Гумеров Ф.М., Сабирзянов А.Н., Гумерова Г.И. Суб - и сверхкритические флюиды в процессах переработки полимеров
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81
, , [115÷118].
-
[12] .
, , -
. -
.
-
∫
∫
=
dqdp)p,q(
dqdp)p,q()p,q(f
)p,q(f
ρ
ρ
, (1.168)
f(q,p) - q p
, -
;
)p,q(f - ,
;
ρ
(q,p) -
.
,
.
-
. -
,
f
C
)p,q(f
)p,q(f
=
′′
′
,
f
C
)p,q(f
)p,q(f
=
′′
′
. (1.169)
ρ
ρ
ρ
C
)p,q(
)p,q(
=
′′
′
,
ρ
ρ
ρ
C
)p,q(
)p,q(
=
′
. (1.170)
ρ
(q,p) , -
(1.168) 1.
(1.169)
82
f
C
pdqd)p,q()p,q(f
pdqd)p,q()p,q(f
)p,q(f
)p,q(f
=
′′′′′′′′
′′′′
=
′′
′
∫
∫
ρ
ρ
. (1.171)
f
′
(q,p)
ρ′
(q,p) C
f
f
′
(q,p) C
ρ
ρ′
(q,p) -
dq
′
dp
′
=dq
′′
dp
′′
ff
C
pdqd)p,q()p,q(f
pdqd)p,q()p,q(f
CC
)p,q(f
)p,q(f
=
′′′′′′′′
′′′′
=
′′
′
∫
∫
ρ
ρ
ρ
. (1.172)
ρ
= 1 . (1.173)
ρ
(q,p)=idem ,
idem)p,q( =
ρ
. (1.174)
(1.174)
, ,
.
, , , -
.
. -
. ,
ρ
U
rel
=
ϕ
(grad
ρ
) , (1.175)
U
rel
- ;
ρ
-
,
, .
,
-
83
−=
−
=
= 1
lll
U
1
2112
rel
ρ
ρρ
Ψ
ρρ
Ψ
ρ∆
Ψ
, (1.176)
ρ∆
ρρ
U
U
U
12
rel
−
=
- -
, -
12
ρρ
−
ρ∆
,
1
ρ
; l - -
, , -
.
(1.175) (1.176) ,
.
η
Ψ
.
.
,
−
=
kT
EF
exp
ρ
, (1.177)
k
S
kT
EF
=
−
, (1.178)
F - ; E - , -
- ;
E
- -
, ; S - .
(1.176)
−
−
−= 1
R
SS
exp
R
S
expU
211
rel
Ψ
, (1.179)
84
R - .
1
ρ
-
S
1
, -
−
R
S
exp
1
-
.
−
=
R
SS
U
21
rel
ϕ
, (1.180)
(S
1
- S
2
) - -
.
-
. -
-
.
. -
,
µ
-
[12].
-
. ,
[119, 120]
−
=
R
SS
x
x
21
SS
ϕ
µ∆
µ∆
∆∆
, (1.181)
x
∆µ
-
(S
1
- S
2
); x
∆
S
∆µ
∆
S
- -
85
∆S. x
x
∆
S
(S
1
- S
2
)
∆
S.
[121],
[122],
(1.181) -
,
[65, 123], ,
[124]
2
, -
[124].
.1.16÷1.20.
. 1.16. -
-
-
2
. 1- [115], 2-
[126],
3- [126], 4-
[127].
86
.1.17.
2
. ) -
. 1 - [128], 2– [128], 3- [129];
) . 1 - [125].,
2 - [130].
-4 -3 -2 -1 0 1 2
(S - S )/R
-8
-6
-4
-2
0
2
4
- 1
- 2
- 3
- 4
- 5
- 6
1 2
-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5
(S - S )/R
-3
-2
-1
0
1
2
- 1
- 2
- 3
- 4
- 5
- 6
1 2
.1.18. -
(), -
() -
() [131]
2
. 1 – ( = 313 ), 2 –
(= 333 ), 3 – ( = 313 ),
4 – ( = 333 ), 5 –
( = 313 ), 6 – ( = 333 ).
.1.19. -
()
() -
[124]. 1 –
( = 373 ), 2 – ( = 378 ),
3 – ( = 383 ), 4 –
( = 373 ), 5 – ( = 378 ),
6 – ( = 383 ).
87
.1.20. -
. 1 –
2
( = 313 ) [131], 2 –
2
( = 333 )
[131], 3 –
3
8
( = 373 ) [124],
4 –
3
8
( = 378 ) [124], 5 –
3
8
( = 383 ) [124].
-3 -2 -1 0 1 2
(S - S )/R
-8
-6
-4
-2
0
2
- 1
- 2
- 3
- 4
- 5
1 2
,
. ,
, .
, ,
. ,
,
.
- (
), –
( ).
(1.181). -
, (1.15) -
-
.
-
. -
-
-
.
[132], -
. -
88
, -
.
, -
2.1.1 [133], -
-
25 150 °
10 80 [134]. [135]
, -
(1.181),
. -
.1.21.
, -
.
-
,
-
, -
-
-
. -
-
, -
-
, -
, .
-
.
, , ,
, -
-4 -3 -2 -1 0 1
(S - S )/R
-10
10
30
50
70
- 1
- 2
- 3
- 4
- 5
1 2
.1.21. -
[134]. 1 - 10 , 2 - 20 , 3 -
40 , 4 - 60 , 5 - 80 .
89
. . -
, , -
, -
.
1.7.
, -
, -
.
-
. [136], -
,
,
-
-. -
-, -
. , -
, -
.
, , .
[92]. -
( I ) .1.22.
. 1.22. - ()
(
1
<
1
) () I. 1 –
, 2 – .
1,
2. -
. -
90
()
1
<
1
(. 1.22), x
2
=0 x
2
=1, -
. -
.
, – . -
(-
) . 1.22 . .
1.22 -
, – ,
-
. , , -
,
.
, . 1.22,
, ,
, -
.
. -
.
,
, [137].
,
, .1.23
. 1.23. - ()
(
2
>
1
) () II. 1 –
, 2 – , 3 – .
,
1
,
-. - -
, -