I.

Cc bc tin hnh gii mt bi ton cn bng ion :

I.1.Gii chnh xc :
+ M t y cc qu trnh c th xy ra trong h.
+ Ghi r cc d kin thc nghim cho, chn n s cho bi ton ng thi
t iu kin cho n s nu c.
+ Da vo cc nh lut bo ton khi lng, nh lut tc dng khi lng
thit lp cc phng trnh lin h gia cc d kin cho v cc n s cn tm.
Ch s phng trnh lin h bng s n s cn tm.
+ T hp cc phng trnh lin h thnh mt phng trnh duy nht i vi
mt n s thch hp chn. Thay cc s liu tng ng ri gii tm nghim
ca phng trnh. So snh nghim tm c vi cc iu kin n s chn
trn tm p s ca bi ton.
Vic tnh ton y nh trn thng i hi phi gii cc phng trnh
bc cao phc tp, cho nn trong a s trng hp c th tin hnh cc php tnh
gn ng trong phm vi chnh xc ca cc d kin v cn bng.
I.2.Gii gn ng :
Nguyn tc ca vic tnh gn ng l tm cch loi b cc qu trnh ph cc
qu trnh xy ra vi mc khng ng k trong iu kin bi ton cho.
C th :
+ Nu mi trng l Axit hoc kim th c th b qua cn bng phn ly ca
nc.
+ Nu mui rt t tan hoc hp cht rt t phn ly m trong dung dch li c
d ion ng dng vi ion hnh thnh do kt qu ha tan hay phn ly th c th
coi s ha tan hay phn ly l khng ng k.
+ Nu cc cn bng cng loi xy ra ng thi trong dung dch th nhng cn
bng no tng ng vi hng s phn ly qu b th c th loi b chng so vi
cc qu trnh phn ly mnh hn. Chng hn khi xt cc qu trnh phn ly tng
nc ca cc a axit. Nu K
1
K
2
(K
1
/K
2
10
4
) th c th b qua nc phn ly th
hai so vi nc phn ly th nht.
Cc gi thit gn ng ch c chp nhn sau khi kim tra cn thn kt
qu tnh ton. Nu vic kim tra cho thy khng th chp nhn iu kin gn
ng th phi gii li bi ton mt cch chnh xc k c cc qu trnh loi b
trn.
II.Gii gn ng cc phng trnh bc cao
Phng php tng i n gin gii gn ng cc phng trnh bc
cao l phng php tip tuyn (thng gi l phng php Niutn).
Ni dung ca phng php:
Gi thit phng trnh c dng tng qut :
Y = f(x) = 0
Ta c th nh gi s b mt nghim gn ng x
0
. T nghim x
0
ta tm
c nghim x
1
chnh xc hn x
0
. Dng x
1
tm x
2
chnh xc hn x
1
Lp li
php tnh nh vy cho n khi tm c gi tr x
n
ch khc vi nghim thc mt
i lng v cng b
n
.

n
= x - x
n
(1)
x = x
n
+
n
(2)
Vn t ra l phi nh gi i lng
n
.
Khai trin phng trnh f(x) theo cp s Taylo tiim x = x
n
.
Ta c : Y = f(x) = f(x
n
+
n
) = 0
Y = f(x
n
) + f(x
n
).
n
+
! 2
). x ( ' ' f
2
n n

+
! 3
). x ( ' ' ' f
3
n n

+ = 0 (3)
V
n
l i lng v cng b, nn cc s hng bc cao i vi
n
rt b c
th b qua
T (3) Y = f(x) f(x
n
) + f(x
n
).
n
= 0

n
= -
) x ( ' f
) x ( f
n
n
thay vo (2) ta c :
x = x
n
+
n
= x
n
-
) x ( ' f
) x ( f
n
n
(4)
Ni mt cch ng hn,phng trnh (4) cho php tm gi tr x
n+1
gn vi
nghim thc x hn gi tr x
n
.
x
n+1
= x
n
-
) x ( ' f
) x ( f
n
n
(5)
ngha hnh hc ca phng php Niutn:
Y
x
Y=f(x)
A
B
C
f(x
0
)
x x
2
x
1
x
0

Gin nh gi nghim ca phng trnh Y = f(x) = 0 theo phng php
tip tuyn (Niutn)

ng cong Y = f(x) ct trc honh ti im ng vi nghim x [f(x) = 0]. T gi
tr gn ng x
0
ta tm gi tr x
1
chnh xc hn x
0
.
ng tip tuyn ti A ng vi honh x
0
ct trc honh ti im c honh
x
1
gn vi nghim x hn so vi x
0
.
ngha hnh hc ca phng php Niutn:
Y
x
Y=f(x)
A
B
C
f(x
0
)
x x
2
x
1
x
0

Gin nh gi nghim ca phng trnh Y = f(x) = 0 theo phng php
tip tuyn (Niutn)
+ o hm ti im x
0
: f(x
0
) =
1 0
0
x x
) x ( f

x
1
= x
0
-
) x ( ' f
) x ( f
0
0

T im B trn ng cong ng vi honh x
1
, ta li v tip tuyn vi
ng cong ct trc honh ti im c honh x
2
gn vi x hn so vi x
1
.
Tng t nh trn ta c : x
2
= x
1
-
) x ( ' f
) x ( f
1
1

Tip tc lm nh vy, ta tm c gi tr x
n+1
gn vi nghim thc x hn gi
tr x
n
.
Ta c : x
n+1
= x
n
-
) x ( ' f
) x ( f
n
n

Lu :
+ Khi tm gi tr x
n+1
khc rt t so vi gi tr x
n
th kt qu c chp nhn,
ch nghim thc x ta khng bitc.
C th :
n
n 1 n
x
x x
+
. 100% (trong khong t 0 5%) th gi tr
x
n+1
c chp nhn.
+ n s trong cc phng trnh thu c thng l nng cn bng ca
cc cu t. V vy chng phi c nghim dng.
Theo quy tc cac th s nghim dng ca mt phng trnh bng s ln
i du lin tc trong phng trnh hoc t hn mt s chn 2, 4, 6 nghim.
Chng hn : Y = f(x) = x
3
5x
2
+ 7x -50 = 0
Phng trnh c 3 ln i du lin tc, nn s nghim dng ca phng trnh
hoc 3 nghim hoc 1 nghim.
V d: Tnh nng ion hydro h t phng trnh
F(h) = h
3
+ 3,266.10
-5
h
2
1,527.10
-16
= 0
Gii
Phng trnh c 1 ln i du, nn chng ch c 1 nghim dng.
tm gi tr h
0
ta cho trit tiu 1 s hng cha h
+ h
3
- 1,527.10
-16
= 0 h = 5,345.10
-6

+ 3,266.10
-5
h
2
1,527.10
-16
= 0 h = 2,162.10
-6
(v h > 0)
Nghim thc h phi nh hn 2 gi tr va tm trn
Chn h
0
= 2.10
-6

Ta c : F(h) = h
3
+ 3,266.10
-5
h
2
1,527.10
-16

F(h) = 3h
2
+ 6,532.10
-5
h
Ta c : F(h
0
) = - 1,41.10
-17
; F(h
0
) = 1,426.10
-10

h
1
= h
0
-
) h ( ' F
) h ( F
0
0
= 2.10
-6
+
10
17
10 . 426 , 1
10 . 41 , 1

= 2,1.10
-6

F(h
1
) = 5,9.10
-19
; F(h
1
) = 1,504.10
-10

h
2
= h
1
-
) h ( ' F
) h ( F
1
1
= 2,1.10
-6
-
10
19
10 . 504 , 1
10 . 9 , 5

= 2,096.10
-6

Ta c :
1
1 2
h
h h
. 100% =
6
6 6
10 . 1 , 2
10 . 1 , 2 10 . 096 , 2

. 100% = 0,19%
Vy h = 2,096.10
-6

II.Phng php gii gn ng lin tc
Trong mt s trng hp trnh gii cc phng trnh bc cao phc
tp,ngi ta hay s dng phng php gii gn ng lin tc.
+ Ni dung phng php :
Gi s c mt hm nhiu bin : Y = f(a, b, c, d ) (1)
m a, b, c, d li lin h vi Y theo cc hm sau :
a = F
1
(Y)
b = F
2
(Y)
c = F
3
(Y)
d = F
4
(Y)
(2)

gii theo phng php gn ng lin tc, mi u ngi ta chp nhn cc gi
tr:
a = a
0
; b = b
0
; c = c
0
; d = d
0
(trong cc bi ton, ngi ta thng chp nhn
nng cn bng ca cc cu t bng nng ban u tng ng ca chng)
thay vo (1) ta c :
Y
0
= F(a
0
,b
0
,c
0
,d
0
). T gi tr Y
0
thay vo (2) ta c:

a
1
= F
1
(Y
0
)
b
1
= F
2
(Y
0
)
c
1
= F
3
(Y
0
)
d
1
= F
4
(Y
0
)

T cc gi tr a
1
,b
1
,c
1
,d
1
thay vo (1) ta c:
Y
1
= F(a
1
,b
1
,c
1
,d
1
)
Lp li php tnh nh trn nhiu ln, ta tmc gi tr Y
n+1
tha mn:
n
n 1 n
Y
Y Y
+
. 100% trong khong t 0 5% th gi tr Y
n+1
c chp nhn
V d : Tnh pH trong dung dch hn hp gm HCOOH 0,2000M v HNO
2

0,1000M. Cho bit KHCOOH = 10
-3,75
; KHNO
2
= 10
-3,29
.

Gii
Cc qu trnh xy ra trong h
HCOOH H
+
+ HCOO
-
K
1
= KHCOOH = 10
-3,75
(1)
HNO
2
H
+
+ NO
2
-
K
2
= KHNO
2
= 10
-3,29
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c : KHCOOH .C HCOOH = K
1
C
1
= 0,2.10
-3,75
= 10
-4,45

KHNO
2
.CHNO
2
= K
2
C
2
= 0,1.10
-3,29
= 10
-4,29

Ta c : K
1
C
1
K
2
C
2
W = 10
-14
b qua (3) so vi (1) v (2)
p dng iu kin proton vi mc khng l HCOOH, HNO
2

[H
+
] = h = [HCOO
-
] + [NO
2
-
]
h = [HCOOH].K
1
.h
-1
+ [HNO
2
]. K
2
h
-1

h = | | | |
2 2 1
K HNO K OH HCO + (a)
Theo nh lut bo ton nng ban u ta c :
C
1
= [HCOOH] + [HCOO
-
]
= [HCOOH] + [HCOOH] K
1
h
-1
= [HCOOH](1+K
1
h
-1
)
[HCOOH] = C
1
.
1
K h
h
+

Tng t : [HNO
2
] = C
2
.
2
K h
h
+
(b)
Gii theo phng php gn ng lin tc
Chp nhn : [HCOOH] = C
1
= 0,2000M ; [HNO
2
] = 0,1000M thay vo (a)
ta c: h
0
=
29 , 3 75 , 3
10 . 1000 , 0 10 . 2000 , 0

+ = 9,32.10
-3
M
Thay vo (b) ta c:
[HCOOH]
1
= 0,2000.
75 , 3 3
3
10 10 . 32 , 9
10 . 32 , 9

+
= 0,1963M
[HNO
2
]
1
= 0,1000.
29 , 3 3
3
10 10 . 32 , 9
10 . 32 , 9

+
= 0,0948M thay vo (a) ta c
h
1
=
29 , 3 75 , 3
10 . 0948 , 0 10 . 1963 , 0

+ = 9,14.10
-3
M
Ta c :
0
0 1
h
h h
. 100% =
3
3 3
10 . 32 , 9
10 . 32 , 9 10 . 14 , 9

.100% = 1,93%
Vy h = 9,14.10
-3
= 10
-2,04


pH = 2,04
III. VN KH KHI CN BNG AXIT BAZ
Hu ht cc qu trnh xy ra trong dung dch nc u c lin quan ti c tnhAxit-
Baz ca cc cht. Do vic nghin cu cn bng Axit-Baz s cho php gii thch c
nhiu hin tng phn tch xy ra trong dung dch.
Mt khc, nm c phng php kho st cn bng Axit-Baz s l c s cho vic tm
hiu cc loi cn bng khc nh: Cn bng oxi ha-kh, cn bng to phc, cn bng to
hp cht t tan
III.1.Cn bng trong cc dung dch n Axit v n Baz
III.1.1.Dung dch n Axit mnh v n Baz mnh
III.1.1.1.Dung dch n Axit mnh
III.1.1.2.Dung dch n Baz mnh
III.1.2.Dung dch n Axit yu v n Baz yu
III.1.2.1.Dung dch n Axit yu
III.1.2.2.Dung dch n Baz yu
III.2.Cn bng trong cc dung dch Axit- Baz nhiu cu t
III.2.1.Dung dch hn hp gm 1 n Axit mnh v 1 n Axit yu
III.2.2.Dung dch hn hp gm 1 n Baz mnh v 1 n Baz yu
III.2.3.Dung dch cha hn hp nhiu n Axit yu
III.2.4.Dung dch cha hn hp nhiu n Baz yu
III.2.5.Dung dch cc a Axit
III.2.6.Dung dch cc a Baz
III.2.7.Dung dch mui Axit
III.2.8.Dung dch mui Axit yu v Baz yu
III.2.9.Dung dch m
III.2.10.Cn bng trong dung dch cha
cation kim loi
III.1.1.1.Dung dch n Axit mnh
Thnh phn dung dch : (HX , C ; H
2
O)
Cc qu trnh xy ra trong h
HX H
+
+ X
-
(1)
H
2
O H
+
+ OH
-
W (2)
Theo nh lut bo ton in tch ta c:
[H
+
] = [OH
-
] + [X
-
]
[H
+
] - [OH
-
] - [X
-
] = 0 (3)
t : [H
+
] = h [OH
-
] =
h
W
; [X
-
] = CHX = C thay vo (3) ta c:
h -
h
W
- C = 0 (4)
a.Gii chnh xc:
Gii phng trnh (4) phng trnh bc 2 i vi h. Tm h.T h pH ; [OH
-
]
b.Gii gn ng: C 2 cch
Cch 1: V dung dch n Axit mnh nn h
h
W
. T (4) h = C
T h pH ; [OH
-
] .
Cch 2: V dung dch cha n Axit mnh HX, nn nng H
+
do chng phn
ly ra trong dung dch ln lm cn bng (2) chuyn dch mnh sang tri. V vy
c th b qua (2) so vi (1)v da vo (1) tnh.
T (1) [H
+
] = CHX = C . T [H
+
] pH ; [OH
-
]
Lu :
Phng php gii gn ng ch c p dng cho cc dung dch n Axit
mnh c nng CHX 10
-7
M. Nu nng CHX 10
-7
M th phi gii chnh
xc phng trnh (4).
V d 1: Tnh pH trong dung dch HCl 5.10
-7
M
Gii
Cc qu trnh xy ra trong h
HCl H
+
+ Cl
-
(1)
H
2
O H
+
+ OH
-
W (2)
Theo nh lut bo ton in tch ta c:
[H
+
] = [OH
-
] + [Cl
-
]
[H
+
] - [OH
-
] - [Cl
-
] = 0 (3)
t : [H
+
] = h [OH
-
] =
h
W
; [Cl
-
] = CHCl = C thay vo (3) ta c:
h -
h
W
- C = 0 h
2
- hC - W = 0 (4)
V C = CHCl = 5.10
-7
M 10
-7
M nn phi gii chnh xc phng trnh (4).
Thay cc gi tr C , W vo (4) ta c:
h
2
- 5.10
-7
h - 10
-14
= 0
Gii ra ta c : h = 5,193.10
-7
= 10
-6,285


pH = 6,285
V d 2: Tnh th tch (ml) dung dch HClO
4
10
-4
M cn phi ly iu ch 1
lt dung dch ny c pH = 6,0.
Gii
Cc qu trnh xy ra trong h
HClO
4
H
+
+ Cl
-
(1)
H
2
O H
+
+ OH
-
W (2)
Gi C l nng ca dung dch HClO
4
trong 1 lt dung dch c pH = 6,0
Theo nh lut bo ton in tch ta c:
[H
+
] = [OH
-
] + [ClO
4
-
]
[H
+
] - [OH
-
] - [ClO
4
-
] = 0 (3)
t : [H
+
] = h [OH
-
] =
h
W
; [ClO
4
-
] = C thay vo (3) ta c:
h -
h
W
- C = 0 C = h -
h
W
(4)
pH = 6,0 h = 10
-6
;
h
W
= 10
-8
thay vo (4) ta c:
C = 10
-6
- 10
-8
= 9,9.10
-7
M
Gi v(ml) l th tch dung dch HClO
4
10
-4
M cn phi ly
Ta c: v.10
-4
= 9,9.10
-7
.1000 v = 9,9ml
Vy v = 9,9ml
III.1.1.2.Dung dch n Baz mnh:
Thnh phn dung dch : (BOH , C ; H
2
O)
Cc qu trnh xy ra trong h
BOH B
+
+ OH
-
(1)
H
2
O H
+
+ OH
-
W (2)
Theo nh lut bo tonin tch ta c:
[OH
-
] = [H
+
] + [B
+
]
[OH
-
] - [H
+
] - [B
+
] = 0 (3)
t : [OH
-
] = x [H
+
] =
x
W
; [B
+
] = CBOH = C thay vo (3) ta c:
x -
x
W
- C = 0 (4)
a.Gii chnh xc:
Gii phng trnh (4) phng trnh bc 2 i vi x. Tm x. T x [H
+
] pH
b.Gii gn ng: C 2 cch
Cch 1: V dung dch n Baz mnh nn x
x
W

T (4) x = C . T x [H
+
] pH
Cch 2: V dung dch cha n Baz mnh BOH, nn nng OH
-
do chng
phn ly ra trong dung dch ln lm cn bng (2) chuyn dch mnh sang tri. V
vy c th b qua (2) so vi (1)v da vo (1) tnh.
T (1) [OH
-
] = CBOH = C . T [OH
-
] [H
+
] pH
Lu :
Phng php gii gn ng ch c p dng cho cc dung dch n Baz
mnh c nng CBOH 10
-7
M. Nu nng CBOH 10
-7
M th phi gii chnh
xc phng trnh (4).
V d 1: Tnh pH trong dung dch NaOH 1,5.10
-7
M
Gii
Cc qu trnh xy ra trong h
NaOH Na
+
+ OH
-
(1)
H
2
O H
+
+ OH
-
W (2)
Theo nh lut bo tonin tch ta c:
[OH
-
] = [H
+
] + [Na
+
]
[OH
-
] - [H
+
] - [Na
+
] = 0 (3)
t : [OH
-
] = x [H
+
] =
x
W
; [Na
+
] = CNaOH = C thay vo (3) ta c:
x -
x
W
- C = 0 x
2
- Cx - W = 0 (4)
V C = CNaOH = 1,5.10
-7
M 10
-7
M nn phi gii chnh xc phng trnh (4).
Thay cc gi tr C , W vo (4) ta c:
x
2
- 1,5.10
-7
x - 10
-14
= 0
Gii ra ta c : x = 2.10
-7
[H
+
] = 5.10
-8
= 10
-7,3

pH = 7,3
V d 2: Tnh pH trong dung dch hn hp gm NaOH 3.10
-4
M v KOH 5.10
-4
M
Gii
Cc qu trnh xy ra trong h
NaOH Na
+
+ OH
-
(1)
KOH K
+
+ OH
-
(2)
H
2
O H
+
+ OH
-
W (3)
Theo nh lut bo tonin tch ta c:
[OH
-
] = [H
+
] + [Na
+
]+ [K
+
]
[OH
-
] - [H
+
] - [Na
+
] - [K
+
] = 0 (4)
t : [OH
-
] = x [H
+
] =
x
W
; [Na
+
] = CNaOH ; [K
+
] = CKOH thay vo (4)
ta c:
x -
x
W
- CNaOH - CKOH = 0 (5)
Ta c: CNaOH + CKOH = 3.10
-4
+ 5.10
-4
= 8.10
-4
M 10
-7
M . Nn b
qua (3) so vi (1) v (2). Ngha l x
x
W
.
T (5) x = CNaOH + CKOH = 8.10
-4
M
[H
+
] =
x
W
=
4
14
10 . 8
10

= 1,25.10
-11
= 10
-10,903

pH = 10,903
III.1.2.1.Dung dch n Axit yu
Thnh phn dung dch: (HA ,C
a
, K
a
; H
2
O)
Cc qu trnh xy ra trong h
HA H
+
+ A
-
K
a
(1)
H
2
O H
+
+ OH
-
W (2)
Theo nh lut bo ton in tch ta c:
[H
+
] = [OH
-
] + [A
-
]
[H
+
] - [OH
-
] - [A
-
] = 0 (3)
t : [H
+
] = h [OH
-
] =
h
W
thay vo (3) ta c:
h -
h
W
- [A
-
] = 0 (4)
Theo nh lut bo ton nng ban u ta c :
CHA = C
a
= [HA] + [A
-
]
= [A
-
] h K
a
-1
+ [A
-
] = [A
-
] (h K
a
-1
+ 1)
[A
-
] = C
a
a
a
K h
K
+
thay vo (4) ta c:
h -
h
W
- C
a
a
a
K h
K
+
= 0 (5)
a.Gii chnh xc:
Gii phng trnh (5) phng trnh bc 3 i vi h. Tm h
T h pH ; [OH
-
] ; [A
-
] ; [HA]
b.Gii gn ng:
T (1) [H
+
].[A
-
] = K
a
[HA] K
a
C
a

(2) [H
+
].[OH
-
] = W
+ Nu K
a
C
a
W ngha l cn bng cho proton (1) xy ra mnh hn nhiu
so vi (2). Do b qua (2) so vi (1) v da vo (1) tnh.
HA H
+
+ A
-
K
a

C C
a
0 0
[ ] C
a
h h h
Theo nh lut tc dng khi lng ta c :
K
a
=
h C
h
a
2

(6)
Gii phng trnh (6) phng trnh bc 2 i vi h. Tm h
T h pH ; [OH
-
] ; [A
-
] ; [HA]
+ Nu K
a
C
a
W th phi gii chnh xc phng trnh (5)
V d 1: Tnh pH trong dung dch gm HCN 10
-3
M
Cho bit : KHCN = 10
-9,35

Gii
Cc qu trnh xy ra trong h
HCN H
+
+ CN
-
K
a
= 10
-9,35
(1)
H
2
O H
+
+ OH
-
W = 10
-14
(2)
Ta c: KHCN . CHCN = K
a
C
a
= 10
-9,35
.10
-3
= 10
-12,35
khng W = 10
-14
. V
vy phi gii chnh xc.
T phng trnh : h -
h
W
- C
a
a
a
K h
K
+
= 0 (3)
h
3
+ K
a
h
2
(W + K
a
C
a
)h WK
a
= 0 (4)
Thay cc gi tr : W = 10
-14
; K
a
= KHCN = 10
-9,35
; C
a
= CHCN = 10
-3
M vo (4)
ta c:
h
3
+ 4,467.10
-10
h
2
4,567.10
-13
h 4,467.10
-24
= 0 (5)
Gii theo phng php tip tuyn (phng php Niutn).
Chn h
0

+ h
3
4,567.10
-13
h = 0 h = 6,758.10
-7
(v h > 0)
+ 4,467.10
-10
h
2
4,467.10
-24
= 0 h = 10
-7
(v h > 0)
Nghim thc h phi tha mn : 10
-7
< h < 6,758.10
-7

Chn h
0
= 6.10
-7

F(h) = h
3
+ 4,467.10
-10
h
2
4,567.10
-13
h 4,467.10
-24

F(h) = 3h
2
+ 8,934.10
-10
h 4,567.10
-13

Ta c: F(h
0
) = - 5,786.10
-20

F(h
0
) = 6,238.10
-13

Ta c: h
1
= h
0
-
) h ( ' F
) h ( F
0
0
= 6.10
-7
+
13
20
10 . 238 , 6
10 . 786 , 5

= 6,93.10
-7

F(h
1
) = 1,653.10
-20

F(h
1
) = 9,847.10
-13

h
2
= h
1
-
) h ( ' F
) h ( F
1
1
= 6,93.10
-7
-
13
20
10 . 847 , 9
10 . 653 , 1

= 6,76.10
-7

Ta c:
1
1 2
h
h h
. 100% =
7
7 7
10 . 93 , 6
10 . 93 , 6 10 . 76 , 6

. 100% = 2,45%
Vy : h = 6,76.10
-7
= 10
-6,17

pH = 6,17
V d 2: Tnh cn bng trong dung dch HAc 2.10
-2
M.
Cho bit : KHAc = 10
-4,76

Gii
Cc qu trnh xy ra trong h
HAc H
+
+ Ac
-
K
a
= 10
-4,76
(1)
H
2
O H
+
+ OH
-
W = 10
-14
(2)
Ta c: KHAc.CHAc = 2.10
-2
.10
-4,76
= 10
-6,46
W = 10
-14
. V vy ta b qua (2) so
vi (1) v da vo (1) tnh ton.
HAc H
+
+ Ac
-
K
a
= 10
-4,76

C 2.10
-2
0 0
[ ] 2.10
-2
h h h
Theo nh lut tc dng khi lng ta c:
h 10 . 2
h
2
2

= 10
-4,76

h
2
+ 10
-4,76
h 10
-6,46
= 0
Gii ra ta c: h = 5,8021.10
-4

[H
+
] = [Ac
-
] = h = 5,8021.10
-4
M
[HAc] = 2.10
-2
- h = 2.10
-2
-5,8021.10
-4
= 1,942.10
-2
M
[OH
-
] =
h
W
=
4
14
10 . 8021 , 5
10

= 1,7235.10
-11
M
pH = 3,24
III.1.2.2.Dung dch n Baz yu
Thnh phn dung dch: (A
-
,C
b
, K
b
; H
2
O)
Cc qu trnh xy ra trong h
A
-
+ H
2
O HA + OH
-
K
b
(1)
H
2
O H
+
+ OH
-
W (2)
p dng iu kin proton m rng vi mc khng: A
-
, H
2
O
[OH
-
] = [H
+
] + [HA]
[OH
-
] - [H
+
] - [HA] = 0 (3)
t : [OH
-
] = x [H
+
] =
x
W
thay vo (3) ta c:
x -
x
W
- [HA] = 0 (4)
Theo nh lut bo ton nng ban u ta c :
CA
-
= C
b
= [A
-
] + [HA]
= [HA] x K
b
-1
+ [HA] = [HA] (x K
b
-1
+ 1)
[HA] = C
b
b
b
K x
K
+
thay vo (4) ta c:
x -
x
W
- C
b
b
b
K x
K
+
= 0 (5)
a.Gii chnh xc:
Gii phng trnh (5) phng trnh bc 3 i vi x. Tm x
T x [H
+
] ; pH ; [A
-
] ; [HA]
b.Gii gn ng:
T (1) [HA].[OH
-
] = K
b
[A
-
] K
b
C
b

(2) [H
+
].[OH
-
] = W
+ Nu K
b
C
b
W ngha l nng ion OH
-
to ra (1) ln hn nhiu so vi
(2). Do b qua (2) so vi (1) v da vo (1) tnh.
A
-
+ H
2
O HA + OH
-
K
b

C C
b
0 0
[ ] C
b
x x x
Theo nh lut tc dng khi lng ta c :
K
b
=
x C
x
b
2

(6)
Gii phng trnh (6) phng trnh bc 2 i vi x. Tm x
T x [H
+
] ; pH ; [A
-
] ; [HA]
+ Nu K
b
C
b
W th phi gii chnh xc phng trnh (5)
V d : Tnh cn bng trong dung dch NH
3
10
-4
M. Cho bit KNH
4
+
= 10
-9,24
.
Gii
Cc qu trnh xy ra trong h
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= (KNH
4
+
)
-1
. W = 10
-4,76
(1)
H
2
O H
+
+ OH
-
W = 10
-14
(2)
Ta c: K
b
.CNH
3
= 10
-4,76
.10
-4
= 10
-8,76
W = 10
-14
. V vy ta b qua (2) so vi
(1) v da vo (1) tnh ton.
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= 10
-4,76

C 10
-4
0 0
[ ] 10
-4
x x x
Theo nh lut tc dng khi lng ta c:
x 10
x
4
2

= 10
-4,76

x
2
+ 10
-4,76
x - 10
-8,76
= 0
Gii ra ta c: x = 3,39.10
-5

[NH
4
+
] = [OH
-
] = x = 3,39.10
-5
M
[NH
3
] = 10
-4
- x = 10
-4
- 3,39.10
-5
= 6,61.10
-5
M
[H
+
] =
x
W
=
5
14
10 . 39 , 3
10

= 2,9499.10
-10
= 10
-9,53

pH = 9,53
III.2.Cn bng trong cc dung dch Axit- Baz nhiu cu t
III.2.1.Dung dch hn hp gm 1 n Axit mnh v 1 n Axit yu
Thnh phn dung dch : (HX , C ; HA , C
a
, K
a
; H
2
O)
Cc qu trnh xy ra trong h
HX H
+
+ X
-
(1)
HA H
+
+ A
-
K
a
(2)
H
2
O H
+
+ OH
-
W (3)
V dung dch cha n Axit mnh HX, nn nng ion H
+
phn ly ra trong
dung dch ln,cn bng (3) chuyn dch mnh sang tri. V vy ta b qua (3) so
vi (1) v (2), da vo (2) tnh vi lu : Nng ban u ca ion H
+
cn
bng (2) chnh bng nng ban u ca n Axit mnh HX.
HA H
+
+ A
-
K
a

C C
a
C 0
[ ] C
a
x C + x x
Theo nh lut tc dng khi lng ta c:
x C
) x C ( x
a

+
= K
a
(4)
a.Gii chnh xc:
Gii phng trnh (4) phng trnh bc 2 i vi x. Tm x
T x [H
+
] ; pH ; [A
-
] ; [HA] ; [OH
-
]
b.Gii gn ng:
+ Nu x C, C
a
. T (4) x = K
a
C
C
a
.
T x [H
+
] ; pH ; [A
-
] ; [HA] ; [OH
-
]
+ Nu x C C
a
. T (4) x(C + x) = K
a
C
a

x
2
+ Cx - K
a
C
a
= 0 (5)
Gii phng trnh (5) phng trnh bc 2 i vi x. Tm x
T x [H
+
] ; pH ; [A
-
] ; [HA] ; [OH
-
]
+ Nu x C
a
C . T (4) Cx = K
a
(C
a
x)
(C + K
a
)x = K
a
C
a
x =
a
a a
K C
C K
+

T x [H
+
] ; pH ; [A
-
] ; [HA] ; [OH
-
]
V d: Tnh cn bng trong dung dch gm HCl 10
-2
M v HAc 0,2M. Cho bit :
KHAc = K
a
= 10
-4,76
.
Gii
Cc qu trnh xy ra trong h
HCl H
+
+ Cl
-
(1)
HAc H
+
+ Ac
-
K
a
= 10
-4,76
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c : [H
+
] CHCl = 10
-2
M [OH
-
] = 10
-12
M [H
+
]
V vy ta b qua (3) so vi (1) v (2), da vo (2) tnh.


HAc H
+
+ Ac
-
K
a
= 10
-4,76

C 0,2 10
-2
0
[ ] 0,2 x 10
-2
+ x x
Theo nh lut tc dng khi lng ta c:
x 2 , 0
) x 10 ( x
2

= 10
-4,76
(4)
+ Gi s: x 10
-2
. T (4) x = 10
-4,76
2
10
2 , 0

= 10
-3,46
khng 10
-2

+ Gi s x 0,2
T (4) x
2
+ 10
-2
x - 10
-5,46
= 0
Gii ra ta c: x = 3,355.10
-4
0,2
[Ac
-
] = x = 3,355.10
-4
M ; [Cl
-
] = CHCl = 10
-2
M
[HAc] = 0,2 - x 0,2M
[H
+
] = 10
-2
+ x = 10
-2
+ 3,355.10
-4
= 1,034.10
-2
= 10
-1,986
M
[OH
-
] =
| |
+
H
W
=
986 , 1
14
10
10

= 10
-12,014
M ; pH = 1,986
III.2.2.Dung dch hn hp gm 1 n Baz mnh v 1 n Baz yu
Thnh phn dung dch : (BOH , C ; A
-
, C
b
, K
b
; H
2
O)
Cc qu trnh xy ra trong h
BOH B
+
+ OH
-
(1)
A
-
+ H
2
O HA + OH
-
K
b
(2)
H
2
O H
+
+ OH
-
W (3)
V dung dch cha n Baz mnh BOH, nn nng ion OH
-
phn ly ra
trong dung dch ln, cn bng (3) chuyn dch mnh sang tri. V vy ta b qua
(3) so vi (1) v (2), da vo (2) tnh vi lu : Nng ban u ca ion OH
-
cn bng (2) chnh bng nng ban u ca n Baz mnh BOH.
A
-
+ H
2
O HA + OH
-
K
b

C C
b
0 C
[ ] C
b
x x C + x
Theo nh lut tc dng khi lng ta c:
x C
) x C ( x
b

+
= K
b
(4)
a.Gii chnh xc:
Gii phng trnh (4) phng trnh bc 2 i vi x. Tm x
T x [OH
-
] ; [H
+
] ; pH ; [A
-
] ; [HA]
b.Gii gn ng:
+ Nu x C, C
b
. T (4) x = K
b
C
C
b
.
T x [OH
-
] ; [H
+
] ; pH ; [A
-
] ; [HA]
+ Nu x C C
b
. T (4) x(C + x) = K
b
C
b
x
2
+ Cx - K
b
C
b
= 0 (5)
Gii phng trnh (5) phng trnh bc 2 i vi x. Tm x
T x [OH
-
] ; [H
+
] ; pH ; [A
-
] ; [HA]
+ Nu x C
b
C . T (4) Cx = K
b
(C
b
x)
(C + K
b
)x = K
b
C
b
x =
b
b b
K C
C K
+

T x [OH
-
] ; [H
+
] ; pH ; [A
-
] ; [HA]
V d: Tnh cn bng trong dung dch gm NaOH 10
-3
M v NaAc 0,5M. Cho
bit : KHAc = 10
-4,76
.
Gii
Cc qu trnh xy ra trong h
NaAc Na
+
+ Ac
-

NaOH Na
+
+ OH
-
(1)
Ac
-
+ H
2
O HAc + OH
-
K
b
= (KHAc)
-1
.W = 10
-9,24
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: [OH
-
] CNaOH = 10
-3
M [H
+
] = 10
-11
M [OH
-
] .Nn ta b qua (3)
so vi (1) v (2), da vo (2) tnh.
Ac
-
+ H
2
O HAc + OH
-
K
b
= 10
-9,24

C 0,5 0 10
-3

[ ] 0,5 x x 10
-3
+ x
Theo nh lut tc dng khi lng ta c:
x 5 , 0
) x 10 ( x
3

= 10
-9,24
(4)
Gi s x 10
-3

T (4) x = 10
-9,24
3
10
5 , 0

= 10
-6,54
= 2,877.10
-7
10
-3

[Na
+
] = CNaOH + CNaAc = 0,5 + 10
-3
= 0,501M
[Ac
-
] = 0,5 - x 0,5M , [HAc] = x = 2,877.10
-7
M
[OH
-
] = 10
-3
+ x 10
-3
M [H
+
] = 10
-11
M
pH = 11
III.2.3.Dung dch cha hn hp nhiu n Axit yu
Thnh phn dung dch:(HA
1
,Ca
1
,Ka
1
; HA
2
,Ca
2
,Ka
2
; ; HA
n
,Ca
n
,Ka
n
; H
2
O)
Cc qu trnh xy ra trong h
HA
1
H
+
+ A
1
-
Ka
1
(1)
HA
2
H
+
+ A
2
-
Ka
2
(2)
----------------------------------------------------
HA
n
H
+
+ A
n
-
Ka
n
(n)
H
2
O H
+
+ OH
-
W (n+1)
+ Trng hp 1: NuCa
1
.Ka
1
Ca
2
. Ka
2
; ; Ca
n
.Ka
n
; W
b qua cc cn bng (2) n (n+1) so vi (1),da vo (1) tnh.
HA
1
H
+
+ A
1
-
Ka
1

C Ca
1
0 0
[ ] Ca
1
h h h
Theo nh lut tc dng khi lng ta c:
Ka
1
=
h C
h
1 a
2

(a)
Gii phng trnh (a) phng trnh bc 2 i vi h. Tm h.
T h [HA
1
],[A
1
-
] , [H
+
]
tnh [HA
i
], [A
i
-
] (vi i = 2 n)
Ta da vo cn bng th i vi lu : nng ban u ca ion H
+
cn bng i
chnh bng nng cn bng ca ion H
+
cn bng (1) .
V d: Tnh cn bng trong dung dch gm HAc 5.10
-2
M v HCN 2.10
-1
M. Cho
bit : KHAc = 10
-4,76
; KHCN = 10
-9,35
.
Gii
Cc qu trnh xy ra trong h
HAc H
+
+ Ac
-
KHAc = 10
-4,76
(1)
HCN H
+
+ CN
-
KHCN = 10
-9,35
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: KHAc.CHAc = 10
-4,76
.5.10
-2
= 10
-6,06

KHCN.CHCN = 10
-9,35
.2.10
-1
= 10
-10,05

Ta thy: KHAc.CHAc KHCN.CHCN W = 10
-14
.Ta b qua cn bng (2)
v (3) so vi (1), da vo (1) tnh.
HAc H
+
+ Ac
-
KHAc = 10
-4,76

C 5.10
-2
0 0
[ ] 5.10
-2
h h h
Theo nh lut tc dng khi lng ta c:
h 10 . 5
h
2
2

= 10
-4,76

h
2
+ 10
-4,76
- 10
-6,06
= 0
Gii ra ta c: h = 9,235.10
-4
= 10
-3,0346

[H
+
] = [Ac
-
] = h = 9,235.10
-4
M
[HAc] = 5.10
-2
h = 5.10
-2
- 9,235.10
-4
= 4,91.10
-2
M
tnh nng ca [HCN], [CN
-
] ta da vo cn bng (2)
HCN H
+
+ CN
-
KHCN = 10
-9,35

C 2.10
-1
9,235.10
-4
0
[ ] 2.10
-1
x 9,235.10
-4
+ x x
Theo nh lut tc dng khi lng ta c:
x 10 . 2
) x 10 . 235 , 9 ( x
1
4

= 10
-9,35
(4)
Gi s : x 9,235.10
-4

T (4) x = 10
-9,35
4
1
10 . 235 , 9
10 . 2

= 9,6737.10
-8
9,235.10
-4

[HCN] = 2.10
-1
x 2.10
-1
M ; [CN
-
] = x = 9,6737.10
-8
M
[H
+
] = 9,235.10
-4
+ x 9,235.10
-4
= 10
-3,0346
pH = 3,0346
[OH
-
] =
| |
+
H
W
=
0346 , 3
14
10
10

= 10
-10,9654
M
+ Trng hp 2: NuCa
1
.Ka
1
Ca
2
. Ka
2
Ca
n
.Ka
n
W
Cc cn bng xy ra mc tng ng nhau
Trc ht ta xt dung dch hn hp gm 2 n Axit yu HA
1
v HA
2

p dng iu kin proton vi mc khng l HA
1
, HA
2
, H
2
O
[H
+
] = [OH
-
] + [A
1
-
] + [A
2
-
]
[H
+
] - [OH
-
] - [A
1
-
] - [A
2
-
] = 0 (b)
t : [H
+
] = h [OH
-
] =
h
W
thay vo (b) ta c:
h -
h
W
- [A
1
-
] - [A
2
-
] = 0 (c)
Theo nh lut bo ton nng ban u ta c :
CHA
1
= Ca
1
= [HA
1
] + [A
1
-
]
= [A
1
-
] h Ka
1
-1
+ [A
1
-
] = [A
1
-
] (h Ka
1
-1
+ 1)
[A
1
-
] = Ca
1
1 a
1 a
K h
K
+

Tng t: [A
2
-
] = Ca
2
2 a
2 a
K h
K
+
thay vo (c) ta c
h -
h
W
- Ca
1
1 a
1 a
K h
K
+
- Ca
2
2 a
2 a
K h
K
+
= 0 (d)
Tng qut cho h gm n n Axit yu:
h -
h
W
- Ca
1
1 a
1 a
K h
K
+
- Ca
2
2 a
2 a
K h
K
+
- - Ca
n
an
an
K h
K
+
= 0
Hay : h -
h
W
-
+
=
n
1 i
ai
ai
ai
K h
K
C = 0 (e)

Gii phng trnh (e) phng trnh bc (n+2) i vi h. Tm h.
T h [OH
-
] ; pH ; [A
i
-
] ; [HA
i
] (vi i = 1 n).
+ NuCa
1
.Ka
1
Ca
2
. Ka
2
Ca
n
.Ka
n
W phng trnh (e) tr thnh
h -
+
=
n
1 i
ai
ai
ai
K h
K
C = 0 (f
Lu :
i vi trng hp ny, ngoi vic gii cc phng trnh bc cao ngi ta cn
gii theo phng php gn ng lin tc.
V d: Tnh pH trong dung dch cha hn hp HCOOH 2.10
-2
M v HAc 10
-1
M.
Cho bit : KHCOOH = K
1
= 10
-3,75
; KHAc = K
2
= 10
-4,76
.
Gii
Cc qu trnh xy ra trong h
HCOOH H
+
+ HCOO
-
K
1
= 10
-3,75
(1)
HAc H
+
+ Ac
-
K
2
= 10
-4,76
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c:
K
1
.CHCOOH = 10
-3,75
.2.10
-2
= 10
-5,45
K
2
.CHAc = 10
-4,76
.10
-1
= 10
-5,76
W = 10
-14

B qua cn bng (3) so vi (1) v (2), da vo (1) v (2) tnh.
Cch 1: Gii theo phng php tip tuyn (Niutn)
T phng trnh :
h -
+
=
n
1 i
ai
ai
ai
K h
K
C = 0 hay h -
+
=
n
1 i
i
i
i
K h
K
C = 0 (4)
p dng phng trnh (4) vi n = 2 ta c:
h - C
1
1
1
K h
K
+
- C
2
2
2
K h
K
+
= 0 (Vi C
1
= CHCOOH, C
2
= CHAc )
h
3
+ (K
1
+ K
2
)h
2
+ (K
1
K
2
C
1
K
1
C
2
K
2
)h - K
1
K
2
(C
1
+C
2
) = 0 (5)
Thay cc gi tr K
1
, K
2
, C
1
, C
2
vo (5) ta c:
h
3
+ 1,952.10
-4
h
2
- 5,283.10
-6
h - 3,71.10
-10
= 0
Chn h
0

+ h
3
- 5,283.10
-6
h = 0 h = 2,299.10
-3
(v h > 0)
+ 1,952.10
-4
h
2
- 3,71.10
-10
= 0 h = 1,379.10
-3
(v h > 0)
Nghim thc h phi tha mn : 1,379.10
-3
< h < 2,299.10
-3
.
Chn h
0
= 2.10
-3

F(h) = h
3
+ 1,952.10
-4
h
2
- 5,283.10
-6
h - 3,71.10
-10

F(h) = 3h
2
+ 3,904.10
-4
h - 5,283.10
-6

F(h
0
) = - 2,1562.10
-9
; F(h
0
) = 7,4978.10
-6

h
1
= h
0
-
) h ( ' F
) h ( F
0
0
= 2.10
-3
+
6
9
10 . 4978 , 7
10 . 1562 , 2

= 2,29.10
-3

F(h
1
) = 5,6357.10
-10
; F(h
1
) = 1,1343.10
-5
h
2
= h
1
-
) h ( ' F
) h ( F
1
1
= 2,29.10
-3
-
5
10
10 . 1343 , 1
10 . 6357 , 5

= 2,24.10
-3

Ta c :
1
1 2
h
h h
100% =
3
3 3
10 . 29 , 2
10 . 29 , 2 10 . 24 , 2

100% = 2,18%
Vy : h = 2,24.10
-3
= 10
-2,65

pH = 2,65
Cch 2: Gii theo phng php gn ng lin tc
p dng iu kin proton vi mc khng : HCOOH , HAc
[H
+
] = [HCOO
-
] + [Ac
-
]
h = [HCOOH]
h
K
1
+ [HAc]
h
K
2

h = | | | | HAc K OH HCO K
2 1
+ (6)
Theo nh lut bo ton nng ban u ta c:
CHCOOH = C
1
= [HCOOH] + [HCOO
-
]
= [HCOOH] + K
1
[HCOOH] h
-1

= [HCOOH] (1+ K
1
h
-1
)
[HCOOH] = C
1
1
K h
h
+
; tng t: [HAc] = C
2
2
K h
h
+
(7)
Gii theo phng php gn ng lin tc da vo (6) v (7)
Chp nhn: [HCOOH] = C
1
= 2.10
-2
M ; [HAc] = C
2
= 10
-1
M
thay vo (6) ta c:
h
0
=
1 76 , 4 2 75 , 3
10 . 10 10 . 2 . 10

+ = 2,3.10
-3
thay vo (7) ta c:
[HCOOH]
1
= 2.10
-2
.
75 , 3 3
3
10 10 . 3 , 2
10 . 3 , 2

+
= 1,86.10
-2
M
[HAc]
1
= 10
-1
.
76 , 4 3
3
10 10 . 3 , 2
10 . 3 , 2

+
= 9,925.10
-2
M thay vo (6) ta c:
h
1
=
2 76 , 4 2 75 , 3
10 . 925 , 9 . 10 10 . 86 , 1 . 10

+ = 2,24.10
-3

Ta c:
0
0 1
h
h h
100% =
3
3 3
10 . 3 , 2
10 . 3 , 2 10 . 24 , 2

100% = 2,61%
Vy : h = 2,24.10
-3
= 10
-2,65

pH = 2,65
III.2.4.Dung dch cha hn hp nhiu n Baz yu
Thnh phn dung dch:(A
1
-
,Cb
1
,Kb
1
; A
2
-
,Cb
2
,Kb
2
; ; A
n
-
,Cb
n
,Kb
n
; H
2
O)
Cc qu trnh xy ra trong h
A
1
-
+ H
2
O HA
1
+ OH
-
Kb
1
(1)
A
2
-
+ H
2
O HA
2
+ OH
-
Kb
2
(2)
------------------------------------------------------------------
A
n
-
+ H
2
O HA
n
+ OH
-
Kb
n
(n)
H
2
O H
+
+ OH
-
W (n+1)
+ Trng hp 1: NuCb
1
.Kb
1
Cb
2
. Kb
2
; ; Cb
n
.Kb
n
; W
b qua cc cn bng (2) n (n+1) so vi (1),da vo (1) tnh.
A
1
-
+ H
2
O HA
1
+ OH
-
Kb
1

C Cb
1
0 0
[ ] Cb
1
x x x
Theo nh lut tc dng khi lng ta c:
Kb
1
=
x C
x
1 b
2

(a)
Gii phng trnh (a) phng trnh bc 2 i vi x. Tm x.
T x [HA
1
],[A
1
-
] , [OH
-
]
tnh [HA
i
], [A
i
-
] (vi i = 2 n)
Ta da vo cn bng th i vi lu : nng ban u ca ion OH
-
cn bng i
chnh bng nng cn bng ca ion OH
-
cn bng (1) .
V d: Tnh cn bng trong dung dch gm KAc 2.10
-1
M v KCN 5.10
-2
M.
Cho bit: KHAc = 10
-4,76
; KHCN = 10
-9,35
.
Gii
Cc qu trnh xy ra trong h
KCN K
+
+ CN
-

KAc K
+
+ Ac
-
CN
-
+ H
2
O HCN + OH
-
Kb
1
= (KHCN)
-1
W = 10
-4,65
(1)
Ac
-
+ H
2
O HAc + OH
-
Kb
2
= (KHAc)
-1
W = 10
-9,24
(2)
H
2
O H
+
+ OH
-
W (3)
Ta c: Kb
1
.CCN
-
= 10
-4,65
.5.10
-2
= 10
-5,95
Kb
2
.CAc
-
= 10
-9,24
.2.10
-1
= 10
-9,94
W.
Ta b qua cn bng (2) v (3) so vi (1), da vo (1) tnh.
CN
-
+ H
2
O HCN + OH
-
Kb
1
= 10
-4,65

C 5.10
-2
0 0
[ ] 5.10
-2
x x x
Theo nh lut tc dng khi lng ta c:

x 10 . 5
x
2
2

= 10
-4,65

x
2
+ 10
-4,65
x - 5.10
-6,65
= 0
Gii ra ta c: x = 1,047.10
-3

[HCN] = [OH
-
] = x = 1,047.10
-3
M = 10
-2,98
M
[CN
-
] = 5.10
-2
- x = 5.10
-2
- 1,047.10
-3
= 4,9853.10
-2
M
tnh nng [HAc] [Ac
-
] ta da vo cn bng (2)
Ac
-
+ H
2
O HAc + OH
-
Kb
2
= 10
-9,24

C 2.10
-1
0 10
-2,98

[ ] 2.10
-1
y y 10
-2,98
+ y
Theo nh lut tc dng khi lng ta c:
y 10 . 2
) y 10 ( y
1
98 , 2

= 10
-9,24
(4)
Gi s: y 10
-2,98

T (4) y = 10
-9,24
98 , 2
1
10
10 . 2

= 10
-6,96
10
-2,98

[HAc] = y = 10
-6,96
M = 1,096,10
-7
M
[Ac
-
] = 2.10
-1
- y 2.10
-1
M
[OH
-
] = 10
-2,98
+ y 10
-2,98
M [H
+
] =
| |

OH
W
=
98 , 2
14
10
10

= 10
-11,02
M

pH = 11,02
+ Trng hp 2: Nu Cb
1
.Kb
1
Cb
2
. Kb
2
Cb
n
.Kb
n
W
Cc cn bng xy ra mc tng ng nhau
Trc ht ta xt dung dch hn hp gm 2 n Baz yu A
1
-
v A
2
-

p dng iu kin proton m rng vi mc khng l A
1
-
, A
2
-
, H
2
O
[OH
-
] = [H
+
] + [HA
1
] + [HA
2
]
[OH
-
] - [H
+
] - [HA
1
] - [HA
2
] = 0 (b)
t : [OH
-
] = x [H
+
] =
x
W
thay vo (b) ta c:
x -
x
W
- [HA
1
] - [HA
2
] = 0 (c)
Theo nh lut bo ton nng ban u ta c :
CA
1
-
= Cb
1
= [A
1
-
] + [HA
1
]
= [HA
1
] x Kb
1
-1
+ [HA
1
] = [HA
1
] (x Kb
1
-1
+ 1)
[HA
1
] = Cb
1
1 b
1 b
K x
K
+

Tng t: [HA
2
] = Cb
2
2 b
2 b
K x
K
+
thay vo (c) ta c
x -
x
W
- Cb
1
1 b
1 b
K x
K
+
- Cb
2
2 b
2 b
K x
K
+
= 0 (d)
Tng qut cho h gm n n Baz yu:
x -
x
W
- Cb
1
1 b
1 b
K x
K
+
- Cb
2
2 b
2 b
K x
K
+
- - Cb
n
bn
bn
K x
K
+
= 0
Hay : x -
x
W
-

+
=
n
1 i
bi
bi
bi
K x
K
C = 0 (e)

Gii phng trnh (e) phng trnh bc (n+2) i vi x. Tm x.
T x [H
+
] ; pH ; [A
i
-
] ; [HA
i
] (vi i = 1 n).
+ NuCb
1
.Kb
1
Cb
2
. Kb
2
Cb
n
.Kb
n
W phng trnh (e) tr thnh
x -

+
=
n
1 i
bi
bi
bi
K x
K
C = 0 (f)
Lu :
i vi trng hp ny, ngoi vic gii cc phng trnh bc cao ngi ta cn
gii theo phng php gn ng lin tc.
V d: Tnh pH trong dung dch gm NH
3
0,2500M v KCN 0,2000M.
Cho bit: KNH
4
+
= 10
-9,24
; KHCN = 10
-9,35
.
Gii
Cc qu trnh xy ra trong h
KCN K
+
+ CN
-

CN
-
+ H
2
O HCN + OH
-
Kb
1
= (KHCN)
-1
W = 10
-4,65
(1)
NH
3
+ H
2
O NH
4
+
+ OH
-
Kb
2
= (KNH
4
+
)
-1
W = 10
-4,76
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: Kb
1
.CCN
-
= 10
-4,65
.0,2 = 10
-5,35
Kb
2
.CNH
3
= 10
-4,76
.0,25 = 10
-5,362
W.
B qua cn bng (3) so vi (1) v (2), da vo (1) v (2) tnh.
Cch 1: Gii theo phng php tip tuyn (Niutn)
T phng trnh :
x -
+
=
n
1 i
bi
bi
bi
K x
K
C = 0 (4)
p dng phng trnh (4) vi n = 2 ta c:
x - Cb
1
1 b
1 b
K x
K
+
- Cb
2
2 b
2 b
K x
K
+
= 0
x
3
+ (Kb
1
+ Kb
2
)x
2
+ (Kb
1
Kb
2
Cb
1
Kb
1
Cb
2
Kb
2
)x - Kb
1
Kb
2
(Cb
1
+ Cb
2
) = 0 (5)
Thay cc gi tr Kb
1
, Kb
2
, Cb
1
, Cb
2
vo (5) ta c:
x
3
+ 3,977.10
-5
x
2
- 8,822.10
-6
x - 1,751.10
-10
= 0
Chn x
0

+ x
3
- 8,822.10
-6
x = 0 x = 2,970.10
-3
(v x > 0)
+ 3,977.10
-5
x
2
- 1,751.10
-10
= 0 x = 2,098.10
-3
(v x > 0)
Nghim thc x phi tha mn : 2,098.10
-3
< x < 2,970.10
-3

Chn x
0
= 2,9.10
-3

F(x) = x
3
+ 3,977.10
-5
x
2
- 8,822.10
-6
x - 1,751.10
-10

F(x) = 3x
2
+ 7,954.10
-5
x - 8,822.10
-6

F(x
0
) = - 1,0354.10
-9
; F(x
0
) = 1,6639.10
-5

x
1
= x
0
-
) x ( ' F
) x ( F
0
0
= 2,9.10
-3
+
5
9
10 . 6639 , 1
10 . 0354 , 1

= 2,962.10
-3

Ta c:
0
0 1
x
x x
100% =
3
3 3
10 . 9 , 2
10 . 9 , 2 10 . 962 , 2

100% = 2,14%
Vy: x = 2,962.10
-3
= 10
-2,53
[H
+
] =
x
W
=
53 , 2
14
10
10

= 10
-11,47

pH = 11,47
Cch 2: Gii theo phng php gn ng lin tc
p dng iu kin proton m rng vi mc khng : NH
3
, CN
-

[OH
-
] = x = [HCN] + [NH
4
+
]
x = [CN
-
]
x
K
1 b
+ [NH
3
]
x
K
2 b

x = | | | |
3 2 b 1 b
NH K CN K +

(6)
Theo nh lut bo ton nng ban u ta c:
CCN
-
= Cb
1
= [HCN] + [CN
-
]
= [CN
-
] Kb
1
x
-1
+ [CN
-
]
= [CN
-
] (Kb
1
x
-1
+ 1)
[CN
-
] = Cb
1
1 b
K x
x
+
; tng t: [NH
3
] = Cb
2
2 b
K x
x
+
(7)
Gii theo phng php gnng lin tc da vo (6) v (7)
+ Chp nhn: [CN
-
] = Cb
1
= 0,2000M ; [NH
3
] = Cb
2
= 0,2500M
thay vo (6) ta c:
x
0
= 25 , 0 . 10 2 , 0 . 10 .
76 , 4 65 , 4
+ = 2,97.10
-3
thay vo (7) ta c :
[CN
-
]
1
= 0,2
65 , 4 3
3
10 10 . 97 , 2
10 . 97 , 2

+
= 0,1985M
[NH
3
]
1
= 0,25
76 , 4 3
3
10 10 . 97 , 2
10 . 97 , 2

+
= 0,2490M thay vo (6) ta c
x
1
= 2490 , 0 . 10 1985 , 0 . 10
76 , 4 65 , 4
+ = 2,962.10
-3

Ta c:
0
0 1
x
x x
100% =
3
3 3
10 . 97 , 2
10 . 97 , 2 10 . 962 , 2

100% = 0,27%
Vy: x = 2,962.10
-3
= 10
-2,53
[H
+
] = 10
-11,47

pH = 11,47
III.2.5.Dung dch cc a Axit:
Thnh phn dung dch: (H
n
A, C, c cc hng s phn ly tng nc K
1
, K
2
,...K
n
)
C th coi cc a Axit nh l hn hp ca nhiu n Axit.Trong a s trng
hp nht l i vi nhngAxit v c th K
1
K
2
K
n
.
+ Dng quy tc Pauling c th d on mnh yu ca cc a Axit nh sau:
K
1
: K
2
: K
3
1 : 10
-5
: 10
-10

Chng hn: H
3
PO
4
c K
1
= 10
-2,23
; K
2
= 10
-7,21
; K
3
= 10
-12,32

H
3
AsO
4
c K
1
= 10
-2,22
; K
2
= 10
-6,98
; K
3
= 10
-11,53

H
2
CrO
4
c K
1
= 10
-0,08
; K
2
= 10
-6,50
H
2
SO
3
c K
1
= 10
-1,76
; K
2
= 10
-7,21

+C th biu din cng thc tng qut ca cc oxy Axit di dng XO
n
(OH)
m
Khi n = 0 th K
1
10
-7
Axit rt yu
Chng hn: HClO c K = 10
-7,53
; HBrO c K = 10
-8,60

H
3
AsO
3
c K
1
= 10
-9,10
; H
3
BO
3
c K
1
= 10
-9,24

Khi n = 1 th K
1
10
-2
Axit yu
Chng hn: HNO
2
c K = 10
-3,29
; HClO
2
c K = 10
-1,97
; H
3
PO
4
c K
1
= 10
-2,23

Khi n = 2 th K
1
10
3
ccAxit mnh nh HNO
3
, HClO
3
, H
2
SO
4

Khi n = 3 th K
1
10
8
ccAxit rt mnh nh HClO
4
, HMnO
4
.
i vi cc a Axit c cu trc phc tp khi cc nhm sinh proton cch xa
nhau th cc hng s phn ly k tip c th c gi tr rt gn nhau. Trng hp
ny thng gp cc Axit hu c c mch cacbon di xen k gia cc nhm
Axit. Chng hn:
Axit Tactric H
2
C
4
H
4
O
6
c cng thc cu to:

HC CH
OH
COOH HOOC
OH
c K
1
= 10
-3,04
; K
2
= 10
-4,37

Axit Xitric H
4
C
6
H
4
O
7
c cng thc cu to:

C CH
2
COOH
OH
H
2
C COOH HOOC

c : K
1
= 10
-3,13
; K
2
= 10
-4,76
; K
3
= 10
-6,40

Xt dung dch a Axit ni trn :
Cc qu trnh xy ra trong h
H
n
A H
+
+ H
n-1
A
-
K
1
(1)
H
n-1
A
-
H
+
+ H
n-2
A
2-
K
2
(2)
---------------------------------------------------------------------
HA
(n-1)-
H
+
+ A
n-
K
n
(n)
H
2
O H
+
+ OH
-
W (n+1)
p dng iu kin proton vi mc khng : H
n
A , H
2
O
[H
+
] = [OH
-
] + [H
n-1
A
-
] + 2[H
n-2
A
2-
] + + n[A
n-
]
[H
+
] - [OH
-
] - [H
n-1
A
-
] - 2[H
n-2
A
2-
] - - n[A
n-
] = 0
Hay: h -
h
W
- [H
n-1
A
-
] - 2[H
n-2
A
2-
] - - n[A
n-
] = 0 (vi h = [H
+
]) (a)
Theo nh lut bo ton nng ban u ta c:
CH
n
A = C = [H
n
A] + [H
n-1
A
-
] + [H
n-2
A
2-
] + + [A
n-
]
C = [H
n
A] + [H
n
A]K
1
h
-1
+ [H
n
A]K
1
K
2
h
-2
+ + [H
n
A]K
1
K
2
K
n
h
-n

= [H
n
A] (1 + K
1
h
-1
+ K
1
K
2
h
-2
+ + K
1
K
2
K
n
h
-n
)
[H
n
A] = C
n 2 1
2 n
2 1
1 n
1
n
n
K ... K K ... h K K h K h
h
+ + + +

=
MSC
h
n

Vi : MSC = h
n
+ K
1
h
n-1
+ K
1
K
2
h
n-2
+ + K
1
K
2
K
n

[H
n-1
A
-
] = [H
n
A]K
1
h
-1
= C
MSC
h K
1 n
1

[H
n-2
A
2-
] = [H
n
A]K
1
K
2
h
-2
= C
MSC
h K K
2 n
2 1

[A
n-
] = [H
n
A]K
1
K
2
K
n
h
-n
= C
MSC
K ... K K
n 2 1
thay vo (a) ta c:
h -
h
W
- C
n 2 1
2 n
2 1
1 n
1
n
n 2 1
2 n
2 1
1 n
1
K ... K K ... h K K h K h
) K ... K nK ... h K K 2 h K (
+ + + +
+ + +


= 0 (b)

+ Trng hp 1: Nu K
1
K
2
K
n
v K
1
C W
Phi gii chnh xc phng trnh (b), phng trnh bc (n+2) i vi h. Tm
h. T h pH , [OH
-
] , [H
n-i
A
i-
] (vi i = 0 n)
+ Trng hp 2: Nu K
1
K
2
K
n
v K
1
C W
B qua cn bng phn ly ca nc. Phng trnh (b) tr thnh :

h - C
n 2 1
2 n
2 1
1 n
1
n
n 2 1
2 n
2 1
1 n
1
K ... K K ... h K K h K h
) K ... K nK ... h K K 2 h K (
+ + + +
+ + +


= 0 (c)
Gii phng trnh (c) phng trnh bc (n+1) i vi h.Tm h.
T h pH , [OH
-
] , [H
n-i
A
i-
] (vi i = 0 n)
+ Trng hp 3: Nu K
1
K
2
K
n
(K
1
/K
2
10
4
) v K
1
C W
B qua cc cn bng t (2) (n+1) v da vo (1) tnh
H
n
A H
+
+ H
n-1
A
-
K
1

C C 0 0
[ ] C - h h h
Theo nh lut tc dng khi lng ta c:
h C
h
2

= K
1
(d)
Gii phng trnh (d), phng trnh bc 2 i vi h, tm h.
T h [H
n
A] ; [H
n-1
A
-
]
tm nng : [H
n-i
A
i-
] ,da vo cn bng th i (vi i = 2 n). Vi lu :
Nng ban u ca ion H
+
cn bng th i chnh bng nng cn bng ca
ion H
+
cn bng (1).
V d 1: Tnh pH trong dung dch H
2
A 10
-2
M.
Cho bit H
2
A c: K
1
= 10
-2,00
; K
2
= 10
-2,67
.
Gii
Cc qu trnh xy ra trong h
H
2
A H
+
+ HA
-
K
1
= 10
-2,00
(1)
HA
-
H
+
+ A
2-
K
2
= 10
-2,67
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c : K
1
K
2
; K
1
C = 10
-2
.10
-2
= 10
-4
W = 10
-14

B qua cn bng (3) so vi (1) v (2), da vo (1),(2) tnh.
T phng trnh:
h - C
n 2 1
2 n
2 1
1 n
1
n
n 2 1
2 n
2 1
1 n
1
K ... K K ... h K K h K h
) K ... K nK ... h K K 2 h K (
+ + + +
+ + +


= 0 (4)
p dng phng trnh (4) vi n = 2 ta c:
h - C
2 1 1
2
2 1 1
K K h K h
) K K 2 h K (
+ +
+
= 0
h
3
+ K
1
h
2
+ K
1
(K
2
C)h - 2CK
1
K
2
= 0 (5)
Thay cc gi tr K
1
, K
2
, C vo (5) ta c:
h
3
+ 10
-2
h
2
- 7,862.10
-5
h - 4,276.10
-7
= 0
Chn h
0
:
+ h
3
- 7,862.10
-5
h = 0 h = 8,87.10
-3
(v h > 0)
+ 10
-2
h
2
- 4,276.10
-7
= 0 h = 6,54.10
-3
(v h > 0)
Nghim thc h tha mn : 6,54.10
-3
< h < 8,87.10
-3

Chn h
0
= 8.10
-3

F(h) = h
3
+ 10
-2
h
2
- 7,862.10
-5
h - 4,276.10
-7

F(h) = 3h
2
+ 2.10
-2
h - 7,862.10
-5

F(h
0
) = 9,544.10
-8
; F(h
0
) = 2,7338.10
-4

h
1
= h
0
-
) h ( ' F
) h ( F
0
0
= 8.10
-3
-
4
8
10 . 7338 , 2
10 . 544 , 9

= 7,65.10
-3

F(h
1
) = 3,879.10
-9
; F(h
1
) = 2,4995.10
-4

h
2
= h
1
-
) h ( ' F
) h ( F
1
1
= 7,65.10
-3
-
4
9
10 . 4995 , 2
10 . 879 , 3

= 7,634.10
-3

Ta c :
1
1 2
h
h h
100% =
3
3 3
10 . 65 , 7
10 . 65 , 7 10 . 634 , 7

100% = 0,21%
Vy h = 7,634.10
-3
= 10
-2,12

pH = 2,12
V d 2: Tnh cn bng trong dung dch gm H
3
PO
4
10
-2
M.
Cho bit H
3
PO
4
c : K
1
= 10
-2,23
; K
2
= 10
-7,21
; K
3
= 10
-12,32
.
Gii
Cc qu trnh xy ra trong h
H
3
PO
4
H
+
+ H
2
PO
4
-
K
1
= 10
-2,23
(1)
H
2
PO
4
-
H
+
+ HPO
4
2-
K
2
= 10
-7,21
(2)
HPO
4
2-
H
+
+ PO
4
3-
K
3
= 10
-12,32
(3)
H
2
O H
+
+ OH
-
W = 10
-14
(4)
Ta c : K
1
K
2
K
3
(K
1
/K
2
> 10
4
) ; K
1
C = 10
-2,23
.10
-2
= 10
-4,23
W = 10
-14

B qua cn bng (2) (3) (4) so vi (1) v da vo (1) tnh.
H
3
PO
4
H
+
+ H
2
PO
4
-
K
1
= 10
-2,23

C 10
-2
0 0
[ ] 10
-2
h h h
Theo nh lut tc dng khi lng ta c:
h 10
h
2
2

= 10
-2,23

h
2
+ 10
-2,23
h - 10
-4,23
= 0
Gii ra ta c : h = 5,275.10
-3

[H
+
] = [H
2
PO
4
-
] = h 5,275.10
-3
M
[H
3
PO
4
] = 10
-2
- h = 10
-2
- 5,275.10
-3
= 4,725.10
-3
M
tnh nng ca [HPO
4
2-
] ta da vo cn bng (2)
H
2
PO
4
-
H
+
+ HPO
4
2-
K
2
= 10
-7,21

C 5,275.10
-3
5,275.10
-3
0
[ ] 5,275.10
-3
x 5,275.10
-3
+ x x
Theo nh lut tc dng khi lng ta c:
x 10 . 275 , 5
) x 10 . 275 , 5 ( x
3
3

= 10
-7,21
(5)
Gi s : x 5,275.10
-3

T (5) x = 10
-7,21
3
3
10 . 275 , 5
10 . 275 , 5

= 10
-7,21
5,275.10
-3

[HPO
4
2-
] = x = 10
-7,21
M ; [H
2
PO
4
-
] = 5,275.10
-3
- x 5,275.10
-3
M
[H
+
] = 5,275.10
-3
+ x 5,275.10
-3
M
tnh nng [PO
4
3-
] ta da vo cn bng (3)
HPO
4
2-
H
+
+ PO
4
3-
K
3
= 10
-12,32

C 10
-7,21
5,275.10
-3
0
[ ] 10
-7,21
a 5,275.10
-3
+ a a
Theo nh lut tc dng khi lng ta c:
a 10
) a 10 . 275 , 5 ( a
21 , 7
3

= 10
-12,32
(6)
Gi s : a 10
-7,21

T (5) a = 10
-12,32
3
21 , 7
10 . 275 , 5
10

= 10
-17,25
10
-7,21

[PO
4
3-
] = 10
-17,25
M ; [HPO
4
2-
] = 10
-7,21
a 10
-7,21
M
[H
+
] = 5,275.10
-3
+ a 5,275.10
-3
M
pH = 2,28
III.2.6.Dung dch cc a Baz:
Thnh phn dung dch:(A
n-
, C
b
, c cc hng s cn bng tng nc Kb
1
, Kb
2
,...Kb
n
)
Cc qu trnh xy ra trong h
A
n-
+ H
2
O HA
(n-1)-
+ OH
-
Kb
1
(1)
HA
(n-1)-
+ H
2
O H
2
A
(n-2)-
+ OH
-
Kb
2
(2)
---------------------------------------------------------------------
H
n-1
A
-
+ H
2
O H
n
A + OH
-
Kb
n
(n)
H
2
O H
+
+ OH
-
W (n+1)
p dng iu kin proton m rng vi mc khng : A
n-
, H
2
O
[OH
-
] = [H
+
] + [HA
(n-1)-
] + 2[H
2
A
(n-2)-
] + + n[H
n
A]
[OH
-
] - [H
+
] - [HA
(n-1)-
] - 2[H
2
A
(n-2)-
] - - n[H
n
A] = 0
Hay: x -
x
W
- [HA
(n-1)-
] - 2[H
2
A
(n-2)-
] - - n[H
n
A] = 0 (Vi x = [OH
-
]) (a)
Theo nh lut bo ton nng ban u ta c:
CA
n-
= C
b
= [A
n-
] + [HA
(n-1)-
] + [H
2
A
(n-2)-
] + + [H
n
A]
C
b
= [A
n-
] + [A
n-
]Kb
1
x
-1
+ [A
n-
]Kb
1
Kb
2
x
-2
+ + [A
n-
]Kb
1
Kb
2
Kb
n
x
-n

= [A
n-
] (1 + Kb
1
x
-1
+ Kb
1
Kb
2
x
-2
+ + Kb
1
Kb
2
Kb
n
x
-n
)
[A
n-
] = C
b
bn 2 b 1 b
2 n
2 b 1 b
1 n
1 b
n
n
K ... K K ... x K K x K x
x
+ + + +


t : x
n
+ Kb
1
x
n-1
+ Kb
1
Kb
2
x
n-2
++ Kb
1
Kb
2
Kb
n
= MSC
Ta c: [HA
(n-1)-
] = [A
n-
]Kb
1
x
-1
= C
b
MSC
x . K
1 n
1 b

[H
2
A
(n-2)-
] = [A
n-
]Kb
1
Kb
2
x
-2
= C
b
MSC
x K K
2 n
2 b 1 b

[H
n
A] = [A
n-
]Kb
1
Kb
2
Kb
n
x
-n
= C
b
MSC
K ... K K
bn 2 b 1 b
thay vo (a) ta c:
x -
x
W
- C
b
bn 2 b 1 b
2 n
2 b 1 b
1 n
1 b
n
bn 2 b 1 b
2 n
2 b 1 b
1 n
1 b
K ... K K ... x K K x K x
) K ... K nK ... x K K 2 x K (
+ + + +
+ + +


= 0 (b)

+ Trng hp 1: Nu Kb
1
Kb
2
Kb
n
v Kb
1
C
b
W
Phi gii chnh xc phng trnh (b), phng trnh bc (n+2) i vi x.
Tm x. T x [H
+
] , pH , [H
i
A
(n-i)-
] (vi i = 0 n) .
+ Trng hp 2: Nu Kb
1
Kb
2
Kb
n
v Kb
1
C
b
W
B qua cn bng phn ly ca nc. Phng trnh (b) tr thnh :

x - C
b
bn 2 b 1 b
2 n
2 b 1 b
1 n
1 b
n
bn 2 b 1 b
2 n
2 b 1 b
1 n
1 b
K ... K K ... x K K x K x
) K ... K nK ... x K K 2 x K (
+ + + +
+ + +


= 0 (c)
Gii phng trnh (c) phng trnh bc (n+1) i vi x.Tm x.
T x [H
+
] , pH , [H
i
A
(n-i)-
] (vi i = 0 n) .
+ Trng hp 3: Nu Kb
1
Kb
2
Kb
n
(Kb
1
/Kb
2
10
4
) v Kb
1
C
b
W
B qua cc cn bng t (2) (n+1) v da vo (1) tnh.
A
n-
+ H
2
O HA
(n-1)-
+ OH
-
Kb
1

C C
b
0 0
[ ] C
b
x x x
Theo nh lut tc dng khi lng ta c:
x C
x
b
2

= Kb
1
(d)
Gii phng trnh (d), phng trnh bc 2 i vi x, tm x.
T x [A
n-
] ; [HA
(n-1)-
]
tm nng : [H
i
A
(n-i)-
] ,da vo cn bng th i (vi i = 2 n). Vi lu :
Nng ban u ca ion OH
-
cn bng th i chnh bng nng cn bng ca
ion OH
-
cn bng (1).
V d 1: Tnh pH trong dung dch gm Na
2
A 10
-2
M.
Cho bit H
2
A c: K
1
= 10
-6,00
; K
2
= 10
-6,72

Gii
Cc qu trnh xy ra trong h
Na
2
A 2Na
+
+ A
2-

A
2-
+ H
2
O HA
-
+ OH
-
Kb
1
= K
2
-1
. W = 10
-7,28
(1)
HA
-
+ H
2
O H
2
A + OH
-
Kb
2
= K
1
-1
. W = 10
-8,00
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: Kb
1
Kb
2
v Kb
1
C
b
= 10
-7,28
.10
-2
= 10
-9,28
W = 10
-14

B qua cn bng (3) so vi (1) v (2),da vo (1),(2) tnh.
T phng trnh:
x - C
b
bn 2 b 1 b
2 n
2 b 1 b
1 n
1 b
n
bn 2 b 1 b
2 n
2 b 1 b
1 n
1 b
K ... K K ... x K K x K x
) K ... K nK ... x K K 2 x K (
+ + + +
+ + +


= 0 (4)
p dng phng trnh (4) vi n = 2 ta c:
x - C
b
2 b 1 b 1 b
2
2 b 1 b 1 b
K K x K x
) K K 2 x K (
+ +
+
= 0
x
3
+ Kb
1
x
2
+ Kb
1
(Kb
2
- C
b
)x - 2C
b
Kb
1
Kb
2
= 0 (5)
Thay cc gi tr Kb
1
; Kb
2
; C
b
vo (5) ta c:
x
3
+ 5,248.10
-8
x
2
- 5,248.10
-10
x - 1,0496.10
-17
= 0
Chn x
0

+ x
3
- 5,248.10
-10
x = 0 x = 2,29.10
-5
(v x > 0)
+ 5,248.10
-8
x
2
- 1,0496.10
-17
= 0 x = 1,414.10
-5
(v x > 0)
Nghim thc x phi tha mn : 1,414.10
-5
< x < 2,29.10
-5

Chn x
0
= 2,25.10
-5

F(x) = x
3
+ 5,248.10
-8
x
2
- 5,248.10
-10
x - 1,0496.10
-17

F(x) = 3x
2
+ 1,0496.10
-7
x - 5,248.10
-10

F(x
0
) = - 4,013.10
-16
; F(x
0
) = 9,963.10
-10

x
1
= x
0
-
) x ( ' F
) x ( F
0
0
= 2,25.10
-5
+
10
16
10 . 963 , 9
10 . 013 , 4

= 2,29.10
-5

F(x
1
) = 8,025.10
-18
; F(x
1
) = 1,0508.10
-9

x
2
= x
1
-
) x ( ' F
) x ( F
1
1
= 2,29.10
-5
-
9
18
10 . 0508 , 1
10 . 025 , 8

= 2,289.10
-5

Ta c :
1
1 2
x
x x
100% =
5
5 5
10 . 29 , 2
10 . 29 , 2 10 . 289 , 2

100% = 0,044%
Vy : x = 2,289.10
-5
= 10
-4,64
[H
+
] = 10
-9,36

pH = 9,36
III.2.7.Dung dch mui Axit:
V d: NaHCO
3
, NaHS , NaHSO
3
, Na
2
HPO
4
, NaH
2
PO
4

Xt dung dch muiAxit NaHA c nng C
Cc qu trnh xy ra trong h
NaHA Na
+
+ HA
-

HA
-
H
+
+ A
2-
K
2
(1)
HA
-
+ H
+
H
2
A K
1
-1
(2)
H
2
O H
+
+ OH
-
W (3)
a.Gii chnh xc:
p dng iu kin proton vi mc khng: HA
-
, H
2
O
[H
+
] = [OH
-
] + [A
2-
] - [H
2
A]
Hay : h -
h
W
- [A
2-
] + [H
2
A] = 0 (4)
Theo nh lut bo ton nng ban u ta c:
CHA
-
= C = [HA
-
] + [A
2-
] + [H
2
A]
= [HA
-
] + [HA
-
]K
2
h
-1
+ [HA
-
]hK
1
-1

= [HA
-
] (1 + K
2
h
-1
+ hK
1
-1
)
[HA
-
] = C
2 1 1
2
1
K K h K h
h K
+ +

Ta c : [H
2
A] = [HA
-
]hK
1
-1
= C
2 1 1
2
2
K K h K h
h
+ +

[A
2-
] = [HA
-
]K
2
h
-1
= C
2 1 1
2
2 1
K K h K h
K K
+ +
thay vo (4) ta c
h -
h
W
+ C
2 1 1
2
2 1
2
K K h K h
) K K h (
+ +

= 0 (5)

Gii phng trnh (5) phng trnh bc 4 i vi h. Tm h.
T h pH ; [OH
-
] ; [HA
-
] ; [A
2-
] ; [H
2
A]
b.Gii gn ng:
Trng hp 1:Nu K
2
C W . Ngha l cn bng cho proton ca H
2
O v ca
HA
-
tng ng nhau
p dng iu kin proton vi mc khng: HA
-
, H
2
O
[H
+
] = [OH
-
] + [A
2-
] - [H
2
A]
Hay : h + [H
2
A] =
h
W
+ [A
2-
] (Vi h = [H
+
])
h + [HA
-
]hK
1
-1
=
h
W
+ [HA
-
]
h
K
2

h =
| |
| |

+
+
HA K 1
HA K W
1
1
2
(6)
Chp nhn : [HA
-
] = CHA
-
= C thay vo (6) ta c:
h =
C K 1
C K W
1
1
2

+
+
(7)
Lu : tnh h mt cch chnh xc hn, ta c th dng phng php tnh gn
ng lin tc, da vo cc biu thc sau tnh:
h =
| |
| |

+
+
HA K 1
HA K W
1
1
2
; [HA
-
] = C
2 1 1
2
1
K K h K h
h K
+ +

V d: Tnh pH trong dung dch gm NaHCO
3
2.10
-3
M. Cho bit H
2
CO
3
c:
K
1
= 10
-6,35
; K
2
= 10
-10,33

Gii
Cc qu trnh xy ra trong h
NaHCO
3
Na
+
+ HCO
3
-

HCO
3
-
H
+
+ CO
3
2-
K
2
(1)
HCO
3
-
+ H
+
H
2
CO
3
K
1
-1
(2)
H
2
O H
+
+ OH
-
W (3)
Ta c: K
2
C = 10
-10,33
.2.10
-3
= 10
-13,03
W = 10
-14

p dngiu kin proton vi mc khng: HCO
3
-
, H
2
O
[H
+
] = [OH
-
] + [CO
3
2-
] - [H
2
CO
3
]
Hay : h + [H
2
CO
3
] =
h
W
+ [CO
3
2-
] (Vi h = [H
+
])
h + [HCO
3
-
]hK
1
-1
=
h
W
+ [HCO
3
-
]
h
K
2

h =
| |
| |

+
+
3
1
1
3 2
HCO K 1
HCO K W
(6)
Chp nhn : [HCO
3
-
] = CHCO
3
-
= C = 2.10
-3
M vo (6) ta c :
h =
3 35 , 6
3 33 , 10 14
10 . 2 . 10 1
10 . 2 . 10 10

+
+
= 4,81.10
-9
= 10
-8,32

pH = 8,32

Nu gii theo phng php gn ng lin tc ta s dng cc cng thc:
h =
| |
| |

+
+
3
1
1
3 2
HCO K 1
HCO K W
(a) ; [HCO
3
-
] = C
2 1 1
2
1
K K h K h
h K
+ +
(b)
Chp nhn : [HCO
3
-
] = CHCO
3
-
= C = 2.10
-3
M vo (a) ta c :
h
0
= 4,81.10
-9
thay vo (b) ta c:
[HCO
3
-
]
1
= 2.10
-3
33 , 10 35 , 6 9 35 , 6 2 9
9 35 , 6
10 . 10 10 . 81 , 4 . 10 ) 10 . 81 , 4 (
10 . 81 , 4 . 10


+ +
= 1,96.10
-3
M
Thay vo (a) ta c :
h
1
=
3 35 , 6
3 33 , 10 14
10 . 96 , 1 . 10 1
10 . 96 , 1 . 10 10

+
+
= 4,8137.10
-9
10
-8,32

pH = 8,32
Trng hp 2:Nu K
2
C W . Ngha l cn bng cho proton ca HA
-
chim u
th hn cn bng cho proton ca nc. V vy c th b qua cn bng phn ly
ca nc.
T hp 2 cn bng (1) v (2) ta c:
2HA
-
H
2
A + A
2-
K
2
.K
1
-1
(8)
V ta cng c: HA
-
H
+
+ A
2-
K
2
(9)
Nh vy trong dung dch c 2 cn bng phn ly cho ion A
2-

Nu K
2
C K
2
K
1
-1
C
2
K
1
C B qua (9) so vi (8) v da vo (8) l
cn bng ch yu trong dung dch tnh ton
2HA
-
H
2
A + A
2-
K
2
.K
1
-1

C C 0 0
[ ] C 2x x x
Theo nh lut tc dng khi lng ta c:
2
2
) x 2 C (
x

= K
2
.K
1
-1

x 2 C
x

=
1
1 2
K K

(10)
Gii phng trnh (10) ta c x. T x [HA
-
] ; [A
2-
] ; [H
2
A]
T (9) [H
+
] = K
2
| |
| |

2
A
HA
= K
2
x
x 2 C
(11)
T (10) v (11) [H
+
] =
1
1 2
2
K K
K

=
2 1
K K
Nh vy khi K
2
C W v K
1
C th :
[H
+
] =
2 1
K K

pH =
2
pK pK
2 1
+
(12)
V d: Tnh cn bng trong dung dch gm NaH
2
PO
4
0,5M. Cho bit:
H
3
PO
4
c K
1
= 10
-2,23
; K
2
= 10
-7,21
; K
3
= 10
-12,32

Gii
Cc qu trnh xy ra trong h
NaH
2
PO
4
Na
+
+ H
2
PO
4
-

H
2
PO
4
-
H
+
+ HPO
4
2-
K
2
(1)
HPO
4
2-
H
+
+ PO
4
3-
K
3
(2)
H
2
PO
4
-
+ H
+
H
3
PO
4
K
1
-1
(3)
H
2
O H
+
+ OH
-
W (4)
Ta c : K
2
K
3
(K
2
/K
3
> 10
4
) ; K
2
C W B qua (2) v (4) so vi (1).
T hp (1) v (3) ta c:
2H
2
PO
4
-
HPO
4
2-
+ H
3
PO
4
K
2
K
1
-1
(5)
Ta c : K
1
= 10
-2,23
C = 0,5 B qua (1) so vi (5), da vo (5) tnh
2H
2
PO
4
-
HPO
4
2-
+ H
3
PO
4
K
2
K
1
-1
= 10
-7,21
.10
2,23
= 10
-4,98

C 0,5 0 0
[ ] 0,5 2x x x
Theo nh lut tc dng khi lng ta c:
2
2
) x 2 5 , 0 (
x

= 10
-4,98

x 2 5 , 0
x

= 10
-2,49
x = 1,6076.10
-3

[HPO
4
2-
] = [H
3
PO
4
] = x = 1,6076.10
-3
M
[H
2
PO
4
-
] = 0,5 2x = 0,5 - 2.1,6076.10
-3
= 0,4968M
[H
+
] =
2 1
K K =
21 , 7 23 , 2
10 . 10

= 10
-4,72

HPO
4
2-
H
+
+ PO
4
3-
K
3
= 10
-12,32

C 1,6076.10
-3
10
-4,72
0
[ ] 1,6076.10
-3
a 10
-4,72
+ a a
Theo nh lut tc dng khi lng ta c:
a 10 . 6076 , 1
) a 10 ( a
3
72 , 4

= 10
-12,32
(6)
Gi s : a 10
-4,72

T (6) a = 10
-12,32
72 , 4
3
10
10 . 6076 , 1

= 4,0381.10
-11
10
-4,72

[PO
4
3-
] = a = 4,0381.10
-11
M ; [HPO
4
2-
] = 1,6076.10
-3
a 1,6076.10
-3
M
[H
+
] = 10
-4,72
+ a 10
-4,72
M ; [OH
-
] =
| |
+
H
W
=
72 , 4
14
10
10

= 10
-9,28
M
[Na
+
] = CNaH
2
PO
4
= 0,5M ; pH = 4,72
Trng hp 3: Nu K
2
C W . Ngha l cn bng cho proton ca nc chim
u th hn cn bng cho proton ca HA
-
.B qua (1) so vi (3).
T hp (2) v (3) ta c:
HA
-
+ H
2
O H
2
A + OH
-
K
1
-1
W (13)
Ta c: H
2
O H
+
+ OH
-
W (14)
Nu K
1
-1
WC W C K
1
B qua cn bng (14) so vi (13) v da
vo (13) tnh:
HA
-
+ H
2
O H
2
A + OH
-
K
1
-1
W
C C 0 0
[ ] C x x x
Theo nh lut tc dng khi lng ta c:
x C
x
2

= K
1
-1
W (15)
Gii (14) ta c x. T x [H
+
] ; pH ; [HA
-
] ; [H
2
A] ; [A
2-
]
V d: Tnh cn bng trong dung dch gm NaHS 8.10
-6
M. Cho bit:
H
2
S c K
1
= 10
-7,00
; K
2
= 10
-12,92

Gii
Cc qu trnh xy ra trong h
NaHS Na
+
+ HS
-

HS
-
H
+
+ S
2-
K
2
(1)
HS
-
+ H
+
H
2
S K
1
-1
(2)
H
2
O H
+
+ OH
-
W (3)
Ta c: K
2
C = 10
-12,92
.8.10
-6
= 10
-18,02
W = 10
-14

B qua cn bng (1) so vi (3)
T hp cn bng (2) v (3) ta c:
HS
-
+ H
2
O H
2
S + OH
-
K
1
-1
W = 10
-7,00

H
2
O H
+
+ OH
-
W = 10
-14

Ta c : K
1
= 10
-7,00
C = 8.10
-6
M
Trong dung dch cn li cn bng duy nht l:
HS
-
+ H
2
O H
2
S + OH
-
K
1
-1
W = 10
-7,00

C 8.10
-6
0 0
[ ] 8.10
-6
x x x
Theo nh lut tc dng khi lng ta c:
x 10 . 8
x
6
2

= 10
-7,00

x
2
+ 10
-7,00
x - 8.10
-13
= 0
Gii ra : x = 8,46.10
-7

[H
2
S] = [OH
-
] = x = 8,46.10
-7
M
[H
+
] =
| |

OH
W
=
7
14
10 . 46 , 8
10

= 1,182.10
-8
M = 10
-7,93
M
[HS
-
] = 8.10
-6
x = 8.10
-6
- 8,46.10
-7
= 7,154.10
-6
M
[S
2-
] = [HS
-
]K
2
h
-1
= 7,154.10
-6
.10
-12,92
.10
7,93
= 7,32.10
-11
M

pH = 7,93
III.2.8.Dung dch mui Axit yu v Baz yu:
Thnh phn dung dch: (MHA , C ; H
2
O)
Chng l nhng cht in ly lng tnh: Chng hn nh NH
4
CN, NH
4
Ac
Cc qu trnh xy ra trong h
MHA MH
+
+ A
-

MH
+
H
+
+ M KMH
+
(1)
A
-
+ H
+
HA K
-1
HA (2)
H
2
O H
+
+ OH
-
W (3)
a.Gii chnh xc:
p dng iu kin proton vi mc khng: MH
+
, A
-
, H
2
O
[H
+
] = [OH
-
] + [M] - [HA]
Hay : h -
h
W
- [M] + [HA] = 0 (4)
Theo nh lut bo ton nng ban u ta c:
CMH
+
= C = [MH
+
] + [M]
= [M]K
-1
MH
+
h + [M] = [M](K
-1
MH
+
h + 1)
[M] = C
+
+
+
MH
MH
K h
K
(5)
CA
-
= C = [A
-
] + [HA]
= [HA]KHAh
-1
+ [HA] = [HA](KHAh
-1
+ 1)
[HA] = C
HA
K h
h
+
(6)
Thay (5) v (6) vo (4) ta c:
h -
h
W
- C
+
+
+
MH
MH
K h
K
+ C
HA
K h
h
+
= 0 (7)

Gii phng trnh (7) phng trnh bc 4 i vi h.Tm h.
T h pH ; [OH
-
] ; [M] ; [HA]; [MH
+
] ; [A
-
]
b.Gii gn ng:
Trng hp 1: Nu KMH
+
C W B qua (3) so vi (1).
Nu | | | |
+
OH H [M] ; [HA]; [MH
+
] ; [A
-
] th cn bng (1) v (2) xy ra
vi mc tng ng nhau :
Chng minh:
Theo nh lut bo ton in tch ta c:
[MH
+
] - [A
-
] + [H
+
] - [OH
-
] = 0 (8)
Theo nh lut bo ton nng ban u ta c:
CMH
+
= C = [MH
+
] + [M] [MH
+
] = C - [M] thay vo (8) ta
CA
-
= C = [A
-
] + [HA] [A
-
] = C - [HA] c
C - [M] - C + [HA] + [H
+
] - [OH
-
] = 0
[HA] - [M] + [H
+
] - [OH
-
] = 0 (9)
T (8) nu : | | | |
+
OH H [MH
+
] ; [A
-
] th [MH
+
] = [A
-
]
T (9) nu : | | | |
+
OH H [M] ; [HA]th [M] = [HA]
Nh vy: [MH
+
] = [A
-
] ; [M] = [HA] (2 cn bng (1) v (2) xy ra
vi mc tng ng nhau) th:
| | | |
+
OH H [M] ; [HA]; [MH
+
] ; [A
-
] iu phi chng minh.
T hp 2 cn bng (1) v (2) ta c:
MH
+
+ A
-
M + HA KMH
+
.K
-1
HA
C C C 0 0
[ ] C x C x x x
Theo nh lut tc dng khi lng ta c:
2
2
) x C (
x

= KMH
+
.K
-1
HA
x C
x

=
1
HA MH
K . K
+
(10)
Gii phng trnh (10) tmc x. T x [M] ; [HA]; [MH
+
] ; [A
-
]
T (1) [H
+
] = KMH
+
| |
| | M
MH
+
= KMH
+
x
x C
(11)
Thay (10) vo (11) ta c: [H
+
] =
1
HA MH
MH
K . K
K
+
+
=
HA MH
K . K
+

pH =
2
pK pK
HA MH
+
+
(12)
V d: Tnh cn bng trong dung dch HCOONH
4
0,2M. Bit rng:
KHCOOH = 10
-3,75
; KNH
4
+
= 10
-9,24

Gii
Cc qu trnh xy ra trong h
HCOONH
4
NH
4
+
+ HCOO
-

NH
4
+
H
+
+ NH
3
KNH
4
+
= 10
-9,24
(1)
HCOO
-
+ H
+
HCOOH K
-1
HCOOH = 10
3,75
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: KNH
4
+
.C = 10
-9,24
.0,2 = 10
-9,94
W = 10
-14
B qua (3) so vi (1)
T hp (1) v (2) ta c:
NH
4
+
+ HCOO
-
NH
3
+ HCOOH KNH
4
+
.K
-1
HCOOH = 10
-5,49

C 0,2 0,2 0 0
[ ] 0,2 x 0,2 x x x
Theo nh lut tc dng khi lng ta c:
2
2
) x 2 , 0 (
x

= 10
-5,49

x 2 , 0
x

= 10
-2,745

(1 + 10
-2,745
) x = 0,2.10
-2,745
= 3,598.10
-4

x =
745 , 2
4
10 1
10 . 598 , 3

+
= 3,592.10
-4

[NH
3
] = [HCOOH] = x = 3,592.10
-4
M
[NH
4
+
] = [HCOO
-
] = 0,2 x = 0,2 3,592.10
-4
0,2M
[H
+
] =
OH HCO 4 NH
K . K
+
=
75 , 3 24 , 9
10 . 10

= 10
-6,495
= 3,199.10
-7
M
[OH
-
] = 10
-7,505
= 3,126.10
-8
M
Ta c: | | | |
+
OH H =
8 7
10 . 126 , 3 10 . 199 , 3

= 2,886.10
-7
M
[NH
3
] ; [HCOOH] ; [NH
4
+
] ; [HCOO
-
]
Nh vy cch gii trn hon ton ph hp vi gi thit gn ng.
Trng hp 2: Nu KMH
+
C W .Tnh ton c 3 cn bng
| | | |
+
OH H khng b hn gi tr nh nht trong cc gi tr nng ca cc
cu t c mt trong dung dch.
p dng iu kin proton vi mc khng: MH
+
; A
-
; H
2
O
[H
+
] = [OH
-
] + [M] - [HA]
Hay : h + [HA] =
h
W
+ [M]
h + [A
-
] hK
-1
HA =
h
W
+ KMH
+
| |
h
MH
+

h =
| |
| |

+
+
+
+
A . K 1
MH . K W
1
HA
MH
(13)
Mt cch gn ng ta chp nhn: [MH
+
] = CMH
+
= C thay vo (13) ta
[A
-
] = CA
-
= C c:
h =
C . K 1
C . K W
1
HA
MH

+
+
+
(14)

Lu :
tnh chnh xc hn ,ngi ta dng phng php tnh gn ng lin tc. S
dng cc biu thc sau:
h =
| |
| |

+
+
+
+
A . K 1
MH . K W
1
HA
MH
(a)
[MH
+
] = C
+
+
MH
K h
h
; [A
-
] = C
HA
HA
K h
K
+
(b)
V d: Tnh pH ca dung dch Metyl amoni xianua (CH
3
NH
3
CN) 3.10
-3
M.
Cho bit: KCH
3
NH
3
+
= 10
-10,60
; KHCN = 10
-9,35
.
Gii
Cc qu trnh xy ra trong h
CH
3
NH
3
CN CH
3
NH
3
+
+ CN
-

CH
3
NH
3
+
H
+
+ CH
3
NH
2
KCH
3
NH
3
+
= 10
-10,60
(1)
CN
-
+ H
+
HCN K
-1
HCN = 10
9,35
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: KCH
3
NH
3
+
.C = 10
-10,60
.3.10
-3
= 7,54.10
-14
W = 10
-14

Cc cn bng (1), (2), (3) u xy ra ng k .
p dng iu kin proton vi mc khng: CH
3
NH
3
+
; CN
-
; H
2
O
[H
+
] = [OH
-
] + [CH
3
NH
2
] - [HCN]
Hay : h + [HCN] =
h
W
+ [CH
3
NH
2
]
h + [CN
-
] hK
-1
HCN =
h
W
+ KCH
3
NH
3
+
| |
h
NH CH
3 3
+

h =
| |
| |

+
+
+
+
CN . K 1
NH CH . K W
1
HCN
3 3 3 NH 3 CH
(4)
Mt cch gn ng ta chp nhn:
[CH
3
NH
3
+
]= CCH
3
NH
3
+
= 3.10
-3
M thay vo (4) ta c:
[CN
-
] = CCN
-
= 3.10
-3
M
h =
35 , 9 3
60 , 10 3 14
10 . 10 . 3 1
10 . 10 . 3 10

+
+
= 1,1274.10
-10
= 10
-9,95
M
pH = 9,95
tnh h chnh xc hn, ta gii theo phng php gn ng lin tc.
S dng cc cng thc:
h =
| |
| |

+
+
+
+
CN . K 1
NH CH . K W
1
HCN
3 3 3 NH 3 CH
(4)
[CH
3
NH
3
+
] = CCH
3
NH
3
+
+
+
3 NH 3 CH
K h
h
; [CN
-
] = CCN
-
HCN
HCN
K h
K
+
(5)
Chp nhn: [CH
3
NH
3
+
]= CCH
3
NH
3
+
= 3.10
-3
M ; [CN
-
] = CCN
-
= 3.10
-3
M
thay vo (4) ta c: h
0
= 1,1274.10
-10
M. Thay vo (5) ta c:
[CH
3
NH
3
+
]
1
= 3.10
-3
60 , 10 10
10
10 10 . 1274 , 1
10 . 1274 , 1

+
= 2,4534.10
-3
M thay vo (4)
[CN
-
]
1
= 3.10
-3
35 , 9 10
35 , 9
10 10 . 1274 , 1
10

+
= 2,3954.10
-3
M ta c:
h
1
=
3 35 , 9
3 60 , 10 14
10 . 3954 , 2 . 10 1
10 . 4534 , 2 . 10 10

+
+
= 1,1557.10
-10
M
Ta c:
0
0 1
h
h h
100% =
10
10 10
10 . 1274 , 1
10 . 1274 . 1 10 . 1557 , 1

100% = 2,51%
Vy : h = 1,1557.10
-10
= 10
-9,94
pH = 9,94
+ Kim tra li gi thit:
[CH
3
NH
2
] = CCH
3
NH
3
+
- [CH
3
NH
3
+
] = 3.10
-3
- 2,4534.10
-3
= 5,466.10
-4
M
[HCN] = CCN
-
- [CN
-
] = 3.10
-3
- 2,3954.10
-3
= 6,046.10
-4
M
[CH
3
NH
3
+
] = 2,4534.10
-3
M ; [CN
-
] = 2,3954.10
-3
M
[OH
-
] =
| |

OH
W
=
10
14
10 . 1557 , 1
10

= 8,6528.10
-5
M
| | | |
+
OH H =
5 10
10 . 6528 , 8 10 . 1557 , 1

8,6528.10
-5
M
khng nh hn nhiu so vi: [CH
3
NH
2
] ; [HCN] ; [CH
3
NH
3
+
] ; [CN
-
]
Nhn xt:
+ Nu KMH
+
C W B qua cn bng phn ly ca nc .
v nu: | | | |
+
OH H [M]; [HA]; [MH
+
] ; [A
-
] th qu trnh phn ly ca ion
MH
+
v qu trnh proton ha ca ion A
-
xy ra vi mc tng ng nhau,
v ta t hp 2 qu trnh ny li vi nhau gii:
+ Nu KMH
+
C W . C 3 cn bng u xy ra vi mc ng k .
v nu: | | | |
+
OH H khng [M]; [HA]; [MH
+
] ; [A
-
] th qu trnh phn ly
ca ion MH
+
v qu trnh proton ha ca ion A
-
xy ra vi mc khc nhau
III.2.9.Dung dch m:
Cch tnh pH ca dung dch m
Xt h m: HA C
1
M , NaA C
2
M (HA ln Axit yu)
Cc qu trnh xy ra trong h
NaA Na
+
+ A
-

HA H
+
+ A
-
K
a
(1)
A
-
+ H
2
O HA + OH
-
K
b
(2)
H
2
O H
+
+ OH
-
W (3)
a.Gii chnh xc:
Theo nh lut bo ton in tch ta c:
[H
+
] - [OH
-
] + [Na
+
] - [A
-
] = 0
Hay : h -
h
W
+ C
2
- [A
-
] = 0 (4)
Theo nh lut bo ton nng ban u ta c:
CHA + CA
-
= C
1
+ C
2
= [HA] + [A
-
]
= [A
-
] hK
a
-1
+ [A
-
] = [A
-
](hK
a
-1
+ 1)
[A
-
] = (C
1
+ C
2
)
a
a
K h
K
+
thay vo (4) ta c:
h -
h
W
+ C
2
- (C
1
+ C
2
)
a
a
K h
K
+
= 0 (5)

Gii phng trnh (5) phng trnh bc 3 i vi h. Tm h.
T h pH
b.Gii gn ng:
T (1) [H
+
] = K
a
| |
| |

A
HA
K
a

A
HA
C
C
= K
a
2
1
C
C

+ Nu[H
+
] 10
-7
M mi trng ca dung dch l Axit, nn cn bng (1)
l ch yu, da vo (1) tnh pH.
+ Nu[H
+
] 10
-7
M mi trng ca dung dch l Baz, nn cn bng (2)
l ch yu, da vo (2) tnh pH.
+ Nu[H
+
] 10
-7
M cc cn bng xy ra vi mc tng ng
nhau, nn phi gii chnh xc phng trnh (5).
c.Cc h qu:
+ Nu C
2
= 0 (dung dch ch cha n Axit yu HA)
T (5) h -
h
W
- C
1
a
a
K h
K
+
= 0 (6)
(6) l phng trnh tng qut tnh nng ion H
+
trong dung dch gm 1
n Axit yu:
+ Nu C
1
= 0 (dung dch ch cha n Baz yu NaA)
T (5) h -
h
W
+ C
2
a
K h
h
+
= 0
Hay: x -
x
W
- C
2
b
b
K x
K
+
= 0 (7) vi x =
h
W

(7) l phng trnh tng qut tnh nng ion OH
-
trong dung dch gm 1
n Baz yu
V d 1: Tnh pH trong dung dch gm HCOOH 10
-2
M v HCOONa 10
-3
M.
Cho bit: KHCOOH = 10
-3,75

Gii:
Cc qu trnh xy ra trong h
HCOONa Na
+
+ HCOO
-

HCOOH H
+
+ HCOO
-
K
a
= 10
-3,75
(1)
HCOO
-
+ H
2
O HCOOH + OH
-
K
b
= 10
-10,25
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: [H
+
] = K
a
| |
| |
-
O HCO
OH HCO
K
a

O HCO
OH HCO
C
C
= 10
-3,75
3
2
10
10

= 10
-2,75
10
-7
M
mi trng ca dung dch l Axit, nn cn bng (1) l ch yu, da vo (1)
tnh pH.
HCOOH H
+
+ HCOO
-
K
a
= 10
-3,75

C 10
-2
0 10
-3

[ ] 10
-2
h h 10
-3
+ h
Theo nh lut tc dng khi lng ta c:
h 10
) h 10 ( h
2
3

= 10
-3,75

h
2
+ 1,178.10
-3
h - 1,778.10
-6
= 0
Gii ra dc: h = 8,687.10
-4
= 10
-3,06
M pH = 3,06
V d 2: Tnh pH trong dung dch gm NH
3
2.10
-2
M v NH
4
Cl 10
-2
M.
Cho bit: KNH
4
+
= 10
-9,24
.
Gii:
Cc qu trnh xy ra trong h
NH
4
Cl NH
4
+
+ Cl
-

NH
4
+
H
+
+ NH
3
K
a
= 10
-9,24
(1)
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= 10
-4,76
(2)
H
2
O H
+
+ OH
-
W = 10
-14
(3)
Ta c: [H
+
] = K
a
| |
| |
3
4
NH
NH
+
K
a
3 NH
4 NH
C
C
+
= 10
-9,24
2
2
10 . 2
10

= 10
-9,54
10
-7
M
mi trng ca dung dch l Baz, nn cn bng (2) l ch yu, da vo (2)
tnh pH.
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= 10
-4,76

C 2.10
-2
10
-2
0
[ ] 2.10
-2
x 10
-2
+ x x
Theo nh lut tc dng khi lng ta c:
x 10 . 2
) x 10 ( x
2
2

= 10
-4,76
(4)
Gi s: x 10
-2

T (4) x = 10
-4,76
2
2
10
10 . 2

= 10
-4,46
10
-2

[OH
-
] = x = 10
-4,46
[H
+
] =
| |

OH
W
=
46 , 4
14
10
10

= 10
-9,54

pH = 9,54
III.2.10.Cn bng trong dung dch cha cation kim loi:
Trong dung dch nc , cc cation kim loi tn ti di dng ion hydrat ha,
cc ion ny l nhngAxit chng phn ly cho proton v phc hydroxo tng ng.
[M(H
2
O)
x
]
n+
[M(OH)(H
2
O)
x-1
]
(n-1)+
+ H
+

1

[M(H
2
O)
x
]
n+
[M(OH)
2
(H
2
O)
x-2
]
(n-2)+
+ 2H
+

2

-----------------------------------------------------------------------------
[M(H
2
O)
x
]
n+
[M(OH)
x
]
(n-x)+
+ xH
+

x

n gin ngi ta thng vit
M
n+
+ H
2
O [M(OH)]
(n-1)+
+ H
+

1

M
n+
+ 2H
2
O [M(OH)
2
]
(n-2)+
+ 2H
+

2

-----------------------------------------------------------------------------
M
n+
+ xH
2
O [M(OH)
x
]
(n-x)+
+ xH
+

x

Khi tng pH cc cn bng trn chuyn dch sang phi dn ti s to thnh
cc mui baz kh tan hoc cc kt ta hydroxyt kim loi v sau c th to ra
cc phc hydroxo bc cao hn.
Trong cc dung dch mui, ngoi cc cation kim loi cn c cc anion th
hin tnh cht nh cc Baz yu.
Mt s cation kim loi c khuynh hng to thnh cc phc hydroxo a
nhn nh: Fe
2
(OH)
2
4+
; Be
2
(OH)
2
2+

V vy m vic tnh ton cn bng tr nn phc tp.
Ta xt trng hp n gin nht l khng c s to phc hydroxo a nhn v
anion ca mui l Baz rt yu.
Chng hn i vi mui Cu(ClO
4
)
2
, trong dung dch c cc qu trnh xy ra
nh sau: Cu(ClO
4
)
2
Cu
2+
+ 2ClO
4
-

Cu
2+
+ H
2
O Cu(OH)
+
+ H
+

1
(1)
Cu
2+
+ 2H
2
O Cu(OH)
2
+ 2H
+

2
(2)
Cu
2+
+ 3H
2
O Cu(OH)
3
-
+ 3H
+

3
(3)
Cu
2+
+ 4H
2
O Cu(OH)
4
2-
+ 4H
+

4
(4)
H
2
O H
+
+ OH
-
W (5)
a.Gii chnh xc:
Theo nh lut bo ton in tch ta c:
[H
+
] - [OH
-
] + 2 [Cu
2+
] + [Cu(OH)
+
] - [Cu(OH)
3
-
] - 2 [Cu(OH)
4
2-
] - [ClO
4
-
] = 0
t: [H
+
] = h [OH
-
] =
h
W
; [ClO
4
-
] = 2C Cu(ClO
4
)
2
= 2C
h -
h
W
- 2C + 2 [Cu
2+
] + [Cu(OH)
+
] - [Cu(OH)
3
-
] - 2 [Cu(OH)
4
2-
] = 0 (6)
Theo nh lut bo ton nng ban u ta c:
CCu
2+
= C = [Cu
2+
] + [Cu(OH)
+
] + [Cu(OH)
2
] + [Cu(OH)
3
-
] + [Cu(OH)
4
2-
]
= [Cu
2+
] +[Cu
2+
]
1
h
-1
+ [Cu
2+
]
2
h
-2
+ [Cu
2+
]
3
h
-3
+ [Cu
2+
]
4
h
-4

= [Cu
2+
](1 +
1
h
-1
+
2
h
-2
+
3
h
-3
+
4
h
-4
)
[Cu
2+
] = C
4
4
3
3
2
2
1
1
h h h h 1
1

+ + + + q q q q
= C
MSC
1

[Cu(OH)
+
] = [Cu
2+
]
1
h
-1
= C
MSC
h
1
1

q

[Cu(OH)
3
-
] = [Cu
2+
]
3
h
-3
= C
MSC
h
3
3

q
thay vo (6)
[Cu(OH)
4
2-
] = [Cu
2+
]
4
h
-4
= C
MSC
h
4
4

q
ta c:
h -
h
W
- 2C + C
4
4
3
3
2
2
1
1
4
4
3
3
1
1
h h h h 1
) h 2 h h 2 (


+ + + +
+
q q q q
q q q
= 0 (7)
Gii phng trnh (7) ta tm h . T h pH ; [OH
-
] ;
[Cu(OH)
i
(2-i)+
] (Vi i = 0 4)
b.Gii gn ng:
Nu
1

2

3

4
B qua cc cn bng t 2 4.
Phng trnh (7) tr thnh:
h -
h
W
- 2C + C
1
1
1
1
h 1
) h 2 (

+
+
q
q
= 0 (8)
Trong trng hp khi dung dch mui c mi trng Axit r th c th b
qua cn bng phn ly ca nc, da vo cn bng to phc hydroxo nc u
tnh ton.
V d: Tnh pH trong dung dch gm Zn(NO
3
)
2
0,08M. Cho bit Zn
2+
c :

1
= 10
-8,96
;
2
= 10
-10,90
;
3
= 10
-25,90
;
4
= 10
-41,00
.
Gii:
Cc qu trnh xy ra trong h
Zn(NO
3
)
2
Zn
2+
+ 2NO
3
-

Zn
2+
+ H
2
O Zn(OH)
+
+ H
+

1
= 10
-8,96
(1)
Zn
2+
+ 2H
2
O Zn(OH)
2
+ 2H
+

2
= 10
-10,90
(2)
Zn
2+
+ 3H
2
O Zn(OH)
3
-
+ 3H
+

3
= 10
-25,90
(3)
Zn
2+
+ 4H
2
O Zn(OH)
4
2-
+ 4H
+

4
= 10
-41,00
(4)
H
2
O H
+
+ OH
-
W = 10
-14
(5)
Ta c:
1
>
2

3

4
. Mt cch gn ng b qua (2) (3) (4) so vi (1)

1
.C = 10
-8,96
.0,08 = 10
-10,06
W = 10
-14
b qua (5) so vi (1) .
Nh vy trong dung dch ch cn mt cn bng duy nht l cn bng (1),
da vo (1) tnh ton.
Zn
2+
+ H
2
O Zn(OH)
+
+ H
+

1
= 10
-8,96

C 0,08 0 0
[ ] 0,08 h h h
Theo nh lut tc dng khi lng ta c:
h 08 , 0
h
2

= 10
-8,96
(6)
Gi s: h 0,08
T (6) h =
96 , 8
10 . 08 , 0

= 10
-5,03
0,08
[H
+
] = h = 10
-5,03
pH = 5,03