5.

113

114

5.1.

.
.
.
, .
. , t.
, t
( , k)
T .
.
, ,
, "
.
. : , ( ) , ( ).
.
,
.
.
, , .


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

115

. , - . , , , .
.

5.2.

. 5.1
.


. ,

,
.

, :
.

5.1


,
5.2..

, 5.2.. ,
, , 5.2. , , 5.2. , .
: () () .
,

116

,
.




.

, G,
G = H T S
(5.1)
H , S
T .

.
.
.

(5.1)
5.2
,


,
.
5.3 , Gl
, Gs , .
,
t, .
. , t, ,
.
, . . ,
,
.
, k,
, Gv .

Gv = H v T Sv

(5.2)

117

: Gv , H v Sv

, Tk ,
, Tk .

, T , :

T = Tt Tk

(5.3)

Tt a , Tk
.

, Gl
, Gs
, Tk , :

Gv ,Tk = H v ,Tk Tk STk

5. 3

(5.4)

Gv ,Tk
Tk , a H v ,Tk Sv ,Tk
Tk .
, , Tt , Gv ,Tt = 0 :

Gv ,Tt = 0 = H v ,Tt Tt STt

STt =

H v ,Tt
Tt

H f

(5.5)
(5.6)

Tt

H v Sv

H f = H v ,Tt H v ,Tk

(5.7)

S f = Sv ,Tt Sv ,Tk

(5.6) (5.5) ( 5.7)

:

Gv ,Tk

H v ,Tt
Tt

(Tt Tk ) =

H f T
Tt

(5.8)

118

H f
.
(5.8)
, ,

.

T = 0, 2 Tt

5.4.

( )


5.4.

, Tt .

5.3.



.

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

. , ,
,
.
. .
,
.
. ,
, Gv ,

119

. , , . , .
G , 5.5.
4
G = V Gv + S = 4 r 2 r 3 Gv
3

(5.9)

S , r, V
, r, , Gv .
, 5.5.
, r*.
r*, ,
. , r*, ,
. , G*,
.

5.5.
-

, r*, , G * , , G, (5.9).

d (G )
2
= 0 = 8 r * 4 r *2 Gv ; r * =
dr
Gv

(5.10)

120

G * =

16 3
3 ( Gv )

(5.11)

G G * ,
.
, (5.8) (5.10) :
r* =

2 Tt
H f T

(5.12)

5.6

(5.12)
,
, r*,


5.6.



.

5.1. , ,

Tt

( C)
0

271

327

962

1080

1453

1538

H f J m3
543 106
237 106
965 106
1628 106
2756 106
1738 106

( J m2 )
54 103
33 103
126 103
177 103
255 103
204 103

( C)
0

90
80
250
236
480
420

121

.
Gv , (5.12).
5.1
,

T = 0, 2 Tt

(5.13)

5.1.

10 100 . Tt = 1538 0 C H f = 1,737 109 J m3 . = 204 103 J m 2
:
(5.12) 1 = 10

r1* =

2 Tt 2 204 103 J m 2 1811 K

=
= 42,5 nm
1,737 109 J m 2 10 K
H f T1

2 = 100
r1* =

2 Tt 2 204 103 J m 2 1812 K

=
= 4, 25 nm
H f T1
1,5 109 J m 2 100 K

.
5.2.

) ( Tt = 1453 C ,
H f = 2756 106 J m3 = 255 103 J m 2 , , a0 = 0,352 nm )

, )
.
:
) :

T = 0, 2 Tt = 0, 2 1453 K = 291 K

(5.12) :
r1* =

2 Tt 2 255 103 J m 2 1358 K

=
= 95 09 m = 95nm
3
6
2660 10 J m 291 K
H f T

122

:
4
4
Vr* = r1*3 = 95 109 m
1
3
3

= 3,59110-27 m 3

:
V0 = a03 = (0,352 nm)3 = 4, 361 10-29 m 3

4
V
4,361 1029
= 1,09 1029 m
VNi = 0 =
4
4

n1* =

Vr*
1

VNi

3,591 1027 m3
= 329
1,09 1029 m

. n0, n0 1029 atom m3 , -

, n G ,
*

n* = n0 e-G

kT

klaster
m3

(5.14)

k .

. .
, ,
, m , . ,
i

N

i

N = n* m*

(5.15)

je N
.

123

, .
, ,
, GD

= eG

kT

(5.16)

(5.14) (5.16) (5.15)

i

N = m*e GD
i

kT

N = A n0 e G

n0 e G
kT

kT

nukleus
m 3 s

(5.17)
(5.18)

,

1011 s 1 .
5.7 (5.14), (5.16) (5.18)
N .

5.7

:
. , - , G*
. G*,
, GD
, -

124

(5.19). .

.
, G * .
(5.16) ( 5.14) 5.7 ,
kr . , kr
.
.
5.3.

) 180, 200, 220 : Tt = 1356 0 C, = 177 103 J m 2 , H f = 1,88 109 J m3 , A 1011 s 1 ,

n0 1029 atom m3 , k = 1,38 1023 J K .

:
(5.8) (5.11)
16 3Tt 2
16 3
16 3
(5.18)
G * =
=
=
2
2
3H 2f T 2
3 ( Gv )
H f T
3

Tt

) T = 180 K

(
(

)
)

3
2
16 3Tt 2 16 177 10 J m T (1356 K )
G =
=
= 1, 491818 J
2
9
3 2
3H 2f T 2
3 1,88 10 J m (180 K )
*

N = N hom
i

N = A n0 e G

kT

= 143,163 103

nukleus
m3 s

i
nukleus
T = 200 K N = 5,0487 1011
T = 220 K
3
m s
i
nukleus
N = 3,9823 1016
.
3
m s

125

5.4.


, , .
.
(5.8), (5.11)
(5.18)
G * =

3
16 TC
Tt 2
3H 2f T 2

(5.19)

(5.19)
TC - - .
.

TC




5.8
( ): - ,
, TC -
5.8.
5.8
- , CP - - ( ),

TP -

CP = TP TC cos

(5.20)

G ,
.

126

G = V Gv + S = V Gv + STC TC + SCP CP SCP TP

V - , SCP , STC ,
-.


.
(
)- .
5.9.
5.9 .

5.9.

STC = 2 r (1 cos ) ; SCP = r sin ; V =

2

(5.21)

r 2 ( 2 + cos )(1 cos )

(5.21)

Ghet
Ghet

( 2 cos )(1 cos )

= 4 r 2 r 3 Gv
3
4

= 4 r 2 r 3 Gv S ( )
3

(5.22)

() ,
-. .
-, -, , , 5.10.
(2) (3)

Ghet
< Ghom

. , 5.11.

5.10

127

5.11

. . ,
.
,
,
.
5.4.

.

T = 0, 2 Tt ,
h = 0, 2 r * , r* ,
5.12. 1085 C,
1628 Jcm3,
5.12

7
2

17710 Jcm , a

0,3615 nm.

128

V = h 2 (3r h) 3 , r , h .
.
:
) :

T = 0, 2 Tt = 0, 2 1358 K = 272 K
(5.12) :
r1* =

2 Tt 2 177 103 J m 2 1358 K

=
= 108,5nm
H f T
1,628J m 3 272 K

:
4
4
Vr* = r1*3 = 108,5 109 m
1
3
3

= 5, 274 10-21 m 3

:
V0 = a03 = (0,3615nm)3 = 47, 24 10-24 m 3

n1* =

Vr*
1

V0

5274 1024 m3
= 112
47, 24 1024 m3

4 N1* = 4 113 = 448

)
Vk* =

h2
3

(3r * h) =

(0, 2r * ) 2
3

3r * 0, 2r * = 0,117 r *

r * = 108,5 109 m , :

Vk* = 0,117 108,5 109 m

= 149 10-24 m 3

:
n2* =

Vk*
149 1024 m3
=
3
V0 47, 24 1024 m3

N 2* = 4 13 = 12

129

,
. 10 C.

.
.
. .

5.5.

. : - , 5.13., -
, 5.13..

()
()
5.13 , )
, )

130

, 5.13.

.
.
,
. 5.13. .

.
- STt = H f Tt . STt = 4 R . STt = 4 R . Bi, Ga, Sb, As Si Ge
STt > 4 R o .

. : () ; ()
() .
.

.


,
4
V (t ) = v 3 (t t0 )3
3

(5.23)

: V(t) t, v
, t0 , t t0 .

. dt N dt . ( t0 = 0 ) 0 t
t

4
Vuk = v 3 N (t t0 )3 dt0
3
0

(5.24)

, y
, Vuk V0

y = Vuk V0

131

(5.25)

,
. . dy
,

(1 ) dy = d

(5.26)

(5.26) = 0 = 1
= 1 e y
(5.27)

(5.25) (5.24) (5.27) ,

4
3

N
(t t0 )3 dt0
0 V0

= 1 exp v3

(5.28)

(5.28)

= 1 exp ( kt n )
k , t n
, 3 n 6. O


.
(5.29)

5.14. , r,
, t0,5
50%
, r = 1 t0,5 .

5.14

(5.29)

132

.

.
, , ,
, 5.15.

5.15
() -

, , ,
, ,
.

.

G = A e Q / RT

(5.30)

5.15 , N , G
.
N G ,
N .
, . , . , , ,
. .

133

5.5.

900 C G ()
. 400 C 6 ,
. .
:
(5.30) .

G900o C
G400o C

Q=

A e Q R (900 + 273)K
= eQ
A e Q R (400 + 273)K

R ln G900 o C G400 o C

R ((1/1173) (1/673))K 1

) = 8,314 J mol

(1 / 1173 1 / 673) K 1

K 1 ln 6
= 181 kJ mol1
1
(1 / 1173 1 / 673) K

-.

, .
.

. {110} .
5.16
, {111}, 5.16.

{110} {111}

.
, .
.
, 5.17.
{111}
: {100}, {311}, {331}, {210}, .

134

5.17

.

, T = Tt ( T )
.
T < Tt


.

,
, , ,
5.17.

5.6. -

.
.
. ,
.


,
-
,
. 5.18
. ; )

, ) (GK
, GR


.


, Tt . ,

135

.
.
.
, 5.19.

( ),
5.17.

. ,
(

).
, , ,
5.19



, .
, ,
.
. , (

) .


.
, 5.20,


5.20
.

.

136

-, .
, .
,
.
.

.
.
.
, .


.
,
,
, .
,

, 5.21.

, .
5.21

.
:

1-,
( 100 ).
2-

3-

10% .

. ,
. , f,

f = C T H f

(5.31)

C , T H f .

137

5.6.
: ) ) 10 C. 1628 J cm3 4,4 J cm3C1.
:
() 272 C ( 6.2)
6.25

f1 =

C T 4, 4 J cm 3 o C 1 272 o C
=
= 0,735
H f
1628 J cm 3

() 10 C
f2 =

4, 4 J cm 3 o C 1 10 o C
= 0,027
1628 J cm 3

5.7.
- , , , .
, , .
,
5.22.
.

5.22

138

.
: .
, ,
. . ,
.
.

,
, 5.21.

5.21 () , )
)

,
. , , . .

5.1.

1 C,
204,3 kJ kg1 1085 C.
G v = 9,5 J mol-1

139

5.2.

. 1453 .
[1108 ]

5.3.

.
: Tt = 1538 0 C , H f = 1, 737 109 J m3 .

[1,175 nm]
5.4.

)
. T = 0, 2 Tt . )
.
: Tt = 1356C , H f = 1,88 109 J m3 , = 177 103 J m 2 , a = 0,361nm .
[) 96,9 nm, ) 325 ]

5.5.

)
. T = 0, 2 Tt . )
.
: Tt = 1453 C , H f = 2, 66 109 J m3 , = 255 103 J m 2 , a = 0,352 nm
[) 95 nm, ) 329 ]

5.6.

)
. T = 0, 2 Tt . )
.
: Tt = 327 C , H f = 2,80 109 J m3 , = 33,3 103 J m 2 , R = 0,124 nm
[) 118 nm, ) 228 ]

5.7.

: ) 10 , ) 40 ; ) 80 .
Tt = 327 C , C p = 1,58 MJ m 3 C1 ,
H f = 2,80 109 J m3 ,

= 33,3 103 J m 2 .
[a) 0,067; ) 0,267; ) 0,533]

140