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..

-
2004 .

: ..



43

29.01.04

1.

1.1.

1.2.

12

1.3.

13

1.3.1.

13

1.3.2.

13

2.

14

2.1.

14

2.2.

17

2.3.

21

2.4.

23

2.5.

24

3.

26

3.1.

26

3.2.

28

3.3.

30

3.4.

32

3.5.

32

3.6.

35

4.

37

5.

39

5.1.

39

5.2.

40

5.3.

42

5.4.

42

5.5.

43

6.

44

6.1.

44

6.2.

45
3

6.3.

45

6.4.

45

6.5.

46

6.6.

46

7.

47

7.1.

47

7.2.

48

7.3.

48

7.3.1.

48

7.3.2.

()

49

7.3.3.

49

8.

49

8.1.

49


8.2

51

8.3

51

8.4.

51

8.5

52

8.6.

52

9.

53

9.1.

53

9.1.1.

53

9.1.2.

54

9.2.

55

9.2.1.

56

9.2.2.

56

9.2.3.

57

9.2.4.

57

9.3.

57


9.3.1.

58

9.3.2.

59

10.

63

66

n+ -

[R],[Ox] - R Ox
- -
, , ba, b -
-
D -
pMMn+/M
pMOx/R

- , R

-
-
-
-
-
-
G
r
iOx
s
iR
r
iM n +
s
iM
i0M

n+

- -
-
- R
- // Mn+
- //
/M

i0Ox / R

-
- , R

iR

- R

iOx - Ox

iH 2 - H2
i O2 -
5

i -

i -
id -

I - (. i)
j -

J -

-
-
R -
S

, -
-
-
R - R
- , .. ,



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

.. .
..
.

,
,
2-4%
.
, , ,
.

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

.

. - ,
, - . ,

. ()
.

, ,
.
,
. : ( /2),
(/), ( /), (/2),
, , ,
.
8

:
(, , , , )
( , , , , , ,
, .); : , ,
, ( , , ),
, , , ,
; : ,
, , .
: (
),
( ,
), (
), ( ),
( ), ( ).
1.
,
( 2)
. .
t ,
- .
1.1 ,


, (1) G< 0.
(2) (3)
mM +

mn
O2 = MmOmn/2 (1)
4

G = RTln(PO2)-mn/4 RTln(PO2)-mn/4
PO2 > PO2

(2)
(3)
9

n , PO2 - 2 , PO2
, .. .
PO2 >> PO2. Au, Ag Cu t.
, ..
: , .
, .
VM VMmOmn/2
1< VMmOmn/2/ VM < 2,5

(4)

<1 , 2,5 ,
.
, .. .
:
, ,
, n+ 2- , .
.
.

:
d/d = kcCox

(5)

= 0 + kcCox

(6)

- , 0
= 0 ( ), 00, kc .
( ), <1,
(W, Mo) .
() . , ,
, -
DO2- DMn+. .

d/d = kcC = D (C0 C)/

(7)

10

C0 C .
(7) ,
- :
2/2D + / kc = const + C0

(8)

const=0 (9) (10)


2 + k1 = k2

(9)

p = k ,

(10)

1 < p< 2. D >> kc, (8) (6), D << kc , ..


, =0, - (11).
2 = 2DC0 + const

(11)

t < 150-300C ,
. Mn+ - 2 -
.
.

:
d/d = k3C exp (-p)

(12)

= const + k4lg

(13)


(14), (15) n- (16), (17)
p-.
d/d = 1/

(14)

2 = 21 + const

(15)

d/d = 2/2

(16)

3 = 32 + const

(17)

n-
, ,
:
-1 = 3 k5 ln

(18)

, , ,
: , -, ,
.
11

,
, , Fe|FeO|Fe3O4|Fe2O3|O2.
1.2.

. < 1
. ( Fe, Ni, Cu,
Mn, Ti) t
. .
(Zn, Al,
Cr) ,
. V, W, Mo, Ru, Os
. .
,
2 2
.
2 .
, ,
:
Fe3C + CO2 3 Fe + 2 CO

(19)

Fe3C + H2O 3Fe + CO + H2

(20)

Fe3C + 2H2 3Fe + CH4

(21)

.
. CO,
H2 CH4 .

.
,
-
H2 CH4. ,
.
(22), (23), V2O5 ,
, .
4Fe + 3 V2O5 2 Fe2O3 + 3 V2O3

(22)
12

V2O3
1.3.

+ O2

V2O5

(23)

1.3.1.
, ,
.
, , ,
.
.
, .

.
1.3.2.
- ,
, .
.

, .
(
2, 2 , N2 .), .
,
. ,
. ,
t t .
:
, ;
; .
,
, ,
, .
,
, .
13

2.

.
R . ,
,
. -
, .
2.1.

.
, (24) (25), .1.
n+ + ne M

(24)

Ox + ze R

(25)


.1.
,
, ,
, , ..
, .
E-i E-lgi.
i ,
14

,
(i =0), i (
), .
i ,
, i.
r
i
s
i ,

(26)-(29) i i.
r
s
(26)
i= i n+ - i
r
s
(27)
i = i - i n+
r
s
iR = i Ox - i R
(28)
r
s
iOx = i R - i Ox
(29)
(26)-(29) , , , , i ,
()
( ) n+. (.1),
. ,
R ( ) (
), R ( )
r
( ). -lg i Es
lg i - (24) (25)
r s
i0 = i = i .
(26)-(29) i= i=0 iR= iOx=0.
E-lgi, , , =f(i),
: 0-1, i << i0, ;
r s
1-2, < 2,3RT/(nF) i0, i i ,
r
s
r
2-3 , i n+>> i i i n+ .
-i 0-1 , 1-2 2-3
.
( , n+ , R)
n+/ /R , ..
. (
) :
r
s
r
s
i n+ + i Ox = i + i R

(30)

(27) (28) (31), , j ipM.


15

j ipM = iR

(31)

ipM iR,
. ipM > iR,
, ,
.1 ipM iR .
.
,
iR > ipM, . i:
i = iR - ipM

(32)

(32)
. :
i = ipM - iR

(32)

(32) (33) , . Elg i E-lg i .1 .


ipM ( =ba
), iR =b,
r
E-lg iR E-lg i Ox. > b (b)
s
i ipM i . E-lg iR E-lg i
E-lg i E-lg i.

, , = i/ i. , i= 0, = .
< < /R (33) = 1+ iR/ i >1
. = n+/ iR=0 =1. > /R i = i + i
=1- i/ i<1, i<< i (.1), 1. ,
. ,
R .
.1

. ,
.
R i R.
i
16

i iR (.2).
,


.2.
j.
( .2 ), i
, R ( 1-2 1`-2` ).
iRR c i


jR.

iR jR
.
R


=
-
= jRR

(34)

R, jR.
2.2.
, :
?
19
,
,
.
. ,
, .

j
17

.
.
i iR .2, j.
, (34) (35),

, R.
/R

- n+/ = jR + jR + RjR

(35)

jR:
jR= (/R - n+/)/( + + R)

(36)

- , i R
. , ,
.. 50
.
,
. ,
( Hg HNO3),
, (Au
), , ( Pb, Cd)
Zn. , .2
jR .
.
,
,
:
1.
. R ,
R, .
R
, ,
R iR
j.
2.

. R ,
jR , .2 (36) .
18

, R = const jR (.3)
(34) (36). .3
, . ,
.


.3.

,
.
:
1.

( ,
, .)

, .

)
. , .4 - i ,
1

, , - iR
2
- - iR
.

19

,

.4.
=f (i).
i.
( , =0) (.4)
( ) (, i = i 0pM ) .
,
, .
1
,
, j1 i1pM ,
2
2
j2 i pM
.

. iR
, i pM - .
, :
ia =ipM ( )
j i pM .
.
s
r
n+/ /R, i pM i , iR i Ox (.1)
( 1 = 0)
:

i pM = kMexp[(1- M)nFE/(RT)]

(37)

iR = kOx[Ox] exp[-OxzFE/(RT)]

(38)

i pM = iR, (37) (38) :


=

[ z Ox

k
RT
ln Ox [Ox]
+ n(1 M ) F k M

(39)

(37) (38), :
20

j = const [Ox]1/[1+z Ox / n (1-M)]

(40)

, Ox=M =0,5, (39) (40) :


0
=

0,116

1+ n

(41)

1+ n

lg j =lg j0 -

(42)


idOx , :
j = iR = idOx
=
2.

RT
(1 )nF

(43)
ln

idOx
k

(44)

,
, ,
.
3.

>

n+/M,

R ( , 2) (,

2) </R (.1). (t, C),



. , , ..
:
n+/M

<

/R

n+/M < < /R

(45)

=0 n+/M = - , .. [Mn+] =0, /R = , .. [R]=0.


, ,
. (45)
[Mn+]. ,
[Ox] [R] , ..
.
2.3.
. , ,
- .
, .
21


. , , ,
, .. R ()
. , S
S .
, ..
:
JpM = ipM S = JR = iR S

(46)

- S = S, ipM = iR .
ipM i iR i. ,
, -lg i -lg i =
ipM iR. ,
,
. .1.

,
. -
.
S S, , JpM = JR ,
(ipM iR ).
ipM iR. .5 ipM > iR, (46) , S > S.

-
.5.
- ,
( , ), (, ,
), ,

22

( n+, , , ),
( , , ).
2.4.

,
j. j
. ,
,
, () .
i b
i0. b i0, .
- ,
i0Ox / R i0M

n+

/M

bkR baM , R M

j (.1). . 6.


.6.
23

.6, i0. i0Ox / R pp i0M

n+

/M

(.6) j,
n+/M.

M 0.

.6 , j ,
R 0.
, [Mn+].
.6 , . b ,
, j idOx , .. iR.
, ,
. b
i.
, ..
.
4, ,
.
2.5.
O ( R0),
, , , ..

. , ,

J, i.

JpM = JR

(47)

(46), . (32) (33) ,


J i , (47) (48)
J = J

(48)

, ( - JpM
- JR) (- J - J) ,
- JpM - JR - J , - J. J,

.

- J - J

(.7). J ( J = J 1 + J 2 + J 3
24

3
2
)

J 3 , ..
2
J 1 = J 2 = 0 <
J 3 J 2 . 1: J (

0-3) = J 2 ( 0-2) + J 3 (0-1),

2-3 0-1 .

1
2

J 1 .
J ,

(48) J J .

J , -
. .7
1 2

, J 1 > J 2 , 3 . | J 1 + J 2 |= J 3 = J
,
JpM JR .

.7

.8

, (32) (33), J i ,
JpM = J + JR

(49)

JR = J + J pM

(50)

, (J pM )
(J )
(JR ). R (JR )
R (J )

25

(J pM ) . J < J pM J < JR , J

.
J = JpM = JR

J ,
(.8) - J - J , (.7).

J
J R
J.

- J
p M n1+
1

/ M1

, .. p M n 2 +
2

/ M2

. Red/Ox
,

,
3 . J > J

M1
M1
M2
.7. .8
1 , J aM 1 = J pM1 - J R
; J pM 2 < J R

J pM 1 > J R
M2
- J pM 2 0, 3
2 , J M 2 = J R

, J pM 3 =0.
. , 1

. , 1
J M 1 = J pM 1 , J pM 1

J pM 1 , ..
>
,

. 3

0,..
< p M n 3+
3

/ M3

3
<
. ,

2,

, .

.8 - J 3 . , 3
n+

J dM 3 , J .
J pM - i pM , , .

.
3.
3.1

(. 9).
26

: (1, 2, 3),
(4, 2, 5),

(5, 6),

(6, 7, 8, 9)
() (7, 10) (8, 11).
, .
, [Cl-]

;
,
, , , .
, . 9 .
= f(e). (.
1). , ,
, , 2.
9 .

.
.

j ( )
[]. ( /e , Ox/R b)
. , ,
,
.

27

,
,
.
.
3.2.

,
, (
) .
.

.
2+ ,
.

. 9 ,
. .
, ..
.

.
:
+ - (MAy)-()n-y +

(51)

-, -- --
. -- - , -, . - -- ,
--, . --
, -- .

, ,
c , b=2,3RT/(nF)
= 0,5.
:
28

Fe + OH- FeOH + e

(52)

FeOH + OH- FeO + 2 +

(53)

FeO + OH- HFeO2-

(54)

HFeO2- + 2 Fe(OH)2 + OH-

(55)

(53) :
Fe = [FeOH][ OH-]exp[FE/(RT)]

(56)

(52):
= + RT/F ln [FeOH]/[OH-]

(57)

: [FeOH] = 2[ OH-]exp[FE/(RT)]

(58)

(58) (56)
Fe = [ OH-]2exp[(I+)FE/(RT)]

(59)

-- (lg/pH)E = 2
s
(E/lgFe)pH = 2,3RT/ F = 40 mB .
s
( = I+) :
s
= (n-m)/ l
(60)
n- , m -
, - (
=I), l- .
,

,

.
s
(60).
, :
Fe + 2 FeOH-+ +

(61)

FeOH- FeOH + e

(62)

FeOH + HSO-4 FeSO4 + H2O + e

(63)

Fe = [HSO-4][OH-]exp[(2- )FE/(RT)]

(64)

= (2- 0)/I-I = 2- .

29

- ,
-.
b .
3.3


. .
1
> , (. 10)
2
M1
M2
( iR
), [].
( iR
1

.
,
:
<()<()

(65)


:
< R /R >

(66)

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

H 2 O2 +
MO + H 2 O
2e
+
2OH

(67)


2 .

,
.
(68) (69),
(70), .
30

mOn + 2nH3O+ + 2ne mM + 3nH2O

(68)

MmOn + nH2O + 2ne mM +2nOH-

(69)

= 0,058

(70)

:
(37), (59), (64)
.
, ,
, (70) .
.

. . 11

.11. -

Zn H2O.

(24), n+ ,
(68), (69), ( ),
:
n+ + nOH- = M(OH)n

(71),

( ). ,
() (Zn), (Zn2+ ZnO22-)
(Zn(OH)2),
.
- (Cl-, SO42- .),
.
, .
-
, [+].
- ,
,
31

.
,
.
2- :
.
, .

.

.
. . ,
,
, .
.
3.4.
,
, ..
.
,
(Cr2O3) (Cr2O72-)
. , ,
-, ,
II+
.
3.5


.
() ,
, .
. ,
,
32

, .
:

, - , Cl-,
, .
,
(
).
.
1. , ,

-.
2.

.
3.
: SO42-, ClO4 .
4. ,
, .
, ,
( 108/).
,

.
, . ,
.. ,
, .. .
.
.
.
< ,
. .
.
,
33

.
SiO2 , ipM (. 9)
,
- . [-]
, .
(
)
,
,
.

pH ,
(
). , XI8H8 (pH 8)
pH 1,2 - 2,0 [Cl-]=12 .
, .

, .

.
.

, .

.

( )
( 1 ), .


. ,
.
,
. :
= ()

(72)
34

, , ()<
.
3.6.

( 1-3 .9)
( 4-5 .9)
.

1. iap=/=f(E)

1.
(37), (59 (64)

2.
-

2-

(OH , SO4 , Cl

2.
-

..)

(59) (64)

3.

3.-


, j

4.

4. 3+

3+,


- (59) (64)

.
, .
, (59) (64) ipM

(56)
Fe(OH)ac
.
. , ,
, 3+.
35


.
,
, :
+ 3+ = + + 2

(73)


(3+) (73)
.

.
- ,
() ()
ipM=iap+i . < iap>>i ipM=iap , > i>>iap ipM=i (.9). .12
j,
,
.

-
.12
.12 j<< iap , ..
.
,
t. .

36

4.
,
,
.


. :

ZA =
ZA =

([ A] : [ B])

(74)

([ A0 ] : [ B0 ])

i pA AA n B [ B ]0

(75)

i pB AB n A [ A0 ]

: , [A]o [B]o ;
ipA ipB . ZA>1, [A]o
ipB . ipA ipB ZA .
ZCr>1, ZCr<1.
,
PEMn+/M .
: ,
An+ ,
, (ZA=J)
, .
[A]o
ipA
:
i =

nA F[A]0 Da /

(76)

.. i- -1/2 ,

DA .

, .
DA .
[A]o, ,
, , ,
, ..
.
37

()
-
, .

.
, .
,
, :
= aB + bB lgi

(77)

, ZA=I, (74) ipA=kA ipB (kA=AB[B]o/AAA[A]o)


(77) :
= aB + bB lgi bB lgkA

(78)

i. = ipA + ipB = ipB (I+kA)


= aB + bB lgi. bB lg(I+kA)

(79)

(78) 79) ,
, ..
.
,
.
[A]o,
, .

. ia=const
(.13)

. 13

.14

, .
ia :
38

ia=ipA + ipB iBR + i3

(80)

i3 = ia + iBR
. i3 = ia + iBR - ipA , -
. ipA , i3
,
, i3 .
ZA= , ZA=I.
(E=const, i3=0) (.14) I EB>E>EA 2
E>EB. I

ipA>iBR ipA .

ipA= iBR ia=ik=0 , .


ik iBR. iBR ia

, ipA0,
, ipA

, (76). 2, ia=ipA + ipB


iBR ,

ia

.

.
5.

c R
<pEx/R. , ,
,
(. 9).
5.1.
,
H3O+-. (84),(85) (8l)
(82),(83) ,
. - (. 15).
2 30+ + 2 = 2 + 2 20

(81)

02 + 2 20 + 4 = 4 -

(82)
+

02 + 4 30 + 4 = 6 20

(83)
39

pEH+/H2 = RT/2F ln([H+]2/ 2 ) = -0,029 lg 2 - 0,058 pH

(84)

pEO2/OH- = pE0 + RT/4F ln ( 2 /[OH-]4) = 1,23 + 0,014 lg 2 0,058 (85)


, PE=f(pH)
02, 2, ,
+ -. , I
02 2, II-
02 2 III - 2 02.

pH .
.15
pE I,
, , ; II III - - .
5.2.
:
E = pEx/R (a + b lgiR) + b`lg(1 iR / ioxd),

(86)

b` - const. ,
- ,
, . 16. - i 1
2

:
2 20 + 2 = 2 + 2 -

(87)

40

, idH3O 30+ 0.
.
+

idH3O .
02 ( ioO2/OH- = 10-5 -10-7 A-2),
-
02, ,
. . 16 .



,

, -

.16

.
O

id 2 ,
,
, .
(.3.1),
= f(i) = f(j) .
j = id
2, id.

.

41

5.3.
(82) (83)
:
+

+2

2H2O
O2 + 2 H+ + 2 e 2202 2

(88)

2 + 2
02 + 20 + 2 > 0- + 0-2

4OH-

(89)

,
:
+

2
2

2
2 2

2 2

2 2

(90)

H2O2.


:

i O2 = K [O2 ] exp[F ( E 1 ) /( RT )]

(91)

5.4.

.
- (93)
(94), (92) -
.
3 + + 2 +

(92)


3 + + 2 + +
2

(93)

3 +
3 + + 2 + +
2 + 2

(94)

M , ,
ioH

/ H2

7*10-9 /2 20 /2. ,

-
3 : 42

, ;
-, ;
.
,
.
-
, , ,
(W, Mo, Nb Ta).
,
() H> 120 .
bK=2,3RT/(0,5F)=116 , bK=2,3RT/2F=28 (0,5= -
, 2 H, ).
H (1-H),
H.
5.5.

( )
, .
(10-10 ), ( rH+=10-15 )
(95) - (rH=4*10-11 )
(96) (94)
+ + +
+ + + MH

(95)
(96)

,
. 2
.
("") +
. H2 -
, ,
.
.

43



. ,

.
.
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6.
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44

6.2.
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.
(2)
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.
6.3.

.
65%. ,
Fe(OH)2,
2 Fe(OH)2 Fe(OH)3.
6.4.
,
( )
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.
,
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1 ( 17).

45


.17.

/Fe,r/236. ,
( 1)
2.
2
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2)(. 18),
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, 2,
.
.
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,
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46

6.6.

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,

400 - 850.
7.

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47

7.2.


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48

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8.
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49


j = i d02f (E.) J = J d02f
(E.), - j J E..
j
.
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, .
. ,

.
.

.19. ()
() .
,
3+,
(. 19 ), t, pH,
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50

, ,
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8.2.

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51

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.

52

9.
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), (
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.
9.1
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-, .. i
i .
:
=[(j - ipM)/j]100%

(97)

, ..
ik, - , .
=(j -ipM)/jk

( 98)

=(ik /j)100%

(99)

, . I
. ik=j ipM

53

=(ik/j)100%

(100)


. , , .20,
, .. ,
, .21. .21
.8.
IpZn IpFe 0.

. 20.

.21.

i (.20).
ipM=0 =100% pEMn+/M. pEMn+/M , ..
ik ipM, [+] pEMn+/M.
.
E .100% -
, =[(j - i)/j]100%. , ..
iki, -
(.16), .
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=[(j-i)/j]100%

(101)
54


()
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i>i, i
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, .
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.
.
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);
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) ( 50-70, 70-100, 100-150,
200c);
) o (, , );
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) (, ,
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.

55

9.2.1.
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56

(), ,
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10-5 - 10-7 .

.

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57

,
.

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.

.
9.2.4.

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.
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9.3.1.

:
1) 02 (,
), (),
, ;
2) , , Ca(OH)2
NaO;
3) ;
4) ,
, ;
58

5) (),
t.
9.3.2.
,
,
, .
.

(102) Z (103).
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Z=

j
100
=
j 100 Z

(102)

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K 1
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100%
jo
K

(103)

j j - .

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j ,
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() (A)
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1 -

59

.
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0).


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().

().

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60


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:

lg K = ( E E
) / b

(104)


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idO2 .
j,
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61

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Z .

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62

.
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( 10-1_10-8 g- ).
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10.
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1.
.
2. ,
.
3. .
(
Ir, Ru, Os ), ( Mo, V, Re ),
V M m mn / 2 /VM>2,5 ( Ta, Nb, W ), . :
(Nb+Ti, Mo+Ni, Mo+Ni+Mn); VMmOmn/2/VM 1 (Nb+Mo); -

63

, ( Nb+Ti, Ta+Hf); (Mo+Al2O3).


, , , . . , Fe
(105) =/2=2,2
2,22
Fe+CO2 Fe +CO ( 105)
( , ), (, ),
.
(r, Al, Ti, Ni), (Cu), ( ) , ,
.
:
,
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:
; ; ,
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;
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64


( - )
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- , ,
;

; ,
;
.

.
, .
.

, ,
,
.

, ,
, .
65

:
, , , .

1. .. . : 1974. 472 .
2. . . .: , 1984. 400 .
3. .. . .: , 1970. 448 .
4. . . .: , 1978. 223 .
5. .. . .: , 1973. 263
.
6. .. . . .: , 1981.216 .

7. .., .., .. . .: , 2001. 624 .


8. .. . .: , 1984. 519 .
9. .., .., .. .
, , 1981. 183 .
10. .., ..
. - : . , 1978. 184 .
11. .. . .: , 1985.88 .
12. .., .. . . .:
. , 1974, .3, . 5-76.
13. .., .. , .5, . 5-45.
14. .. , 1967, .3, 2, . 131-144 ,
1980, . 16, 6, . 660-673.
15. .., .. . . .: . , 1979,
.15, . 62-131.
16. .. . : . , 1983.168 .
17. .., .., .., ..
. : . , 1988. . 208.

66

18. .. . .: , 1982. 320 .


19. .. . .: , 1977. 350 .
20. .., .., .. . .: ,
1981. 423 .
21. .. . .: . , 1959. . 591.
22. .., ..
. .: , 1986. 359 .
23. .., .. . .: , 1965. 208 .
24. .., .. .
.: , 1973. 232 .
25. .., .. .
.: , 1981. 300 .
26. .., .., ..
. .: , 1972. 258 .
27. .. . : . , 1994. 473 .

67