
+
tc dng vi dung dch Cl
-
, s to thnh kt ta AgCl. Cht kt
ta s ngng to ra khi phn ng sau t n cn bng :

Tc khi vn tc kt ta (v
kt
) bng vn tc ha tan (v
ht
).
Vn tc kt ta t l vi b mt S ca kt ta tip xc vi dung dch v nng ca ion
kt ta. Vn tc ha tan ch t l vi b mt S ca kt ta tip xc vi dung dch.
v
kt
=k
1
.C
Ag+
.C
Cl-
.S
v
ht
= k
2
.S
trng thi cn bng : v
kt
= v
ht
, tc : k
1
.C
Ag+
.C
Cl-
.S = k
2
.S, do :

pT = -logT
i vi dng kt ta tng qut :



v
ht
> v
kt
, A v B khng kt hp vi nhau to kt ta. Dung dch lc ny gi l dung dch
cha bo ha. Nu thm cht rn vo dung dch, cht rn s tan ra cho n khi t c
cn bng (*).

v
ht
= v
kt
, kt ta khng c to thnh m cng khng tan trong dung dch, dung dch lc
ny l dung dch bo ha.

v
ht
< v
kt
, kt ta c to thnh lm gim nng (chnh xc hn l hot ) cho n
khi t c cn bng (*).

II/ Tch s tan v tan
tan ca A
m
B
n
l nng ca cht y trong mt dung dch bo ha, biu din l
mg/100g hay mol/l.
Tch s tan v tan c mi quan h vi nhau, c th tnh tch s tan t tan v ngc
li.
Gi S l tan ca A
m
B
n
th C
A
= mS, C
B
= nS.
T = (mS)
m
. (nS)
n
= m
m
.n
n
.S
m + n


.
m n
m n
T
S
m n
+
= (1)
Bi tp p dng :
1/ Tnh tch s tan ca BaSO
4
20
0
C bit rng 100 ml dung dch bo ha nhit
ny cha 0,245 mg BaSO
4
.
S : 1,03.10
-10

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2/ So snh tan ca AgCl v Ag
2
CrO
4
cng iu kin. Bit tch s tan ca AgCl,
Ag
2
CrO
4
ln lt l 1,08.10
-10
v 4,5.10
-12
.
S : AgCl (1,33.10
-5
mol/l), Ag
2
CrO
4
(4,5.10
-12
mol/l)
3/ Tnh tan ca CaSO
4
bit tch s tan ca n 20
0
C l 6,1.10
-5
.
S : phi tnh theo hot (xem ch thch phn di), 1,7.10
-2
mol/l

III. Cc yu t nh hng n tan ca kt ta
1. nh hng bi ion chung
Trong mt dung dch bo ha nh AgCl, nu thm vo dung dch ny mt t AgNO
3
th
tch s nng ion Ag
+
v Cl
-
vt qu tch s tan, theo quy lut v tch s tan nh
phn I, AgCl sinh ra tch khi dung dch lm cho tch s nng gim bng tch s
tan. Kt qu cng tng t nu them vo dung dch bo ha ny mt t ion Cl
-
.
Tm li, nu trong dung dch c sn ion chung vi hp cht t tan th tan ca hp
cht ny s gim t hay nhiu ty thuc vo lng ion chung trong dung dch.
Thit lp cng thc tnh :

thm vo dung dch ny ion B
-
vi nng C
A
, ta c :
C
A
= mS, C
B
= nS + C
A

T = (mS)
m
. (nS + C
A
)
n

Nu C
A
kh ln so vi S, c th ly nS + C
A
C
A

T = m
m
.S
m
.C
A
n


.
m
m n
A
T
S
m C
= (2)
Nhn thy, C
A
cng ln th S cng nh.
Bi tp p dng : Tnh tan AgCl trong cc dung dch KCl 0,001M; 0,01M v
0,1M. Bit T
AgCl
= 10
-10
.
S : 10
-7
; 10
-8
; 10
-9
M

2. nh hng ca lc ion
Khi thm ion l (khng c chung ion vi kt ta) th cng nh hng n tan.
T = a
A
m
.a
B
n
(a : k hiu hot , xem thm ch thch di)
= [A]
m
.[B]
n
.f
M
m
.f
A
n

vi [A] = mS, [B] = nS
T = m
m
.n
n
.S
m + n
.f
M
m
.f
A
n

Thay f
A
m
.f
B
n
bng f

m + n
l h s hot trung bnh, suy ra :

. .
m n
m n m n
T
S
m n f
+
+

= (3)
Vy tan S tng theo lc ion ca dung dch.

3. nh hng ca pH
a) Tch s tan iu kin
Ngi ta thng dng khi nim tch s tan iu kin T ni ln nh hng ca nhng
phn ng ph n tan ca kt ta.

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Phn ng kt hp A v B cho ra A
m
B
n
l phn ng chnh, cc phn ng gia A vi OH
-

hay gia B v H
+
c xem l phn ng ph.
Gi [A] l tng nng gm c [A] t do v [A] kt hp vi OH
-
.

( )
[ ]
[ '] [ ] [ ] ... [ ( ) ]
m
A OH
A
A A AOH A OH
a
= + + + =
Ghi ch : trong biu thc ny, bin i cc s hng [AOH], [A(OH)
2
], [A(OH)
3
],
theo [A], [OH
-
], K
phc
, K
phc
chnh l hng s cn bng ca A
n+
kt hp vi OH
-
(v d :
Al(OH)
2+
, Fe(OH)
2
+
,). t [A] l nhn t chung v t
A(OH)
= [A]/[A]
Tng t cho B :

( )
[ ]
[ '] [ ] [ ] ... [ ]
n
B H
B
B B HB H B
a
= + + + =
Ta c : T = [A]
m
.[B]
n
= [A]
m
.[B]
n
.
A(OH)
m
.
B(H)
n

Gi T l tch s tan iu kin, T = [A]
m
.[B]
n


( ) ( )
'
.
m n
A OH B H
T
T
a a
= (4)

A(OH)
v
B(H)
thng << 1 nn T > T, chng t khi c phn ng ph th tan tng
ln.
Khi c phn ng ph : [A] = mS, [B] = nS, T = [A].[B] = m
m
.n
n
.S
m + n




'
.
m n
m n
T
S
m n
+
= (5)
Cng thc ny tng t (1), ch thay T bng T.
b) Bin thin ca tan S theo pH
pH kh thp, phn ng gia A
n+
v OH
-
khng ng k, ly
A(OH)
= 1, tan S khi
ch ph thuc vo
B(H)
.
Tng t phn 3a, ta c :

2
( ) 1 1 1
1 [ ] [ ] [ ]
1 ...
. . ...
n
B H n n n n n
H H H
K K K K K K a
+ + +
- -
= + + + + (6)
Khi pH > pK
n
, 1/
B(H)
1, T = T, S = S ( tan khng ph thuc pH vi iu kin

A(OH)
= 1).
Khi pH < pK
n
, 1/
B(H)
tng nhanh theo nng H
+
nn tan S cng tng nhanh.
Bi tp p dng :
1/ Tnh h s lgo
Y(H)
ca EDTA (acid etilen diamin tetraacetic, k hiu H
4
Y), bit
H
4
Y c pK
1
= 2,1; pK
2
= 2,7; pK
3
= 6,3; pK
4
= 10,4 trong iu kin pH = 1; 2; 3; 4;
5; 6; 7; 8; 9; 10.
S : 17,4; 13,7; 10,8; 8,6; 6,6; 5,8; 3,4; 2,3; 1,4; 0,3
2/ Tnh nng [Cu
2+
] t do trong dung dch, bit dung dch Cu
2+
ban u c nng
0,1M. Thm NH
3
vi nng 10
-4
M to phc cht Cu(NH
3
)
i
. Cho bit pK
i
ln
lt l 2,11; 2,87; 3,48; 4,13.
S : Tnh o
Cu(NH3)
= 10
2,55
, dng cng thc [Cu
2+
] = [Cu]. o
Cu(NH3)
= 0,035M
3/ Tnh tan ca CaC
2
O
4
trong cc dung dch nc pH = 4 v pH = 1. Bit T =
1,8.10
-9
, K
1
= 6,5.10
-2
, K
2
= 6.10
-5
.
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S : 6,84.10
-5
mol/l, 2,7.10
-3
mol/l

c) tan ca kt ta khi cha bit pH
TH
1
: Tch s tan kh b
V d : tnh tan ca Ag
2
S trong nc, bit T = 6,3.10
-50
. H
2
S c pK
1
= 7 v pK
2
= 13.
T = [Ag
+
]
2
.[S
2-
],
3
( )
4
S H
T
S
a
=
V tch s tan kh b, c th coi pH ca dung dch bng pH ca nc, tc bng 7, [H
+
]
= 10
-7
M.

2
6
( ) 2 2 1
1 [ ] [ ]
1 2.10
.
S H
H H
K K K a
+ +
= + + =
T = 6,3.10
-50
.2.10
6
= 12,6.10
-44

44 15
3
12, 6
.10 3, 15.10 /
4
S mol l
-
= =
TH
2
: Tch s tan kh ln
V d : tnh tan ca Ag
2
S trong nc, bit T = 1,0.10
-11
. H
2
S c pK
1
= 7 v pK
2
= 13.
Cch 1 :

Nng H
+
phi nh hn 10
-7
M nhng khng th ln hn 10
-13
M v nu [H
+
] = 10
-13
M
th [OH
-
] = 0,1M tc tng ng mt dung dch baz mnh m MnS khng th tan
cho [OH
-
] = 0,1M theo cn bng trn.
Vy : 7 > pH > 13

2
( ) 2 2 1
1 [ ] [ ]
1
.
S H
H H
K K K a
+ +
= + +
B qua s hng th 3 v s hng ny tng ng nng H
2
S m theo gi thit trn th
nng H
2
S s rt nh.

13
( )
1
10 [ ]
S H
H
a
+
=
[OH
-
] = [Mn
2+
] = S v [H
+
] = 10
-14
/[OH
-
] = 10
-14
/S


13 14 1
( )
11 1
2
( )
1 10 .10 10
10 .10
'
S H
S H
S S
T
T S
S
a
a
-
- -
= =
= = =

S = 10
-4
mol/l
Cch 2 :

2 2
2
.
[ ].[ ].[ ]
H O
T K
K Mn HS OH
K a
+ - -
= =
[HS
-
] = [OH
-
] = [Mn
2+
] = S
Tnh c S = 10
-4
mol/l
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Bi tp p dng : Tnh tan CuS trong nc. T
CuS
= 6,3.10
-36
. H
2
S c pK
1
= 7 v
pK
2
= 13. Hng s bn tng cng ca phc to bi Cu
2+
v OH
-
ln lt l |
1
= 10
7,0
,
|
1-2
= 10
13,68
, |
1-3
= 10
17
, |
1
= 10
18,5
.
S : tnh 1/o
Cu(OH)
= 2,48; 1/o
s(H)
= 2.10
6
, T = 31,2.10
-30
, S = 5,5.10
-15
mol/l

d) nh hng ca pH trn tan cc hydroxid
TH
1
: Hydroxid ch c tnh baz
Cc hydroxid ny kt ta pH kh cao v tan tr li khi pH kh thp.

2
[ ][ ] [ ].
[ ]
n
H O
n n n
K
T M OH M
H
+ - +
+



= =






14
1 10
.
[ ] [ ]
n
n n
T
H M
+ +
=
hay
0
1
14 (log log )
M
pH T C
n
= + -
pH
1
l pH bt u kt ta ng vi [M] = C
M
:

0
1
1
14 (log log )
M
pH T C
n
= + - (7)
pH
2
l pH kt ta hon ton ng vi [M] = C
M
/1000 :

0
2
1
14 (log log 3)
M
pH T C
n
= + - +
hay
2 1
3
+ pH pH
n
= (8)

TH
2
: hydroxid c tnh lng tnh
Cc hydroxid loi ny kt ta khi thm baz nhng khi pH kh cao th tan tr li.
V d :

C
0
= 10
-2
M, p dng (7) v (8) tnh c pH
1
= 3,8 v pH
2
= 4,8.
Al(OH)
3
bt u tan tr li di dng AlO
2
-
khi [AlO
2
-
] = 10
-5
M, ng vi 1/1000 C
0

[H
+
] = 10
-13,9
/10
-5
= 10
-8,9
pH = 8,9
Al(OH)
3
tan hon ton khi [AlO
2
-
] = 10
-2
M
[H
+
] = 10
-13,9
/10
-2
= 10
-11,9
pH = 11,9

4. nh hng ca phn ng to phc
a) Ligand to phc khc vi anion B

Gi s cation A to phc vi ligand X, cn anion B th khng tham gia phn ng ph.
T = [M]
m
.[A]
n


( )
[ ]
[ ']
A X
A
A
a
=
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( ) ( )
[ ] .[ ]
'
m n
m m
A X A X
M A T
T
a a
= = (9)
S thit lp h s
A(X)
trong phn ng phc cht (phn ng ph) cng tng t nh
trong (6).
V T > T nn phn ng phc cht lm tng tan.
b) Ligand l anion B. Tnh lng tnh
Anion B to vi cation A kt ta AB t tan, va cho cc phc tan AB
*
, AB
2
, AB
3
,AB
n

nu trong dung dch c d B. Nu thm dung dch B vo, khi d B th tan gim xung
do nh hng ca ion chung nhng khi t n gi tr cc tiu th tan li tng ln
do c s to phc v kt ta c th tan hon ton.
Thit lp cng thc ( n gin khng ghi in tch cc ion) :
Phn ng kt ta :

Phn ng to phc :

Gi [A] l tng nng cc dng tan ca cation A, vy A chnh l tan S.

2
[ '] [ ] [ *] [ ] ... [ ]
n
A S A AB AB AB = = + + + +
( ) : [ ]
[ ]
T
a A
B
=
1 1
2 1 2 1 2
1 1
1 2 1
b b
b b b
b b b b
( ) : [ *] .[ ].[ ] .
( ) :[ [ [ *].[ ] . . .[ ] . .[ ]
( ) : [ ] . ... . .[ ] . .[ ]

= =
= = =
= =
n n
n n n
b AB A B T
c AB MA B T B T B
d AB T B T B

tan ca kt ta :

1
1 1 2 1
1
b b b [ ] ... [ ]
[ ]


| |
= + + + +
|
\ .
n
n
S T B B
B


1
1 1 1
1 1 [ ] [ ]
...
[ ] . . ...


| |
= + + + +
|
\ .
n
n n n n n
B B
T
B K K K K K K
(10)
Nu phc cht ch to thnh ch c s phi tr 2 :

2 2 1
1 1 [ ]
[ ] .
| |
= + +
|
\ .
B
S T
B K K K
(11)
tan s cc tiu khi 0
[ ]
=
dS
d B
, (11) ng vi :

2
2 1
1 1
0
[ ] [ ] .
= + =
dS
d B B K K

Vy nng ca B t gi tr c tan cc tiu l :

1 2
[ ] . = B K K
Thay [B] vo (10) s tm c S
min
.
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V d : Tnh tan ca AgCl c T = 1,0.10
-10
trong dung dch clorur 1M. Gi thit rng
trong dung dch c cha acid b qua s to phc gia ion Ag
+
v OH
-
.
Hng s to thnh ln lt gia Ag
+
v Cl
-
l
1
= 10
3,04
;
1
= 10
2,0
;

3
= 10
0
;

4
= 10
0,26
.
Gii :


AgCl Ag
+
+ Cl
-
T = 10
-10
Ag
+
+ Cl
-
AgCl*
AgCl + Cl
-
AgCl
2
-
2
= 10
2,0
AgCl
2
-
+ Cl
-
AgCl
3
2-
3
= 10
0
AgCl
3
2-
+ Cl
-
AgCl
4
3-
3
= 10
0

C
Cl-
= 1 = [Cl
-
] + [AgCl] + 2[AgCl
2
-
] + 3[AgCl
3
-
] + 4[AgCl
4
-
]
= [Cl
-
] +
1
.T + 2
1-2
.T.[Cl
-
] + 3
1-3
.T.[Cl
-
]
2
+ 4
1-4
.T.[Cl
-
]
3

thay s vo, b qua 10
-6,96
v 10
-4,96
so vi 1, ta c :
1 = [Cl
-
] + 10
-4,96
[Cl
-
]
2
+ 10
-4,7
[Cl
-
]
3

tan S ca AgCl l :

2 3
4 4 3 4 3 2 4 3 2 1
10 3 04 5 04 2 5 04 5 3
5
1 1
10 1 10 1 10 1 10 13 10
4 18 10
, , , ,
[ ] [ ] [ ]
[ ] . . . . . .
( . . . )
, . /

| |
= + + + +
|
\ .
= + + + +
=
AgCl
Cl Cl Cl
S T
Cl K K K K K K K K K K
mol l


3 04 2 2 52
7
10 10 10
1 75 10
, ,
min
[ ] .
, . /

= =
=
Cl
S mol l


V. S kt ta phn on
S lm kt ta hai hay nhiu ion bng mt ion chung gi l s kt ta phn on.
Hai phng php tch thng dng l tch di dng sulfur v hydroxid.
Tch di dng sulfur :
H
2
S l thuc th kh quan trng do c nhng c im :
- Sulfur c tan thay i rt khc nhau : MnS c T
MnS
= 10
-11
n HgS c T
HgS
= 3.10
-
52
hoc PtS c T
PtS
= 10
-72
. Do vic la chn pH thch hp lm kt ta chn lc mt
sulfur hay mt nhm sulfur rt d dng.
- H
2
S l kh, tng i t tan trong nc nn c th cho vo t t, to iu kin thun li
cho vic tch.
- Dung dch H
2
S c tnh acid nn vic lm kt ta cc sulfur lun gn vi pH ca dung
dch.
T = [M].[S]
H
2
S c pK
1
= 7 v pK
2
= 13 v tan trong dung dch bo ha nhit phng 1 atm
l 0,1M.
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2 2 2
20
1 2
2 2
21
2
2 2
21
2
21
2
10
10
0 1
10
10
[ ][ ] [ ][ ] [ ][ ]
.
[ ] [ ] [ ]
[ ] , [ ]
[ ]
[ ].
[ ][ ]
[ ]
[ ].
[ ]
+ + +

= = =
= =
= =
=
S H S H HS H
K K
H S HS H S
H S M S
H
M
T M S
H
M
H
T

Gi pH
1
l pH bt u kt ta MS khi [M] = C
M
(nng u)
Gi pH
2
l pH kt ta hon ton khi [M] = 1/1000 C
M
:

1
2
1
21
2
1
21 3
2
( log log )
( log log )
= +
= + +
M
M
pH T C
pH T C

Bi tp p dng : C th tch phn on cc cp ion kim loi sau y c khng ?
- dung dch cha Zn
2+
v Mn
2+
vi C
0
Zn
= C
0
Mn
= 0,1M.
- dung dch cha Cd
2+
v Sn
2+
vi C
0
Cd
= C
0
Sn
= 0,1M.
Cho bit T
ZnS
= 10
-21
, T
MnS
= 10
-11
, T
CdS
= 10
-28
, T
SnS
= 10
-26

S : khng th tch Cd
2+
ra khi Sn
2+


Ch thch v hot
Biu thc hng s cn bng ta vn quen s dng gi tr nng . Tuy nhin, vi dung
dch m c th K
c
khng cn hng s na, do vy ta phi s dng gi tr hot , k
hiu a.
H s hot :
a = f.C, f l h s hot
Lc ion :
2
1
1
2
m
=
=

n
i i
i
C z
Cng thc tnh f :
+) < 0,02
p dng cng thc Debye-Huckel :
2
m log =
i i
f Az
25
0
C vi nc l dung mi th A 0,5 nn
2
0 5 m log , =
i i
f z
+) 0,02 < < 0,2 :
2
8
0 5
1 0 33 10
m
m
,
log
, . . .

=
+
i
i
z
f
b

b l bn knh ion ngm nc
Mt s ion c bn knh ion ngm nc khong 3.10
-8
cm, vd OH
-
, F
-
, Cl
-
, Br
-
, I
-
, NH
4
+
,
Ag
+
,
b = 4.10
-8
cm cho Na
+
, H
2
PO
4
-
, Pb
2+
, CO
3
2-
, SO
4
2-
, PO
4
3-
,
b = 9.10
-8
cm cho H
+

Chemist2408@gmail.com
n gin, thng ly b = 3.10
-8
cm (thng gp), vy :

2
0 5
1
m
m
,
log

=
+
i
i
z
f
+) > 0,2 (dung dch kh m c)

2
8
0 5
1 0 33 10
m
m
m
,
log
, .
= +
+
i
i
z
f B
b

B l mt hng s thc nghim.
Bi tp p dng :
1/ Mt dung dch cha KCl 10
-3
M v MgSO
4
10
-3
M.
a) Tnh lc ion.
b) Tnh hot cc ion trong dung dch.
S : a) 5.10
-3
b) a
K+
= a
Cl-
= 0,92.10
-3
iong/l, a
Mg2+
= a
SO42-
= 0,72.10
-3
iong/l
2/ Tnh hot ca ion Pb
2+
trong dung dch Pb(NO
3
)
2
0,005M v KNO
3
0,04M bit
bn knh Pb
2+
l 4.10
-8
cm.
S : 0,215.10
-3
iong/l