Sotnikov_Vatolin_vce

+ 0, .% i -

( μi ) 0,

. 0 . ! 0

– . 0, .

0. , 0,

P,T=const 0

C +CO2 =2CO

. %

+ CO2:

G = 2μCO − (μC + μCO2 ) .

, 2μCO < (μC + μCO2 ), ,

		,			0 . %
(	G< 0),	,	0		0.	, /
2μCO > (μC + μCO2 ) ,			G > 0,	0		0
		.	,		G = 0

0 .

- , . % - ( μi )

“ ” . ,

0, .

.

2 ,

. , , μi

. 0.

μi

, (

P=1 ), μi0 . # 0 / μi μi0

0 ai :

20

μi − μi0 = RT ln ai .			(1.31)
- μ	i	− μ 0	0
		i

.

- 0 ( ai )

.

P<300 , , 0,

ai =	pi ,		=		pi ,			,	(1.32)
	1			1,013		×105

pi – 0 i - .

1.5.1%$ $0 )-$. /%$2 $$%$.$

* ,

.

,

( , P T)

0 -

. " 0 ,

P,T=const G = min , . % 0

.

#

A+2B=D ,

P,T=const. ( ,

G = μD − μA − 2μB = 0 .

!

( . 1.31),

21

0	0	0			aD
μD - μA - 2		μB = - RT ln						.	(1.33)
				a		× a2
					A		B

7 0 . % , ,

A, B D P=1 (

):

μD0 − μA0 − 2μB0 = G0 .

+ 0, . %

( G0 ) 0 . (

, 0 (1.33),

, 0

. *

. ka :

	a	D
ka =			.	(1.34)
	a × a2
	A	B
+ ,	ka
. %:
G0 = − RT ln ka .				(1.35)

" ,

$ (1.32), / 0 0 0

, / $ . "

. kp :

	k		=		pD			.
		p
					p × p2
					A	B

!

ka = ∏(ai± νi )	,
i

22

ai – 0 i - , ν i –

.$$ . 3 “+”

. .$$ , “-” –

.

# 0 / , / ,

. & 0

. (0)

G = (μD − μA − 2μB )"= μD0 − μA0

− 2μB0

a

D

+ RT ln

=

(1.36)

a

A

a2

B "

G0

a

D

=

+ RT ln

.

a a2

A

B "

3 0 μD0 , μA0 μB0 , ,

. % 0 / ( . 1.33 1.35),

0. 0

/ (1.36) 0 ,

$ ka , / , $ . !

(1.39) / 0 :

G = G0 + RT ln ,		(1.37)
Π =∏(ai± νi ) .
i	"
0 (1.37) , /		G0
ka 0 $ (1.35),
G = RT[ln Π-lnka ].		(1.38)

(1.38), (1.37),

. ) .

0 G , − 0

23

0 P, T=const. ,

G <0 , G >0 – ,

G =0 $ .

0 0 . ,

0 $

( 0 ).

', G0 0 0

0 . +

(1.37) 0 ( RT ln )

G .

# 0 .

' 1. ' =1173 "

C +CO2 =2CO

kp =31,4. # 0 $

P=1 . ! 0, , /

0 10 .

3 /

		= k		=		a2
k	a		p			CO
					a a
						C CO2

=		p2		.
		CO
		1× p
		CO2

3 0 pCO pCO2 / $ . ' 0

/ / 0 /

P:

pCO = %CO100 P ; pCO2 = %CO100 2 P .

- / kp

kp =	P(%CO)2	.
	100(%CO2 )

24

' 0 %CO+%CO2 =100% , , 0 kp , /

, P=1 %CO = 97% ; %CO2 = 3% . , 0

10 , /,

0 . *

.

10(%CO)2

31,4= 100(100-%CO) ,

P=10 %CO=80% ; %CO2 = 20% .

- ,

( .

). ( 0

7-5 0,

0. ,

, 0 , ,

, 0 0

. ' 0

( ) (

). #

. ' .

/ CO , CO2

0. ) ,

, .

' 2. ) 0 . % , 0, /

0 0 , / 90% CO 10% CO2 ,

FeO / =1073 "

FeO +CO=Fe +CO2 . ( )

# ( ) / $0 0

(b) ( ) :

25

2CO+O2 =2CO2 ;	(b)
2Fe +O2 =2FeO ;	(c)

( )=[(b)-(c)]/2. ( ,

, 0, DG0 / 0

(DGT0 (b) - DGT0 (c) ) / 2 = DGT0 (a) .

' 0 DG10730(b) = - 385 #/$ O2 ;

DG10730(c) = - 400 #/$ O2 , DG10730 (a) =[(-385) - (-400)] / 2 =

= +7,5 #/$ Fe = + 7500 #/$ Fe . ! Π ( )

/ , 0

P = %CO%CO2 = 1090 = 0,1.

' (1.37),

G = G0 + RT ln = 7500 + 8,314 ×1073× ln 0,1 = -13 //0.

- DG 0 0, ( ) /

0 , . . FeO 0

CO /.

' 3. ! 0, 0

=873 ".

. 0

2Ag +O2 =2Ag2O

=873 ". , . 0, . 0

0 : ka = 8,1×10−3 . ! P .

	a2	O			1
P=	Ag			=			.
	2
	2
aAgaO2			"		1× pO2 "

26

!			p =1		/	21%	,	,
( pO2 )	= (21×1)/100 =0,21 ; Π=1/0,21=4,76 . '
		DG = RT[ln -lnk			] = 8,31×873 ln(4,76) - ln(8,1×10−3) »
			≈ +46260 #/$ O2 .
" ,		G > 0 , / .
,						0

/ Ag2O .

1.6.$%) 3 ).. $4 . 3.

0

(!):

MeO+B=Me+BO .

(1.39)

' ( Me)

0 ( BO ). 0 0,

. / 0. !

.

, / ( !)

0. ! / 0 / 0, /,

.

.

:

Me+	1 O2 =MeO ;	( )
	2

27

B+	1 O2 =BO .	( )
	2
+ (1.39) ( ) − . ( ), .

	G0	=	G0	−	G0
	1.39		(%)		( )
, (1.35),
	(− G(0%) )−(−				G(a0 ) )		(1.40)
ka(1.39) = exp			RT			.

- , (1.39)

0 (− G(0 ) )−(− G(0 ) ). 6 0 . 0, 0

, .

! (− G(0a) ) (− G(0%) ) 0

( ) ( ), . . .

" / . 0

.- . ,

0,

(− G(0%) ) >> (− G(0a) ) ,

ka(1.39) >>1 0 .$$ .

+ ( . 1.1) , /

. / 0

. - =1273 " .

Ca-Mg-Zr-Al-Ti-V-Si-Mn-Cr-Na-Zn-Fe-H2-CO-Sn-Ni-Pb-Cu

* / 0 . (

), / ,

		/		0
( . 1.40).	6	/	.-0

, .$$

. . 0,

28

0

		O
	g2
A
2

100		O
	H 2
	2	g

200

300

		O
	u
C
2

		O
	u2
C
2

	O2
n
S

		O
	b
P
2		iO
	N							O
	2
						C			2
					2
					=
					O2
				+
			O
		C
		2						O
							e
					2	F

			O
		o
	C
2
			O
2	H2

	400
2	500
0 *	600
8 /	700
T0,
G
-	800
	900

1000

1100

1200

	O
K
2	2
			O
		n
	Z
	2

					2	C
		O				O
	a2				n
				M
N
				2
2
			iO
			S	2

					O
				r2		3
			C
		3
		/
		2
+ O
2	=
	2 C
		O					O3
							V2
						3
						/
						2

					O2
					r
iO					Z
T	2
				O
				l	3
			A
		3		2
		/
		2

	O
g
M
2				O
			a
		C
		2

200

400

600

800

1000

1200

1400

1600

1800

2000

-, ',#&- #&, 0+

#. 1.1. + . %

29