pH

13.1

1
2
3
4
5

1.

MeSO 4(s) aqMeSO 4(l) aq 1

MeCl 2(s) aqMeCl 2(l) aq (2)
12

2.

l

MeO (s) H 2 SO 4 MeSO 4(l) H 2 O 3

Me(OH) 3(s) NaOHNaMe(OH) 4(l) 4
34

2 MeSMeCO 3

MeS (s) H 2 SO 4 MeSO 4(l) H 2 S (g) 5

MeCO 3(s) H 2 SO 4 MeSO 4(l) H 2 CO 3 6

H 2 OCO 2(g)
5 ZnS 6 ZnCO 3
3 Me Me
Me Me

MeS (s) MeSO 4 MeS (s) MeSO 4

NiS (s) CuSO 4 CuS (s) NiSO 4

CaWO 4(s) Na 2 CO 3 CaCO 3(s) Na 2 WO 4(l)
3.

1
MeH 2 SO 4 MeSO 4 H 2

2
MeH 2 SO 4 1/2O 2 MeSO 4 H 2 O

3
MeFe 2 (SO 4 ) 3 MeSO 4 2FeSO 4
2+
2Fe MnO 2 4H 2 SO 4 MnSO 4 Fe 2 (SO 4 ) 3 2H 2 O

MeSH 2 SO 4 1/2O 2 MeSO 4 H 2 OS

MeSMeCl z MeCl 2 2MeCl z-1 S
MeCl z-1 FeCl 3

SO 4 2-
MeS2O 2 MeSO 4

5

3CuO2FeCI 2 3H2OCuCl 2 2CuCl2Fe(OH) 3

6

2Au4NaCNH 2 O1/2O 2 2NaAu(CN) 2 2NaOH

1
Ni 3 S 2 10NH 4 OH(NH 4 ) 2 SO 4 4 O 2 3Ni(NH 3 ) 4 SO 4 11H 2 O
2

13.2

13-l
13-1



-pH

13-1

G 0298


kJmol -1-
CuH 2 SO 4 CuSO 4 H 2 +80.33
Cu2H 2 SO 4 CuSO 4 H 2 SO 4 H 2 +46.44
CuH 2 SO 4 1/2O 2 CuSO 4 H 2 O -156.48
Cu2HClCuCl 2 H 2 +86.61
Cu2HCl1/2O 2 CuCl 2 H 2 O -150.62
Cu3HNO 3 Cu(NO 3 ) 2 HNO 3 +H 2 -73.22
CuFeCl 3 CuClFeCl 2 -83.68
Cu2FeCl 3 CuCl 2 2FeCl 2 -106.69
CuCuCl 2 2CuCl -60.25
CuOH 2 SO 4 CuSO 4 H 2 O -29.71
CuO2HCICuCl 2 H 2 O -23.43
CuO2HNO 3 Cu(NO 3 ) 2 H 2 O -3.35
3CuO2FeCl 3 3H 2 O3CuCl 2 2Fe(OH) 3 -150.62
3CuO2FeCl 2 3H 2 OCuCl 2 2CuCl2Fe(OH) 3 -35.15
CuO2H 2 SO 4 1/2O 2 2CuSO 4 2H 2 O -167.78
Cu 2 OH 2 SO 4 CuSO 4 H 2 OCu -10.46
Cu 2 O2H 2 SO 4 2CuSO 4 H 2 OH 2 +69.45
CuO2FeCl 3 CuCl 2 2FeCl 2 S -58.58
CuSCuCl 2 2CuClS -15.48
CuS4FeCl 3 2CuCl 2 4FeCl 2 S -128.03

Cu 2 S2CuCl 2 4CuClS -36.82

CuS2H 2 SO 4 1/2O 2 CuSO 4 H 2 O+S -108.37
CuSH 2 SO 4 CuSO 4 H 2 S +128.87
CuS2H 2 SO 4 O 2 2CuSO 4 2H 2 O+S -228.45
CuS2H 2 SO 4 2CuSO 4 2H 2 S +175.31

ZnOH 2 SO 4 ZnSO 4 H 2 O

Me z O y yH 2 SO 4 Me z (SO 4 ) y yH 2 O
FeO
FeOH 2 SO 4 FeSO 4 H 2 O

-H 2 O -pH
-H 2 O -pH
Zn 1.988molL -1 Fe 3.810 -4 molL -1 Cd
l.4510 -3 molL -1 Co 2.010 -4 Ni 8.5310 -5 molL -1 Cu 4.7210 -3 molL -1
13-2 13-2
13-3 13-3 =1

13-2

0.001 0.005 0.01 0.05 0.1 0.3 0.5 1.0 2.0 3.0
molL -1
NiSO 4 - - - - 0.15 0.084 0.063 0.043 0.034 0.041

ZnSO 4 0.7 0.477 0.387 0.202 0.15 0.083 0.063 0.043 0.035 0.04
CuSO 4 0.74 0.53 0.41 0.21 0.15 0.083 0.062 - - -
CdSO 4 0.699 0.476 0.383 - 0.16 0.083 0.061 0.041 0.032 0.036
FeSO 4 - - 0.75 0.62 0.68 - 0.51 0.61 - -

Zn 2+ 2e=Zn

Zn 2+ Zn = 0.763 + 0.0295 log Zn 2+ (1)

Zn(OH) 2 2H + Zn 2 +2H 2 O
13-3
Zn Fe Cd Co Ni Cu

1.988 3.5810 -4 4.4510 -3 2.010 -4 8.52510 -5 4.7210 -3

molL -1
0.035 1 0.476 1 1 0.53
-2 -4 -3 -4 -5
6.99510 3.5810 2.1210 2.010 8.52510 2.5010 -3
lg -1.158 -3.4465 -2.674 -3.7 -4.07 -2.6
1
pH = 5.9 log Zn 2+ 2
2
Zn(OH) 2 2H + 2e=Zn2H 2 O

Zn ( OH )2 Zn = 0.763 0.0591pH 3

=6.95510 -2 Zn-H 2 O
Zn 2 +

-pH 13-1

Zn 2+ Zn =0.7630.0295lg(6.95510 -2 )=-0.797V pH=5.9

1/2lg(6.95510 -2 )=6.321-0.0591
CuCdCoNiFe Me-H 2 O
-pH
-pH -pH 13-1
13-1 1.988 molL -1
pH 6.321 pH
pH
pH
pH 5.25.1

pH

pH =1 Zn(OH) 2
Zn 2 +

pH 5.9

13-1
13-l Fe-H 2 O -pH
Fe 10 0 10 -6
3+

pH Fe 2+
Fe 2+ Fe 3+ Fe 3+
Zn 2+ Fe 2+


MeS s 2H + =Me 2+ H 2 S l
H 2 S
H 2 SHS - H +
HS - =S 2- H +
H 2 S
pH

MeS-H 2 O 298K -pH ZnS-H 2 O 298K

-pH
ZnS-H 2 O
298K pH 13-4
13-4 ZnS-H 2 O -pH 13-2

1 H2S
H 2 SSS 2 O 3 2- SO 3 2- HSO 4 - SO 4 2- S 2 O 3 2- SO 3 2-

2-pH H 2 S

13-4 ZnS-H 2 O 298K pH

pH

1Zn 2+ S2eZnS 0.2650.0295log

Zn 2 +

pH
+ 2+
2ZnS2H Zn H 2 S
-0.2084-0.5log -0.5log H 2S
Zn 2 +

3S2H + 2eH 2 S 0.142-0.0591pH-0.0295log H 2S

0.338-0.0689pH

4HSO 4 H + 6eS4H 2 O
0.0985log
HSO 4

5SO 4 2- H + HSO 4
PH1.91log log
HSO 4 SO 24

0.357-0.0788pH
6SO 4 2- 8H + 6eS4H 2 O
0.0985log
SO 24

0.320-0.0517pH
7Zn 2+ HSO 4 7H + 8eZnS
4H 2 O 0.0074log HSO
Zn 2 + 4

0.334-0.0591pH
8 Zn 2+ SO 4 2- 8H + 8e ZnS
4H 2 O 0.0074log SO2
Zn 2 + 4

2+ 2-
9 2Zn SO 4 2H 2 O PH3.77-0.5log -log
+ SO 24 Zn 2 +
ZnSO 4 Zn(OH) 2 2H

0.364-0.0665pH
10 ZnSO 4 Zn(OH) 2 SO 4 2- 18H +
16e2ZnS10H 2 O 0.037log
SO 24

11 ZnSO 4 Zn(OH) 2 2H 2 O pH8.440.5log

SO 24
2Zn(OH) 2 2H + SO 4 2-
0.4250.0739pH
12 Zn(OH) 2 10H + 4SO 4 2- 8e
ZnS6H 2 O 0.0074log
SO 24

13ZnO 2 2- 2H + Zn(OH) 2 pH14.250.5log

ZnO22

0.635-0.0887pH
14ZnO 2 2- SO 4 2- 12H + 8eZnS
6H 2 O 0.0074log SO 2
ZnO22 4

0.216-0.0709pH-0.0591log
S2
15ZnO 2 2- SO 4 2- 12H + 10eZn
S 2- 6H 2 O 0.0591log SO 2
ZnO22 4

16ZnS2eZnS 2- 0.1.461-0.0295log
S2

17S 2- H + HS

PH12.43log -log
S2 HS

+
18ZnSH 2eZnHS
-1.093-0.0295pH-0.0295log
HS

19HS H + H 2 S pH7.0log -log H 2S
HS

+
20ZnS2H 2eZnH 2 S
-0.886-0.0591pH-0.0295log H 2S

21Zn 2+ 2eZn -0.7630.0295log

Zn 2 +

22O 2 4H + 4e2H 2 O 1.229-0.0591pH0.0148log PO 2

232H + 2eH 2 -0.0591pH-0.0295log PH 2

0.06 0.12molL -1

Zn 2+ =0.1= ZnO2
2

298K PH 2S =101325Pa H 2 S 0.l molL -1

H 2S 0.1

13-2 ZnS-H 2 O 298K -pH

3 PO 2 PH 2 101325Pa

4
MeS-H 2 O -pH ZnS-H 2 O -pH

5-pH ZnS

13-2 ZnS

pH

10


2ZnSO 2 4H+2Zn 2+ 2S2H 2 O

ZnS2O 2 2Zn 2+ SO 4 2-
ZnS2O 2 2H 2 OZn(OH) 2 SO 4 2- 2H +
ZnS2O 2 2H 2 OZnO 2 2- SO 4 2- 4H +

O 2 4H + 4e2H 2 O

ZnSZn 2+ S 2e
ZnS 4H 2 OZn 2+ SO 4 2- 8H + 8e
ZnS6H 2 OZn(OH) 2 SO 4 2- 10H + 8e
ZnS6H 2 OZnO 2 2- SO 4 2- 12H + 8e
13-2
ZnS pH
pH
pH

FeSNiSCoSZnSCdSCuS
MeS 2H +
Me 2+ H 2 S H 2 S 1/2O 2 SH 2 O H 2 S

ZnS
101325Pa 5066250Pa
298K 0.025V

6 13-2 ZnS pH

7 G T
0

298K -pH 383K PO 2 =141855Pa

11


NaCN Ca(CN) 2
L -pH
l pCN -pCN
2 pH pCN
3-pCN pCN pH -pH

Ag-CN-H 2 O --pH
l. -pCN

CN

Ag + CN AgCN

K f = AgCN Ag+ CN = 1013.8

pCN = log CN = 13.8 + log Ag+ 1

AgCNCN Ag(CN) 2

K f = Ag ( CN ) Ag+ CN = 10 5.0
2

pCN = 5.0 log Ag ( CN ) 2

2

Ag + 2CN Ag(CN) 2

K f = Ag ( CN ) Ag+ CN
2
= 10
18.8
2

1
pCN = 9.4 + log Ag+ Ag ( CN ) 3
2 2

2Ag + H 2 OAg 2 O2H +

pH = 6.32 log Ag+ 4

Ag 2 O 2H + 2CN 2AgCNH 2 O
pHpCN20.1 5
+
Ag 2 O 2H 4CN 2Ag(CN) 2 H 2 O

pH + pCN = 25.1 log Ag ( CN ) 6

2

Ag + eAg

= 0.799 + 0.0591log Ag+ 7

AgCNeAgCN

12


=-0.0170.0591pCN 8

Ag(CN) 2 eAg2CN

= 0.31 + 0.12pCN + 0.0591log Ag ( CN ) 9

2

-pCN -pCN 13-3 13-3

pCN CN
13-3

13-3 Ag-CN -H 2 O pCN
2. pH pCN

CN H + CN HCN

H + CN 2HCN

HCN
Kf = = 10 9.4
H + CN

pH -pH pCN pH
pCN pH

pHpCN9.4 log HCN

B B = + HCN pH
CN

pCN
pHpCN9.4logBlogl10 pH-9.4 10
B pH pCN

13


B10 -2 molL 10
pH pCN 13-5
13-5 89 pHpCN
pH 0 1 2 3 4 5 6 7 8.4 9.4 10.4
pCN 11.4 10.4 9.4 8.4 7.4 6.4 5.4 4.4 3.04 2.3 2.04

AgCN Ag ,V 0.667 0.607 0.547 0.479 0.420 0.367 0.302 0.247 0.165 0.121 0.105

Ag ( CN ) ,V 0.82 0.70 0.58 0.46 0.34 0.22 0.10 0.02 -0.18 -0.27 -0.30
2 Ag

3. Ag-CN -H 2 O -pH

Ag 10 -4 molL -pCN pH
pCN B Ag
pH
1 2 8 9 pCN pH

Ag+ =10 -4 molL - 1

pCN = 13.8 + log Ag+ = 9.8

pH11.4-pCN11.4-9.81.6
2

pCN5.0 log 9.0

Ag ( CN ) 2

pH11.4-pCN11.4-9.02.4

9 pCN pH AgCN Ag
8

Ag ( CN ) 13-5
2 Ag

1
2
7
8
9 pH

13-4 AuCN H 2 O ZnCN
H 2 O -pH 13-4
pH 810


2Ag(CN) 2 Zn2AgZn(CN) 4 2-

2Au(CN) 2 Zn2AuZn(CN) 4 2-

13-4 Ag(CN) 2 Au(CN) 2 Zn(CN) 4 2-

14


13-4

13.3

dC
= K D (C s C ) 13-1
d
dC

d
K D
C S
C
13-l K D
D
D K D =

15


1 RT
D= (13-2)
3d N
T
d
R

N

K
= 133
n
K

n 0.6
=0C =0 13-l
C dC

0 d
= K D d
0

C
d ln(C S C ) = K D d
0 0

CS
2.303 lg = K D (13-4)
CS C

13-4 13-4
lgC s /(C s C ) T K D

13-5
13-5

16


ZnO H 2 SO 4 ZnSO 4 H 2 O
ZnO H 2 SO
ZnO

13-6 H 2 SO 4 ZnO
C

1
2
3

4
5
6
[ 3 4 5 ]
[l26]

17


dC C Ci
VD = =D L = K D (C L C i ) 13-5
d
VD

C L Ci


D 1
C L
C i
K D D/

dC
VR = = K R C in (13-6)
d
V R

K R
C i
n

dC K R K D
V= = CL (13-7)
d K R + K D
1 K R <<K D 13-7
K R K D K D 13-7
V=K R C L

2 K D <<K R 13-7
K R K D K R 13-7
V=K D C L

18


K D K R /(K R K D ) K 13-7

dC
= KC L 13-8
d
=0C L =C 0 8-8
CL dC
= K d
C0 CL 0

C0
ln = K (13-9)
CL
C 0
13-9 lnC 0 /C L
K
13-9

1.

2Ag4NaCNO 2 2H 2 O2NaAg(CN) 2 2NaOHH 2 O 2

2Ag4CN 2e2Ag(CN) 2

O 2 2H 2 O2eH 2 O 2 2OH

13-7

19


A1 A2
A=A 1 A 2
13-7

>>[CN ] S 0[O 2 ] S 0

CN

d[CN ] D CN D
= A 2 ([CN ] [CN ]S ) = CN A 2 [CN ]
d

D CN
CN

CN CN

A 2

[CN ] S CN

O 2

d[O 2 ] D O2 D O2
= A1 ([O 2 ] [O 2 ]S ) = A 1 [O 2 ]
d

D O 2 O 2

[O 2 ] O 2

A 1

20


[O 2 ] S O 2

CN - O 2

V O 2

CN

d[O 2 ] DO
V=2 = 2 2 A 1 [O 2 ]
d

1 d[CN ] 1 D CN
V= = A 2 [CN ]
2 d 2

D O2 1 D
2 A1[O 2 ] = CN A 2 [CN ]
2

A=A 1 A 2
2D CN D O2 [CN ] [O 2 ]
V= A 1310
D CN [CN ] + 4D O2 [O 2 ]
1310

1[CN ][O 2 ]
1
V= D CN [CN ] A
2

[CN ]

2[CN ][O 2 ]
2
V = D O 2 [O 2 ] A

[O 2 ]

[CN ] 4D O 2
A 1 =A 2 =
[O 2 ] D CN

O 2 CN

D O2 2.7610 -5 cm2 s -1

D CN 1.8310 -5 cm2 s -1

21


[CN ]
D O 2 D =1.5 =41.5=6
CN
[O 2 ]

[CN ]/[O 2 ]=6

[CN ]/[O 2 ] 4.697.4
13-6
13-6

-3 [CN ]
K PO2 Pa [O 2 ]10 [CN - ]10 -3
[O 2 ]
molL -1 molL -1
298.15 101325 1.28 6.0 4.69
298.15 21278.25 0.27 1.3 4.85
308.15 101325 1.10 5.1 4.62
298.15 101325 1.28 8.8 6.80
298.15 21278.25 0.27 1.7 6.30
297.15 798441 9.55 56 5.85

297.15 344505 4.35 25 5.75

308.15 273577.5 2.96 22.0 7.40
298.15 101325 1.28 9.4 7.35

308.15 101325 1.10 8.1 7.35

308.15 21278.25 0.27 2.0 7.40
-3 -1
0.2710 molL
60.2710 -3 molL -1
2.
MeS-H 2 O MeS
pH ZnS

ZnS 373K 13-8

ZnS

22


13-8 ZnS 373K

ZnS1/2O 2 2H + Zn 2+ S 0 H 2 O

ZnS2eZn 2+ S 0
1/2O 2 2H + 2eH 2 O

S 0 2/3O 2 H 2 OSO 4 2- 2H +
393K 393K

pH

13-8

13.4


1

23


WK

K K K = K ce RT

K C
R
W K
2928883680Jmol -1
283K 24
24

WD

K K D = K ce RT

K D
W D


836.829288 Jmol -1

1.5
3
1

24


1. Me-H 2 O 298K
1.898 molL -1 -pH

2. l molL -1 3
Fe3+

298K -pH
3. pH=5Au(CN ) 10 -5 molL -1


Au ( CN ) 2 Au

pH =9 pH
4. ZnS-H 2 O

1pH=1=0.4
2pH=3=0.8
5. 1L3mol
20g 65.391

25


2 50g 310min

6. 353K 9% H 2 SO 4
min 10 30 60 80 100 120
% 13.58 36.95 63.45 76.17 85.53 92.05
95%

26