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( I )

( . ..)

2002


. ... ,
. - , , 2002, - 154 .

11
,
- .

. .,
.. , .. , .. , .. , ..
, ....,

.
: ..., .. ,
... ..

2002, .

, 2002 .
.. , 2002 .

1..

, -
.
2

(f(x)) - , ,

- . f(x) -
, f(x) .
((x)) (
) -
,
:
() = f(x) ().
/.

:
f() = 1/[( )( )];
f() = 1/ ;
f() = 1/ ;
f() = 1/[( )( )];

f= 1/[( )( )].

1.
,
.

2.


,
.

1
H2SO4, CaO, Ca(OH)2, Al2(SO4)3:
1) (H2SO4) = 1/298 = 49 /;
2) () = 1/256 = 28 /;

3) (()2) = 1/274 = 37 /;
4) (Al2(SO4)3)= 1/(23)342 = 57 /.

.

, .
:
:
mA/m = /
mA/ = m/ ,
mA/ = N1; m/ = N2 -
, N1 = N2. ,
:
.


, 8 /, ,
1 /.
2
2,81 3,21 .
.

mo = 3,21 - 2,81 = 0,4 - .


2,81/0,4 = (d)/8 (d) = 2,81 8/0,4 = 56,2 /.
3
0,183 Mg.
182,7 20 750 .
Mg.

=750/7601,013105=1105 ; =273+20=293 ; V=182,710-6 3,


=2 /.
4

-
:
m(H2)=pVM/(RT)=1105182,710-62( )=0,015 .

0,183/0,015 = Mg/1 Mg = 0,183 1/0,015 = 12,2 /.

()
:
() = /n,
- , n - .
4
,

Cr - 68,42 %, O - 31,58 %.

:
mr/m = Cr/ r = 68.42 8/52 = 17.3 /.
:
=/n n(Cr) = 52/17,3 = 3.

,
, .
,
:
34 + NaOH Na24 + 2.
1 +
f (H3PO4) = 1,
(34) = f(34) (34) = 1 98 / = 98 /.

34 + 2 NaOH Na24 + 22

,
, f(34) = 1/2,
(34) = f(34) (34) = 98 =
=49 /. , 1
:
34 + 3 NaOH Na34 + 32.

+ f(H3PO4) = 1/3,
(34) = f(H3PO4) (34) = 1/3 98 =
32,66 /.

1.
2.
3.
4.
5.
6.
7.

8.

?
CrC13
Cr 2(SO4)3 ?
FeCl2
FeCl3?
H2SO4 H2SO3?
?
500 944 .
.
9 /.
.
10,17
2,25 2,
9 /. ,
.
.
,
6

.
?
9. , 3,24
3,48 3,72 .
10. 1,80 883
, .
.
11. 1,11 404,2
, 19 770 .
,
.
12. , 65,2 %
(.) As, - 75,7 % (.) As.
.
13. ,
1 1,07 ,
16.
14. 0,4375 0,1400 NaOH.
.
15. -, 0,3333 ,
0,5440 AgNO3.
.
16. NaOH
, 140 .
17. 3(4)2, , 6,2
3,923 H2SO4,
49,04. 3(4)2?

1. H2SO4
).SO4, ). 2SO4.
2. Fe(OH)3 c c ,
:
)

3.

4.

5.
6.
7.

Fe(OH)21, ) Fe(OH)12, ) Fe13.


Fe(OH)3 .
)
(3)2, ) AlOHCl2.
1 .
H2SO4 ;
, , H2SO4 NaOH
.
KNO3, CuSO4, FeCl3
, , .
Cr 2(SO4)3, ()2, NaOH
, , .
Al(OH)3 ,

Al(OH)3 + HCl Al(OH)2Cl + H2O

Al(OH)3 + 3HNO3 Al(NO3)3 + 3H2O.


1. Al2(SO4)3 c
NaOH:
Al2(SO4)3 + 6NaOH 2Al(OH)3 + 3Na2SO4.
2. KAl(SO4)2
:
KAl(SO4)2 + 3KOH Al(OH)3 +K2SO4.
10. () 2

()2+1 1 + 2,
()2 + 21 12 + 22.
11. C ,
NaNO3, NaHSO4, NaH2PO4.
,
.

12. ,
1; 1/2.
13. 2
NaOH: ) Na3, ) Na23.
14. KHSO4

KHSO4 + BaCl2 BaSO4 + KCl + HCl.


15. Cu(OH)Cl

Cu(OH)Cl + H2S CuS + HCl + H2O.
2.
( ,
) -
( ),
- .
- (m)
(m):
= m /m.
, % = 100 %. ,
,
.
mp, (, /) (V, )

m = V,

= m/(V).
, m= m+ m, m - ,
= m /(m+ m).
: -
V. , ,
9

1
750 10 % - ,
1,063 /?

mHCl = V( %/ 100%) = 1,063 / 750 (10/100) = 79,7 .


2
1 250 2 10
% - 1?
:
1. 250 2 90 % , 1 10 %,
250 - 90

- 10,
=25010/90=27,7 .
2. = m /(m+ m), . . 0,1=m/(250+m),
m = 27,7.
3
450 50 CuSO45H2O.

.

500 .

500 100 %
50 - %,

10

= (50 100 %) / 500 = 10 %=(CuSO45H2O)%.

CuSO45H2O

(CuSO4)+5M(H2O)=

=160+518=250 /, CuSO4 - 160 /.


, CuSO4 CuSO45H2O
160/250=0,64, uSO4 50 CuSO45H2O 500,64=32
, CuSO4
(CuSO4)%=(32 /500 )100 % = 6,4 %.
(, ) -
(, ) (V,
), :
= /V.
,
.
, 3 1 , 3
1, .. = 3 /.
(, ) (n,
, ) ,
:
= n/V.
,
( N) .
, 2 H2SO4 ,
2 H2SO4, .. (2SO4)= 2/.

= n/V=(m/)/V, = f, = (m/M)/(Vf) = /f,
..
=/f =f.

11

4
0,2 r2(SO4)3?

= Cf, f = 1/6 = 0,21/6 = 0,0333 M


= m/m m = m,
= m/M = m/M
,
= (m/M)/V = /V = CV=C(m/).
(1) (2),
= M/ C = /M

(1)
(2)

:
/.
5
36 % 1,
= 1,18 /

m = /M=0,361180 //36,5 / = 11.6 /.



,
. :
.

m1/m2 = ()(),
m1 m2 -
V1/V2 = (2/1) (()/()),

12

V1 V2 - ; 2 1 - .
,

m=m1+m2

mm11 m22 .
: ,

1.


;
;

2.


(1=1) (2=0);

3.

(1= )
.
6.
15 % - H2SO4 100 50 % - H2SO4,
30% - ?

m1/m2 = ( )() m1 /100 = (30 - 15)/(50 - 30) = 15/20


m1= 133 .
,
:
1

- 2 =

50

A=15
30

1 - =

15

13

B=20

m1/m2 = 15/20 = 3/4


7
20 5 % - 1 =
=1,1 /, 2 % = 1,02
/.

m1=V11=201,1/=22 .
:
5
2
2
m1/m2=2/3 m2= 223/2=33 .
0
3
m= m1+m2 =55, V=m/=
=55/1,02/=53.9 .

1.
2.

3.

4.
5.


,
250 50 .

, ) 60 AgNO3 750 ; ) 15 NaCl
450 ; ) 75 K2CO3 300 .

) 205 8 % - 23; ) 400 12 % H2SO4; ) 750 15 % - 1.

50 3 % - ?
(III) 20 4 % -,
1,133 /?

14

6. ,
500 20 % - , 1,133 / 3?
7. 1 100
5 % - ?
8. Na2SO4 400
8 % - ?
9. 100
5 % - ?
10. 100 Na2CO3102
, 4 % ?
11. 450 100 CuSO45H2O.
.
12. 250 50 FeSO47H2O.

FeSO4.
13. MnSO45H2O 100
, 20 % ?
14. 750 48 % - Na2SO4 300 2.
Na2SO4
.
15. 400 20 % - 50
.
?

1. CuSO4 10 0,2 ?
?
2. 12 25 0,5 ?
3.
, 20 1,74
.

15

4. , 2,0 0,5
?
?
5. Na2CO3 1 0,16 ,

23 ?
6. 3 FeC13 ?
7. 3
20 K2SO4?
? 1.15 /3.
8. 5 3 NaCl ?
9. 0,1 8 CuSO4?
10. Na2CO3 500 0,25 ?
11. H2SO4 49 H2SO4 1 .
, ,
H2SO4 NaOH Na2SO4.
12. CaCl26H2O,
700 3 1.41 CaCl2 (
1.12 /). ?
13. 5 105 (
).
,
0.95 /.
14. 300 3 12 (
).
, 1.15
/.
15. 2 HClO4 0.5
1.4 ?

3
1.115 1.080 / .

16


1. 15 % - H2SO4
( =1,1 /).
2. , H2SO4 c = 20 %.
1,15 /.
3. Al2(SO4)3 20 %
1,23/3.
4. 450 50 NaOH.
1,05 /.
.
5. 34 = 20 % ( = 1,33 /)
0,2 34 300 .
6. 1 2 666 , 1,395 /.
) ; ) ; )
.
7. 20 % - ,
1,186 /3.
8. 10 % - ,
1,056/3.
9. ( )
5 %- , 1,027 /.
10. 20 % ,
1,22/, 10
?
11., 20 30 %- ,
1,22 /, 6,54 .
12. 6,0 1
25 2,5 1?
13. 0,5 H2SO4
15 2,5 ?
14. 0,1 34 75
0,75 ?
17

15. 20 0,1
8 NaOH. NaOH 1
?
16. 40 25
0,5 H2SO4. ?
0,5 1
?

1.

100 0,2 1 250 0,2 NaOH.


, ,
.

2.

1,5 20 %-
, 1,057 /,
10 %- , 1,029 /?

3.

10 %-
1,105/, 1 2 %
-, 1,020 /, 3 %?

4.

25,0 40 %-
, 1,41 /, 2
% - ?

5.

1 20 % - ,
1,225 /, 10 .
.

6.

500 1, 1,1 /,
2,5 , 4 - .
.

7.

10 % - ,
1,05/,

18

, 100 2%-,
1,022 /?

8.

20 % - 1 50
%- , 25 % - ?

9.

,
300 25 - 400 40
.

10.

500 20 % -
NaCl, 1,152 /, 4,5 %
-, 1,029 /.

11.

30 % NaCl 300
, 10 % - ?

12.

20 27,7 % - H2SO4, 1,1 /,


50 2 H2SO4 1,05 /.

, 1,07 /.

13.

,
40 23,0 % - 1
1,15 / 25 3 1 1,05 /.
1.07/.

1.

K2SO4 22 % ( = 1,1 /)
12 % ( = 1,01 /).
1,2
1,022 /3.
?

14.

K2SO4 16 % (=

1,13/) 24 % ( = 1,15 /) 250


2 1,14
/.
?

19

3.
, ,
,
. ,
NaOH + HCl NaCl + H2O
, ,
,
:
N(NaOH) = N(HCl),

C(NaOH) V(NaOH) = C(HCl) V(HCl),


C(NaOH) C(HCl) - NaOH
1, /; V(NaOH) V(HCl) - NaOH 1,
, .
()
:
= N/V (/).
,
,
,
1V1 = C2V2.
1
42 H2SO4 14
0,3 .
.

V = C V2,
C - ; V
V - .
= ( V)/V = 0,314/42 = 0,1 /.

20

H2SO4 f = 1/2 C = f =1/2 0,1 = 0,05


/.

1.

30 0,1
12 .
.

2.

0,2
Fe(OH)3 , 100
0,5 FeCl3 ?

3.

20 0,1
8 NaOH. NaOH 1
?

4.

40 24
0,5 H2SO4.
? 0,5 1
?

5.

20 , 2.4
, 25 2 .
.

6.

20 , 1 12
, 24 0,25 .
.

7.


, 25 ,
0,18 , 50 NaOH, 0,1
.

21

8.

250 1,6 H2SO4 400 0,35 NaOH.



.

9.

100 0,2 H2SO4 200 NaOH


0,01 /. 0,1 NaOH
?

10.

0,3
, 0,32 NaOH?

11.

HNO3 ,
35 0,4 NaOH ?

12.

SO4 100 15 % - BaCl2


14,4 H2SO4.
H2SO4.

13.

- , 0,924
NaCl, 16,00 AgNO3.
.

14.

0,50 ,
Cu(OH)2 , 15 1,2
CuCl2?

15.

0,2 Na2CO3
50,0 0,1 1 2 ?

4.

-
.
,
, ,
;

22

CaCO3 CaO + CO2 ,



+2+4-23 +2-2 + +4-22
,
, :
2Hg+2O-2 2Hg0 + O02;
2K+J- + Cl02 2K+Cl- + J02
,
.
, ,

().


,
-
(): ,
, .
, .
1. ,
; ,
,
Al - 3 e- Al3+
H2 - 2 e- 2H+
Fe2+ - e- Fe3+

2Cl-- 2e- Cl2

2.
, ;
, ,
S0 + 2 e - S2-, Cl20 + 2 e - 2Cl-, Fe3+ + e- Fe2+
3.

;
,
(
).

23

: ,

(-).

,
, ,
32 + N2 2NH3,
4NH3 + 5O2 4NO + 6H2O.
,

:
22S + H2SO3 = 3S + 3H2O,
5HCl + HClO3 = 3Cl2 + 3H2O.
,

.
:
2NaNO3 2NaNO2 + O2,
(NH4)2Cr 2O7 N2 + Cr2O3 + 4H2O.
,
:
NH4NO2 N2 + 2H2O,
NH4NO3 N2O + 2H2O.


. ,
,
:
4Na2SO3 3Na2SO4 + Na2S,
4KClO3 3KClO4 + KCl,
3K2MnO4 + 2 H2O 2KMnO4 + MnO2 + 4KOH.

24


, , ,
. . ,
, ,
. .
,

.
, , , .
KMn+7O4, K2Cr62+O7, Pb+4O2,
NaBi+5O3, HN+5O3, H2S+6O4 ,
.
,
- Mn4+O2, HN3+O2, H2O21-, S+4O2 -
,
, ,
:
2SO2 + O2 2SO3
SO2 -
SO2 + 2H2S 3S + 2H2O
SO2 -

- .
-
.

1. F2, O3, O2, Cl2, Br2.
2.,
: KMnO4, K2Cr 2O7, PbO2, NO3,
H2SO4.

1. .
2. H2, C.

25

3. : H2S, HI,
NH3.
4.
: FeSO4, CO, SnCl2, Na2SO3.
5. : H2C2O4, C2H5OH, C6H12O6.




.
.
1. - ,
- ,
; , ,
- .
.
2. ,
,
+ ,
-
-, :
MnO4- + 8H+ + 5 e Mn2+ +4H2O,
MnO4-+2H2O+3 e MnO2 + 4OH.
3. ,
,
, -
-. (
) ( ),
:
SO32-+H2O - 2 e SO42-+2H+ ,
SO32- + 2OH- - 2 e SO42-+H2O.
26

4.
,
.
5.

-

.
.
KMnO4
H2S,
. ,
: H2S S.

(
-2 0) - :
2S - 2 e S + 2H+ .

MnO4- ( ) Mn2+ (
), MnO4- Mn2+.
, MnO4- ,
+ ( 4
MnO4- 8 +), :
MnO4- + 8 + Mn2++4H2O .
( - (+7), (+2)), 5
(
(+7) (+2)):
MnO4-+8H++5 e Mn2++4H2O.

27

- MnO4-.

,
.
( 5 2),
.
:
H2S - 2 e S + 2H+
5
MnO4- + 8H+ + 5 e Mn2++4H2O

5H2S + 2MnO4- + 16H+ 5S +10H+ +2Mn2++8H2O


( +)

5H2S + 2MnO4- +6H+ 5S + 2Mn2++8H2O.


;
: -2+(+6) = 2(2+).

. ,

.

, ,

2K++3SO42-+ 5H2S+2MnO4- +6H+ 2K++3SO42-+ 5S + 2Mn2++8H2O,
5H2S + 2KMnO4+3H2SO4 5S+2MnSO4 + K2SO4 + 8H2O.
-
: ( + - ), (2)
( - -).

;
.

28

:
KMnO4, H2O2, K2Cr2O7.

- MnO4-,
.

MnO4-+8H++5 e- Mn2++4H2O,
.

MnO4-+ 22 + 3 - MnO2 + 4OH- ,
MnO2.
-,
-:
MnO4-+ - MnO42-.

. :
,
.
NaOH.
-
:

H2O2 + 2H+ + 2 e- 2H2O ,


H2O2 + 2 e- 2OH- .
(KMnO4, K2Cr 2O7,
(NH4)2S2O8) :
22 - 2 - 2 + 2+ .
+6
+3.
, - .
Cr (VI) :
2CrO42- + 2H+ Cr2O72-+H2O; Cr2O72- +2OH- 2CrO42- + H2O .

29

r2O72- - ,
Cr 3+:
r2O72- + 14H++6 e- 2Cr 3++7H2O.

Cr(OH)63- CrO42-:
Cr(OH)63- + 2OH- - 3 e- CrO42- + 4H2O.

,
, .
,
. ,

:
.
: ,
, - ,
.

()
(),
()
- .
-
( - /).
()
()
= /n,
n - ,
. ,

Fe2+ - e- Fe3+
x6
30

Cr2O72- + 14H++ 6 e- 2Cr3++7H2O

x1

6Fe +Cr2O +14H 6Fe +2Cr +7H2O


2+

27

3+

3+

6FeSO4+K2Cr2O7 + 7H2SO4 3Fe2(SO4)3 + Cr2(SO4)3 + K2SO4 +7H2O


K2Cr 2O7 1/6 ,
- (K2Cr 2O7) = /6 = 49 /;
FeSO4 1 , (FeSO4) =/1 =152 /.
-
(
). ,
(K2Cr2O7) = /6,
K2Cr 2O7 + 2 2 K2CrO4 + 2
(K2Cr 2O7) = /2.
,
-

,
.
- .
.
- ,
,
. , Fe3+(FeCl3)
(KJ),
:
2Fe3++2J- 2Fe2++J2.
-
Fe3+ - ,
-

Fe3+

, .
, Fe3+ J-,

31

( )

(
)

( ) .

.
, - ,
,
Fe3+. -, , :
2J- - 2 e J2.
Fe3+, , :
2Fe3++2 e- 2Fe2+.
- Fe3+
Fe2+ . ,

, ,

-
.
-

, .

= + RT/(nF) ln(Ox/Red),
- -
(, )
, ,
, 25 = 298 ; R - , 8,31
/( ); - ; n - ,


; F - , 96500 /;
Ox Red - (, ) ,

32

Ox
Red .
- ,

kA + lB pC + qD,

= o + RT/(nF) ln((CAk CBl)/(CCp CDq)).

-
MnO4- + 8H++5 e- Mn2++4H2O

= o +RT/(5F) ln((MnO4- H+8)/ Mn2+).

,
, .

,

,
.. .

().
( ) ,
, , . . ,
,

, ,
,
- Fe3+,
= (Fe3+/Fe2+) - Eo (J2/2J-) =+0,77-0,54=+0,23 B.

33

, -
,
-
, , . .

, . ,
, ,
, . . = +0,23 ,
- Fe3+ ,

= (Fe3+/Fe2+) - Eo(Br2/2Br-) = +0,77-1,08 = -0,31B 0.


, Fe3+. ,
Fe2+ Fe3+, . .
:
2Fe2++Br2 2Fe3++2Br = Eo(Br2/2Br-) - (Fe3+/Fe2+) = +1,08 - 0,77 = +0,31B
,
- -
,

( 0).

I. ,
- ,
,
,
.
1. SO2+K2Cr2O7 + H2SO4 ...
2. H2O2 + K2Cr2O7 + H2SO4 ...
3. H2O2+PbO2+CH3COOH Pb(CH3COO)2 +...

34

4. Na2SO3 + KJO3 + H2SO4 ...


5. KJ + O3 + 2 2+ ...
6. H2S + H2SO3 ...
7. O2 + FeSO4 + H2O ...
8. KJ + KNO2 +H2SO4 ...
9. HC1 + HNO3 ...
10. H2S + KMnO4 + H2SO4 ...
11. KBr + MnO2 + H2SO4 ...
12. H2O2 + KMnO4 + H2SO4 ...
13. KBr + KMnO4 + H2O ...
14. MnSO4 + KMnO4 + 2 ...
15. PbO2 + HC1 ...
16. FeSO4 + H2O2 + H2SO4 ...
17. Cr(OH)3 + Br2 + NaOH ...
18. NaNO2 + KMnO4 + H2SO4 ...
19. NaNO2 + KMnO4 +2 ...
20. A1 + NaOH + 2 ...
21. K2Cr 2O7 + KJ + H2SO4 ...
22. K2Cr 2O7 + HBr ...
23. K2Cr 2O7 + Na2SO3 + H2SO4 ...
24. C12 + KOH KC1O + ...
25. Cu + HNO3 NO2 + ...
26. Zn + HNO3 NH4NO3 + ...
27. Mg + HNO3 N2O + ...
28. Ag + HNO3 NO + ...
29. KC1O + KJ + H2SO4 KC1 + ...
30. KC1O + KJ + H2O KC1 + ...

35

II.
.
1. H2S + HC1O H2SO4 + C12 + ...
2.

KC1 + J2 + K2SO4 KC1O3 + KJ + H2SO4

3.

JO3- + A1 + H+ J-+A13++...

4.

C1O- + C1- + H+ C12 + ...

5.

Zn +OH- + ... Zn(OH)42- + H2

6.

A1 + OH- +... Al(OH)63- + H2

7.

S + J- + ... S2-+JO3- + H+

8.

Mn2++Br2 MnO4- + Br- + ...

9.

Cr3++Fe3+ Cr2O72- + Fe2+ + ...

10.

Cr(OH)63- + C1O- CrO42- + C1-+ ...

11.

HC1 + H2SO4 C12 + H2SO3

12.

H2S + H2O2 SO42- + H+ + H2O

13.

Pb2++NO3- +H2O PbO2 + H++NO2-

14.

C12 + J2 + H2O HC1 + HJO3

15.

1.
2.

3.

4.

FeSO4 + HNO2 + H2SO4 Fe2(SO4)3 + NO + ...


III
Mn2+ MnO4- 12,
NO3-, S2O82-, JO3- ?
) KMnO4
, ) NO
?
.
( ) ,
a) KC1, KNO2, H2SO4; ) KJ, KNO2, H2SO4; ).
HgCl2 KJ?
KJO3 KJ; HJ
HClO; KBr KMnO4?

36

5. C ) KMnO4 FeSO4; ) KNO3


KMnO4 )Fe2(SO4)3 K2Cr2O7.
?

5.
-
.
(v) t1 t2

v = (2 - 1)/ (t2 - t1) = /t,


1 2 -
t1 t2;
,
( ), -
( ).
-
t.
v = dc/dt.

, ,
+ bB cC + dD,
(1)

-1/dC()/dt= -1/bdC(B)/dt = 1/dC()/ dt =1/ddC(D)/dt.


1

3 + 2C + D

37

= 0,03 /;

0,01 /; = 0,08/.
?


(t = 0) (t) .
3 + 2C + D
t=0
x
y
0
0
t
0,03 0,01 0,08
, t
Z. ,
,
3 , , ,
, 3Z.
2Z,
D - Z. :
2Z = 0,08 /, Z = 0,04 /;
= 0,03 + 3Z = 0,03 + 30,04 = 0,15 /,
= 0,15 /;
= 0,01 + Z = 0,01 + 0,04 = 0,05 /,
= 0,05 /.
, , ; (,
); ; ;
( ).
()

. (1)

38

v kb,
- ;
k - ; , -
.
.
()
.

.
2
+ ,
, 0,05 0,01
/, 510-5 /.


v = k 1 1,
v = 510-5,
k = v/([][])= 510-5/(0,050,01) = 110-1 -1 -1 .
3

2NO() + O2() 2NO2().
,
3 ?

). v = k [NO2[O2].
).
. ,
v0,

v = k (3[NO)2 (3[O2]) =27 k [NO2[O2] = 27 v0.


, 27 .
39

4
,
2 + ,
4 , 2 .


:
v0 = k 2.

v = k (4[)2(1/2[)= 8 k 2[] = 8v0.
, 8 .


-,
v2 = v1 t/10,
v1 v2 - t1 t2
, t = t2 - t1, -
( -).
5
50 2 . 15 .
70,

3.

- ,

v2/ v1 = t/10=3(70-50)/10= 9 .

40

, 9
70 = 50/9 = 135/9 = 15 (c).
6
50
1200 .
.

-
v2/ v1 = t/10 1200 = 50/10= 5 =51200=4,13.

pe
:
k = xp[-Ea/(R)],
, R - (8,314
-1-1); - ,
; - , ; -
, /.

.
7
3() + NO() O2() +N2() 10
/. 27 37?


v = k [3][N].

41

, [3] [N]
k.

k 2/ k 1=[xp(-Ea/(R2))]/[xp(-Ea/(R1)) =
= exp[- (Ea/R)(1/T2 -1/T1)]=
= exp[(Ea/R)(T2-T1)/(T1T2)] ,

1n (k 2/ k 1) =(Ea/R)(T2-T1)/(T1T2).
,
1n (k 2/ k 1) =(10 000/8.314)(310-300)/(300310)=0.129.
k2/k1=1.14, . . , ,
, 1.14 :
v2 / v = 1.14.
8
, c
120 5,8810-4, 170 6,710-2.

1). 7
1n (k 2/ k 1) =(Ea/R)(T2-T1)/(T1T2)
=1n (k 2/ k 1)RT1T2 /(T2-T1) =
=ln(6.710 / 5,8810-4) 8.31393443 /(443-393)=137 029 /=
137 /.
2). -
k 2/ k 1= v2/ v1 = t/10
-2

1n (k 2/ k 1)= (t/10) 1n
1n =(10/t)1n (k 2/ k 1)=(10/50)ln(6.710-2/ 5,8810-4)= 0.947
= 2.58

42

,
.
.
9

75 /, - 50 /.

, 25?


k 2/ k 1 = xp[-Ea2/(R)]/xp[-Ea1/(R)] = xp[(Ea1-2)/(R)]
v2/ v1 = k 2/ k 1 = xp[(75 000-50 000)/(8.31298)] = 24 231.
, 25
24 231 .

,
, .
,
-
:
---------
+ + dD
--------
,
.

= ([C]cp[D]dp) / ([A]ap[B]bp) ,
(2)
[C]p, [D]p, [A]p, [B]p - ; a, b, c
d - ; 43

( ,
).
.
(2)
.
, ,
(2) ,
; :

1)
2)

;
,
;

3)


; -
( )
.
, ,
,
Pi :
= (PcCPdD) / (PaAPbB).
10
+ 2
[] [,
[] = 0,3 /, [] =1,1 / [] = 2,1 /.


= [C]p / ([A]p[B]2p)
= 2.1/(0.31.12) = 5.79.
, 2,1
2,1 2,12 = 4,2

44

.
,
:
[ = 0,3 +2,1 = 2,4 (/),
[] = 1,1 + 4,2 = 5,3 (/).
11
2+J2 2HJ,
[2 ]o = 0,03 /; [ J2]= 0,05 /,
[HJ] = 0,04 /.


.
.

1
,

()

2 +

J2

0.03
0.02
0.01

0.05
0.02
0.03

2HJ

0
0.04

2 J2
1/2 HJ
.
2 J2
.

= [HJ]2p / ([H2]p[J2]p)=0.042/(0.010.03)=5.33.
12

45

+ = +D
4.
, V = 1 2
1 .

1 ,

()

2-

1-

= ([C]p[D]p) / ([A]p[B]p) 4 = 2/[(1-)(2-)].


x1 = 3,15 2 = 0,85.
e , . .
2. , []=[D]= 0,85 /,
[]=1,15 /, [] = 0,15 /

: , ,
- ( , ,
),
,
.
13

46


N2 + 32 2N, = - 92,4
1) 2 N2;
2) N3;
3) ;
4) .

1). ,
,
,
, ..
. :
=N]2/ ([N2[2]3).
|N2] [H2] .
,
, ..
[NH3,
N3, .. .
,
N3
.
2).
.

- ,
.
3).
,
. ,

47

, . .
.

. , 2 .
2
. , v = k23
16 , v = k [NH3]2 4 .
.
4).
, . .
, .

1.

2 + 2,
2 ,
2 ?

2.

2
22() + 2() 22(),
4
?

3.

+ 12 12
0,03 0,12 /, 1 2 - 0,02 0,06
/. ?

4.

N2() + 3H() 2
NH3 ) 3 ; )
2 ; ) N2 4 ?

48

5.

,
N2 2N + 2 2 N2 1000
?

6.

(II)
+ 1 2 12.
) 2 ; )
12 2 ; ) 2 ?

7.

.
. ,
2 2 ,
2
4 .
.
3 ?

8.

,
D. D
4
16 . 2
D,
2 .
D
4 .
.

9.

() + ()
(), 210-1 -1 ,
0,025
0,01 /.
3 .

49

10.

+ 2 2,
,
0,1 0,05 / , 7 10-5 /().

11.

2
4,5 3 .
+ = . 20
2 .
.
?

12.

+ . = 0,03
/, = 0,05 /. 0,4.

0,01 /.

13.

+ .
0 = 0,03 /, 0 = 0,03/.
0,1.
0,015 /.
,

?

14.

,
27 ?
3.

15.

20 2 .
) 50, ) 0 ?
2.

50

16.

30 25 ,
50 4 .
.

17.

0 1 / .
30 ,
3.

18.

50
32 .
.

19.

25 .
2,0,
- 2,5.
95.

20.

,
290 300
2 ?

21.

,
298 ,
4 /?

22.

,
300 10 , 280 .

23.

3() +NO() 2() +NO2()


40 /.
27 37?

24.

300
20 /, - 40 /.
?
.

25.

150 16 .

51

2,5, ,
, ) 200, ) 80.

26.

10

2 . 20 0,04 /().
) 40, )0?

27.

20 0,04 /

(). 70, ,
70 /.

28.

120 5,8810-4,
170 - 6,710-2.

29.


300 400 ,
= 2? ?

30.

2 4
40.
- . 2.

31.

2() + () 2()
3
30?
2.

32.

+ .
0 = 0,05 / 0 = 0,05 /.

. , ,

52

, ) 2,
) 70 ,
27?

33.

1.

2.

3.

4.

, 290 300
.
.
310 , ,
10 /?

2NO2
2NO+O2 [NO]=0.4 /,
[NO2]=0.2 /, [O2]=0.1 /.
NO2,
.
NO,
?
++D .
,
3 5 ?

, ?

()+H2O()CO2()+H2()
[CO]0=[H2O]0=0.03 /, [CO2]0=[H2]0=0.
,

0.01 /.
,
?

2NO()+Cl2()2NOCl()

53

5.

6.

7.

8.

9.

[NO]0=0.5 /, [Cl2]0=0.2 /, [NOCl]0=0 / .


,

20% .

NOCl, ?

H2() + I2() 2HI(),
10 1 2
(=50).
,
?
()+H2O()CO2()+H2() , [CO]0=[H2O]0=1 /,
[CO2]0=[H2]0=0. (%.),
=1.
,
?
() () +().
=0.04.
, 0.02 /.

, ?
10 800
CaCO3() CaO()+CO2() .
=300 . 3 ?

Fe()+H2O() FeO()+2().
, =1,
.

54


, ?
10.
2HI() H2()+I2(), HI 0.05
/, =0.02.
I,
?
11. ()+2() 2() =2.
2
[CO2]0=0, [CO]0=5 /.
,
?
12. 26()24()+2()
0.2, 0.4, 0,4 /.
,
24?

, ?
13. 2AlCl3 () Al2Cl6 ()

1.

,
AlCl3 Al2Cl6 2
3 /.
, ?
14. SbCl3 ()+ Cl2 () SbCl5 ()
, ,
80% SbCl3, SbCl3 , Cl2
SbCl5 1, 2, 1.5 /.
,
?

55

15. SO2 () + Cl2 () SO2Cl2 ()


SO2Cl2, 1.5,
SO2, Cl2 SO2Cl2 2,
1 0 /.
, ?

6.
, ,
(U), (), (S)
(- (G).
:
= U + p V,
G = - T S,
p, V, - , .
U, H, S ,
.. ,
,
.


. ,
, ,
,
dU .
dU = Q - pdV,
(1)
Q - ,
, ,
.
,

, ,

56

- .
,
, .
(V= const)
: QV = U;
- Q = .
, (1). ,

,
.

.

,
()
:
o..= (iiof) - (jjof) ,
- , .
()
1
,
.
=1,013105 =298 .
,
.
f298 .
f298 - /.
1

2NaOH() + CO2() = Na2CO3() + H2O()

57


(/): NaOH()- -426,6, Na2CO3()- -1129, CO2()- -393,51,
H2O()- -285,8.

o
..

= (iiof) - (iiof) =
=[1f298 (Na2CO3)+1 f298(H2O)]- [2f298(NaOH)
+1f298(CO2)]=

= -1129 - 285,8 + 2 426,6 + 393,51 = -168,1


2NaOH() + CO2() = Na2CO3() + H2O(); o = -168,1 .


: o. - , . . f298 /, - .
2

f298(2)= -393,5/
() + 2N2O() = CO2 () + 2N2(): o = -557,5
N2O().


o = [1f298(CO2) + 2f298(N2)] -[1f298() + 2f298(N2O)],

f298(N2O)=1/2[o + f298()- f298(CO2) - 2f298(N2)]=


=82 /.

58

, , ,
,
,
.
3
, 100
25 ,
, .

()
2 ()
()2
()
-635,1
-285,8
-986,2
f298,
/


() + 2() = ()2() o = ?

o = (iiof). - (iiof).. = 986,2 + 635,1 + 285,8 = -65,3
.
, (65,3
) 1 .
, :
() = m(CaO)/M(CaO) = 100/(40+16) = 1,78 .

Q = 65,3 /( ) 1,78 ( ) = 116,61 .
4
,
, 24 804,48 ..

+ 2 = 2 , = ?

59

1
(12 ) . , 24 ,
24/12 (/)=2 . , 1

= 804,48 /2=402,24 / .

() + 2 ()= 2 (), = -402,24 .


:
1) ,
( 0);
2)
.

S 0. S
.
(w)
S = klnw,
k - .

,
.

(S 0). ,
.
, S 0
1). .
2). ,
.

60

3). .
4). (n)
( ).
,
() + 2() = 2(), n = 1 S 0.
(U) ()
.
S298 ()
. , S298 (
f298) .
, ,
,
.
S298 = (i Si298) - (jSj 298) .

, . = const,
( ) G

G = - So.

= const = const G 0.
,
- .
G , ,
S
G = (iGiof248) - (jGjof248)
5

61

,

SO2()+ NO2() SO3() + NO().


Go
.
:
. = (iif298). - (ijf298)..
. = f298 (SO3) + f298(NO) - f298(SO2) - f298(NO2) =
= -395,2 + 90,37 - (- 296,9 + 33,89) = - 41,82 () = 41,82 103
()
S = So(SO3) + So(NO) - So(SO2) - So(NO2) = 256,2 + 210,6 - (248,1 +
240,4) = -21,7().

Go = - S = -41820 - 298 (-21,7) = -35353 .


Go = -35,4 0.
298
.
Go

(Gof) , .

G = (iGiof248) - (jGjof248j)
G = -370,4 + 86,57 - (-300,4 + 51,84) = -35,27 .
G
= - So .
6

62

,
() + 2() 2()
. So
. .


Go 0:
G = - So 0,

/So.
, So
,
0298/So298.
= 2 f298() - f298(2) = 2 (-110,5) - (-393,5) = 172,5
.

S = 2S298 () - [S298 () + S298(2)] = 2 197,4 -( 5,73 + 213,6)


= 175,47 /.
172500/175,47 = 983 .
, 298 ,
,
G = - So = 172500 - 198 175,47 = 120210 0.
G ,
(
,
1 /, - 1 )
- .
G0,
, G0

- .

() , G=0.
63


() ()
() -
G = -Rln K,
R - , 8,314 /(); , .
7

(IV) 298 .
.
,
.

f298
/
S
/()

NO2()
33,89

N2O4()
9,67

240,4

304

2NO2() N2O4()

(N2O4) - 2 f298(N2) = 9,67 - 2 33,89 = -58,1

f298

S = S298(N2O4) - 2 S298(N2) = 304 - 2 240,4 = -176,8 /.


G = -5,423 0.

- .
- :
G = -RT ln K ln = -Go/(RT) = 5423/(8,314 298) = 2,18,
= 8,93
8

64

,
() + 2 () + 2() = 298
.

G 298 = Gof(2) - Gof() = - 228,6 - (-137,1) = -91,5 .


lg K = 91500/(8,3142,302298) 16 = 1016.
- .
, (
)
.


1. , (1),
, ,
,
, ,
.
2.
298

,
f298 .
2.1. 2Mg() + 2() = 2MgO() + C()
2.2. 4() + 22() = 2() + 22 ()
2.3. N2 () + 32() = 2NH3 ()
2.4. ZnO() + C() = Zn() + CO()
2.5. 2() = 2 ()
2.6. 2() = 2 ()
2.7. 2NH3() + H2SO4() = (NH4)2SO4()
2.8. 2H4() + 3O2() = 2CO2() + 2H2O()
2.9. CO() + 12() = 12 ()
2.10. 4NH3() + 3O2() = 2N2() + 6H2O()

65

2.11. 2NO() + O2() = 2NO2()


2.12. 4H2S + 3O2() = 2() + SO2()
2.13. 2SO2() + O2() = 2SO3()
2.14. 2() + 2() = 2() + 2()
2.15. C() + 2() = () + 2()
3. 2()

22() = 2() + 1/22()


= -97,9
22 ().
4. 298 FeS2
4FeS2() + 112() = 2Fe2O3() + 8SO2(),
, f298

FeS2()
Fe2O3()
SO2()

-177
-821,3
-296,9
f298
/
5.
() + SiO2() = SiO3(),
f298
-636,
-908, -1582 /. , ,
224 .

6.

,
10
Na2CO3() = Na2O() + CO2(),
,
Na2CO3() + SiO2() = Na2SiO3() + CO2(), =81,04 ,
Na2() + SiO2() = Na2SiO3(),

7.
8.

=-234,17 .

4,2 7,15
. Fe + S =
FeS.

66

24 + 32 = 22 + 2,
= -1400 .
,
)1 2; ) 16 ; ) 336 (..) .

9.

32 (IV),
, 146,3 .
.

10.

9,3 (V)

229,5 . f298(25).

11.


SO2() + H2S() = 3S()+ H2O()

= - 234,5 .
H2S,
SO2().

12.


CS2, , S2() + 3O2 = CO2 + 2SO2
= - 1075 . .

13.

3() = () + 2(), = 157 .


, 3() ,
510,3 .

14.

As2O3

As2O3() + 2() = As2O5()
= -270,9
3As2O3() + 2O3() = 3AsO5()
= -1096 ,

23() 32()
= ?

15.

Fe2O3,
Fe2O3() + 3CO() =

67

2Fe() + 3CO2(). 2() ()


.

16.

HBr() HJ()

2() + Br2() = 2HBr()
= -72
2() + J2() =2HJ()
= 51,8 .
Br2() J2(),
,
Br2() = Br2()
= 31
= 62,2 .

J2() = J2()


1. , So
:
1.1. 2NH3() N2() + 3H2()
1.2. 2() 2()
1.3. 2NO() + 2() 2NO2()
1.4. 22S() + 32() 22() + 2S2()
1.5. 23() + 32() 42 + 22()
1.6. MgO() + H2() Mg() + H2O()
1.7. C() + CO2() 2CO()
1.8. 41() + O2() 2C12() + 22()
1.9. NH4NO3() N2O() + 2H2O()
1.10. Fe() Fe()
1.11. 2() 2()
1.12. 3() () + 2()
1.13. 32() 23()
1.14. N2() + 2O2() 2NO2()

68

2. ,
So Go298
,
1.
3.
22() + 2() = 222()?
4.
: ). S0; ). S 0; ).
S 0?
5. Go298
PbO2() + Pb() 2PbO()

Go298 0,

SnO2() + Sn() 2SnO()


Go298 0
,
.
6. ,
2() 2() 2()
.
7.
2() + 2() 22() 298 .
8.
(II) () + () () + () ?
.
9.
(IV) () + 2() = () + () ?
.
10. () + 2()
() + 2() ?
,
.
11. () + 1 2()
12 1000 , , S
69

.

.
12. G298 4, 22 NH3
f298 S298.
.
13. Go 3() () + 2()
25; 500; 1500. S .
14. ,
,
,
S ?
15.
+ 1 2 = 12 700
,
= 1,0685 10-4.
16. G298 NH3 -16,64 /.
N2 + 3H2 2NH3
.
17.
2NO2() N2O4() .
,
.
18. 2 2() + 2 =
22 G298 = - 457,2 .
.
19. 25 1,75
10-5.
?
?

70

20.
,
() + 2() () + 2()
. S .
21. +
298 -8 /.
, ,
.
22. , S 41() + 2() 22() +
212() , ,
.
23. ,
298 1000 :
) 2() + () 2() + 2(),
) 2() + () 2(),
) N2() + 3H2() 2NH3().
S .
24.
300,
-57,3 /.
25.
1000 , =
1010.
26.
500 , = 107.

7. .

,
.
, .
71


, . .
-
.
,
, ,
+:
1 ++123 ++3, - ,
:
++ (OH)2 ()++OH .

.
, ,

().
, . ,

- . ).

- , ;
- H2SO4; HClO4; HNO3; HMnO4 ,
7 , HF;
- Fe(SNC)3; CuCl2.

72


.


:
NaCl Na++ClHCl H++Cl
, ().
,
:

H2SO4 H+ + HSO4- ,
HSO4- H+ + SO42- ;

Ba(OH)2 Ba(OH)+ + OH-,
Ba(OH)+ Ba2+ + OH-.

:
Fe2(SO4)3 2Fe3+ + 3SO42-.

:
3 ++3- .

, ().

(
)

=3-+ / 3,
3, 3- + -
,

73

/.
. ,
.
(acid - ), - b (base - ).

=2/(1-),
- . 1
( )
=(/).

( ),
:
34 ++241 = 7.5 10-3
24- ++42-

2 = 6.3 10-8

42- ++43 3 = 1.3 10-12


,
- (
1):
Ca(OH)2 Ca(OH)+ + OH-

Kb1

Ca(OH) Ca + OH
Kb2
,
, . .

,
(
),
, , 1 2 3 ..

.
.

+

2+

74

2 ++- .

K = H+OH- /H2O.

,
Kw = KH2O =H+OH- = const.
, Kw,
. . 25
Kw = H+OH- = 1 10-14.
Kw ,
(, ) ,
.. .
, .
,
:
H+=OH-=1 10-14 = 10 - 7 / - ;
H+ 10-7 / - ;
H+ 10-7 / - .

, , .


:
= - lgH+; pOH = - lgOH-.

+ = 14.

()
().
.
75

= 1, ..
.
1
1 Al2(SO4)3.

Al2(SO4)3 - , . . .
:
Al2(SO4)3 2Al3+ + 3SO42-.
,
2 3 -
[Al3+]=2C = 2 /;

[SO42-]= 3 = 3 /.

2
0.1 NaOH.

- ( ), ,
:
NaOH Na++OH- ;
, ,
[OH-]= = 0.1 /,
= - lg [OH-]= 1,
pH= 14- = 13.
.
, , ,
.
3
0.2
.

76

, :

H2SO3 HSO3- + H+,

1= [HSO3-][H+]/[H2SO3]= 1.610-2 ;

HSO

SO

23

(1)

+H,

Ka2= [SO32-][H+]/[HSO3-]= 6.310-8 .


(2)
,
HSO3- H+,
SO32- H+,
,
[HSO3-]+ 2[SO32-]= [H+],
(3)

[H2SO3]= C - [HSO3-]- [SO32-].
(4)
(1)-(4)
, , Ka1Ka2.
, + HSO3- ,
, .
SO32-.
[+], [HSO3-] [H2 SO3]
(1) ,
+ HSO3-, ,
= [+] = [HSO3-2],
[H2 SO3]= - ..
,
1= 2 /( - )= 1.610-2

2 /(0.2- )= 1.610-2,
1 = -6.510-2 2 = 4.910-2.
,
.
[+] = [HSO3-] = 4.910-2 /, [H2 SO3]= 0.151 /,

77

1 = [+]/ = 4.910-2 //0.2 / = 0.245, 24.5%.


[SO32-]
[+] [HSO3-]
(2)
[SO32-][H+]/[HSO3-]= [SO32-] = 2 = 6.310-8 /,
2 = [SO32-]/[HSO3-]= 6.310-8 /./ 4.910-2 / = 1.29 10-6.
:
.
4
5% ( =0.97 /).

1).
. 1 :
mp= V = 1000 0.97 / = 970 ;
m= mp = 970 0.05 = 48.5 ;
= m/ = 48.5 /35/
=1.39 ;
=/ V= 1.39 /1 = 1.39 /.
2). :
NH4OH NH4+ + OH-.
= [NH4+][OH-]/[NH4OH]= 1.810-5 .

= (/) = =(1.810-5 /1.39) = 3.6 10-3 ;
1, , .
1
-;
,
, ,

78

[-]= =3.6 10-3 1.39 / = 5.0010-3 /,


= - lg[-] = - lg 5.0010-3 = 2.30,
pH = 14-pOH= 14 -2.30 = 11.70.
:
, 0.1,
= 2/(1-)
(.
3), ..

,
,
,
,
.
5
ClO- , 500
0.005 HClO 0.0005 HCl.


(HClO) = ( HClO)/V=0.005 /0.5 =0.01 /;
(HCl) = ( HCl)/V = 0.0005 /0.5 = 0.001 /.

HClO H+ + ClO-,
HCl H+ + Cl, H+.
, HCl , HClO
,

= [H+][OCl-]/[HClO] = 510-8.
79

:
[H+]1= (HClO) - (1);

[H+]2= (HCl) = (HCl) = 0.001 /


(=1);
[H+] = [H+]1 + [H+]2 = = [H+]1 + 0.001 = +0.001.
ClO- ClO
:
[OCl-]= (HClO) = [H+]1= ,
[HClO] = (HClO) - = 0.01- ,
Cl- -
:
[Cl-]= (HCl) = 0.01 /.

,
(+0.001) / (0.01-) = 510-8.
,
, 0.001 , ,
0.01,
0.001 / 0.01 = 510-8,
= [OCl-]= 510-7 /,
.

1.1.

5%- (=1.042 /).

1.2.

100 0.01
HCN,
4 ? ?

80

1.3.

HCN,
0.1 HNO3?

2.1.
2.2.

0.01 .

22 .
1
, =1.410-12.

2.3.

2- , 1
1 0.001 HCl.

3.1.

- 0.03
.

3.2.

,
H2S 0.05 .

3.3.

0.2 HCN KCN,


0.02 /.
?

4.1.

2%- (=1.021
/).

4.2.

NH4OH,
2%.
.

4.3.

, 1 1
100 20%-
(=1.057 /)?

5.1.

: 2%-

(=1.016 /) 1.6%- NaOH (=1.016 /)?

5.2.

HClO
0.001 0.71%.
.

81

5.3.

ClO- , 150
1.5 10-3 HClO 1.5 10-3 HCl.

6.1.

ClO4- ,
3 HClO4 300 .

6.2.

HF
, 0.25
5.1%.

6.3.


6.1 6.2, HF
6 ?

7.1.

1 ,
12?

7.2.

HBrO
0.04% 5.3.

.

7.3.

BrO 1 HBrO
,
5

8.1

- 3%-

BaCl2 (=1.025 /).

8.2


,
100 ?

8.3


, ,
,
? .

82

9.1

- 0.02
Al(NO3)3.

9.2

0.01
.

9.3

0.1 HClO ClO,


0.005 /.
?

10.1

Sr2+ NO3- 8%-

Sr(NO3)2 (=1.072/).

10.2

300 0.0025 H2S, 3


? ?

10.3


,
1 ?

11.1
11.2

0.3%- HClO4 (=1.002 /).

11.3

Cl- , 1

0.01
HClO.

110-5 HClO 110-6 HCl.

12.1
12.2

0.2%- ()2 (=1.002 /).

12.3

, 2

HClO,
0.2%. .
1 2%- KClO (=1.013 /)?

13.1

: 1% - HCl

(=1.003 /) 1%- HClO4 (=1.005 /)?

83

13.2


NH4OH, 0.1 11.13.

13.3

, 300
0.1 NH4OH 0.1 .

14.1

3
, 11.5?

14.2

HClO
0.63% 5.1.
.

14.3

ClO 1
,
7 ?

15.1


, 200 0.8 .

15.2

NH4OH ,
0.2
0.95%.

15.3


15.1 15.2, NH4OH
20 ?

16.1

HPO42- 3%

- K2HPO4 (=1.021 /).

16.2

20 0.1 NH4OH,
10 ? ?

16.3

NH4OH,
1 NOH?

17.1

-
0.003 - (N3)2.

84

17.2

+, 23- 32- 0.8 ,


1=1.6 10-3 2=6.310-7.

17.3

0.15 - NH4OH
NH4Cl, 0.2 /.
.

18.1

0.2%- (=1.001
/).

18.2
18.3

0.1 N.

19.1

SO42- 3%-

N- , 2
0.1 N 0.0005 HCl.
Al2(SO4)3 (=1.025 /).

19.2


, 4.5.

19.3

100
0.02 ,
23 150 ?

20.1

0.1%- (=1.00
/).

20.2


HBrO, 0.001 5.85.

20.3

BrO- , 200
0.01 HBrO 0.005 HBr.

21.1

LiOH 1 ,
11?

21.2

NH4OH
1.8% 11.
.
85

21.3

NH4Cl 1
,
10 ?

22.1

, 100
0.5 Cl2.

22.2

HBrO ,
HBrO 0.01
0.0447%.

22.3

BrO 1
, HBrO
10 ?

23.1


200 , 2.5?

23.2

N
0.089% 6.05.
.

23.3

N 1
,
200 ?

24.1

5.2%- 23 (=1.044 /).

24.2

10 0.02
23,
2 ? ?

24.3


,
0.001 ?

25.1

0.2 .

86

25.2

H2S
, 5.3.

25.3

NaHS 750 0.001 H2S,


10 ?

8.

, , ,
.
,
.
.

: ,
,
- .
1 .
1
Na2CO3 ( ).
I :
32-+2 3- + (- )
Na2CO3 + H2O NaHCO3+ NaOH
( )
2 :
HCO3-+ H2O H2CO3 + OHNaHCO3 + H2O H2CO3 + NaOH.
(- 32-)
, I - (3- ), 2
- (H2CO3).

87

- (-),
(7).
2
NH4Cl ( )
NH4++H2O NH4OH + H+
NH4Cl + H2O NH4OH + HC1.
3
rCl3 ( , 3,
). Cr 3+ - ,
-, Cr(OH)2+, Cr(OH)2+
Cr(OH)3. I :
Cr 3++H2O Cr(OH)2++H+.

CrCl3 + H2O CrOHC12 + HC1.
7.
4
Al(CH3COO)3 ( )
Al3++3CH3COO- + 3H2O Al(OH)3 + 3CH3COOH
-
( 7), ,
.
.
(), (h)
(W)
() + -
:
) ( )
= W/a,
h (/),
-= h C (),
+ W/-,
- ;

88

) ( )
= W/b,
h (/),
+ = hC(),
b - ;
) (
)
= W/(ba).

1.

h1. , h

=C h2/(1-h).
2.
,
, ,

HPO42- + H2O H2PO4- + OH


H2PO4- HPO42- + H+.
( -
,
).
5
0,1
.


89

3-+2 3 + -.
a=1,810-5.
= W/a = 10-14 /(1,810-5) = 5,56 10-10 .
h = (/) = (5,5610-10 /0,1) = 7,510-5.
- = hC = 7,510-50,1 = 7,510-6 /.
+ = W/- = 10-14/(7,510-6) = 1,3310-9 /.
= -lg+ = - lg 1,3 10-9 = 8,88.
6
0,1 34.

I
PO43-+H2O HPO42-+ OH-,

a3(34) = 1,3 10-12.
= W/a3 = 10-14/(1,310-12) = 7,710-3.
5.
,
+ -, ,
,
.
.
7.
:
I : Zn2++H2O ZnOH++H+
2 : ZnOH++H2O Zn(OH)2 +H+.
ZnCl2 , -
+ . , ..
2 , Zn(OH)2.

90

(ZnCl2) ,
+ , ..
.
+ ( -) ,
( ), ,
,
.
,
,

8
Zn(NO3)2 Na2CO3
.

I : Zn2++H2O Zn(OH)++H+,
2 : ZnOH++H2O Zn(OH)2 +H+ .

I : CO32- + H2O HCO3-+OH-,
2 : HCO3-+H2O H2CO3 + OH-.

+ + -2
, ( ,
CO2 H2O)
Zn2++CO32-+H2O Zn(OH)2 + CO2

Zn(NO3)2 + Na2CO3 + H2O Zn(OH)2 + CO2 + 2NaNO3.

1. -
I .
(, 7).

91

2. (),
.
3.
( /).
4. (
!).
5. ,
?
6. -
,
.


(/)

1
NH4Cl
0,1
5 + 12
2
KF
0,01
6 + 16
3
KCN
0,001
7 + 16
4
NaNO2
0,02
8 + 18
5
ZnCl2
0,03
10 + 18
6
CrCl3
0,05
11 + 19
7
AlCl3
0,06
5 + 18
8
FeCl3
0,07
5 + 15
9
NH4NO3
0,002
2 + 19
10
CuJ2
0,003
3 + 10
11
Na2CO3
0,004
10 + 11
12
KNO2
0,005
8 + 16
13
RbCN
0,006
8 + 16
14
CsF
0,007
10 + 15
15
Rb2SO3
0,04
7 + 15
16
Rb3PO4
0,08
18 + 19
17
Na2Se
0,008
16 + 19
18
Na2S
0,009
10 + 16
19
BeCl2
0,07
7 + 11

92

20

CH3COONa

0,08

6 + 18

9. . -


.
:
)


;
) ,
;
) ,
.
.
S(x).
1

20 50,00 8,05 .
Na2SO4 ,
.

S(Na2SO4) = 8,05/50,00 100% = 16,1% -


.
S(Na2SO4) = 8,05/(50,00+8,05) 100% = 13,9 % -
.
2

18 200
32,66 .
Na2SO4 18.

93



S(Na2SO4) = (32,66 /142 /)/0,2 = 1,15 /.
3
100 6,985
.
.

6,985 2 :
VO2 = (6,985 / 32 /)22,4 = 4,90 .
100 , ,
, 1 , 0,049 / =49 /.
4
1 KNO3
450 . KNO3
25 . KNO3
25 38,5 % .

:
m(H2O) = 1000 - 450 = 550 .
KNO3 ,
:
m = 550 0,385 = 211,8 .
:
m = 450,0 - 211,8 = 238,2 .
-. .

, . .
.

mn (T) mn+ (P)+nm- (P).
94

():
=n+mm-n.

, .
,
.
5
20 810-9.
( / /)
.

S(/), ,

PbJ2 () Pb2+() + 2J-() ,
PbJ2 S / Pb2+
2S / J-,
= Pb2+ J- 2 = S (2S)2 = 4S3,
S = ( /4)1/3=1,3 10-3 /.
PbJ2 461 /,
PbJ2, /, 1,3 10-3 461=0,6 /.
6
18 1,7 10-4 /.
18.

Mg(OH)2 1
Mg2+ 2 -:
Mg(OH)2() Mg2+()+ 2 -() ,

95

Mg2+ = 1,7104

/; - = 3,410-4 /, ,

= Mg2+ - 2 = 1,710-4 (3,410-4)2 = 1,96 10-11.


7
SO4 6,110-5.
0,01 1 2
0,02 Na2SO4?

2
,
2 :
12 = 0,005 /; Na2SO4 = 0,010 /.

1 2 Ca2+ +21-,
Na2SO4 2 Na+ + SO42-,
Ca2+ = 0,05 /; SO2-4 = 0,01 /
Ca2+ SO2-4 = 0,005 0,01 = 5 10-5
.

-
, .
, -

. ,
.
8
Ag+ AgCl,
NaCl 0,1 /.

96

AgCl() 1-() + Ag+()


1 - Ag+.
NaCl
1-,
NaCl AgCl. NaCl

NaCl Na+ + 1-,

NaCl, .. 0,1 /, . . ,
AgCl, ,
1 - 0,1 /,

= 0,1 [Ag+] [Ag+]=/0,1=1,210-10/0,1=1,210-9 /.

1.

2.

3.

4.

5.

25 100 11,2 .
Na2CO3 ,
.
1 = 20,
120 2 80 1.
.
20 100
, K2SO4
0,18.
100
113,6 % .
800 KHSO4 ?
30 40,0 %
. ,
500 NaNO3 ?
97

6. (II) 100
127,3 % .
750 ?
7. 60 46,4 %
. 1 22
400 ?
8. 20 250
50 .
1 2 20.
9. 100
25,
2 / ?
10. ()2 18 0,02 /.
()2 500 ,
?
11. PbJ2 18 2 10-3 /.
,
1,00 PbJ2 ?
12. 10 2 0,3 N2.
.
13.
300 , ,
, 34,5 / ?
14.
K2Cr 2O7 40,0 % .
K2Cr2O7 1
20 ? 20
11,1 % .
15.
Na2SO4 30,0 % .
Na2SO4102 1,2
18 ? Na2SO4
98

15 11,7 %, 20 - 16,1 %
.

1.
2.

3.
4.
5.
6.
7.

-.
AgBr 4,010-13.
Ag+ AgBr.
PbCO3 1,510-13 .
Pb2+, 1
PbCO3, .
PbJ2 8,710-9.
Pb2+ J- PbJ2.
1,16 PbJ2 2 .
PbJ2.
3
3, 100 .
3 8,910-5 /.
3.
Ag2SO4 2,6810-2 /. .

8. (JO3)2 2,810-4 /. .
9. PbJ2 1730 .
.
10. 500 PbF2 245
. .
11. Ag2Cr2O7 2,010-7.
0,01 AgNO3
2Cr 2O7 ?
12. , 0,02
AgNO3 1 H2SO4 ? (Ag2SO4)
= 210-5.

99

13. 50 0,001 1 450 0,0001 AgNO3. ?


(AgCl)=1,810-10.
14. , 0,1
Pb(NO3)2 0,4 NaC1?
(PbCl2 )=210-5.

1.

2.

3.

4.

5.
6.
7.

8.


3 4,810-9.
2+ 0,01 Na2CO3,
3.
Cu(JO3)2 1,410-7.
JO3- Cu(JO3)2,
CuSO4
0,05 /.
PbJ2 8,710-9.
, J-
PbJ2 500 0,02 KJ ?
MgCO3 1,010-5.
32-
MgCO3, MgCl2 0,01 /.
CaSO4 1,010-5.
SO4 0,2 2SO4.
Mg(OH)2 3,410-11.
Mg(OH)2 0,001 .
Pb12 1,610-5.
1 -
Pb12, Pb(NO3)2 0,02 /.
, 242-
24 100 0,01
Na2C2O4, ( 24)=2,610-9.
100

9.
AgCl,
, 1 -
0,03 / ?
10. 2+
CrO4,
, CrO42-
0,015 /.
11. , Sr 2+
SrCrO4 200 0,02
2CrO4, (SrCrO4) = 3,510-5.
12. CdO3 5,210-12.
32-
Cd3, Cd(NO3)2 0,02
/.
13. 0,01 2SO4 ,
0,01 / 1 2 0,01 / SrC12.
- SrSO4 SO4 ?
14. F2 0,05 1 2.
,
?
15. AgC1 0,001 NaCl
, ? (AgC1) = 1,810-10.

10.

,
. ,
, ,
, .

101

:
-,
- ,

,
,

(..). .. =
6; 4; 2, 3; 8; 12. -
d- (Fe2+, Fe3+, Co3+, Ni2+, Zn2+, Ag+, Cu2+,
Cr 3+ .). : H2O, NH3, Cl-, OH-, NO2-, CN-, Br-,
J- . :
K4Fe(CN)6;
K3Fe(CN)6; NaAl(OH)4; Cr(H2O)5ClCl2;
Cu(NH3)4SO4; K2NiCl4).

.


.
:
, - .
:
( :
, , , , ..)
(- - , CN- , CNS- - , NO2 - , S2O32- - , l- -
..);
(2 - , NH3 - );
,
. : Pt(NH3)3ClCl -

(II);
(NH3)5BrSO4

(III).

102

. : BaCr(NH3)2(SCN)42 -
(III) , (NH4)2Pt(OH)2Cl4 - (IV)
.


().
,
:
K4Fe(CN)6 4K++Fe(CN)64- ,
Cu(NH3)4SO4 Cu(NH3)42++SO42-.

() .
:
Cu(NH3)42+ u2++ 4NH3 .


:
K = Cu2+NH34/(Cu(NH3)42+) = 2,14 10-13.

. , .
: ,
; .
,
, ,
. ,

g(NH3)2Cl + 2KCN Kg(CN)2 + 2KCl + 2NH3


, ..
g(NH3)2+ = 9,3 10-8 g(NH3)2- = 8 10-22.

103

, Ag+
(CN-), (NH3).
.

.
1
2Cd(CN)4 + 2NaOH Cd(OH)2 + 2KCN + 2NaCN,

Cd(CN)42-+2OH- Cd(OH)2 + 4CN- .
2Cd(CN)4
(.. - ) d(OH)2
, ..
=CN-4/ (Cd(CN)42-OH-2) =
=CN-4/(Cd(CN)42-OH-2)(Cd2+/Cd2+)=
= Cd(CN)42- / [Cd()2]= (7,8 10-18)/(4,5 10-15)=1,7310-3
1.

.
2
2Cd(CN)4 + Na2S CdS + 2NaCN + 2KCN
Cd(CN)42- + S2- CdS + 4CN-.
(Na2S) 2d(CN)4
dS, ..
=CN-4 / (d(CN)42- S-2) (Cd2+/Cd2+) =
=/= (7,810-18)/(810-27) 1.
3
g+ 0,1
[Ag(NH3)2]NO3, 1 / .
[Ag(NH3)2]+ 5,7 10-8.

104



[Ag+] [NH3] 2 / [ [Ag(NH3)2]+] = 5,7 10-8.
NH3
[Ag(NH3)2+] ? Ag+ + 2NH3
,
NH3,
, 1 /.
[Ag(NH3)2]NO3
, ,

[Ag(NH3)2]+ , . . 0,1 /,

[Ag+] 12 / 0,1 = 5,7 10-8; [Ag+] = 0,6 10-8 /.


I

1) ( , ,
);

105

2)
;
3) ;
4) ;
5)
();
6) .

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20


K2HgJ4
Cu(NH3)4SO4
K4Fe(CN)6
K3Fe(CN)6
Ag(NH3)2 C1
KAg(CN)2
K2Ag(NO2)2
K2Cu(CN)4
Co(NH3)5(H2O)C13
Co(NH3)5C12
PtC1(NH3)3C1
CoBr(NH3)5SO4
CoSO4(NH3)5NO3
(NH4)3RhC16
Na2PdJ4
K3[CoSO4(NO2)4(NH3)2
K2PtC1(OH)5
Na3Co(CN)6
Na3Ag(S2O3)2
BaCr(SCN)4(NH3)22
2

106

1).
- ,
.
.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20


Cu2++NH3
Cu2++CN-
Ag++NH3
Cu++NH3
Sn2++OH-
Ag++S2O32-
Be2++OH-
Zn2++OH-
Cr3++OH-
Be2++F-
Co2++SCN-
Hg2++J-
Fe3++CN-
Fe3++F-
Ni2++NH3
Cd2++NH3
Pb2++OH-
Cr 3++H2O
Al3++F
Ni2++CN-

2). ,
, ,

107

(,
.

1
Cr(NH3)4(H2O)C13
2
KCo(NH3)2(NO2)4
3
Co(NH3)5(NO2)3
4
Cr(H2O)4C13
5
Pt(NH3)6C14
6
CoC1(SO4) 5 NH3

..),

6
6
6
6
6
6

CoC1(SO4) 5 NH3

8
9
10
11
12
13

Cr(H2O)5C13
NaCo(NO2)4(NH3)2
Cr(NH3)3(H2O)2C13
KPt(NH3)C15
PdC12(NH3)3
Co(SO4)(NO3)(NH3)5

6
6
6
6
4
6

14
15

Cu(NH3)4(NO3)2
PbC12(H2O)(NH3)2

4
4

16
17
18
19
20

CoNa3(CN)6
AgBr(NH3)2
Na3(S2O3)2Ag
Na3(OH)6Cr
KAg(CN)2

6
2
2
6
2

12

AgNO3

12

gNO3

Cl


(
108

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

)
Hg(NO3)2 + KJ
Cu(OH)2 + NH4OH
Fe(OH)2 + KCN
Ag2O + NH4OH
AgCl + KCN
Fe(OH)3 + KCN
Zr(OH)4 + KF
AgCl + NH4OH
Al(OH)3 + NaOH
Be(OH)2 + NaOH
BeF2 + KF
Zu(OH)2 + NaOH
Zu(OH)2 + NH4OH
CoCl2 + NH4CNS
Cr(OH)3 + NaOH
AgBr + Na2S2O3
Co(NO3)2 + NH4OH
NiSO4 + NH4OH
ZrF4 + KF
Cd(OH)2 + NH4OH

4
4
6
2
2
6
6
2
4
4
4
4
4
4
6
2
6
6
6
4

4
-
. ,
.
:

().

109

1
2
3
4
5
6
7
8
9
10
11
12
13

K3Fe(CN)6 + NaOH
u(NH3)4 SO4 + Na2S
Ag(NH3)2OH + KJ
K4Fe(CN)6 + NaOH
KAg(CN)2 + KJ
KAg(CN)2 + K2S
K2HgJ4 + KBr
K2HgJ4 + KCN
Ag(NH3)2C1+ K2S2O3
KAg(CN)2 + K2S2O3
KAg(CN)2 + NH3
KAg(NO2)2 + NH3
Ag(NH3)2C1+ NiC12

14

K3Cu(CN)4 + Hg(NO3)2

15
16
17

Ag(NH3)2NO3 + KBr
K4Fe(CN)6 + Na2S
Cu(OH)2 + Na2C2O4

18
19
20

KAg(CN)2 + 1
Ni(NH3)6SO4 + (NH4)2S
Ni(NH3)6SO4 + NaOH

e
e
C2O42- (-)
e
e
e

5
1.

2.

[Cd(CN)4]2- c 7,8 10-18.


0,1 -
K2[Cd(CN)4], 0,1 KCN
.
[Ag(CN)2]- 1,4 10-20.
0,05 -

110

3.

4.

5.

6.

7.

8.

9.

10.

K[Ag(CN)2], , , 0,01 KCN


.
[Ag(S2O3)2]3- c3,5 10-14.
1 0,1 Na3[Ag(S2O3)2], , , 25
Na2S2O3 5H2O.
[Ag(NH3)2]+ 5,7 10-8.
0,08 -
[Ag(NH3)2]NO3, , , 0,8 ?
NaCl 1
AgCl?
AgCl 1,8 10-10.
0,05 -
K2[Ag(CN)3], , , 0,05 KCN?
[Ag(CN)3]2- 2,8 10-21.

AgCl 0,1 - [Ag(NH3)2]NO3, 1
1 ? AgCl = 1,8 10-10.

1 0,1- [Ag(NH3)2]NO3, 1
: ) 1 10-5 ; ) 1 10-5 ? AgBr
= 5,3 10-13, AgI = 8,3 10-17.
S2-
CdS 0,05 - K2(Cd(CN)4],
0,1 KCN 1 ? CdS= 7,9 10-27.
[Cd(CN)4]2- 7,8 10-18.
1 0,1 [Ag(NH3)2]NO3, 1,5 KCl 1
?
AgCl = 1,8 10-10.

1 0,01 - K2[HgI4], 0,05 KI,

111

11.

12.

13.

14.
15.
16.

17.

18.

S2-, 1
CdS?
[HgI4]2- 1,5 10-31. CdS = 7,9 10-27, HgS= 1,6 10-52.
,
1 0,01 K2[Ag(CN)3], 0,02
KCN, 1 10 -3 KI?

10 MnS?
[Ag(CN)3]2- c 2,8 10-21.
AgI, Ag2S MnS
8,3 10-17; 6,3 10-50 2,5 10-10.
Cl [Cr(H2O)4Cl2]
20 . 0,1 . AgNO3.
?
AgNO3 Cl-
[Cr(H2O)5Cl]Cl2?
NH3, 9,75 Cu(OH)2?
NH3, 0,1 AgCl?
,
0,005 - [Zn(NH3)4](NO3)2, 0,05
NH3, 0,001 - K2CO3?
[Zn(NH3)4]2+ 2 10-9.
ZnCO3 6 10-11.
S2-
FeS 0,003 - K4[Fe(CN)6],
0,01 KCN 2 ? FeS = 3,7 10-19, [Fe(CN)6]4- =
1 10-24.
CdCO3, 2 0,05 K2[Cd(CN)4], 0,6 KCN,
1 0,03 - K2CO3? [Cd(CN)4]2- = 7,66 10-18;
CdCO3 = 2,5 10-14.

112

19.

20.

NaCN 1 0,005 Na2[Ni(CN)4], 0,004 NaOH


2 Ni(OH)2?
Ni(OH)2 = 1,6 10-14, [Ni(CN)4]2- = 1 10-22.

[HgCl4]2- 6,0310 16
. (II), 1
0,005 K2[HgCl4], 0,002
KCl, 1 0,005- K2S?
(II), 1
0,02 KOH? HgS = 4,010-53;
Hg(OH)2=110-26

11.

:
n - ,
;
L - () ,
0 (n-1);
mL - ,
- L + L ( 0);
ms - , +1/2 -1/2.
,
. ,

,
.
,
95%. ,
.

113

,
95%.

().
n L
.


()
( R) . (Z) ,
-1/n2 Rn2.

(. )
. : s - , p , d -
, f - .
.

. ml
.

,
, (
) ().

(): s-. 1s-.
1s

114

( 1 , ).
(L): s- p-. -
:
(px) , - (py), -
z (pz). s- 2s-. -
2-.

2s
2px 2py 2pz
(): s- (3s-), -
(3-), d- (3d-).

3s
3px 3py 3pz
3dxy 3dxz 3dyz 3dx-y 3dz
(N): s- (4s-), (4-), d- (4d-), f (4f-).

(, , Q ...)
(g, h ....),
s-, -, d- f-.
, ,
.
, , ,
.

.

115

1. :
,
.
.
1). ,
(n+L).
2).
(n+L) , n.

:
1s
2s2p
3s3p
4s3d4p
5s4d5p
6s4f5d6p
7s5f6d7p
2. :
,
. :
,
ms .
3. :

.

,
.

, , ,

116

, .
4s 3d; 5s 4d; 6s, 5d 4f ; 7s, 6d 5f.
1
.

7, , 7
.

, 5
, 2s- 3-, ,
, -
:


1s22s22p3 .
, 2- .
, ,
.
,

2s22p3.
22.

:

117

3s- 3p-:

4s-

3d:

,
:


L3s23p63d24s2 .

s- ,
s-. p, d- f-.

.
. , ,
- , .
s- ().
s-() - ()
d- (). s-
( ) d-,
f- (

118

- ),
d- , , .
8 , -
. s -, - d-.
- 1-3 .
.
(
).



. - ,
. ,

. s- -
. d d-
s- - . f-
(n-2)f-, (n-1)d-, ns- np-, n-

,
.
- , .
2

( ).

.

119

1). .
16. ,
, . , -,
- , .
.

n=3, . . .
:
n=3, L=0 ( s-), ml=0 ( s
), ms=+1/2 (
);
n=3, L=0, ml=0 ( ,
, . . ), ms= -1/2
( , );
n=3, L=1 ( -), ml=+1 ( ml=
1, 0 - , ), ms= +1/2;
n=3, L=1, ml= +1, ms=-1/2;
n=3, L=1, ml= 0 ( -), ms= +1/2;
n=3, L=1, ml= -1 ( z-), ms= +1/2.
.
,
. ,
II. - .
,
,
, ,

120

-2. , . .
. ,
(S* )

IV, (S**) VI:

,
, ,
,
+6.
2). .
26. ,
, . d-,
d- .
() 3d- (,
d-) 4s- ():

:
n=3, L=2, ml= +2, ms= +1/2;
n=3, L=2, ml= +2, ms= -1/2;
n=3, L=2, ml= +1, ms= +1/2;
n=3, L=2, ml= 0, ms= +1/2;
n=3, L=2, ml= -1, ms= +1/2;
n=3, L=2, ml= -2, ms= +1/2;
n=4, L=0, ml= 0, ms= +1/2;
n=4, L=0, ml= 0, ms= -1/2.

121

,
(II)
:

, ,
4
3d-. ,
VI.

,
+2 ( 4s-)
+6 ( 4s- 3d-).


1. . ml ms 2 ?
.
( ).
. 1s- 2s-?
2. . s- d . .
. d-
( ).
. s- f-.
3. . ml ms 3 ?
. d-
( ).
. p- d-.

122

4. .
l=3
?
. d-
( ).
. d-.
5. . ?
. f-
( ).
. -.
6. . ( )
l=0?
.
( ).
. 2- 3-?
7. .
?
.
( )?
. 2x 3s-.
8. . ( )
l=1?
.
( ).
. y dxy .
9. . ( )
l=1?
.
( ).
. pz dxz .
10.. s, p, d, f ?
?

123

. d-
( ).
. 4dyz 3s-.
11..
: 3p, 3d, 4s, 5f, 2p, 4f, 5d?
.
( ).
. 2 3 .
12.. 4f ?
. d-
( ).
. 2- 3-.
13..
4d- ?
.
( ).
. 2z- 3pz-.
14..
3?
.
( ).
. 3dxy- 4dxy-.
15.. ?
. d-
( ).
. 3dxz- 4dxz-.
16.. ?
.
( ).
. 3dyz- 4dyz-.

124

17.. ,
.
.
( ).
. d(x2)- d(x2-y2)-.
18..
: 1s, 3d, 2d, 4f, 5f, 1p, 3p, 3f. .
.
( ).
. 3d(x2)- 4d(x2)-.
19. .
.
.
( ).
. 3d(x2-y2)- 4d(x2-y2)-.
20. . l
: 3p, 3d, 5f, 2s, 4d,4f?
.
( ).
.
?
21. . - f . .
. d-
( ).
. ?
.
22..
.
. d-
( ).
. 1s- 2s-.

125

23.. l
: 1s, 3s, 4s, 4f, 4p,3d, 4f ?
. f-
( ).
.
? .
24. .
: 3d, 1s, 5p, 2s, 4f.
. d-
( ).
. 2 3 .
25..
, : 2s, 2p, 3p, 3f, 2d, 5f, 6p.
.
. d-
( ).
.
: 1s 2s, 2s 3s? .

1). , ,
.
2). (s, p, d, f) ?
3). .
4). ?
5). .

126


1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

30
13
7
17
43
10
47
8
38
14
48
92
71
80
87
64
54
94
9
19
66
88
45
62
78
36
96
16
85
76

35
44
59
63
56
93
65
69
57
20
60
46
12
61
95
79
11
15
67
58
77
68
90
86
70
91
18
89
37
84

127

81
83
73
24
75
35
52
74
33
41
50
34
21
32
26
53
28
72
82
39
31
27
51
29
49
25
42
22
23
40

1.
(0.1 N)

2
()
33

I
II
III


() HVO3

22

H2WO4

H2GeO3

1,8 10-16
5,3 10-10
1,8 10-13
1,6 10-14
3 10-5
2,4 10-12


() H2SiO3

24

H2SO3

24

() 34

128

1 10-13

2,6 10-9

II
I

1,9 10-3
2 10-3

II
I

1 10-12
1 10-2

1,7 10-2

II
I

6,8 10-8
2,9 10-7

II
I

6,5 10-12
7,9 10-3

II

1 10-7


1

2CrO4
-
HCN

23

3

224

H2S
HSe
NH4OH

()2

ND4OD

AgOH

Pb(OH)2

III

4,5 10-12
3,2 10-8

1,8 10-10

II

3,2 10-17
4,8 10-10

4,3 10-7

II

5,6 10-11
1,76 10-5

5,9 10-2

II
I

6,4 10-5
8,7 10-8

II

3,6 10-13
1 10-11
1,79 10-5

5 10-6
1,1 10-5

5,3 10-3

129

1 10-3

II
I

2 10-8
4 10-5

Zn(OH)2
II
BeOH+
CuOH+
CrOH2+
AlOH2+
FeOH2+

HF

HNO2

HCOOH

1,5 10-9
5 10-11
3,4 10-7
1 10-10
1,38 10-9
1,35 10-12
6,8 10-4
5 10-4
2,1 10-4

2.
25

Ag2S
AgJ
AgBr
AgCl
Ag2CO3
BaCO3
BaSO4
Be(OH)2

1,6 10-49
1,5 10-6
7,7 10-13
1,7 10-10
5 10-12
8 10-9
1 10-10
2,7 10-10

130

4,8 10-9
2,6 10-9
3,2 10-11
1 10-5
2,5 10-14
1 10-21
2 10-16
1 10-12
2 10-14
5,6 10-20
4 10-38
4,8 10-16
4 10-38
4 10-19
5 10-21
2 10-28
1,7 10-3
1 10-5
3,2 10-11
2,5 10-13
5,6 10-16
2 10-28
1,6 10-14
1 10-28
2,8 10-7
1,5 10-4

CaCO3
CaC2O4
CaF2
CaSO4
CdCO3
Ce(OH)3
Co(OH)2
CoCO3
Cu2S
Cu(OH)2
CuS
Fe(OH)2
Fe(OH)3
FeS
La(OH)3
La2(C2O4)3
Li2CO3
MgCO3
Mg(OH)2
MgNH4PO4
MnS
NiS
Ni(OH)2
Sc(OH)3
SrSO4
TlCl

3.

131


Fe(CN)64Fe(CN)63Fe(SCN)2+
Co (NH3)62+
Co (NH3)63+
Co (CN)42Ni (NH3)62+
Zn (CN)42Cd (NH3)42+
Cd (CN)42CdCl42CdI42Ni (CN)62Cu (NH3)42+
Cu (CN)43Ag (NH3)2+
Ag (CN)2Ag (S2O3)23Zn (NH3)42+
Hg (CN)42Hg (SCN)42HgBr42HgCl42HgI42-

K
1 10-27
1 10-44
5 10-3
8 10-6
6 10-36
8 10-20
2 10-9
2 10-17
8 10-8
1 10-17
9 10-3
5 10-17
3 10-16
5 10-14
5 10-28
9 10-8
1 10-21
1 10-13
4 10-10
4 10-41
1 10-22
2 10-22
6 10-17
5 10-31

4. -
25

,

2
132

,
3

MnO4- +8+
MnO4- + 4+
MnO4- + 22
MnO4MnO2+4H+
Cr2O72- +14H+
CrO42- +4H2O
NO3- + 4H+
2NO3-+12H+
NO3- + 10H+
HNO2+H+
NO3- + 3H+
S2O82H2SO3+4H+
SO42-+8H+
SO42-+4H+
S4O62S+2H+
S
2SO3 +3H2O
F2
2HClO+2H+
Cl2
ClO4-+2H+
ClO-+H2O
2HBrO+2H+
2BrO3-+12H+
Br2
BrO-+H2O
BrO3-+3H2O
2JO3-+KH+
JO3-+6H+
J2
JO3-+3H2O

MnO4- + 8H+ +5 e- = Mn2++4H2O


MnO4- +4H++3 e- = MnO2 +2H2O
MnO4- +2H2O+3 e- = MnO2+
4OHMnO4 + e - = MnO42MnO2+ 4OH++ 2e- = Mn2++2H2O
Cr 2O72- + 14H++6e- = 2Cr 3++7H2O
CrO42-+4H2O+3e- = Cr(OH)63+2OHNO3- + 4H+ + 3e- = NO + 2H2O
2NO3-+12H++10e- = N2+6H2O
NO3- + 10H++8e-=NH4++3H2O
HNO2+H++e-=NO+H2O
NO3- + 3H++e-=HNO2+H2O
S2O82- +2e-=2SO42H2SO3+4H++4e-=S+3H2O
SO42-+8H++6e-=S +4H2O
SO42-+4H++2e-=SO2+2H2O
S4O62- +2e-=2S2O32S+2H++2e-=H2S
S+2e-=S2SO32-+3H2O+4e-=S+6OHF2+2e-=2F
2HClO+2H++2e-=Cl2+2H2O
Cl2+2e-=2ClClO4-+2H++2e-=ClO3-+H2O
ClO-+H2O+2e-=Cl-+2OH
2HBrO+2H++2e-=Br2+2H2O
2BrO3-+12H++10e-=Br2+3H2O
Br2+ 2e-=2BrBrO +H2O+2e-=Br-+2OHBrO3-+3H2O+6e-=Br2-+6OH2JO3-+KH++10e-=J2+6H2O
JO3-+6H++6e-=J-+3H2O
J2+2e-=2JJO3 +3H2O+6e-=J-+6OH-

133

+1,51
+1,69
+0,60
+0,56
+1,23
+1,33
-0,13
+0,96
+1,24
+0,87
+0,99
+0,94
+2,01
+0,45
+0,36
+0,17
+0,15
+0,14
-0,48
-0,90
+2,85
+1,63
+1,63
+1,19
+0,89
+1,59
+1,52
+1,08
+0,76
+0,26
+1,20
+1,09
+0,54
+0,26

Co3+
Fe3+
Fe(OH)3
PbO2+4H+
SnO32-+6H+
O2+2H+
O3+2H+
O3+H2O
H2O2+2H+
H2O2

CO3++e-=Co2+
Fe3++e-=Fe2+
Fe(OH)3+e-=Fe(OH)2+OHPbO2+4H++2e-=Pb2+2H2O
SnO32-+6H++2e-=Sn2++3H2O
O2+2H++2e-=H2O2
O3+2H++2e- = O2+H2O
O3+H2O+2e-=O2+2OHH2O2+2H++2e-=2H2O
H2O2+2e-=2OH-

+1,84
+0,77
-0,56
+1,45
+0,15
+0,68
+2,07
+1,24
+1,77
+0,88

5. 0f , S0
G0f

0f,
/

S0,
-1-1

G0f,
/

Br2 ()
Br2 ()
()
()
Cl2 ()
F2 ()
2 ()
N2 ()
Na ()
O2 ()
O3 ()
S ()
S ()
()
2 ()
Cl2 ()
COS ()
4 ()
CCl4 ()
24 ()

0
30.9
0
1.89
0
0
0
0
0
0
142.3
0
0
-110.5
-393.5
-223.0
-137.2
-74.85
-139.3
52.28

152.3
245.3
5.73
2.38
223.0
203.3
130.6
191.5
51.4
205.0
238.8
31.88
42.44
197.4
213.6
289.2
231.5
186.2
214.4
219.4

0
3.14
0
2.89
0
0
0
0
0
0
163.2
0
0
-137.2
-394.3
-210.4
-169.2
-50.75
-68.2
68.11

134

HCl ()
HF ()
2 ()
2 ()
22 ()
2S ()
2S4 ()
2S ()
NH3 ()
(N4)2S4 ()
NO ()
NO2 ()
N2O ()
NaCl ()
SO2 ()
SO3 ()

-92.3
-268.6
-241.8
-285.8
-187.0
-20.15
-811.3
85.52
-46.19
-1179.0
90.37
33.89
81.55
-410.9
-296.9
-395.2

186.7
173.5
188.7
70.08
105.8
205.6
156.9
221.3
192.5
220.3
210.6
240.4
220.0
72.36
248.1
256.2

-95.19
-269.9
-228.6
-237.3
-120.4
-33.01
-690.1
71.13
-16.61
-900.8
86.57
51.84
103.6
-383.9
-300.4
-370.4

1.
2.

.. . - .:, 1989.
.. . .:, 1985.

135

1.
2.

. ............................................ 3

..10

............................................................

3.


..21

4.

.....................................24

5.


.39

6.


.....................................59

7.

.
...75

8.

.................................................................... ..91

..............................

........................................................

136

9.

. ......................
..98

10.

....................................................

107

11.

.............................................
.120
............................................................................136
.............................................................................145

..
020713
27.04.1998

6084/16

. .. 9,68

1000 .

, 249020, ., .,6

137