. , , , , , , . , 3 + + 2 = 3 + 3O+, .
, , , . , , : + + 1 ↔+Cl.
, ( ) .
- , , , , ν+ ν , :
. , . * , . , .
, :
, :
pK* = lg K* pK0 = lg K0
, . , 22 = 3+ + :
, , , (γ+ = γ = 1). :
. :
t, C t, C
0 0.114 60 9,6
20 0,681 80 25,1
25 1,008 90 38,0
30 1,470 100 65,0
, , . . . 25 º ≈1014, , - , , , 107 /3. , , , () , , . ,
|
|
, , . , , .
, , 25 , , . , , , ,
S, , : 2S == SH+ + S. .
( -)
;
.
.
ΔG = 2,3RT lg K
25
ΔGº = 5696 lg Kº
ΔG /.
. :
+ H2O = 3O+ +
. , -, ђ :
α = ђ / C
ђ = [] = [3O+ ],
α = [A]/C = [H3O+]/C
, , :
αHA = [HA]/C
: [] + [] = α + αHA = 1
, [], [H3+] [] ,
φ = 1/ , .
. , , , . 4.1, .
. , ,
4.1. (t = 20 )
φ∙103,3/ | ∙104, /3 | α | α | φ∙103,3/ | ∙104, /3 | α | α | |
1,000 | 0,140 | 0,0037 | 0,0043 | 126,520 | 0,185 | 0,0472 | 0,0472 | |
7,910 | 0,181 | 0,0191 | 0,0120 | 560,100 | 0,184 | 0,0920 | 0,0921 | |
15,820 | 0,184 | 0,0169 | 0,0169 | 2024,000 | 0,185 | 0,1760 | 0,1750 | |
31,630 | 0,185 | 0,0239 | 0,0239 |
, , .
|
|
α << 1, :
K = α2C
, , ,
[H3O+] = [A]
:
lg [H3O+] = ½ lg K + ½ lg C
pH = ½ lg K ½ lg C
, , α << 1. , :
Cα2 = K (1 α)
Cα2 + Kα K = 0
, , , :
[H3O+][A] = K [HA]
.
C = [HA] + [A]
:
[H3O+] = [OH] + [A]
3O+, , . . :
,
:
[] = []
[] [] :
, :
, , .
.
+ 2O = + +
NH3 + 2O = NH4+ + H
:
, , [] = α .
, [3+] = /[OH], :
α << 1:
pH = lg + ½ lg K + ½ lg C
, .
[OH][H3O+] =
[OH][BH+] = K [B]
C = [B] + [BH+]
[OH] = [H3O+] + [BH+]
:
. , , , , . , , , (. 4.2), .
4.2.
CKCl, /3 | α | K | CKCl, /3 | α | K | |
1,0 | 0,756 | 3,24 | 0,001 | 0,980 | 0,05 | |
0,1 | 0,862 | 0,54 | 0,0001 | 0,994 | 0,02 | |
0,01 | 0,942 | 0,15 |