( ) 158

: p VT

( CIP )
/ - : , 1994
ISBN 7302017360
T Q 0131
CIP ( 94) 16488

: ( , 100084)
:
:
:
: 787 1092 1/ 16 : 24. 25 : 570
: 1995 6 1 1995 6 1
: ISBN 7302017360/ O 159
: 0001
:


, ,
,
10 , 1986 ,

,
; , 10

, ,
,
9 1 2, 3
, 4, 5
6 , ,
, 7 , 8
,
,
,
,
,
, , ,

1993 10


1
0. 1 1
0. 2 2
0. 2. 1 2
0. 2. 2 3
0. 2. 3 3
0. 2. 4 4
0. 2. 5 4
5
6
1 7
11 7
111 7
112 8
113 9
114 13
12 24
121 24
122 25
123 26
124 27
125 29
30
33
2 p - V-T 34
21 p V T 34
22 36
221 36
222 37
223 38

 23 40
231 41
232 51
24 54
241 54
242 55
243 56
25 58
251 58
252 L yders en Greenk orn Hougen 60
253 P itzer 61
254 L ee K es ler Pit zer 61
255 64
26 p V T 65
261 65
262 67
263 68
264 69
27 72
271 A magat , Dalt on 72
272 75
273 79
274 84
86
89
3 91
31 91
311 ( M axwell) 91
312 92
32 96
321 96
322 97
323 103
33 110
331 110
332 111
333 115

334 116
34 118
341 118
342 119
35 120
351 120
352 122
36 128
361 128
362 134
138
140
4 142
41 142
411 142
412 145
413 148
414 150
415 156
416 157
42 159
421 159
422 161
423 162
43 163
166
168
5 169
51 169
511 169
512 175
513 177
52 179
521 179
522 182
53 183

531 183
532 187
533 187
534 189
54 192
541 193
542 194
55 195
551 195
552 195
56 197
57 198
571 199
572 H eylandt

201

204
206
6 208
61 208
62 210
63 212
631 212
632 216
64 221
223
224
7 225
71 225
711 225
712 , 228
713 , Gibbs Duhem 229
72 232
721 Scat chard Hildebrand 232
722 W oh l 233
723 F lory H uggins 235
724 W ils on 235
725 R enon Praus nitz NR T L 237

726 U NIQ U A C ( )

239

73 241
731 Scat chardHildebrand 242
732 W ils on 242
733 N R T L

245

734 U NIQ U A C

245

735 246
74 250
741 250
742 263
266
268
8 269
81 269
811 269
812 270
82 271
821 271
822 274
823 276
824 277
83 280
831 Chao Seader 285
832 288
84 292
841 Gibbs Duhem 292
842 293
843 295
844 298
85 300
851 H enry 300
852 H enry

300

853 301
86 306
861 306
862 311
87 ( ) 313

871 313
872 ( ) 315
88 319
881 319
8. 8. 2 320
883 320
324
326
327
327
327
331
T r , P r , Z c 345
U NIF AC 351
F 12 T S 360
371
375

0. 1
, ,
, ,
, , ,
,
,
, , 10
400 ,
, 100
,

, , ,
,
, ,
,
, ,
,
, ,
, , ,
, ,
, ,
, ,

20 , ,
, ,
,
,
, ,
50% , 80% ,

1944 B. F . Dodge [ 1] ,
1

, , , ,
,
, 01

01

,
, ,
,
, ,
,
, ( )
, ,
, 1969

[ 2]

, , ,

0. 2
,

0. 2. 1
,
2

( , ) ,
:
( 1)
,
( 2)
,

( 3)

, , ,

0. 2. 2
,
, ,
,
, , :
( 1) ( )
,
, , I m ,

I ( T , p , m 1 , m2 ) = I ( T , p ,
m1 ,
m 2 )
( 2) ( )
,
, ,
, E m ,

E ( T , p , m 1 , m 2 ) = E ( T , p ,
m 1 , m2 )
, 1

0. 2. 3
, ,
:
( 1)

A B A B,
3

( ) , BA
, A B

,
, 5, 6
, ,
, ,

, , , ,
,
( 2)
, ,
,

0. 2. 4
,
,
, ,
,
, , , ,

( K ) , , ( )
:
T ( K) = t( ) + 273. 16

0. 2. 5
( 1)

, , ,
,
, ,
,
U ,
, ,
( J )
4

( 2)
, , ,
, , 01
, ,
, , , ,
,
01

p ( )

V( )

E ( )

C ( )

( )

m ( )

( )

( )

H ( )

( )

p dv
E dc
dm
d
H d

( ) ,
( ) , ,
( J )
( 3)
, , , ,
,
,

,
,
, ,

, , ,
, , ( J ) ,

01
,
02 ,

03 , ?
?
04 ?
05 ,
,
06 1mol , T 1 T 2 ,

1 Dodge B F . Chemical E ngineering T hermodynamics . M cGr aw H ill, 1944
2. Praus nitz J M . M olecular T hermodynamics of F luid Phas e Equilibr ia , P rentice H all , 1969
3. Bet t K E . et al . T herm odynamics for Chemical E ngineer s. MIT Pres s, 1975
4. Chao K C and Greenkom R A . T hermodynamics of Fluids , A n Int roduct ion to Equillibrium T heory.
M ar cel Dekker , 1975

11
111
1840 1878 ,
,
,
, , ,
, ,
, 1lb 1
F
772ft lb ,
1cal = 4. 1840J ,
, , ,
, ,

, , ,
,
,
,
,
, ( )
, , , ,

, ,
, , , ,
, , ,
, ,
,

112
, ,
,
, 1850
,
, : , ,

, ,
, ,

, , ,
:
( ) + ( ) = 0

( 11)

, , ,
, ,

, ,
,
,
,

,
,
,
( 11) ,
( ) = Q W
Q W
( 11) , ,
,
( ) = U + E k + E p
( 11) ,
U + E k + E p = Q W

( 12)

U , E k E p ( 12)
, ,
, , ( 12)
8

U + E k + E p = Q - W

( 13)

,
, ( 13) :
U = Q -

( 14)

, , :
dU =
Q-

( 15)

d :
, d , d
, ( ) , d
( )
( 15) U, Q W ,
( 14) ( 15) , ( kJ )
, ,
, , ,

, , ,
,

113
( 14) ( 15) ,
, , ( 13) ,
, ,
, , ,
,

11 ( ) 1
2, 1 1 ,
Z 1 u 1 , v 1 , p 1 U 1 ; 2
2
, 1 2 ,
, ( 13) ,
, 1 2 :
2

u2 - u1
E k =
2g
u , ,
9

:
E p = Z 2 - Z 1
( 13) :
u 22 - u 21
U +
+ Z2 2g

Z1 = Q - W
( 16)

Q W

W 11
W F ,
( )

11

W F ,
,
, 11 , ,
V1 1 A 1 , V 1 / A 1 ,
A 1 p 1 A 1 , :
W 1 = p 1 A1

V1
= p 1 V1
A1

2 ,
, :
W 2 = p 2 A2

V2
= p 2 V2
A2

p V
( 16) W , ,
W = W F + p 2 V2 -

p 1 V1

( 16) , W
u2
U +
+ Z = Q - W F 2g

( p 2 V2 - p 1 V1 )

u2
+ Z = Q 2g

U + ( p V) +

WF

U + ( p V) = H
H 1 2 ,
2

u
H +
+ Z = Q 2g

WF

( 17)

, H Q J kJ ,
1 0

 J k J,
, , ,
, ( 17) :
H = Q -

WF

( 18)

,
( 14) , U = Q- W , , ,
,
( 17) ( 18)
H , ,
,
( 17)
udu
+ dZ =
Qg

dH +

WF

( 19)

,
dH = T dS + Vdp
Q = T dS
( 19)
Vdp +

udu
+ dZ +
WF = 0
g

u2
Vdp =
+ Z + W F
1
2g

( 110)

Vdp

11 , 12
98k Pa( 1kgfcm

- 2

) , 15, 686. 5kPa ( 7kgfcm

- 2

12 ( 1kg cm 2 = 98kP a )

, ,
98k Pa ,
, ,
1 1


[ ] 1 kg ( )
, , ( 110) ,

WF = -

p
p

Vdp

15 1. 706kPa 1. 001L kg

- 1

, ,
W F = - V( p 2 - p 1 )
= 1. 001( 686. 5 = -

589J kg

98)

- 1

, ( 18)
Q - W F = H
,
H = -

W F = + 589Jkg

- 1

( ) ,
H2-

H 1 = 589J kg

- 1

H 1 , H 2 , 15
63kJ kg

- 1

H1 = H

p
p

H
p

dp
T

p = 1. 706kPa
p 1 = 98kPa
H
p

= V-

V
T

, , ,
- 1

H 1 = 63kJ kg

H 2 = 63 + 0. 590 = 63. 59kJ kg -

686. 5 kPa ,
H 3 = 2763k J kg -

S 3 = 6. 715kJ k g

- 1

, , ( 1
8)
Q-

W F = H

, W F = 0,
Q = H = H 3 - H 2 = 2763 - 63. 59
= 2699. 4kJ kg -

1kg 2700kJ kg
,
1 2

- 1

S = S 4 - S 3 = 0

S 4 = S 3 = 6. 711kJ kg -

K -

, p 4 = 1k gf cm - 2 , S 4 P 4 , 4 , S 4 P 4
( M ollier )
H 4 = 583k cal k g -

= 2441k J kg -

,
Q - W F = H
, Q = 0,
- W F = H = H 4 -

H 3 = 2441 -

2763 = -

322. 0kJ kg

- 1

W F = 322. 0kJ k g

- 1

, ,
W = 322 -

0. 59 = 321. 4k J kg

- 1

( ) :
=

W
321. 4
=
= 0. 119
Q
2700

, 11. 9% , 88. 1%

114
,
, , ,

, :
, , U , H , F , G , C p , C V

, ,

, ( )

1
, , ,
, :

( Wm ) =

V
V

p dV

( 111)

p , V , , :
1 3

p V = RT
( 111) :

( W m ) = RT

V
V

2
1

dV
V

V2
V1

= RT ln

RT ln

= -

p2
p1

( 112)

, ( 112) ( ) , ,
p 1 p 2 ( , V1 V2 )
( ) ,
, ? p VT
2

p dV
p dV,
p V= Z RT ( 111) , ,

( Wm) =

V
V

p dV = R T

V
V

dV
V

dV
lnV = X , dX = dlnV =
,
V

( W m ) = RT

Z dX

pV
X = lnV,
RT
, Z X Z = f ( x ) ,
p 1 T 1 , 26 28 Z =

Z dX R T

, :
d( p V) = p dV + Vdp

p 2 V2 -

p 1 V1 =

V
2

p dV +

V
1

Vdp

( 372)

P
P

2
1

Vdp = R T ln

f
f

2
1

( Wm ) =

V
V

2
1

p dV = ( p 2 V 2 - p 1 V 1 ) -

RT ln

f
f

( 113)

3 33 , W m ,
, ; W m , ,
( W m )
1 4

 , , , U T
= 0, ; ,
U T ( 3. 2 ) Q
12 ( 27. 5) :
p / at m( M P a)
V / cm 3 m ol -

125. 4( 12. 7)

181( 18. 3)

228. 2( 23. 1)

313. 9( 31. 8)

380( 38. 5)

310. 0

200. 0

150. 0

100. 0

80. 0

( 1 ) p 1 = 125. 4at m ( 12. 7M Pa ) p 2 = 380at m

( 38. 5M Pa )
( 2) , ,

( 3) p , V 0. 5% ,
?

[ ] ( 1) ( W m ) = -

3 10
80

p dV

p V ( 13) ,
, :
( Wm ) = = -

0. 470 10 atm cm mol

3

4. 76 10 J mol

- 1

- 1

,
( 2) p c = 11. 277M P a
( 111. 3 atm ) , T c = 405. 6K =
0. 250,
Tr =

548
= 1. 35
405. 6

pr1 =

125. 4
= 1. 127
111. 3

pr2

380
=
= 3. 414
111. 3

13 27. 5 p V

1:
2:
,

f ( 0)
f ( 1)
lg
= - 0. 0654, lg
= 0. 038
p
p
( 0)
(1)
f
f
= - 0. 187, lg
= 0. 113
lg p
p
f
lg p 1 = - 0. 0654+ 0. 250 0. 038= - 0. 0559
f 1 = 0. 88 125. 4= 111 atm
f
= - 0. 187+ 0. 250 0. 113= - 0. 1587
p 2
f 2 = 0. 694 380= 264at m
lg

1 5

( 113)
( W m ) = 380 80 - 125. 4 310 - 82. 06 548. 15lg
= 30400 -

38900 -

264
111

103200lg2. 38

= -

4. 74 10 atm cm mol

= -

4. 80 103 J mol -

- 1

( 3) , ( 112)
310
80

82. 06 548. 15lg

( Wm ) = = -

103200 0. 588

= -

6. 07 10 atm cm mol

4
3

= -

- 1

- 1

6. 15 10 J mol
60700- 47000
, , ,
100= 29. 2% ,
47000
, ,

, ,
( ) , 0. 2% , p VT
,
2
, , ,
:
( Wm ) p = p ( V2 - V1 )

( 114)

H
T

= Cp
p

H p =

T
T

C p dT

( 115)

,
U p = H p - p ( V 2 - V 1 )

U p =

T
T

C p dT - p ( V 2 - V 1 )

( 116)

U p =

T
T
T

1 6

T
T
T

C
p dT -

R( T 2 - T 1)

1
2

( Cp -

R ) dT

1
2
1

C
V dT

( 117)

 C
p , C
V
,
Q p = U p + p V = H p

Qp =

T
T

( 118)

Cp dT

( 119)

1
3

13 p = 110. 66kPa 3500N m 1h

t 1 = 10 t2 = 500 1h
,
t

Cp m

= 0. 9956 + 0. 00009299tkJ k g

- 1

- 1

[ ] V 0 = 22. 4Nm 3 kmol- 1 , 1h :

G=

3500
28. 9 = 4520kg h
22. 4

1h
t

Qp = G( H 2 -

H 1 ) = G( C p m

t 2 - C p m

t1 )

= 4520[ ( 0. 9956 + 0. 00009299 500) 500 = 4520( 521. 0475 6

= 2. 31 10 kJ h

9. 9653) kJ h

( 0. 9956 + 0. 00009299 10) 10]

- 1

- 1

:
V = V0

p0 T
760 773 3
= 3500

m h p
T0
830 273

= 9080m 3 h -

3
, Q= 0 , , 1mol
( ) , U = Q - W

U = - W m = -

V
2
V
1

p dV

dU = -

p dV =

- RT
dV
V

dU= C V dT ,
C V dT = - R T

dV
V

dT
= T

R dV

CV V

, R = Cp - C V , , :
lnT = - ( k - 1) lnV +

1 7

ln( T V

k- 1

) =

( 120)

Cp
, , k= 1. 667; k= 1. 40;
CV
k= 1. 33( )
k=

, :
p V k =

( 121)

T
p

( k- 1) / k

( 122)

T1
=
T2

V2
V1

p1
=
p2

k- 1

( 123)

V2
V1

T1
=
T2

p1
p2

( 124)

( k- 1 ) / k

( 125)

( ) W m , :

Wm =

P dV =

p 1 V k1
1
p 1 V1 1 k dV =
k- 1
V

2
1

p2
p1

(k- 1)/ k

:
Wm =

1
1
R( T 1 - T 2) =
( p 1 V1 - p 2 V2 )
k- 1
k- 1

( 126)

, H ,
dH = T dS + Vdp
=
Q -

W F

W F ( ) , , Q
= 0

WF = -

p
p

Vdp = -

( 127)

WF = =

C
p dT =

k
R( T 1 k- 1

T 2)

k
( p 1 V1 - p 2 V2 )
k- 1

k
=
p 1V 1 1 k- 1

p2
p1

( k- 1) / k

( 128)

, k ,
k , , , ,
k
, k
1 8

,
,

T dS =

Q =

S = 0
, , , ,
( 14 )
,
S = S T + S p

S T +

( 129)

dT
= 0
T

( 130)

, 3 ,
C p T , ( 130) T 2 ,
C p p 2
, , ,

14

15

( 129) , , , 15 ,

:
S = S A C + S C D + S D B = 0

(S
A SA ) T +

dT
C
p
+ ( SB T
T
1
2

( 131)
S
B) T =
0

( 132)

1atm
, ( 132) ,
, , U
H , , 14 15
,
1 9

 U = U A B + U BC ( )
( )

= U A C + U CD + U D B
H = H A B + H BC

( 133)

( )
( )

= H A C + H CD + H D B

( 134)

W m W F U H , :
W m = - U

( 135)

( 136)

WF = -

, ,
( 130) ( 132) ,
14 194kmolh

- 1

101. 3kPa 38 3546. 3 kPa ,

:
p V = R T + 0. 053p
3

p , V T kPa, m kmol

- 1

Cp = ( 28. 89 + 6. 28 10

K 101. 3kPa

- 3

T ) k J kmol

- 1

- 1

: ( 1) T 2 ;
( 2)
[ ] ( 1) 311K

S T =

p1

= -

S p =

V
T

8. 314ln
T
T

2
1

dp = -

p
p

2
1

3546. 3
= 101. 3

R
dp = p

Rln

p2
p1

29. 56kJ k mol

- 1

- 1

Cp
dT
T

S T = -

29. 6 =

S p
T
T

2
1

28. 89
+ 6. 28 10
T

= 28. 89ln

dT

T2
- 3
+ 6. 28 10 ( T 2 - T 1 )
T1

T 2 , T 2 = 780 K , t 2 = 507
( 2)

WF = -

- H p = =
= 2 0

= -

H p -

H T

C p dT

28. 89( 780 -

311) -

15156. 1k J kmol

- 1

6. 28 10- 3
2
( 780 2

311 )

H T = -

= -

p
p
p

V
T

V- T

1
2

dp = p

0. 053dp = -

V-

0. 053( 3546. 3 -

RT
dp
p
101. 3)

= - 182. 6kPa m 3 kmol -

= 182. 5k J kmol -

W F = - 15156. 1 - 182. 5 = - 15338. 6kJ kmol

- 1

W F = - 194 15338. 56kJ h 5

= - 8. 28 10 J s

- 1

= -

2. 98 106 kJ h -

( )

, ,
, ,
4
, :
m

p V =

( 137)

m ( 137) ,
, m , m
, m ( 137) p V

( p V = R T )
, :
p1
=
p2

V2
V1

T1
=
T2

V2
V1

m- 1

T1
=
T2

p1
p2

( 138)
( 139)
m- 1
m

( 140)

, m ,
( 138)
m=

lnp 1 lnV2 -

lnp 2
lnV 1

, W m

Wm =

p dV

1
=
p 1V 1 1 m- 1

p2
p1

1
R( T 1 m- 1

T 2)

1
( p 1 V1 m- 1

p 2 V2 )

m- 1
m

( 141)
2 1

, W F -

p
p

Vdp ( 137)

:
mp V m- 1 dV + V m dp = 0

Vdp = mp dV

m
WF =
p 1 V1 1 m- 1

p2
p1

m- 1
m

( 142)

, ( 141) ( 142) (
)
16 ,
U A B = U A C + U CB
T

U
T

2
1

dT +
p

p
p

2
1

U
p

dp
T

( 143)

U p ( 116) , U T
323 A D DB ,

( 143) , ,
:

U =

T
T

C V dT

( 144)

Q :
Q = U + W m

( 145)

16

, :

Q=
=

CV dT +

R
( T 1 - T 2)
m+ 1

R
( T 2 - T 1)
m- 1

CV -

( 146)

, C :
C = CV -

R
= CV m- 1

= CV 1 -

C p - CV
m- 1

k- 1
m= CV
m- 1
m-

k
1

( 147)

( 147) , 1< m< k, C V , C ,

,
, U , ,
, 16
15 , p V :
2 2

p / kP a
V/ m 3 kmol -

3445. 0

2735. 8

2067. 0

1378. 0

689. 0

344. 5

101. 3

0. 915

1. 1

1. 37

1. 97

3. 52

6. 36

17. 3

, Cp = 29. 3kJ k mol K - 1 k = 1. 40

( 1) ? ?
( 2) ?
( 3)
( 4) Q U H
[ ] ( 1) ,
p 1 V1 = p 2 V 2
,
( 13. 6) ( 1. 97) ( 6. 8) ( 3. 52)

,
k

p V =
k = 1. 20, , 1. 20
( 2)
W =
=

( p V)
m- 1

101. 3( 17. 3) + 3445. 0( 0. 915)

1. 20 - 1

= 6998. 65kPa m 3 kmol3

= 7. 00 10 J mol
( 3) p V= RT , T =

- 1

pV
, , :
0. 08205

p / kP a

3445. 0

2735. 8

2067. 0

1378. 0

689. 0

344. 5

101. 3

T/ K

380

364

342

326

293

264

212

( 4) U = H - ( p V ) , ,

C dT =

H =

= U = = -

29. 3( 212 -

380)

4. 92 103 J mol-

4920 + 1400
3

3. 52 10 J mol

Q = U + W = -

- 1

3520 + 7021

= 3. 50 103 J mol-

2 3

12
121
, ,
, , (
) , ( , )
, ,
,
, , ,
40% , ,
,
, , ,
,
, , ,
, ,
, ,
, ,
, 60% ,
, , : 110at m
, 75% ,
, ,
, ,
, ,
, ;
,
,
, ,
, ( ) , ,
, ,
, ,
,

, , - 100
,
, ,
, ,
2 4

,
, ( ) ,
,

122
, ,
, ,
,
, ,
,
, 17( a ) , ,
17( a ) 12341
, , 17( b) ,
, 14321 ,
,
, , , ,
,

, t

17

, , 1 kg
Q1 ; , Q 2
, , ,
1kg , :
W = Q1 - Q2

t =

Q1 - Q2
W
=
= 1Q1
Q1

Q2
Q1

( 148)
2 5

, t < 1 t ,
,
,
=

Q2
Q2
=
W
Q1 - Q2

( 149)

123
, , ,
T 1 T 2 :
( 1) Q1 , (
18)

18

( 2) T 1 T 2 ,
( 3) Q2 T 2 ,

( 4) , , T 2 T 1 ,

( 1) ( 3) ( ) ( 1) ( 3) ,
( 2) ( 4) ,
Q 1 = T 1 S
Q 2 = T 2 S
,

W = Q
, :
W = Q1 - Q2
, :
=
2 6

T 1 S - T 2 S
T1 - T2
W
=
=
Q
T 1 S
T1

( 150)


:
,
, A B ,
Q 1 Q
1 , , Q 2 Q
2 , W W
,
:
A =
A , A

W
W
B =
Q1
Q
1

B , :

W = W
, , , A <
B , W = W
,
1 A , ( 19) , A
Q1 > Q
( B ) , Q 2
Q 1 A , B ,
,
Q
2 =
Q
1 W
Q2 = Q1 - W
W = W
,
Q 1 - Q
1 =
Q2 -

19

Q
2

, , ( Q 2 - Q
2 )
, , ,
, B > A , A

: ,

, A B ,

A
B , A ,
A

B , B , B

A ,

A = B
, ,

124
, , ,

:
Q
1 Q
2
Q
1

Q 1 - Q 2
Q 1

, :
Q
2
Q
1

Q 2
Q 1

( 151)
2 7

, ,

Q2
T2
, :
Q1
T1
Q
2
T2
Q
1
T1
Q
1
T1

Q
2
T2

( 152)

, , ( 152) :
1
2
Q
Q
+
T1
T2

( 153)

( 153) Q
1 Q
2 T 1 T 2
, , Q1
Q 2 , 110 ,
, ( 153) , ,

Q
T

( 154)

( )

( 154) ,
:

Q
= 0
T

110

( 155)

Q
< 0
T

( 156)

, ( 155) , 111 A , B C ,
( 155) , 1A 2B1

Q
=
T

Q
T

2
1

1
2

Q
T

= 0
B

( 157)
1A 2C1,

Q
=
T

Q
T

2
1

Q
T

= 0
C

( 158)
111

( 157) ( 158)

1
2

Q
T

1
2

Q
T

Q
, , ,
T

:
S = S 2 2 8

S1 =

2
1

Q
T

( 159)

1
T
, 112 A , B ,

( 156)

Q
=
T

2
1

Q
T

1
2

Q
T

< 0

( 160)

( 159) ,

S = S 2 - S 1 >

Q
T

( 161)

1
T
( 159) ( 161) , :

dS

Q
T

( 162)

, ( 162)

112

( ) , Q= 0,
dS

( 163)

( 163) , :

, , :
T 1 1 T 2 2 ,
Q 1
2, 1

Q
, 2 , ( )
T
T

:
dS = -

Q
+
=
T1
T2

1
T1

Q> 0
T2

, ,
, ( 163) ,
, , ,
,

125
,
Q T 1 T 2 ,
S + S = S T = -

T1 - T2
Q
Q
+
= Q
T1
T2
T 1T 2

( 164)
2 9

, , T 1 Q,
T 2 , (
) ( 150) :
W= Q

T1 - T2
T1 - T2
= T 2Q
T1
T 1T 2

( 165)

( 164) ( 165) W L :
W L = T 2 ( S + S ) = T 2 S T

( 166)

T 2
( 166) , ,
, ( 166) ,
,
T 0 ,
W L = T 0 S T

( 167)

( 167) ,
( )

11 , 95% , 5%
t 1 = 12 t 2 = 35, N =
40k W , 1h
12 11 , 62. 55kJ kg

- 1

2710. 5kJ kg - 1 , 70% , 1kg 29190kJ ,

4. 5th

- 1

, 1h

11

12

13 ( 12) ,
588. 4kPa ( 6at ) , 25 , 147. 1kPa ( 1. 5at ) , 10,
3 0

588. 4kPa
14 ,
( 13)
- 1

2293. 5k Jkg
2m s

- 1

, 200ms

- 1

125. 1kJ k g

- 1

, 1kg

10, 1kg
?
4. 17k J kg

- 1

- 1

15 1k g t 1 = 17

13

1/ 5,

, ?
16 :
V / Lkg p / kP a

50

100

150

200

250

3932. 4

1412. 1

755. 1

480. 5

343. 2

? ?
p V ,
, p V ( )

17 p V T S :
( 1) ;
( 2) ;
( 3) , ;
( 4) , ;
( 5) , ;
( 6) ,
18 ( 14) t 1 = 0 t 3
= 25 , 10000kg
h

- 1

, 50k W ,

,
( 1) t 2 ;
( 2) kJ h - 1 ;
( 3)
? , ,
14

,
3 1

? ?
19 ,

Q/ kJ

W m / kJ

+ 10. 42

- 9. 81

+ 14. 71

- 17. 93

- 6. 87

+ 15. 85

( 1) ;
( 2) ;
( 3) ;
( 4)
110 ( )
:
3

( 1) : 392. 3kPa( 4at ) , 1m kg

3

( 2) : 1m kg

- 1

- 1

, 98. 07kPa( 1at )

( 3) :
: ( 1) ;
( 2) S 12 , S 23 , S 31 , p V T S

111 35k g, 427 135k g, 21

cp = 0. 5 kJ k g- 1 - 1 , cp = 2. 5kJ kg - 1 - 1 ,
, :
( 1) ?
( 2) ?
( 3) ?
112 , , T 1 ( K ) T 2 ( K ) ;
, T m ( K )
G( kg) , c( kJ k g
( 1) T m =

- 1

- 1

) , :

T 1T 2 ;

( 2) Gc( T 1 + T 2 - 2T m )
113 G , T 1 T 2 ,
2 Gcp ln

T 1+ T 2

2 T 1T 2
114 , , T 1
, T 2 , ,
,
3 2

W = cp

T1
+ T2 T2

2T 1

[ 1] . , 1964
[ 2] , 1964
[ 3] , 1979
[ 4]
.
.

, 1952

3 3

2 p -V-T
,
, , , ,
; , , p ,
V T , p VT
p VT , ,
,
,

2 1 p - V-T
, 21

21 p VT

, ( S)
( L ) ( G ) ( G L ) ( G S) ( L S)
, , A B

, , , ,
3 4

, p T ,
, , p T
, p T : ,
21 p T 21 , p V ,
21 p T p V
, 22 23,

22 p T

23 p V

22 ( 23) ,
,
( 12) ( 2C )
C, , C
, T C p C C
,
, p C
T C ( ) , ,
, ,
23 ( A C) ( C B)
A CB
, , T C , T C T 1 T 2 22
, T c T 3 T 4 ,
, , , ,
, ,
, ,
, A BC , ,
, C ,

3 5

 AC , , ,
, A C (
)
CB , , CB

22
, , p , V, T ,
,
F ( p , V, T ) = 0

( 21)

( 21) ;
, 150
, , ,
, [ 43]

221
, ,
1738 Bernoulli , ,
, ,
, ,
, ,
, ,
, , :
, , ,
, , ,
, , A r, N 2 , O 2 ,
, :
p V t = R T

( 22)

, p , V t , T ( ) , , R

1840 Clapeyron Charles BoyleM ariott e ,

( 22) Clapeyron
,
p , V t , T , , ;

:
3 6

( 1) R p , V, T , 21
R
21

R
82. 06

cm 3 atm m ol - 1 K -

0. 08206

m 3 atm kmol - 1 K -

cal mol - 1 K - 1
J m ol - 1 K - 1

1. 987
8. 314
83. 14

cm 3 barmol - 1 K -

8. 314 103

m 3 P a kmol - 1 K -

( 2) , ,
( 3) , , 273. 16

222
( J M ayer) , ,
p V T
( V irial ) ,

23 T 1 , V p , ,
p V , p V p
,
2

p V = a + bp + cp +

( 23)

b= aB
, c= a C
,
pV = a( 1 + B
p + C
p 2 + )

( 24)

, ( 23) , ,
, ,
, p V p , p 0 ,
p V ( 24) , p 0 , p V a , ,
lim
p V ( p V) = a
p 0

( 25)

, a , ,
( p V) = a = f ( T )

( 26)

( 26) , , , p V
p p V p , p = 0, ( p V ) ( 24)

, ( p V) T ,
( p V)

= a = RT

( 27)

273. 16K ,
3 7

( p V) t = R 273. 16

( 28)

t
( 27) ( 28)

( p V)
T
=
273. 16
( p V) t

( p V)
T = 273. 16

( p V) t

( 29)

( 29)

24 p 0 p V

, ( 24)
a RT , ( 24)
Z=

pV
= 1 + B
p + C
p2 + D
p 3 + ( Berlin )
RT

( 210)

p V/ ( RT ) , Z ( 210) p
, 1/ V ,
Z=

pV
= 1 + B / V + C/ V 2 + D / V 3 + ( Leiden )
RT

( 211)

, B
, C
, D
B , C, D , ; B
B
; C
C , ,
( 210) ( 211) , :
2

B
C- B
D - 3BC + 2B
B =
C=
=

2 D
RT
( RT )
( RT ) 3

( 212)

, ( 212)
,
,

; B / V ; C/ V ,
p VT

223
, ( 210) ( 211) ,
Z=

pV
= 1 + B
p
RT

( 213)

Z=

pV
= 1 + B/ V
RT

( 214)

( 213) , ( 214)
, ( 213) , p , V , T
B B
, B

3 8

B , B
= B / ( R T ) , ( 213) ,
Z=

pV
Bp
= 1+
RT
RT

( 215)

1907 , Bert helot , B

2

9
RT c
B =

1128
pc

Tc
6 2
T

( 216)

6 pr
2
Tr Tr

( 217)

Bert helot ,
9
1128

Z = 1+

, Berth elot ( )
, p r , T r ,
Pit zer :
Bp c
(0)
( 1)
= B + B
RT c
B

(0)

( 1)

( 218)

,
B ( 0) = 0. 083 B

( 1)

= 0. 139 -

[ 1]

0. 422
T r1. 6

( 219)

0. 172
T r4. 2

( 220)

, T sonopoulos Pitzer , [ 2]
Bpc
= f
RT

( 0)

+ f ( 1)

( 221)

( 0)

= 0. 1445 -

0. 330
Tr

0. 1385
T 2r

( 1)

= 0. 0637 +

0. 331
2
Tr

0. 423
3
Tr

0. 0121
T 3r

0. 000607
T 8r

( 222)

0. 008
8
Tr

( 223)

( 218) , ( 221) ( )
, , H aydenO
connell
,

[3]

[4]

21 460K 1. 52 10 kPa
( 1) ;
( 2) Berth elot ;
( 3) ( 218) ;
( 4)
Z= 1+

B
C
+
(B = V
V2

265cm mol

- 1

, C = 30250cm mol

- 2

[ ] ( 1)
V=

RT
8314 460
3
=
3 = 2516cm mol
p
1. 52 10

3 9

 ( 2) Berth elot
: p c = 3. 75 103 kPa , T c = 425. 2K , = 0. 193
3

460
1. 52 10
T r =
= 1. 08 p r =
= 0. 40
425. 2
3. 75 10 3
T r , p r Berth elot ,
9
0. 4

1128 1. 08

Z = 1+

6
= 0. 8927
( 1. 08) 2

V=

0. 8927 8314 460

3
= 2246. 5cm mol
3
1. 52 10

( 3) ( 218)
( 219) ( 220) ,
B(0) = -

0. 290 B ( 1 ) = 0. 014

= 0. 193 ( 218) ,
Bp c
= B ( 0 ) + B ( 1) = - 0. 290 + 0. 193 0. 014 = - 0. 287
RT c
( 215) ,
Z = 1 - 0. 287

0. 4
= 0. 894
1. 08

V=

Z RT
0. 894 8314 460
3
=
= 2250cm mol
3
p
1. 52 10

( 4) ,
Z=

pV
B
C
= 1+
+
2
RT
V
V
3

1. 52 10 V
= 18314 460

265
30250
+
2
V
V

V = 2233cm 3 mol- 1 ,
,

/ cm 3 mol -

/ %

( 1)

2516

12. 7

( 2)

2246. 5

0. 60

( 3)

2250

0. 76

( 4)

2233

2 3
, , ,
4 0

, ,
,
, ,

, , ,
,
, , ,
: , , ;
van der W aals , van der W aals
, ,
,
:
1: van der W aals ( 1873) R edlich K wong ( 1949) W ilson ( 1965)
Soave ( 1972) Peng Robinson ( 1976)
2: Beatt ieBridgeman ( 1928) Benedict W ebbR ubin ( 19401942) Starling
( 1971) St arling H an ( 1972)

231
( 1) van der Waals
1873 J . D . van der Waals :
p +

p =

a
(VV2
RT
V- b

b) = R T
a
V2

( 224)

, ,

( 224) , a
,
, a / V 2 , b,
( covolume ) , V , b

, p 0, V ,
( 224) , ( 224)
pV =

RT
1 - b/ V

a
V

( 225)

, ( 225)
van der W aals , p V , 25 ,
4 1

( 224) V , T , p
, V
, , V
,
T < T c , p 1 p 3 , V
, p 1 p 3 ,
, p 1 , F
p 3
p 1 , V ,
,

25 van der Waals

; T c ,
p c , V , C , ,
V c ,
T c , V, ,
T > T c
T < T c , p 2 A G; ( A )
, ( G ) , p 1 p 3
,

p/ V

, , ,

DE F ,
A D FG , ( p / V ) T ,
, , A D
, FG , , ,
DF ,
van der W aals , p c , V c
3

T c a, b : V , ( V- V c ) = 0,

V -

3V c V + 3V c V -

Vc = 0

( 226)

, van der Waals ,

3

V -

bP c + RT c
2
a
V +
Vpc
pc

, ,
3V c =
2

3V c =
3

Vc =

4 2

bp c + R T c
Pc
a
pc
ab
pc

ab
= 0
pc

( 227)

27 ( RT c )
a=

64
pc

1 RT c

8
pc

b=

P cVc
=
RT c

( 228)

3
8

a b p c , T c ,
, van der W aals ,
c
p cVc 3
=
, van der Waals ,
RT c
8
, , 0. 230. 29

a , b ,
,
2

p
V

= 0
T

p
V2

= 0
T

( 229)

van der W aals ,

p
V

RT c
2a
= 0
2 +
( V c - b)
V3c

= T

p
2
V

=
T

2R T c
3 ( V c - b)

( 230)

6a
0
4 =
Vc

( 231)

( 230) ( 231) ,
b=

1
Vc a =
3

9
RT c V c
8

( 232)

( 224) , ( 232) ,
p cVc
=
RT c

3
8

( 233)

, ( 232) ( 233)
b=

1 RT c
27 ( R T c )

a =

8
pc
64
pc

van der W aals ,

, p VT p VT
a b , , van der
W aals ,

,
( 2) R edlich Kwong ( R K )
2

, R edlichKwong a / V , 1949

[ 5]

4 3

RT
V- b

p =

0. 5

a
V( V + b)

( 234)

a , b , van der W aals ,

, , T c p c
V ,
V3 -

a
Tp

RT
V2 +
p

bRT
- b2 V p

a
b
= 0
p
T

( 235)

van der W aals a , b , R K a b

, ( 229) , ( 226) ( 235)
:
3V c =

RT c
pc

( 236)

ac
T cp c

3V c =

bR T c
2
- b
pc

acb

V 3c =

( 237)
( 238)

Tcpc
p c Vc 1
=
,
RT c
3
, R edlich R wong
( 236) , R edlich K wong

( 236) , ( 237) ( 238) a b,

3

b + ( 3V c ) b + ( 3Vc ) b -

Vc = 0

,
b3 + 3b2 Vc + 3bV 2c + V 3c = 2V 3c
3

( b + V c ) = 2V c

b = ( 21/ 3 -

1) Vc

( 239)

( 236) ( 239) ,
b=

(2

1/ 3

- 1) R T c
RT c
= 0. 08664
3p c
pc

( 240)

( 236) , ( 238) ( 240) ,

R 2 T 2c . 5
R 2 T 2c . 5
ac =
= 0. 42748
9( 21/ 3 - 1) p c
pc

( 241)

Z RT / p V, ( 234) ,
3

Z -

Z + ( A - B - B ) Z - AB = 0

( 242)

A=

Pr
ap
2. 5 = 0. 42748
2. 5
R T
Tr

( 243)

B =

pr
bp
= 0. 08664
RT
Tr

( 244)

4 4

 R edlich Kw ong

a
b
b
2
A , B h , ( 234)
2. 5 ,
RT V
R T
2

A2
B

1
1- h

Z=

RK

h
1+ h

( 245)

( 245) , Redlich K wong 6

( 3) Wilson

[ 6]

R edlich K won g
RT
V- b

p =

a
V( V + b)

( 246)

a = a c

( 247)

( R T c)
a c = 0. 42748
pc

( 248)

- 0. 5

= T r Wilson g ,
, R edlich Kw ong ,
/ T r , T r ,
= T r g ( T r , )

( 249)

, , g 1/ T r ,
g = c + mT -r

; T r = 1, g = 1,
- 1

g = 1 + m( T r

1)

( 250)

, m
, ,
p
T

=
sa t

p
T

( 251)
V
c

m
m = 1. 57 + 1. 62

( 252)

( 250) ,
g = 1 + ( 1. 57 + 1. 62) ( T -r

1)

( 253)

- 1

= T r [ 1 + ( 1. 57 + 1. 62) ( T r

1) ]

( 254)

( 4) Soave ( R KS )
Soave T r ,
W ils on
Soave , T r = 0. 41. 0 ,
0. 5

0. 5

T r

,
0. 5

0. 5

= c - mT r

[ ( 247) ] , T r = 1 , = 1,
4 5

0. 5

0. 5

= 1 + m( 1 - T r )

( 255)

( 255) , Soave ,
m, m
, ,
m = 0. 480 + 1. 574-

0. 1762

( 256)

( 255) ( 256) ,
0. 5

1/ 2

= 1 + ( 0. 480 + 1. 574- 0. 176) ( 1 - T r )

( 257)

Soave RedlichKwong ,
Soave

,
Z3 -

Z 2 + ( A - B - B 2 ) Z - AB = 0

( 258)

A=

pr
a p
0. 42748 2
2 =
( RT )
Tr

( 259)

B =

pr
bp
= 0. 08664
RT
Tr

( 260)

( 5) PengR obinson ( PR )

[7]

Redlich Kwong W ils on Soave ,

, Peng R obinson RedlichK wong
, 1976 :
p =

RT
V- b

p =

RT
V- b

a
V( V + b) + b( V -

a
2 + 1) b] [ V -

[V + (

( 261)

b)

2 - 1) b]

( 261a )

a ( 247) a b ( 2
61) V ,
RT c
a 2bR T c
a bR T c
2
2
2
- b V +
- 3b V- b
- b = 0
pc
pc
pc
pc
pc
( 226) ( 262) , ,
3

V -

3V c =
2

3V c =

RT c
pc
a
pc

ab
V =
pc
3
c

( 262)

( 263)

2bR T c
2
- 3b
pc
b2 RT c
- b3
pc

( 264)
( 265)

( 263) , ( 264) ( 265) , b/ V c = c ,

3

3c + 3c + 3c
4 6

1= 0

( 266)

c = 0. 2530766

( 267)

c ( 263) ,
p cVc
= 0. 3074013
RT c

c =

( 268)

, a c b
( RT c ) 2
a c = a
, a = 0. 457235
pc
b = b

( 269)

RT c
, b = 0. 077796
pc

( 270)

( 268) , 0. 3074 Redlich K wong

1/ 3, (
H 2 H e ) ( 261) Soave ,

( 261) ,
Z3 - ( 1 -

B) Z2 + ( A -

2B -

3B 2 ) Z - ( AB -

B2 -

B3 ) = 0

( 271)

A=

ap
p r
0. 457235 2
2
2 =
R T
Tr

( 272)

B=

bp
pr
= 0. 077796
RT
Tr

( 273)

Peng R obinson Soave , T r

0. 5

0. 5

= 1 + m( 1 - T r )
m ,
,
m = 0. 37646 + 1. 54226-

0. 26992

( 274)

, Peng R obinson
0. 5

= 1 + ( 0. 37646 + 1. 54226-

0. 269922 ) ( 1 -

T 0.r 5 )

( 275)

, Soave Peng R obins on ,

, PengR ob inson
Soave
, , ,
, , Redlich
K wong , Ar , Kr , Xe , N 2 , O 2 , CO , CH 4 (
) , Peng R obins on = 0. 35 ( Z c = 0. 26 )
,

c ,
c
15% ,
,
c , ,
4 7

 , 1980 Schmidt W en zel

[ 8]

, 1981

[ 9] , 1982 Patel T eja [ 10 ]

( 6)
1981
RT
V- b

p =

a
( V + mb) ( V -

( 276)

b)

a = a c ( )
, m, 22
2-2 m n

van der Waals

2 + 1

2 - 1

Redlich Kw ong
Wilson, Soave
P eng Robins on

,
, m , :
m= 1+ 2

= 2(

2 -

1)

( 277)

( 277)
p
V

=
T

p
V2

= 0
T

( 276) ,
2

R Tc
a = a
pc

( 278)

a = c / c + mc c ( 1 + c
c)
b = b

RT c
, b = c
c
pc

c = [ 3 +
(m - -

( 279)

1) c ] -

Vc
3
2
2
2
2
2
c ( m + - m + m - m) + 3c ( m - -

( 280)

c =

m) + 3c -

1 = 0 ( 281)

c = 0. 25990 -

0. 16824+ 0. 75622 -

0. 80732 ( = 0 0. 5)

Soave :
0. 5 = 1 + k( 1 - T 0r . 5 )

k = 0. 4514 + 1. 3210 4 8

0. 5327

( 282)

 z
3

Z + [(m - -

1) B -

1] Z + [ A -

( m - ) B -

+ [ m( B 2 + B 3 ) -

( m - + m) B ] Z

AB ] = 0

( 283)

,
A =

a c p
bp
2 B =
RT
( RT )

, , R KS PR ,

22 0. 5kg , 338. 2K 30000cm

,
( 1) ;
( 2) R edlichKwong ;
( 3) Soave R edlich K wong ;
( 4) Peng R obinson ;
( 5)
[ ] :
3

M = 17. 031, T c = 405. 6K , p c = 11. 28 10 k Pa = 111. 3atm

Z c = 0. 242, = 0. 250
( 1)
V=

VT
VT
=

m/ M

, m , M ,
V=

30000
= 1021cm 3 mol 500/ 17. 02

8. 314 106 338. 15

3
p =
= 2. 753 10 k Pa
1021
( 2)
h=

RT c
b
0. 0867 8. 314 106 405. 6
= 0. 0867
=
V
p cV
11. 28 106 1021
= 0. 0253
1. 5

2
0. 4278 T c
A
a
4. 934
=
1. 5 =
1. 5 =
1. 5
B
bR T
0. 0867 T
Tr

Tr =

T
338. 15
=
= 0. 833
Tc
405. 6

( 245) ,
1
4. 934
h
1
4. 934
0. 0253
=
Z = 1- h 1. 5
1.
5
1+ h 0. 9747 ( 0. 833)
1. 0253
Tr
= 0. 867

4 9

Z RT
0. 867 8. 314 10 338. 15
p =
=
= 2. 387 103 kPa
V
1021
( 3)
6
RT c
8. 314 10 405. 6
b= 0. 08664
= 0. 08664
= 25. 90
6
pc
11. 28 10
2
6
2
( R T c)
( 8. 314 10 405. 6)
a c = 0. 42748
= 0. 42748
6
pc
11. 28 10
11
= 4. 3095 10
2

m= 0. 480+ 1. 574 0. 250- 0. 176( 0. 250) = 0. 8625

0. 5

= [ 1+ 0. 8625( 1- 0. 833

) ] = 1. 156

a = a c = 4. 9817 10 11
6

11

8. 314 10 338. 15
4. 9817 10
p =
1021- 25. 90
1021( 1021+ 25. 90)
6
= 2. 8252 10 - 0. 46606 106 = 2. 359 103 kPa
( 4)
6
RT c
8. 314 10
405. 6
b= 0. 077796
= 0. 077796
= 23. 264
pc
11. 28 10 6
6
( R T c) 2
( 8. 314 10
405. 6) 2
a c = 0. 45724
= 0. 45724
= 4. 6095 1011
pc
11. 28
m = 0. 37646+ 1. 54226 0. 25- 0. 26992 ( 0. 25) 2 = 0. 74515

= [ 1+ 0. 74516( 1- 0. 833 0. 5 ) ] = 1. 13435

11

a = a c = 5. 22875 10

( 261) ,
6

8. 314 10 338. 15
p =
1021 - 23. 264

11

5. 22875 10
1021( 1021 + 23. 264) + 23. 264( 1021 -

23. 264)

= 2. 81776 - 0. 47996 = 2. 3378 10 3 k Pa

( 5)
c = 0. 25990 c =

0. 16824( 0. 25) + 0. 75622( 0. 25) 2 -

1
=
c + 3)
(3+ 2

(2

0. 80732( 0. 25) 3 = 0. 2525

1
= 0. 307457
0. 25 0. 2525)

b =
c
c = 0. 307457
0. 2525 = 0. 077633
m= 1+ 2
= 2(

= 1 + 2

2 -

1)

0. 25 = 2. 4142

0. 25 = 0. 4142

2
c

a = / c + mc c ( 1 + c
c) =
( 0. 307457) / 0. 2525
+ 2. 4142 0. 4142 0. 2525 0. 307457( 1 + 0. 2525 0. 307457)
= 0. 4580
k = 0. 4514 + 1. 321 0. 25 -

0. 5327 ( 0. 25)

= 0. 7484
= [ 1 + ( 1 5 0

0. 5

0. 833

) 0. 7484] = 1. 13466

6
( R T c)
( 8. 314 10 405. 6)
b = 0. 077633
= 0. 077633
= 23. 21
6
pc
11. 28 10
2

6
2
( R T c)
( 8. 314 10 405. 6)
a = 0. 4580
= 0. 4580
1. 13466
6
pc
11. 28 10
11

= 5. 2389 10

8. 314 106 338. 15

p =
1021 - 23. 21
= ( 2. 8179 -

5. 2389 10 11
( 1021 + 56. 034) ( 1021 6

9. 614)

0. 48094) 10 = 2. 337 10 k Pa
3

2. 382 10 kPa , ,
15% , , ,

232
, ,

( 1) Beatt ieBridgeman ( BB )
1928 Beatt ie Bridgeman
p = R T ( 1 + B) ( 1

) - A

B = B 0 ( 1 - b)

( 284)

A = A 0 ( 1 - a )
= c/ T

[ 11]

1
; B 0 , A 0 , a , b, c , p V T
V
B B :

p = p th - p i

( 285)

p p t h p i ,
RT , , van der Waals
, Beatt ie Bridgeman Lorentz ,
, , ,
p t h
p t h = RT ( 1 + B )
, B ,
p t h = RT [ 1 + B 0 ( 1 -

b) ]

( 286)
( 287)

, , ,
,
, R ( = N 0 ) Beat tie
, ,
R = R ( 1 - c/ T )

( 288)
5 1

 T Beatt ie Bridgeman , H e, Ar , Ne,

H 2 , O 2 , CO 2 , CH 4 , 3, ,
c
T3

R = R 1 -

( 289)

,
p t h = R T [ 1 + B 0 ( 1 - b) ] 1 -

c
T3

( 290)

, p i

p i = A2

( 291)

L orent z p i
2

p i = A 0 ( 1 - a )

( 292)

( 290) ( 292) ( 285) , Beat tieBridgeman

( 284) :
p =

RT

+
2 +
3 +
4
V
V
V
V

= R T B 0 -

A 0 - cR / T

( 293)

= - R T B 0 b + A 0 a - cR B 0 / T 2
=

RB 0 bc
T2

, ,
j , , [ 12] , [ 1 3]
( 2) Benedict WebbR ubin ( BW R )

[ 14 ] , [ 15]

Benedict , W ebb R ubin Beatt ie Bridgeman ,

, ,
, , Beat tie
Bridgeman ,
(p -

RT ) / = RT ( ) -

( ) - ( ) / T

( 294)

( ) , ( ) ( ) ,
( ) , ( ) ( ) , ,
( ) = B 0 + b
( ) = A 0 + a ( 1 -

( ) = C 0 - c( 1 + 2 ) exp ( -

( 295)
2 )

BB , BWR : C 0 , , ( 295) ( 294) ,

p = RT +

B 0 RT -

A0 -

C0 2
+ ( bR T - a ) 3
2
T

3
2
2
+ a + c 2 ( 1 + ) exp( - )
T
6

5 2

( 296)

 BWR
, BW R , 1. 8
2. 0 , 0. 3%
, 1967 Cooper Goldfrank [ 16] , [ 2 3] 33
BWR Orge

[ 1 7]

, ,
21 BWR ,
( 3) K . E . Starling BWR ( BWR S )

[ 18]

1971 K. E . Starlin g BWR , 11

, BW RS SHBWR , BW R ,
T r = 0. 3, 3 CO 2 , H 2 S
N 2 , 0. 5% 2. 0%
BWR S
p = RT +
+

B 0R T - A 0 -

bRT -

a-

C0
D0
2 +
T
T3

d
d
3 + a +
T
T

c3
2
+
) exp ( 2 (1 +
T

E0 2

T4
6

( 297)

BWR , D 0 , E 0 d
( 4) St arling Han [ 1 9]
BW R S , 11 c T c
, ,
c B 0 = A 1 + B 1
c A 0
= A2 + B 2
RT c
c C 0
A3 + B 3
3 =
RT c
2c = A 4 + B 4
2

c b = A 5 + B 5
2

c a
= A6 + B 6
RT c
3

c = A 7 + B 7
2c C
A8 + B 8
3 =
RT c
c D 0
B9
4 = A9 +
RT c
2

c d
= A 10 + B 1 0
R T 3c
5 3

c E 0
= A 11 + B 1 1 exp( R T 5c

3. 8)

, BWR S , ,
, A j B j ( j = 1, 2, , 11) 23 C1 C 8
T c , c
2-3 Aj Bj
Bj

Aj

0. 443690

0. 115449

0. 0705233

1. 284380

- 0. 920731

0. 504087

1. 32245

0. 356306

1. 70871

0. 0307452

0. 179433

0. 544979

- 0. 270896

10

0. 0732828

0. 463492

0. 528629

0. 349261

11

0. 006450

0. 484011

0. 754130

Aj

Bj
- 0. 044448

- 0. 022143

M artin [ 20]

2 4
241
: p c , T c V c
p c , V c T c , , ,

pr = p/ pc

( 298)

V r = V/ V c

( 299)

Tr = T /Tc

( 2100)

, ( p r = p r = p r = , V r
= V r = Vr = , T r = T r = T r = ) ,
( a b) , p , V , T ,
a b 5 , van der Waals
a
(VV2

p +

b) = R T

p = p c p r , V= V c Vr T = T c T r ,
2

a = 3c Vc , b =

p c Vc
1
Vc ,
=
3
RT c

3
8

pr +

3
V 2r

Vr -

1
=
3

8
Tr
3

( 2101)

, ,
5 4

, ( 2101)
, , ,
p r , V r T r , , ,
,
,
f ( p r , Vr , T r ) = 0

( 2102)

, , ,

,
p V = RT
,
p r Vr =

RT c
T r
p c Vc

p cVc
p c Vc
,
= Z c ,
RT c
RT c
p r V r = T r / Zc

( 2103)

( 2103) , Z c , ,
Z c , , , ( 2103) ,

242
,

[ 2 1]

V ri , Z , p V T
p V = Z RT

( 2104)

,
p r Vr =

Z
Tr
Zc

( 2105)

V r Z c = Vr i
V ri = V r Z c =

V
Vc

p cVc
V
V
=
=
RT c
RT c / p c
Vc i

( 2106)

V ci = R T c / p c , , Z c
, ( 2105)
p r V ri = Z T r

( 2107)

, Z p r , Vr i , T r
Z = f 1 ( p r , V ri , T r )

( 2108)

, ,
Z P r T r , , N H 3 , H 2 O ,
2% , Z
Z = f 2( p r, T r)

( 2109)
5 5

( 2108) ( 2109) , ( 2108) p r , V ri T r

f ( p r , Vr i , T r ) = 0

( 2110)

( 2110) P r , Vr i T r ,
, ( 2110) ( 2109) ,
, , Z c
, , ,

243
, ,
, P r , V ri T r van der Waals
Tr

pr =

1
8

V ri -

27
2
64V vi

( 2111)

, Redlich Kwong
Tr
V ri - 0. 08664

pr =

[ 22 ]

0. 5
r

0. 42748
V ri ( Vr i + 0. 08664)

( 2112)

Beatt ieBridgeman ,

pr =

Tr
1V2r i
-

0. 05
[ V ri + 0. 1867( 1 3
T r V ri
2

( 0. 4758/ Vr i ) ( 1 -

0. 03833/ Vr i ) ]

0. 1127/ V ri )

( 2113)

BWR , ,

[ 23]

23 ( ClO 3 F ) : p c = 53. 74 bar ( 1bar = 105 Pa ) , T c =

3

368. 28K , V c = 125. 02cm mol

3

cm mol

- 1

- 1

T = 404. 42K , V= 279. 25

3

T = 404. 42K , V = 20382cm mol

- 1

, 69. 23b ar

1. 508bar
( 1) van der Waals ;
( 2) van der Waals ;
( 3) RedlichKwong ;
( 4) Beattie Bridgeman
[ ] T = 404. 42K V = 279. 25cm 3 mol - 1
404. 42
279. 25
( 1) T r =
= 1. 098, V r =
= 2. 234
368. 28
125. 02
( 2101)
8
1. 098
3
pr =
2. 234 - 1/ 3
5 6

3
1. 5405 2 =
( 2. 234)

0. 6011 = 0. 9394

p = 0. 9394 53. 74 = 5048kPa

( 2) V ri =

279. 25 53. 74
= 0. 4901
83. 14 368. 28

( 2111)
pr =

1. 098
0. 4901 - 0. 125

27
= 3. 007 64( 0. 4901) 2

1. 756 = 1. 251

p = 1. 251 53. 74 = 6723kPa

( 3) ( 2112)
pr =

1. 098
0. 4901 - 0. 08664

= 2. 7215 -

0. 42748
1. 098 0. 4901( 0. 4901 + 0. 08664)
0. 5

1. 4433 = 1. 2782

p = 1. 2782 53. 74 = 6870kPa

( 4) ( 2113)
pr =

1. 098
12
( 0. 4901)
-

0. 05
3
( 1. 098) 0. 4901

0. 4758/ ( 0. 4901)

= 2. 793775 -

1-

0. 4901 + 0. 1867 1 -

0. 03833
0. 4901

0. 1127
0. 4901

1. 52536 = 1. 268415

p = 1. 268415 53. 74 = 6817kPa

3

T = 404. 42K V= 20382cm mol

- 1

20382
= 163. 02
125. 02
8
1. 098
3
3
pr=
= 0. 0179
163. 02- 1/ 3 ( 163. 02) 2
p = 0. 0179 53. 74= 96. 2 kPa

( 1) V r =

20382 53. 74
= 35. 771
83. 14 368. 28
1. 098
27
pr=
2 = 0. 03047
35. 771- 0. 125 64( 35. 771)
p = 0. 03047 53. 74= 163. 7kPa

( 2) V ri =

1. 098
0. 42748
0. 5
35. 771- 0. 08664 ( 1. 098) 35. 771 ( 35. 771+ 0. 08664)
= 0. 03045

( 3) p r =

p = 0. 03045 53. 74= 163. 6kP a

1. 098
0. 05
0. 03833
135. 771+ 0. 1867 12
3
( 35. 771)
( 1. 098) 35. 771
35. 771
0. 4758
0. 1127
1= 0. 02984
2
( 35. 771)
35. 771
p = 0. 02984 53. 74= 160. 34kPa

( 4) p r =

5 7

p - p

( 1)

5048

1875

27. 08

( 1)

( 2)

6723

200

2. 88

( 3)

6870

53

( 4)

6817

106

: kP a
p

p - p

96. 2

54. 6

36. 20

( 2)

163. 7

- 12. 9

- 8. 55

0. 77

( 3)

163. 6

- 12. 8

- 8. 49

1. 53

( 4)

160. 34

- 9. 5

- 6. 32

2 5
251
,
, Z p r T r , Z = f ( p r , T r )
, , ,
Nels on O bert
1954 26 28

26 ( )

5 8

[ 24 ]

 27 ( )

28 ( )

5 9

:
( 1) , , ,

( 2) V r i , ,

( p r = 01) 30 , 26
1% ; ( )
3% 4% ( p r = 110) , 30 , ,
2. 5% 7% ; p r > 1
, T r = 13. 5, p r = 1020 ,
5%
Z , :
Tr =

T
p
( : K) , p r =
( : atm)
Tc + 8
pc + 8

24 1kg 253. 2 7. 81 10

- 3

m ,

?
[ ]
T c = 369. 8K p c = 42. 46 bar = 4246kPa
V = 7. 81 10- 3 44. 06 = 0. 3441m 3 kmol = 344. 1cm 3 mol -

T , V , p c T c
Tr =
V ri =

T
253. 2 + 273. 16
=
= 1. 423
Tc
369. 8
V
=
RT c
pc

344. 1
83. 14 369. 8
42. 46

= 0. 4752

V ri = 0. 4752 T r = 1. 423, 27,

p r = 2. 37
p = p r p c = 2. 37 42. 46bar = 10063kPa
10130 kPa
% =

10130- 10063
100= 0. 66%
10130

252 Lyder sen - Gr een kor n - H ougen

[ 25]

, , Z c
0. 20. 3, p VT
, L ydersen Z c , Z
6 0

Z = f ( p r , T r , Zc )

( 2114)

, Lydersen 82 p VT
( p c , T c Z c )
, , Z c 0. 23,
0. 25, 0. 27 0. 29, T r ( 0. 5 15)
p r ( 0. 0130) ,
Hougen , Z c (
) Z c = 0. 27 , 60% Z c
0. 260. 28 L ydersen 0. 27 Z ,
D , Z c 0. 27 Z c 0. 27 Z

Z = Z 0. 27 + D ( Z c -

0. 27)

( 2115)

D T r p r , T r = 0. 515, p r = 0. 0130

253 Pitzer [ 2 6 ]
P itzer , ,
, , T r = 0. 7
0. 1 Pitzer ( H 2 H e ) T r = 0. 7
0. 1,
= -

( lgp r ) T r = 0. 7 - 1. 000

( 2116)

,
,

P itzer , Z ,

Z = Z ( 0) + Z ( 1 )
, Z
Z

( 0)

( 0)

; Z

( 1)

( 2117)

Z ( 1) T r = 0. 8 4 p r = 0. 2- 9 ,

, H 2 O, NH 3
29 210 Z ( 0 ) , Z ( 1) T r p r
, [ ( 218) ] [ ( 2117) ]
, 211

2. 5. 4 Lee - Kesler P itzer

P itzer ,
6 1

 29 Z ( 0)

( T r < 0. 8) , , Chao , L u Greenkorn

Lee K es ler
, Z
Z ( 0 ) Z ( r ) , ,
(0)

Z- Z

( r)
( 0) =
(r)
Z - Z

Z = Z ( 0) + ( Z ( r ) - Z ( 0 ) ) / ( r )

( 2118)

, ( 2117) Z ( 1) ( 2118) ( Z ( r) - Z ( 0) ) / ( r)
( 2117) , ( 2118) , Z ( 0 ) Z ( 1)
, Z ( 1 ) lee K es ler
BWR Z ( 0 ) Z ( 1 )
Z=

p r V ri
Tr

= 1+
6 2

B
C
D
+
2 +
V ri
V ri
Vr5i

 210 Z ( 1)

211

C4

exp 2 +
V 2ri
T V ri
3
r

V 2ri

( 2119)

RT c
pc
2
3
B = b1 - b2 / T r - b3 / T r - b4 / T r

, V ri = V

C = c1 - c2 / T r + c3 / T r

6 3

D= d 1+ d 2/ T r
p
V

, ,

=
T

0,

p
V2

= 0 f i = f i , ( = 0) ,
T

c
( r)

( , = 0. 3978) , 24
2-4 Lee-Kesler

b1

0. 1181193

0. 2026579

c3

0. 0

0. 016901

b2

0. 265728

0. 331511

c4

0. 042724

0. 041577

b3

0. 154790

0. 027655

1
104

0. 155488

0. 48736

0. 623689

0. 0740336

10
2

b4

0. 030323

0. 203488

c1

0. 0236744

0. 0313385

0. 65392

1. 226

c2

0. 0186984

0. 0503618

0. 060167

0. 03754

255

, Lee K esler , :
Z = Z ( 0) + Z ( 1) + Z ( 2)

( 2120)

, , Z ( 2 ) ,

, St iel , ,

25 125cm 3 50 1mol ? :
( 1) ;
( 2) Pit zer ;
( 3) L GH
[ ] ( 1)
p =

82. 06 323. 16
3
= 212at m = 21. 48 10 kPa
125

( 2) Pit zer
p r , :
p =

Z RT
Z ( 82. 06) 323. 15
=
= 212Z
V
125

p = p c p r = 45. 4p r ,
Z=
6 4

45. 4p r
= 0. 216p r
212

 , Z , z 1 p r = 4. 60 , 29
210 Z

(0)

(1)

( 2117) Z Z

p r ,
Z 0. 877 p r = 4. 06, T r = 1. 7, 29 210 Z
Z

( 1)

(0)

( 2117) = 0. 007,
Z= Z
p =

(0)

+ Z

( 1)

= 0. 874 + 0. 007 0. 240 = 0. 876

0. 876 82. 06 323. 15

3
= 185. 8atm = 18. 83 10 k Pa
125

( 3) R edlichKwong

h=

b
0. 0867 RT c
0. 0867 82. 06 190. 6
=
=
V
p cV
45. 4 125

= 0. 239
A
a
4. 934
=
1. 5 =
1. 5
B
bR T
Tr
Tr =

323. 16
= 1. 7
190. 6

( 245)
Z=

1
1- h

4. 934
h
=
1. 5
Tr
1+ h
1-

1
0. 239

4. 934 0. 238
1. 5
( 1. 7)
1. 238

= 0. 883

p =

Z RT
0. 883 82. 06 323. 15
3
=
atm = 187atm = 18. 95 10 kPa
V
125

R edlichKwong 185at m
14. 6%

2 6 p - V - T
, L ee Kesler ,
, ,
10
, ,

261
( 1) R ackett
1970 R ackett
V SL = Vc Z (c 1 -

T )
r

2/ 7

[ 28]

( 2121)
6 5

 16 , ,
, 7% , 2%
,
[ 29]

( 2) Yamada Gun n
Y amada Gunn R ack et t ,
R

V S L = V R Z cr( T r , T r )

( 2122)

Z c r = 0. 29056- 0. 08775
( T r , T Rr ) = ( 1 - T r ) 2/ 7 -

(1 -

T Rr ) 2/ 7

V R T Rr , ,
, 1%
( 3)

[ 3 0]

R acket t , ,

V SL =

RT c
exp{- ( 1. 2310 + 0. 8777) [ 1 + ( 1 - T r ) 2/ 7 ] }
pc

( 2123)

,
, 10 40
, , ( 2123)
, 0. 58% , 2. 7% Rackett
2. 9% , 12. 1%
( 4) SpencerDanner
Spencer Z c

[ 31 ]

RT c
R ackett V c ,
pc
R T c [ 1+ ( 1- T r ) 2/ 7 ]
SL
V =
ZRA
pc

( 2124)

Z R A R ack et t Z c , ,
, Z R A Z c
26 150
95. 0cm 3 mol- 1 : p c = 5. 49 103 kPa ( 54. 2at m ) , T c = 499 K , Vc =
3

- 1

207cm mol , = 0. 190, = 0. 0892

( 1) R ackett ;
( 2) YamadaGun n ;
( 3)
[ ] ( 1) R ackett
Tr =

150 + 273. 16
= 0. 848
499

Zc =

54. 2 207
= 0. 274
82. 06 499

V SL = 207 ( 0. 274) ( 1 6 6

0 . 84 8)

2/ 7

cm 3 mol -

= 97. 218cm 3 mol -

97. 218 - 95. 0

100% = 2. 34%
95. 0

( 2) Yamada Gun n
VR =

1
62. 134 = 74. 057cm 3 mol 0. 839

Z c r = 0. 2905 R
r

( Tr , T ) = ( 1 -

0. 08775 0. 190 = 0. 274

2/ 7

0. 848)

V S L = 74. 057 ( 0. 274) -

0. 1 93

1-

20 + 273. 16
419

= 95. 078cm 3 mol-

2/ 7

= - 0. 193
1

95. 07 - 95. 0
100% = 0. 08%
95. 0

=
( 3)
V

SL

82. 06 499
exp {54. 2
[ 1 + (1 -

( 1. 2310 + 0. 8777 0. 0892)

0. 848) 2/ 7 ] } = 94. 99cm 3 mol-

94. 99 - 95. 0
100% = 95. 0

0. 01%

2. 6. 2
,
,
( 1) T ait

[ 3 2]

,
-

dV
D
=
dp
p + E

D E
dV = - D

dp
p + E

V = V 0 - D ln

p + E
p0 + E

( 2125)

T ait , p 0 V 0
, , D , E ,
Vp
( 2) T homs on Brobst H ankins on
T homson ( 1982) T ait :
V = Vs 1 -

Cln

p + B
s
p + B

( 2126)

V s p s , C , B
6 7

[ 3 3]

[ 34]

( 3) ChuehP rausnit z

Chueh Prausnit z( 1969) p , T , Z c , p c , T c ,

p s)

9Z c D ( p = 1 +
pc
s

( 2127)

, , p ; p c , Z c ; p
; D :
D = (1-

0. 89) [ exp( 6. 9547) 2

+ 191. 3060T r -

76. 2853T r
3

203. 5472T r + 82. 7631T r ) ]

( 2127) , 1%

263
L yders en , ,
212

r =

Vc
=
c
V

( 2128)

c
, T r p r , 212 r ,
c
,
V L2 = V L1
L

r1
r2

( 2129)

V 2 ; V 1 ; r1 , r 2 1 2
, 212
H ou gen T r , p r Z c , ,
27 220 T c =
3

609. 5K , p c = 4. 05 10 kPa, V c = 292cm mol

- 1

, Z c = 0. 23 M = 88. 10 20

0. 949 g cm - 3
[ ] ( 1) L ydersen
2129
V 1 = ( 1/ 0. 949) ( 88. 10) = 92. 8cm 3 mol -

T r1 = ( 20 + 273. 16) / 609. 5 = 0. 481

: T r1 = 0. 481, Z c = 0. 23 , r 1 = 3. 117 220
T r2 =

220 + 223. 16
= 0. 809
609. 5

, r 2 = 2. 505,
6 8

 212

V2 = V1

r1
3. 117
3
= 92. 8
= 115cm mol
r2
2. 505

115 - 122
100% = 122

5. 7%

( 154) , V b = 109cm 3 mol - 1 , ,

V 2 = 121cm 3 mol- 1
( 2) ( 2128)
V c = 292cm 3 mol - 1 220 r 2 = 2. 505
V 2 = 292/ 2. 505 = 116cm 3 mol =

( 116 - 122)
100% = 122

4. 9%

264
Bondi Simkin

[ 35 ]

, , ,
,

V
=
V

( 2130)

V van der Waals ,

25
T r =

( 2131)
6 9

= E / 3CR

( 2132)

0
E V r = 1. 70 ; 3C , E
[ 35 ]

25 V , ,
( 2130) r , r T r :

r = 0. 726 - 0. 249T r

0. 019( T r )

( 2133)

T r , ( 2131) T T T r ,
( 2133) r , ( 2130)
2-5 V
, ,

/ cm 3 mol -

3. 33

CH

6. 78

CH 2

10. 23

CH 3

13. 67

CH 4

17. 12

8. 06

CH

554

( )

474

501

847
H

CH 2

1194

687

7 0

H
( )

1042
665


, ,

/ cm 3 mol -

( )

520

( )

804

11. 70

O ) ( )

NH 4 ( )

10. 54

NH ( )

8. 08

N ( )

4. 33

NO 2 ( )

N ( )

( )

SH ( )

14. 70
16. 8
10. 8
14. 8

5. 72

6. 20

6. 00

5. 80

11. 62

, ,

12. 24

1165

120

1440

, ,

1460

1512

1918

2035

1964

3750

4618

3976

9310

O H , 2. 78

, 1. 05

cm 3 m ol - 1

7 1

 28 1, 1 311K 0. 88gcm
0. 82g cm - 3

- 3

, 422K

[ ] , 546K ; 639K ,
, Bondi 25
V = 10( -

CH ) + 1 ( CH 3 )

CH 2 ) + 3(

= 10 10. 23 + 3 6. 78 + 1 13. 67 = 136. 3cm 3 mol -

136. 3
0. 88= 0. 6183
194
( 2133) , 311K ,

311K r =

0. 6183 = 0. 726 0. 249T r -

0. 019T r

T r = 0. 4192
T
311

T = = 0. 4192 = 741. 9K
Tr

422
= 0. 5688
741. 9
r = 0. 726 - 0. 249 0. 5688 -

422 K , T r =

0. 019 ( 0. 5688) 2 = 0. 5782

V
136. 2
3
V = =
= 235. 73cm mol
0. 5782
r
L

=
=

M
194
=
= 0. 823g cm V
235. 73

0. 82 - 0. 823
100% = 0. 36%
0. 82

27
, ,
, 10
, p VT , , p
V T ,
, , ,
p VT p VT ,
,

271 Amagat , Dalton

( 1) Amagat
A magat , p ,
c

Vm =

y V

= 1

7 2

( 2134)

V p
p V m = y 1 V 1 p + y 2V 2 p + + y c V c p

p = y1 p

p V1
p V2
p Vc
+ y2 p
+ + ycp
p Vm
p Vm
p Vm
pV
, Amagat :
RT
Z ( T , p )
p = y p
( 2135)
Z( T , p )

Z =

Z ( T , p ) = y 1 Z1 ( T 1 p ) + y 2 Z 2 ( T , p ) + + y c Z c ( T , p )
c

y Z ( T , p )

( 2136)

= 1

,
( 2) Dalton
Dalton ,
, V t 1 , 2 , , c , 1mol

V m = V t / ( 1 + 2 + + c )

( 2137)

Dalt on p y ( ) V m , 1mol
V m / y = V , T p ,

Vm
= p V
y

p = y p V / V m , p ,
p V
p Vm

( 2138)

Z ( T , P )
Z( T , p )

( 2139)

p = y p
( 2135) , ( 2138)
p = y p
,
c

p
= 1

y
= 1

= p y
= 1

Z ( T , p )
Z( T , p )

( 2140)

Z ( T , p )
= 1,
Z( T , p )
c

Z( T , p ) =

y Z ( T , p )

= 1

p =

p , Dalt on , ( 2139) , p y p

= 1

29 N 2 : H 2 = 1 3( ) , ,
7 3

400atm ( 40. 5 10 kPa) , 300

, , Z M = 1. 1155
( 1) ;
( 2) Amagat ;
( 3) Dalton
[ ] ( 1) , Z M = 1
Vm =

RT
82. 06( 273. 16 + 300)
3
=
= 117. 6cm mol
p
400

= 1. 176 10

- 4

m mol

- 1

( 2) Amagat

H 2 : p c = 12. 8atm( 1. 30 10 kPa) , T c = 33. 2K

N 2 : p c = 33. 5atm( 3. 39 103 kPa) , T c = 126. 2K
H2: p r =

400
573. 2
= 19. 23, T r =
= 13. 91
12. 8 + 8
33. 2 + 8

N2: p r =

400
573. 2
= 11. 94, T r =
= 4. 54
33. 5
126. 2

27
Z H 2 = 1. 15 Z N 2 = 1. 20
( 2136)
Z m = 1. 15 0. 75 + 1. 20 0. 25 = 0. 863 + 0. 30 = 1. 163
Vm =

1. 163 82. 06 573. 2

= 136. 70cm 3 mol 400

= 1. 367 10

- 4

m mol

- 1

( 3) Dalton p N 2 p H 2 , ,
, p = y p ,
p H 2 = 0. 75 400 = 300atm
p N 2 = 0. 25 400 = 100atm

H2 : p r =

300
= 14. 42
12. 8 + 8

N2 : p r =

100
= 2. 99
33. 5

p r , T r , 26 27
Z H 2 = 1. 10, Z N 2 = 1. 05
( 2136)
Z m = 1. 10 0. 75 + 1. 05 0. 25 = 0. 825 + 0. 263 = 1. 088
Vm =
7 4

1. 088 82. 06 573. 2

3
= 127. 94cm mol
400

- 4

- 1

= 1. 2794 10 m mol

p H2 =
p N2 =

1. 10 0. 75 82. 06 573. 2
= 303. 3atm
127. 94

1. 05 0. 25 82. 06 573. 2
= 96. 50at m
127. 94

303. 3
= 14. 58
20. 8

H2: p r =

96. 50
= 2. 88
33. 5
p r , T r , Z H 2 Z N 2 , Z m V m
N2: p r =

/ m 3 mol -

/ %

1. 155

135. 8

1. 000

117. 6

13. 40

A magat

1. 163

136. 7

- 0. 66

Dalton

1. 088

127. 9

5. 82

, Amagat Z ,
Dalt on Z ,
, Z , ,
210 211 , T r p r ,
, ,

272
,

, ,
van der W aals van der
W aals , :
B =

x x B

( 2141)

B j B B j ,
B=

x B

( 2142)

B j B B j , ( 2141)
B = ( x B )
0. 5

( 2143)

7 5

V an der W aals b a ( 2142) ( 2143)

( 1) R edlich Kwong
( 234) , b a

x b

b=

( 2144)

a = ( x a )
0. 5

( 2145)

b a ( 240) ( 241)
( 242) , A B
A = ( x A )
0. 5

( 2146)

x B

B =

( 2147)

A B ( 243) ( 244)
[ 36]
P rausnitz a :

x x a

a =

( 2148)

a j :
( a + a j ) R 2 T 2c .j 5
a j =
2p cj

( 2149)

Z c j R T cj
Vc j

p c j =

1/ 3

1/ 3

V c + Vc j
2

V cj =

Z cj = 0. 291 -

0. 08

T c j = ( T c T cj )

0. 5

+ j
2

(1 -

kj )

k j
( 2) Wilson
( 246) , b a
b=

x b

( 2150)

a
RT b x g
b

( 2151)

a =

b g ( 240) ( 253)
( 3) Soave
Soave W ils on , Soave
b=

x b

a =

x x ( a a )

7 6

0. 5

( 1 - kj )

 b ( 240) , a ( a j ) ( 247) ( 257) ,

k j 26
2-6 Soave kij

H 2S

CO2

N2

CO

H 2S

0. 102

0. 140

CO 2

0. 102

- 0. 022

- 0. 064

N2

0. 140

- 0. 022

0. 046

CO

- 0. 064

0. 046

0. 0850

0. 0973

0. 0319

0. 03

0. 0829

0. 1346

0. 0388

0. 00

0. 0831

0. 1018

0. 0807

0. 02

0. 0523

0. 1358

0. 1357

0. 0609

0. 1474

0. 1007

0. 1262

0. 0697

0. 1278

0. 1444

n
n

0. 0737

0. 1136

0. 10

0. 0542

0. 0464

0. 1377

0. 1293

0. 0914

0. 1087

0. 0562

0. 01

0. 0810

0. 2131

1, 3, 5

0. 0282

, , k ij= 0

( 258) , A B
A=

x x A

B=

( 2152)

x B

( 2153)

A B ( 259) ( 260)
( 4) PengR obinson
( 261) ,
b=

x b

( 2154)

a =

x x ( a a )

0. 5

(1 -

kj )

( 2155)

b ( 270) , a ( a j ) ( 247) ( 269)

k j 27

7 7

 2-7 k ij
+ H C
CO 2 + HC

0. 12

+ HC
+ HC

0. 01

0. 15
0. 01

C4

0. 02

C5

0. 02

C6

0. 025

C7

0. 025

C8

0. 035

C9

0. 035

C10

0. 035

C20

0. 054

0. 06

0. 03

( 271) ,

x x ( A A )

A=

0. 5

( 1 -

kj )

( 2156)

x B

B=

( 2157)

A ( A j ) B ( 272) ( 273)
( 5) Hu ron Vidal [ 37]
H uron V idal 1979 :

gE
m = ln
RT

x ln

m van der Waals ,

ln
m =

pV
RT

1-

ln

p ( V - b)
RT

ln
=

p V
RT

1-

ln

p ( V - b )
RT

a
RT V
a
RT V

,
E

g
p
=
(V RT
RT

7 8

x V )

a
RT V

ln

RT V

p ( V - b)
RT

x ln

p ( V - b)
RT

lim V = b plim
V = b

lim
p

p ( V - b)
p ( V - b)
= lim
= 1
p
RT
RT

E
p( b g
= plim

RT

x b )

a
RT b

RT

a
RT b

g :
E

b=

x b

a
=
RT b
a
=
b

g E
RT

a
x

R T b

a
- g E
b

( 2158)

RTb
g E / RT ,

,
g E = 0
a
=
b

a
b

,
E

, g , NR T L
, , ( 276) ,
a( T )
b

g =

a ( T )

( 2159)

1
1-
ln
m+ 1+ m

( 2160)

R K , m= 1, = 0,
a( T )
=
b
PR , m =

a ( T )
- ( ln2) - 1 g E
b

( 2161)

2 - 1,

2 + 1, =
a( T )
=
b

a ( T )
b

2
2
E
g
2+
2
ln
22

( 2162)

273
,
7 9

 , , W . B. K ay
( 1936) , ,
, T p c p pc , cm,
p c
[ 38 ]

( 1) Kay
Kay ,
,

x T

T cm =

( 2163)

ci

x p

p cm =

( 2164)

ci

, Kay
Kay , ,
Kay
;
( 2) R K
( 240)
R T cm
p cm

b = 0. 08664

( 2165)

, ( 241) ,
2

2. 5

R T cm
a = 0. 42748 0. 5
T p cm

( 2166)

( 240) ( 2144)
b = 0. 08664R x

T ci
p ci

( 2167)

( 241) ( 2145)
R2
a = 0. 42748 0. 5
T

T 1.c 25
p 0c . 5

( 2168)

( 2165) ( 2167) , ( 2166) ( 2168) ,

T cm
=
p cm

T c
p c

2. 5

T cm
=
p cm

( 2169)
1. 25

T c
0. 5
p c

( 2170)

( 2169) ( 2170) :

T cm =

p cm =

8 0

T 1c . 25
x

p c

T c
x

p c

T cm
T c
x

p c

2/ 3

( 2171)

( 2172)

 , ( 2144) ( 2145) ( 2171) ( 2172)

, , ( 2165) ( 2166) , ( 2171) ( 2172)
, ( 2144) ( 2145) , ( 2144) ( 2145)
( 2165) ( 2166) , ,

, L ee Kesler

[ 39 ]

JoffeL ee

[ 40]

210 29
( 1) Kay ;
( 2) ;
( 3) R K
[ ] ( 1) , ,

T c
T c =
21. 8
1+
mT
0

p c
p c =
44. 2
1+
mT
T c p c , T 0c p 0c
0

( p c p c atm )
0

[ 36 ]

- 1

T c = 43. 6K p c = 20. 2at m, V c = 515cm mol

m , T ,
T c =

p c =

43. 6
= 42. 78K
21. 8
1+
2 573. 2
20. 2
= 19. 45at m
44. 2
1+
2 573. 2

H 2 , N 2 :

T c/ K

p c / atm

H 2 ( 1)

42. 78

19. 45

N 2 ( 2)

126. 2

33. 5

Vc / cm 3 m ol -

Zc

51. 5

0. 305

89. 5

0. 04

0. 290

( 2163) ( 2164) ,
T cm = 0. 75 42. 786 + 0. 25 126. 2 = 32. 09 + 31. 55 = 63. 64K
p cm = 0. 75 19. 45 + 0. 25 33. 5 = 14. 59 + 8. 37 = 22. 96atm
prm =

400
= 17. 42
22. 96
8 1

T rm =
[ 41 ]

573. 2
= 9. 01
63. 64

1. 175 82. 06 573. 2

= 138. 17cm 3 mol 400

Vm =

( 2)
, ( 219)
H2:

(0)

0. 422
1. 6 = 0. 0764
573. 2
42. 78

= 0. 083-

1 = 0, ( 218)
B ( 0) R T c 0. 0764 82. 06 42. 78
=
= 13. 78
B 11 =
pc
19. 45
N2:

( 0)

0. 422
= 0. 045
573. 2 1 . 6
126. 2

= 0. 083-

( 220)
B

( 1)

0. 172
= 0. 139
573. 2 4 . 2
126. 2

= 0. 139 -

B 22 p c
= 0. 045 + 0. 04 0. 139 = 0. 0506
RT c
0. 0506 126. 2 82. 06
= 15. 64
33. 5

B 22 =

Praus nitz [ 42] ,

T c 12 = ( T c1 T c 2 )
Z c 12 =

0. 5

1/ 3

V c1 + V c 2
2
3

1/ 3

= 68. 99cm mol

p c 12 =

0. 5

= 73. 48K

Z c1 + Z c 2
0. 305 + 0. 290
=
= 0. 298
2
2
1/ 3

V c 12 =

= ( 42. 78 126. 2)

51. 5

1/ 3

+ 89. 5
2

3. 72 + 4. 47)
2

- 1

Z c1 2 R T cj
0. 218 82. 06 73. 48
=
= 26. 05atm
V c j
68. 99

B 12 : ( 218) ( 220) ,
B ( 0) = 0. 083 -

0. 422
0. 0672
1. 6 =
573. 2
73. 48

B ( 1) = 0. 139 -

0. 172
= 0. 139
573. 2 4 . 2
73. 48

B1 2 =
8 2

52. 06 73. 48
( 0. 0672 + 0. 02 0. 139) = 16. 20
26. 05

, B m =

x x B

B m = 0. 752 13. 78 + 2 0. 75 0. 25 16. 20 + 0. 252 15. 64

= 14. 81
( 215)
Zm = 1 +
Vm =

BmP
14. 81 400
= 1+
= 1. 126
RT
82. 06 573. 2

1. 126 82. 06 573. 2

= 132. 43cm 3 mol 400

( 3) R K

1
0. 42748 82. 062 42. 782. 5
6
6
a1 =
= 1. 774 10 at m cm K 2 mol
19. 45
2

2. 5

0. 42748 82. 06 126. 2

a2 =
33. 5

= 1. 539 10 7 at m cm 6 K 2 mol -

b1 =

0. 08664 82. 06 42. 78

= 15. 65cm 3 mol 19. 45

b2 =

0. 08664 82. 06 126. 2

= 26. 80cm 3 mol 33. 5

( 2) : T c 12 = 73. 48K, p c1 2 = 26. 05atm,

a 12

2. 5

0. 42748 82. 06 73. 48

=
26. 05

= 5. 118 10 atm cm K 2 mol

- 2

a m = 0. 752 1. 774 10 6 + 2 0. 75 0. 25 5. 118 106 + 0. 25 2

1

1. 539 107 = 3. 879 10 6 at m cm 6 K 2 mol bm = 0. 75 15. 06 + 0. 25 26. 8 = 18. 44cm 3 mol -

( 234)
82. 06 573. 2
400 =
V m - 18. 44
3

V m = 133. 64cm mol

Zm =

3. 879 10
1/ 2
573. 2 V m ( V m + 18. 44)

- 1

400 133. 64
= 1. 137
82. 06 573. 2

, ,
:

1. 155

135. 8

K ay

1. 175

136. 17

- 1. 73%

1. 126

132. 43

2. 51%

RK

1. 137

133. 64

- 1. 56%

/ cm 3 mol -

8 3

274
( 1) R ackett

[ 44]

R ack et t( 1971) :
T
T
cb

11
= V b p = V cm Z cm
bp

2/ 7

( 2173)

Vc m Z c m T cb
, :

x b T / x b

T cb =

( 2174)

b , :

b = exp ( 0. 000633) x j ( T c -

T cj ) 9/ 7 + lnC

( 2175)

j= 1

C , 1;
, 28
28

0. 74

0. 70

0. 82

0. 78

0. 74

1. 16

0. 67

0. 82

0. 74

( 2) [ 4 5]
( 2123) ,
RT c
T c
= R x
pc
p c

( 2176)

( 2177)

T c = ( x Vc T c ) / ( x Vc )

( 2178)

( 3) Spencer Danner [ 46 ]
Spencer Danner ( 2124) :
RT c
T c
= R x
pc
p c

ZRA =

x Z

( 2179)
( 2180)

R A

T c = ( x Vc T c ) / ( x Vc )

( 2181)

211 0. 3749( ) 0. 6251( )

8 4

 T = 310. 94K, p = 8612. 6kPa ( 85atm )

m = 0. 5247 g / cm 3
( 1) R ackett
( 2)
( 3) SpencerDanner
[ ]
: p c = 4. 60 103 kPa , T c = 190. 6 K , V c = 99cm 3 mol -

1 = 0. 0096
3

: p c 2 = 3. 37 10 k Pa, T c 2 = 496. 6K , V c2 = 304cm mol

- 1

2 = 0. 0985
( 1) ( 2175)
b1 = 0. 576 b2 = 1. 3922

T cb =

0. 3749 0. 576 190. 6 + 0. 6251 1. 3922 469. 6

K
0. 3749 0. 576 + 0. 6251 1. 3922

= 414. 133K
:
Vc = 0. 3749 99 + 0. 6251 304 = 227. 1455cm 3 mol -

Z c = 0. 3749 0. 288 + 0. 6251 0. 263 = 0. 27237

1-

V b p = 227. 1455( 0. 27237)

= 94. 7435cm 3 mol -

31 0. 9 4
41 4. 1 33

2/ 7

b p =

x M / V

bp

51. 00
3
= 0. 53835g/ cm
94. 7435

0. 53835 - 0. 5247
100% = 2. 60%
0. 5247

( 2) :
RT c
190. 6
469. 6
= R 0. 3749
3 + 0. 6251
pc
4. 60 10
3. 37 103
= 0. 10263R = 0. 10263 8314
Tc =
=

0. 3749 99 190. 6 + 0. 6251 304 469. 6

0. 3749 99 + 0. 6251 304
96312. 414
= 424. 012K
227. 1455

= 0. 3749 0. 0096 + 0. 6251 0. 0985 = 0. 06517

V bp = 8314 0. 10263exp{

1+

1-

310. 94
424. 012

( 1. 2310 + 0. 8777 0. 06517)

2/ 7

= 97. 22cm 3 mol -

8 5

bp =
=

51. 00
3
= 0. 52464g/ cm
97. 22
0. 52464 - 0. 5247
100% = 0. 5247

0. 01%

( 3) [ 33]
Z R A 1 = 0. 2892, Z RA 2 = 0. 2684
Z R A = 0. 3749 0. 2892 + 0. 6251 0. 2684 = 0. 276

RT c
= 0. 10263 8314
pc

V bp = 0. 10263 8314( 0. 276)

3

= 97. 36cm mol

1+

310. 94
4 24. 012

2/ 7

- 1

bp = 51. 0/ 97. 36 = 0. 5239g/ cm

=

1-

0. 5239 - 0. 5247
100% = 0. 5247

0. 15%

21 van der Waals :
2

RT 1 + y + y + y
p =
3
V
( 1 - y)

a
2
V

y = b/ 4V a , b
c
a = 1. 38R T c V c
b = 0. 5216V c
c = 0. 359
22 ( ) :
p =

RT
V- b

( V - )
( V - b) ( V 2 + V +
)

, , van der Waals,

R K PR ,
23 1bar ( 10 5 Pa ) 25 100L , 1L ,
- 110,
5

24 1. 013 10 kPa ( 1000at m ) , 0

Z Z = 2. 0685
p =

RT
V- b
2

8 6

a
( V + mb)

(m =

Tc
27 R T c
a =

exp
64
pc
T

2 -

1)

b=

c =

RT c

pc
2

1
4 1+

2
4

R K
25 :
RT
V- b

p =

a
2
V + b
2

R Tc
RT c
a = a
b = b
pc
pc
( 1) ;
( 2)
Z3

( 1 + B ) Z 2 + ( A + B 2 ) Z - ( AB + B 2 + B 3 ) = 0

ap
bp
pV
, Z=
2 , B=
RT
RT
( RT )
3
26 R K 294. 3K 1. 013 10 k Pa( 10at m)
A=

294. 3 K 1. 013 10 kPa ( 100at m )

3

V( 10at m, 294. 3K ) = 2370. 27cm mol

3

V( 100atm, 294. 3K ) = 203. 07cm mol

- 1

- 1

27 3446kPa ( 34. 01at m ) 93. 33

0. 02527 m 3 kg - 1 , :
( 1) ;
( 2) ;
( 3) SR K ;
( 4) PR ;
( 5) Berth elot
3

28 P c = 11. 28 10 kPa ( 111. 3at m ) , T c = 405. 6K , Z c =

0. 242,
= 0. 1951, :
( 1) 310K ;
( 2) 1. 013 10 4 k Pa ( 100 atm ) 310 K
:
R ack et t ;
yamadaGunn ;
;

sL

V = 29. 14cm mol

L

V = 28. 60cm mol

- 1

- 1

29 50, 6. 08 10 kPa ( 600at m) 0. 401( ) 0. 599(

) , :
8 7

( 1) ;
( 2) Amagat ;
( 3) Dalton ;
( 4) Kay
Z = 1. 40,
210 0. 283 m 3 , , 290K , 2. 48
10 3 k Pa ( 24. 5atm ) 478K , ?
211 2. 03 10 3 k Pa ( 20 atm ) , 478K 2. 83m 3 0. 1415m 3 ,
450K, ?
212 van der W aals :
RT
V- b

a
2
V

= exp [ m( 1 -

T r) ]

p =

m = 0. 52537 + 1. 82360-

1. 49335 + 1. 50705
4

1mol 25 101kPa ( 1atm ) 1. 03 10 kP a

( 100at m ) ,

W= -

p
p

Vdp

213 0. 30( ) N 2 ( 1) 0. 7( ) C 4 H 10 ( 2)
3

188, 6. 89 10 kPa ( 68atm)

( 1) ;
( 2)
B
C
+
2
V
V

p V = RT 1 +
:

y y B

B =

y y y C

C=

j k

B 11 = 14cm mol
3

C 1 11 = 1300( cm mol

- 1

B 22 = - 265cm mol
B 12 = B 21 = -

- 1

9. 5cm mol

- 1

- 1

C 2 22 = 30250( cm 3 mol- 1 ) 2
3

- 1

- 1

C 1 12 = 4950( cm mol
C 1 22 = 7270( cm mol

( 3)
Z= Z

( 0)

+ Z

(1)

214 43. 91% ( ) ( 1) 56. 09% ( )

( 2) ,
8 8

T = 310. 94K , p = 1. 033 10 kPa( 102at m) ,

V c1 = 99cm 3 mol - 1 ,

p c 1 = 45. 4atm( 4600kPa)

T c1 = 190. 6K ,
p c 2 = 33. 3atm( 3374kPa) ,

1 = 0. 0096
V c2 = 304cm 3 mol- 1 ,
2 = 0. 0985

T c2 = 469. 6K ,
( 1) R ackett
( 2)
V b p = 94. 23cm 3 mol-

3
bp = 0. 5031g cm
4

215 , 2. 027 10 kPa ( 200 atm )

200, , , 709 kPa ( 7atm ) ,
, ?
216 1h 453. 6kg 75% ( ) ,
3

5. 066 10 kPa( 50at m) , 100, 1h

4

217 4. 053 10 kPa ( 400at m ) , 50, CO 2 N 2 ,

3

62. 43cm mol

- 1

, ?

[ 1] Sm ith S M and H C V an N ess . Int roduct ion t o Chemical Engineering T her modynamics, T hird
E dition. M cGraw H ill Book Company, 1975
[ 2] T s onopoulos C. A IChE J . , 1974, 20 263
[ 3 ] P rausnitz J M . Computer Calculat ions for M ult icomponent V apor Liquid and Liquid Liquid
E quilibria . P rentice Hall , IN C, 1980
[ 4] . , 1989, 10( 1) : 10
[ 5] Redlich O and J N S K wong. Chem. Rev. , 1949, 44 233
[ 6] Wils on G M . A dvan. Cryog. Eng. , 1966, 11 392
[ 7] P eng D Y and D B Robins on . Ind . E ng. Chem . F undam . , 1976, 15 59
[ 8] Schm idt G and H W enzel . Chem . E ng. SCi . , 1980, 35( 7) 1503
[ 9] , , 1982, 3( 3) 209
[ 10] P at el N C and A S T eja. Chem. E ng. SCi. , 1982, 37( 3) 463
[ 11] Beatt ie J A and O C Bridgeman P roc. A m . A cad. A rt s SCi. , 1928, 63 229
[ 12] , , , 1988, 28( 3) 12
[ 13] , 1990, 15( 4) : 61
[ 14] Benedict M G B Webb and L C Rubin . J. Chem . P hys . , 1940, 8: 334; 1942, 10 747
[ 15] Benedict M G B Webb and L C Rubin. Chem. E ng. P rog. , 1951, 47 419
[ 16] Cooper H W and J C G oldfrank. H ydrocarbon P roces s . , 1967, 46( 12) : 141
[ 17] O rye R V . Ind. Eng Chem P rocess Des . Dev. , 1969, 8 579
[ 18] St arling K E . Hydr ocarbon Pr ocess . , 1971, 50( 3) 101
[ 19] St arling K E and M S H an . H ydrocarbon P rocess , 1972, 51( 5) 129; 1972, 51( 6) 107

8 9

[ 20] M art in J J and Y C H ou. A IChE . J. , 1955, 1 142

[ 21] Su GJ and CH Chang . Ind . Eng Chem . , 1946, 38 800 801 802
[ 22] Su GJ and CH Chang . J . A m Chem Soc 1946, 68 1080
[ 23] , , , 1982
[ 24] N els on L C and E F O bert , T rans . ASM E , 1954, 76: 1057
[ 25] Lydersen, A L, R. A . G reenkor n and O A H ougen. G eneralized T hermodynamic P ropert ies of
Pure F luids. M adis on U niv . W isconsin Coll . Eng . E ng . Exp . St n . Rep . 4, 1955
[ 26] P itzer K S, D Z L ipmann, R E Cur l JR. C. M . H uggins , and D. E . P et ersen, A m . Chem Soc. ,
1955, 77: 3433
[ 27] L ee B I, and M G K es ler . A IChE J . , 21, 510( 1975)
[ 28] Racket t H G. J. Chem. Eng. Data. 1970, 15: 514
[ 29] Y amada T and R D Gunn . J . Chem . Eng . Dat a , 1973, 18: 234
[ 30] , , 6, 1, 11( 1985)
[ 31] Spencer C F and R P Danner . J. Chem . E ng Dat a , 1972, 17: 236
[ 32] N ewitt D M . H igh Pr es sure P lant and the P roperties of F luids at H igh P res sures . Oxford , 1940
[ 33] Edmis ter W C and B I L ee. A pplied H ydrocarbon T her modynamics, vol. 1. H oust on : Gulf P ub
Co . , 1984
[ 34] Chueh P L and J M P rausnit z. A IChE J . , 1967, B: 1099, 1969, 15: 471
[ 35] Bondi A et al . , A IChE J . , 1960, 6 191
[ 36] P rausnitz J M and P L Chueh. Comput er Calculations for H ighP ress ure Vapor Liquid Equilibria.
P rentice Hall , Englewood Cliffs N . J. , 1968
[ 37] V idal J. Chem . Eng SCi . , 1978, 33 787
[ 38] K ay W B. Ind. E ng. Chem. , 1936, 28 1014
[ 39] L ee B I et al . , AIChE J . , 1975, 21( 3) 510
[ 40] J offe J. Ind. E ng. Chem. F undam . , 1976, 15( 4) 298
[ 41] H ougen O A et al . , Chem P roces s Principles . John W iley and S ons, 1947
[ 42] Praus nitz J M . M olecular T herm odynamics of F luid P hase Equilibr ia . P rent ice H all , E nglewood
Cliffs, N . J. , 1969
[ 43] W alas S M . Phas e Equilibr ia in Chem ical E ngineering . Butt erworth P ublis hers , Bost on , 1985
[ 44] Racket t H G. , J Chem. Eng. Data. , 1971, 16 308
[ 45] , , , 1991, 16( 4) : 54
[ 46] Spencer C F and R P Danner, J Chem Eng. Dat a, 1973, 18 230

9 0

3

, , , , ,
, ,
, , ,

,
, , p , V , T ; , U , H , S ,
p VT

3 . 1
3. 1. 1 ( M axwell )
,
z x , y ,
dz =

z
x

z
y

dx +
y

dy = Mdx + N dy

( 31)

x , y , z ( ) , , M dx + N dy z ( x , y)
:
M
y

N
x

=
x

x y

( 32)

( 32)
, ,
x
y

y
z

z
x

= - 1

( 33)

, ,
:
dU = T dS -

p dV

( 34)

dH = T dS + Vdp

( 35)

dF = - SdT - p dV

( 36)

dG = - SdT + Vdp

( 37)

, ,
9 1

,
,
U = f ( S, V)

( 38)

H = f ( S, p )

( 39)

F = f ( V, T )

( 310)

G = f ( p, T )

( 311)

U , H , F , G , ,
U
S

dU =

H
S

dH =

G
p

dG =

dp

( 313)

dT

( 314)

dT

( 315)

G
T

dp +

( 312)

F
T

dV +

dV
S

H
p

dS +

F
V

dF =

U
V

dS +

, :
U
S

U
V

M
y

=
x

N
x

G
p

= V=
S

F
T

( 316)
p

F
V

= - p =

H
p

H
S

= T =

( 318)
T

G
T

= - S =
V

( 317)
T

( 319)
p

, :
y

T
V
T
p
-

p
T
V
T

= S

=
S

V
S

H
p S

=
p

S
p

= -

U
V S

( 320)

S
V

= -

P
S

( 321)
2

=
T

F
V T

( 322)

=
T

G
p T

( 323)

( M axwell) S
p , V , T

3. 1. 2
,
p VT
9 2

1.
T V , :
S
T

dS =

S
V

dT +
V

dV

( 324)

T ,
S
T

T dS = T

S
V

dT + T
V

dV

( 325)

Q
T

CV =

p
T

=
V

S
V

U
T

=
V

U
S

=
V

S
T

S
T

= T
V

( 326)
V

,
T

dS =

CV
dT +
T

p
T

V
T

dV

( 327)

dp

( 328)

, S T p ,
dS =

Cp
dT T

( 327) ( 328) , p VT ,

2.
, T V
dU = T dS -

p dV

( 34)

( 327) ,
dU = CV dT +

p
T

- p dV

( 329)

p VT ,
U
T

dU =

U
V

dT +
V

dV = C V dT +
T

U
V

dV
T

( 329) ,
U
V

= T
T

p
T

, , p =
, p t = T

p
T

p
T

( 330)

U
V

,
T

,
V

31
[ ]
9 3

RT
V- b

p =

a
2
V

( a)

R
V- b

( b)

p
T

=
V

,
p
T

pt = T

RT
V- b

=
V

( c)

( 330) ,
p = T

p
T

RT
V- b

p =

RT
V- b

a
a
=
2
2
V
V

32 :

= p T

T p

,
=

1
V

V
T

1
V

, = p

V
p

[ ] p VT , V T p ,
V
T

dV =

V
p

dT +
p

dp

( a)

;
( a ) ,
dV
= dT - dp
V

( b)

, ( 32) ( b) , ,

= p T

T p

, p V= RT ,
1
=
T

1
p

, ( b)
dV
dT
=
V
T

dp
p

( c)

33 Ch arles : , ;
Boyle : ,

[ ] Charles , , V = C 1 T , C 1 ,
V
T

= C1 =
p

V
T

Boyle , , p = C 2 / V , C 2 ,
9 4

( a)

V
p

C2
= p2

= T

V
p

( b)

p VT , V p T ,
V
T

dV =

V
T

V
p

V
p

dT +
p

dp

( c)

,
T

dV
dT
=
V
T

dp
p

32 ( c) ,
RT
p

V=
R
3.

, T p
dH = T dS + Vdp

( 35)

( 328) ,
dH = C p dT +

V
T

V- T

dp

( 331)

,
H
T

dH =

H
p

dT +
p

H
p

= C p dT +

dp
T

dp
T

( 331) ,
H
p

= V-

V
T

( 332)
p

4.
, ( 329) ( 331) ,
Cp -

CV = T

V
T

p
T

( 333)
V

( 32) ( 327) ( 328) , p VT

:
CV
V
Cp
p

= T
T

p
2
T

( 334)
V
2

= - T
T

V
T2

( 335)
p

9 5

3. 2
, , :
1. 1at m( 101325Pa )
,
2. p VT , p VT ,
p VT
, , ,
p VT
, p VT ,
,

3. 2. 1
,
,
,
, 0, 0
, U , H S ( )

, , ( )
( ) , p 0
, CP
T :

H T
, p = H T
,
p
+
0
0
0

S T
, p = S T
, p
+
0
0
0

T
T

Cp
dT =
0

T
T

C p
dT =
T

T
T

C p
dT

( 336)

T
T

C p
dT
T

( 337)

H T , p 0 S T , p 0 p 0 ( ) , T
H T
,p
S T
,p
, C p

0 0
0 0
, , H T , p 0 S T , p 0 H T
S T

,
H T
S T
, ,
, , ,

9 6

3. 2. 2
,
,

1.
( 332)

H T - H T=

Vp

V
T

dp = ( H -

H
)T

( 338)

H T T p , H T
T p 0 , ( 3
36) p VT , ( 338) T p
( 338)
( 1) p VT
V , T , V T
( 31)
, T ,
V
T

, ,
p

V , p
V
, p
T p
, p 0 p ,
V- T

31

( 337) ,

V
T

( 2)
p , T ,
,
=

RT
- V
p

( 339)

( 339) ( 338) ,
(H -

H
)T =

- dp
T p

p
p

T p

R
p

V-

dp

, p VT ,
T

( 340)

,
T p

- , p , p 0 p , ( 3
T p

40) ,
9 7

( 3)
p V = Z RT ( 338) ,

H
)T =

(H -

p
p

Z RT
RZ
RT
+
- T
p
p
p

Z
T

dp
p

H
)T = -

(H -

p
p

RT 2
p

Z
T

dp

( 341)

p
2

Z
RT
Z

,
, p ;
T p
p
T p
p 0 p , ( 341)
( 4) RK
V p T , ( 338)
p V , T , , ( 338)
:
V
T

p
T

= p

V
p

V
T

p
T

dp = p

dV

( 342)

p V - p 0 V0 =

Vdp +
p

p dV
V

( 343)

p 0 V 0 R T , ( 342) ( 343) ( 338) ,

(H - H
)T = P V -

RT -

p dV + T
V

p
T

dV

( 344)

R K ( 344) ,
(H - H
)T
= ZRT

3
a
b

1+
1. 5 ln
2 bR T
V

1-

( 345)

a
b
A 2 B ,
2. 5
R T
RT
2
b
Bp
a
A
=

1. 5 =
V
Z
B
bR T

R edlich K wong

(H - H
)T
= ZRT

1-

3 A2
Bp
ln 1 +
2
B
Z

( 346)

R K Z , ( 346) , 32
33

[ 1]

, ,

34

[2]

633. 15K, 98. 06k Pa 5. 75 10 J mol

- 1

R K 633. 15K , 9806 kPa

[ ] T c = 647. 1K , p c = 22048. 3 kPa ,
R K RK
9 8

A2
32 RK Bp ( )
B

633. 15
= 0. 978 , [ 3] a = 0. 43808, b = 0. 08143
647. 1
2
2. 5
2
2. 5
R Tc
8314. 73 647. 1
a = a
= 0. 4381
pc
22048

[ 3] , T r =

10

= 1. 463 10 kPa cm K
b = b

0. 5

mol

- 2

RT c
8314. 73 647. 1
= 0. 0814
= 19. 864cm 3 molpc
22048

9 9

A2
33 RK Bp ( )
B
10

633. 15 8314. 73
1. 463 10
p = 9806. 0=
V- 19. 864
633. 15 0. 5 V( V+ 19. 864)
V = 431. 2 cm 3 mol - 1
3

V= 432cm mol
% =

- 1

432 - 431. 2
100% = 0. 18%
432

Z=
( 346)
1 00

pV
9806. 0 431. 2
=
= 0. 803
RT
8314. 73 633. 15

(H - H
)T
= ( Z - 1) RT

3 A2
Bp
ln 1 +
2
B
Z

b
Bp
bp
19. 864 9806. 23
=
=
=
= 0. 0461
V
Z
Z RT
0. 803 8314. 73 633. 15

A2
a
1. 463 10 10
=
=
= 5. 56
B
bR T 1. 5
19. 864 8314. 73 633. 15 1. 5
(H - H
)T
=
RT
(H -

0. 803 -

H
)T = -

3
5. 56 ln( 1 + 0. 0461) = 2

1-

0. 571 8. 3196 633. 15 = -

0. 571

3007. 76J mol -

- 1

H = H - 3007. 76 = 57496. 72 - 3007. 76 = 5. 449 10 J mol

[ 2] H = 5. 345 104 J mol-

5. 449 10 - 5. 345 10
% =
100% = 1. 95%
4
5. 345 10
2.
, ( 328) :

S T , p = S T
,p
0

p
p

V
T

dp

( 347)

S T , p T p ; S T
, p 0 T p 0 (
)
,
, , ,
M

M= M- M

( 348)

M , S T

S T= S T
, pST , p
V
T

R
, ( 347)
p
p
p
S T
, p = S T
, p 0 - R ln
p0

, p V= RT

( 349)

( 350)

( 349) , ( 350) ( 347)

S T=

p
p

V
T

p
dp - R ln
=
p
p0

p
p

V
T

R
dp
p

( 351)

,
S T
= R

1
R

p
p

dp
T p

( 352)

Z ,
S T
=
R

(Z p

1) + T

Z
T

dp
p

( 353)

R K ,
10 1

S T
=
R

1 A2
Bp
ln 1 +
- ln( Z - B p )
2
B
Z

( 354)

35 633. 15K , 9806kPa 151. 756J mol - 1 K - 1 ,

633. 15K , 9806. 23kPa
b Bp
=
= 0. 0461,
V
Z

[ ] R K , 34 Z = 0. 803,
Bp = 0. 0461 0. 803 = 0. 0370

A2
= 5. 56
B
( 354)
S T 1
= 5. 56ln( 1 + 0. 0461) R
2

ln( 0. 803 -

0. 0370)

= 0. 1253 + 0. 2666 = 0. 3919

S T= 0. 3919 8. 3196 = 3. 260J mol
- 1
S T
, p = 151. 756J mol
K0

- 1

- 1

( 349) ( 350) ,
ST , p = = -

S T- Rln
3. 260 -

% =

9806. 23
+ 151. 256
98. 06

8. 3196ln

= 110. 15J mol S T , p = 108. 35J mol

p
+ S T
,p
0
p0

- 1

K -

- 1

110. 18 - 108. 35
100% = 1. 69%
108. 35

3. Cp
p VT
( 1)
( 331) ,
V- T

dH = C p dT +

V
T

dp
p

, : ,
, ,
, ( T 0 , p 0 ) , ( T , p ) , p 0
, , : ,
T 0 T ; , p 0 p , 34

H - H0 =

T
T

Cp
dT +
0

p
p

V0

V
T

dp

( 355)

( T 1 , p 1 ) ( T 2 , p 2 ) p 1 , ,
35 , T 1 , p 1 p 0 , p 0
1 02

 34

35

, ( T 1 T 2 )
, , ,

H = H 2 - H 1 =

C p
dT +

p
p

V-

V-

V
T

V
T

dp
p

dp
p

( 356)

( 356) ,
T 2 T 1
( 2)
( 328) ,
,

S = S 2 - S 1 =

T
T

2
1

Cp
dT +
T

2
0

V
T

p
p

V
T

1
0

R
p

R
p

dp
T

dp - R ln
T

p2
p1

( 357)

;
p VT T 1 T 2

3. 2. 3
p VT ( ) ,
,
, :
1.
p r T r ( 341)
10 3

p = p c p r dp = p c dp r
T = T c T r dT = T c dT r

(H -

H
)T
Tc

= -

p
p

r
0, r

RT r
pr

Z
Tr

dp r
p

( 358)

p 0, r ,
( 358) , , , ,
36 37

[4]

T r p r ,

(H
- H )T

Tc

36 ( 0. 01< p r < 10)

, ,
(H
- H )T
[ 6]
,
RT c
( H - H ) T
( H - H ) (T 0)
( H - H ) (T 1)
=
+
RT c
RTc
RTc

( 2117) ,

(0)

( 359)
(1)

(H
- H )T
(H
- H )T

( 0) , T r , p r

RT c
RT c
, , T r , p r
(0)

( 1)

(H
- H )T
(H
- H )T
T r p r

RT c
RT c
36 34
633. 15
9806. 23
= 0. 978, p r =
= 0. 445
647. 1
22048. 32
= 0. 348

[ ] T r =
1 04

 37 ( 1< p r < 40)

( 1) : T r p r 36
( H - H
)T
= 1. 1cal mol
Tc
H -

- 1

H = - 1. 1 647. 1 = - 771. 8cal mol

= - 2980. 35 J mol

H
= 57496. 72J mol

- 1

- 1

- 1

H = 57496. 72 - 2980. 35 = 54516. 37J mol H = 53359. 13J mol

% =

- 1

54516. 37 - 53359. 13
100% = 2. 17%
53359. 13

( 2) :
( H - H ) (T 0)
( H - H ) (T 1)
= 0. 52
= 0. 54
RT c
RT c

( H - H ) T
= 0. 52 + 0. 384 0. 54 = 0. 708
RT 2
(H - H
)T = -

0. 708 8. 3196 647. 1J mol -

H = 57496. 72 - 3811. 58 = 53685. 14J mol % =

= -

3811. 58J mol-

53685. 14 - 53359. 13
100% = 0. 61%
53359. 13

, ( T r , p r , )
10 5


2.
( 353) T r p r
S T
=
R

p
p

(Z -

Z
Tr

1) + T r

0, r

dp r
pr

( 360)

( 353) p , T , , ( S T
, p - S T , p )
, ( 360)
38 S T
T r , p r
38 , S T
, ,

38 , , :
( 1) p 0 p , S
S = S p , T -

S p
, T = 0

( S T
, p - S T , p ) + ( S T
, p - S T
, p 0 )

( S T
, p - S T , p ) ( ) , :
S = -

Rln

p
p0

( 361)

, ,
( 2) p p 0 , S
S = S T
, p 0 - S T , p = ( S T
,p 0
0

S T
, p ) + ( S T
,p -

ST , p )

p
+
p0

S = R ln

( 362)

, ,
, , ( T r , p r , )
,
S T ( S- S) ( 0)
( S- S ) ( 1 )
=
+
R
R
R

S T
=
R

( S T
, p 0 - S T , p
p
- ln
R
p0

( S - S)
R

( 0)

( S - S) ( 1)
=
R

( S
- S)
R
310

( 0)

(S
- S)
R

p
p
p
p

( 363)

Z
Tr

( Z ( 0) - 1) + T r

0, r
r
0, r

( 1)

+ Tr

Z
Tr

dp r
pr

dp r
Tr

(1)

p VT , 39

37 298. 15K , 101. 33kP a CO 2 213. 79

J mol

- 1

K - 1 , Cp = 22. 258+ 5. 981 10 - 2 T - 3. 501 10- 5 T 2 + 7. 465 10 - 9 T 3 ,

1 06

 38 ( 1mol , Z c= 0. 27)

373. 15K 10132. 5kPa CO 2

[ ] CO 2
T c = 304. 2K, p c = 7376. 46kPa, = 0. 225
Tr =

373. 15
= 1. 227
304. 2

10 7

 39 [7]

pr =

10132. 5
= 1. 374
7376. 46

38
( S- S ) = 1. 15cal mol

- 1

- 1

( S
T, p
- S T , p ) = 1. 987 ln100 + 1. 15
0

ST
, p S T , p = 10. 30cal mol 0

1 08

K -

= 43. 13J mol -

K -

( a)

 310

10 9

S
( 373. 15K, 101. 33kPa) = 213. 79 +
-

3 73. 2
2

[ 22. 258 + 5. 981 10 T

2 98. 2
- 5

- 9

3. 501 10 T + 7. 465 10 T ]

= 213. 79 + 8. 663 = 222. 453 J mol

- 1

dT
T

- 1

S
( a )
S( 373. 15K , 10132. 5kPa) = 222. 453 - 43. 128 = 179. 32J mol S 177. 75J mol
% =

- 1

K -

- 1

179. 32 - 177. 75
100% = 0. 90%
177. 75

, p r = 1. 374, T r = 1. 226 , 39 310

S- S
R

( 0)

(1)

S- S
= 0. 64,
R

= 0. 30

( 363) ,
S- S
R

ln 100 = 0. 64 + 0. 225 0. 30 = 0. 708

S- S
= 0. 708 + ln100 = 5. 313
R

S
( 373. 15K, 101. 33kPa) = 222. 453Jmol

- 1

S( 373. 15K , 10132. 5kPa) = 222. 453 % =

- 1

( b)

( b) ,

44. 20 = 178. 25J mol

- 1

- 1

178. 25 - 177. 75
100% = 0. 28%
177. 75

3. 3
3. 3. 1
,
, p , V, T
,
dG = - SdT + Vdp
, 1mol ,

G =

p
p

Vdp

( 364)

, , ,
G = R T ln

p2
p1

( 365)

, ,
,
, , G . N . L ewis
1 10


1 mol :
0

= +

p
1

Vdp

( 366)

0 , 1at m , T K , 1mol
,
0

= + R T lnp

( 367)

, Berlin , ( 210) ( 366)

0

= + R T lnp + B
p +

1
2
C
p +
2

1
3
D
p +
3

( 368)

( 368) ( 366) , ( 368) , , B

, C
, D

, , ( 368) ,
, G. N . L ewis f
0

= + RT lnf

( 369)

( 368) , lnf ( 368) f ,

( 368) , ,
( 369) , f
f , ( 369) , ,
, ,
p 0,

f
fV
1 p 0,
1
p
RT

( 370)

f
=
p

fV
=
RT

, p , f =

( 371)
p f 1-

1-

,
( 371) , ,
, ( )
, ,
, ,

3. 3. 2
, , p VT

[ 8]

, ,

11 1

1.
( 366) ( 369)
R T d lnf = ( d) T = Vdp

( 372)

d lnf
V
=
dp
RT

f
1
ln
=
f0
RT

Vdp
p

( 373)

V = Z

RT
p

( 373) ,

f
ln
=
f0

p
p

Z dp
p

( 374)

p 0 , Z / p ,

f
ln
=
f0

p
p

dp
p

p
p

( 1 - Z)
dp
p

( 375)

p 0 0 , p 0 = f 0 ,

f
ln
= p

p
p

( 1 - Z)
dp
p

( 376)

, ( 1- Z ) / p , ( 376)
, ( 376) ,
ln = ln

f
p

= -

r
0, r

( 1 - Z)
dp r
pr

( 377)

, p r Z , Z T r p r ,
T r , p r , Z c ( ) ,

( 1)
( 377) f / p T r p r , 311 [ 9] T r , p r ,
, , 10%
( 2)
, Z c , Z c
[ 5]

311 ,

, ,
,
f
lg
p
1 12

f
= lg
p

( 0)

f
+ lg
p

(1)

( 378)

 311
( 0)

( 1)

f
f
lg
lg
( 0)
p
p
, T r , p r ,
( 0)

( 1)

f
f
( ) , T r , p r lg
lg

p
p
, ( 378)
2.
( 377)

f
ln = ln
p
=

1
RT

1
=
RT

p
p

V0

p
p

Vdp - ln
0

RT
dp
p

p
p0

( 379)

R K ( 379)

p
p

Vdp = p V - p 0 V 0 0

R K

V
V

p dV

( 380)

V
V

p dV ,
0

11 3

p
p

V- b
V0 - b

Vdp = p V - p 0 V 0 - R T ln
0

a
ln
bT 0. 5

V
V0

V0 + b
V+ b

( 380a )

( 379) ( 380a ) ,
p V - p 0 V0
f
V- b
a
=
- ln
+
1. 5 ln
p
RT
V0 - b
bRT

ln

V
V0

V0 + b
V+ b

- ln

p
p0

p V = Z RT , p 0 V 0 = R T ,
ln

f
= Zp

1-

ln

p V - bp
a
+
1. 5 ln
RT - bp 0
bR T

V
V0

V0 + b
V+ b

V0 + b
1,
V0
bp
a
b
ln Z 1. 5 ln 1 +
RT
v
bRT

p 0 0, V 0 , ( RT - p 0 b) R T ,
ln

f
= Zp

1-

( 242)
bp
b
Bp
a
A2
= Bp,
=
,
=
RT
V
Z bR T 1. 5
B

f
ln
= Zp

1 - ln( Z -

Bp ) -

A2
Bp
ln 1 +
B
Z

( 381)

( 381) , f / p Z , Bp
A2

B
38 10203. 43kPa , 407K
( 1) ;
( 2)
[ ]
3

T c = 369. 8K , Vc = 203cm mol

- 1

, p c = 4245. 5kP a, Z c = 0. 281, = 0. 145

407
10203. 43
= 1. 101 p r =
= 2. 403
369. 8
4245. 50
f
311
= 0. 452
p
f = 0. 452 10203. 43k Pa = 4611. 95kPa
( 1) T r =

( 2) Z c
f
= 0. 521,
p
f = 0. 521 10203. 43k Pa = 5315. 99kPa

Z c = 0. 281, T r = 1. 101, p r = 2. 403 ,

[ 5]

, T r = 1. 101, p r = 2. 403, = 0. 145,

f
lg
p
( 378) ,
1 14

(0)

= -

f
0. 311, lg
p

(1)

= 0. 03

lg

f
= p

0. 311 + 0. 145 0. 03 = 0. 3066

f
= 0. 4936
p
f = 0. 4936 10203. 4 = 5036. 41kPa
f = 5034. 84kPa( [ 10] )
:

( )

( Z c )

- 8. 39%

0. 04%

5. 59%

0. 95%

-
100

, , , RK

3. 3. 3
( 369) ,
- 0
lnf =
RT
T
lnf
T

T
T

1
R

=
p

0
1 d
T
R
d T

( 382)

( 318) , ( 372) Gibbs , ( 382)

1
R

T
T

1
RT

S
2 =
RT
RT

2 = RT

H
2
RT

( 383)

( 382) ,
lnf
T p=

1
R

=
p

T
T

p= p

1 d
T
R
d T

( 384)

H
2
RT

( 385)

f
= p 0 , ,
0

d
1
T
R
d T

T
T

1
=
R

= p= p

( 383) ( 385) ( 382)

lnf
T

=
p

( H - H )
2
RT

( 386)
11 5

( 386) ( H
- H ) 3. 2
,
,
lnf
p

( -

1
=
RT

)
p

=
T

1
RT

( 387)
T

= ,
p T V
lnf
p

V
RT

=
T

( 388)

V
, ,

3. 3. 4
, , ( 3
69) , f ,
, , ,

+ RT lnf = + R T lnf

f = f

( 389)

, , ,
,

, 3. 3. 3
,
lnf
T

lnf
p

( H - H L )
=
2
RT

V
=
RT

( 390)

( 391)

, H L VL H
,

39 412 K , 6890. 1 kPa 412K

1309. 1kPa ; 1309. 1 6890. 1kPa ,
2. 06cm 3 g - 1
( 1) ;
( 2) ;
( 3)
[ ] :
p c = 4245. 5kPa , T c = 369. 8K V c = 203cm 3 mol 1 16

Z c = 0. 281, = 0. 145
( 1) 312K 6890. 1kPa , 1309. 1k Pa ,
Tr =

312
= 0. 844
36. 98

pr =

1309. 1
= 0. 308
4245. 5

fV
311 = 0. 81,
p
V
f = 0. 81 1309. 1k Pa = 1060. 37kPa
312 K , 1309. 1kPa , ,
, 1060. 37kP a
( 391) ,
f
ln
f

L
2
L
1

1
=
RT

p
p

V L dp

,
L

f 2
44. 06
ln
=
2. 06( 6890. 1 1060. 37
312 8314. 73

1309. 1) = 0. 195

f 2
= 1. 215
1060. 37
f

L
2

= 1. 215 1060. 37 = 1288. 35kPa

f

( 2) p r = 1. 62, T r = 0. 84, Z c = 0. 281 , [ 5] = 0. 188,

p
L
f = 0. 188 6890. 1 = 1295. 34kPa
( 3) p r = 1. 62, T r = 0. 84, = 0. 145 ,
( 0)

f
lg
p

= -

f
0. 671, lg
p

( 1)

= -

0. 38

( 379)
lg

f
= lg
p

= - 0. 671 + 0. 2145( -

0. 38)

= - 0. 7261

f
p

= 0. 188

f = 0. 188 6890. 1
= 1295. 34kPa
p VT , 1276. 7kPa
, ,
, ,

11 7

3 . 4
3. 4. 1
, p VT
( M ollier ) ( )
:
( 1) p 0 , T 0
( 2) , ,
:
S

p = f (T)

( a)

T , ( a ) p
S

( 3) T p f ( p , V, T ) = 0
V

( 4) V
,
V= f ( T , p )

( b)

T p ( b) , V

( 5) ( a )

dp
dT

dp
( V
- V
) Clapeyron
dT S
V
dp
H
=
dT S
T ( V- V
)

( c)

H V
( 6) f ( p , V , T ) = 0
V
T

V
T

T p S , V

, H
( 3. 2. 2
p
V

) , H
- H = H
H

V
C p
, ( 328) , 34
T p
V
S
; S
= S"- H / T S

( 7)

( 8) C p , T , p

H = H " + Cp m ( T S = S" + Cp m ln

T )

(d)

T
TS

C p m T T

1 18

( e)

3. 4. 2
: , ( lnp H ) ( Mollier
) 312 314

312 T S

313 p H

314 M ollier

, , x
V = V
( 1 - x ) + V"x

( 392)

H = H
( 1 - x ) + H "x

( 393)

S = S
(1-

x ) + S "x

( 394)

x ,
11 9

 312 313 , 1, 2, 3, 4 1
, 2 , , 3 ,
, 34 T S , ,

3. 5
,
, , ,

3. 5. 1
1 , 2 , , m m ,
, U , S V, U, S V ,
,
Q = T d ( S ) ,
W = p d( V)

d( U) = T d( S) -

p d( V)

( 395)

, , ( 316) ( 317)
( U)
( S)

V ,

( U)
( V)

S ,

= T

( 396)

= - p

( 397)

( 396) ,
, , , ,
( 34) ( 395) , ,
, , ( 395)

, , ,

( H ) = ( U ) + p ( V)

( 398)

( F ) = ( U ) - T ( S)

( 399)

( G) = ( U ) + p ( V) - T ( S)

( 3100)

( 398) ( 3100) , ( 395) d ( U ) ,

1 20

:
d( H ) = T d( S) + ( V) dp + d

( 3101)

d( F ) = -

( S) dT -

p d( V) + d

( 3102)

d ( G) = -

( S) dT + ( V) dp + d

( 3103)

( 395) , ( 3101) , ( 3102) ( 3103) ( 3

16) ( 319)
T =

U
S

p =

U
V

V,

S,

H
p

S= -

F
T

= -

( U)

( F )

S,

V,

G
p

S , V ,

( 3105)

T,

( 3106)

T,

G
T

= -

V, T ,

( 3104)

p,

F
V

= -

V= -

H
S

( H )

=
j

( G)

=
j

( 3107)

p,

S , p ,

T, p,

( 3108)
j

j
( 32) ( 395) , ( 3101) , ( 3102) ( 3103) ,
T
V
T
p
p
T
V
T

T
( )
p

S,

S,

V,

p,

p,

T,

T, p ,

V
S

p,

S
V

T,

( 3109)

V,

( 3110)
( 3111)

= -

S
p

= -

( S)

T, p,

( V)

T, p,

= =

p
S

= -

( 3112)

T,

T, p,

( 3113)
j

( 3114)
j

( 3115)
j

j k ( 3109)
( 3112) M axwell , ; ( 320) ( 323) ,
( 32) , 12 ,
, ( 3113) , ( 3114) ( 3115) ( 3103) ,

12 1

3. 5. 2
( 3108) , :
( G)
=
T , p , j
,

p,

T,

= = -

( S )

T, p,

( V)

T, p,

( 3113)
j

( 3114)
j

( 3108) , ( 3113) ( 3114) :

( M)

M =

T, p,

( 3116)
j

M , V , U , H , S , F , G M

, , 1mol
, 1mol

V , U , H , S , F , G ,
V , U ,
G = H - T ( S )
T , p j ,
( G)
=
T , p , j

G = H - T S

( H )

T, p,

( S)

T, p ,

,
, M ,

, V t H t ,
( m) , 1 , 2 , , m ,
M t , , ,
,

M t , 310
, M t ( = M ) M , :
M =

( 3117)

, M x M :
M=
1 22

x M

( 3118)

, ( 3118) M M , x
, , M M
( ) , ( 3116) ( 3
118) , m , m , x , M
, :
: M , U, H , S, G
: M , U , H , S , G
: M , U , H , S , G
3

310 , 2dm 96% ( ) 4% ( )

56% ( ) 44% ( )
, , 25 101. 33k Pa
:
dm 3 / kg

96%

0. 816

0. 953

1. 273

1. 243

25 1. 003dm / kg 2dm dm ,
dm 3 ?
[ ] m a mw m v
:
ma + m w = m v

0. 04ma + m w = 0. 44m v

m w = 0. 7143m a
mv = 1. 7143m a
V tw , V ta V tv :
V tw = m w vw , Vta = ma va , V tv = m v v v

v w V ta
V = 0. 7143
va
t
w

v v V ta
V = 1. 7143
va
t
v

( 3118) , :
v = x 1 v1 + x 2 v 2
,
3

v a = ( 0. 04) ( 0. 816) + ( 0. 96) ( 1. 273) = 1. 255dm / kg

12 3

v v = ( 0. 44) ( 0. 953) + ( 0. 56) ( 1. 243) = 1. 115dm / kg

:
v w = 1. 003dm 3 / kg, V ta = 2dm 3 / kg
,
1. 003 2
3
= 1. 142dm
1. 255

V w = 0. 7143

1. 115 2
3
= 3. 046dm
1. 255

V v = 1. 7143

: 2dm + 1. 142dm = 3. 142dm ,

3

3. 046dm
311

[ ] ( 1)
H = U + pV
mol,
H = U + p ( V)
T , p j , ,
( H )

T, p,

( U )

=
j

T, p ,

+ p
j

( V)

T , p,

( 3116) ,
H = U + p V

( 3119)

( 2)
Cp =

H
T

mol
C p =

( H )
T

p, x

T , p j , ,
( Cp )

T, p,

=
j

[ ( H ) / T ] p , x

T , p,

Cp =

H
T

( 3120)
p, x

( 3) ( )
dG = - SdT + Vdp
mol ,
d( G) = ,
1 24

( S) dT + ( V) dp

G = g ( T , p )
( 3118)

G =

G = f ( T , p )

G
T

dG =

p,

G
p

dT +

T,

dp

( 3108) , G ,
= G

( 3121)

( 3113) ( 3114) dG , , ( 3114)

( 3115) ( 3116) ,

p,

T,

G
T

p,

G
p

T,

= -

( 3122)

= V

( 3123)

dG ,
dG = -

S dT + V dp

( 3124)

: ,
,
, , :
dU = T dS - p dV

( 3125)

dH = T dS + V dp

( x ) ( 3126)

dF = - S dT - p dV

( 3127)

, ,
( 3117) ,
d( M ) =

( dM )

( M d )

( 3128)

d ( M ) T , p M
M
M = f ( T , p , 1 , 2 , 3 )
d( M )
d( M) =

( M )
T

p,

dT +

( M )
p

T,

dp +

M d

( 3129)

d( M) =

M
T

dT +
p, x

M
p

dp +
T,x

M d

( 3129a )

x ( 3128) ( 3129) ,
12 5

M
T

dT +
p, x

M
p

T, x

M
p

T, x

( dM )

dp -

= 0

,
M
T

dT +
p,x

x dM

dp -

= 0

( 3130)

, M
, T , p , ( 3130)

x dM

= 0

( 3131)

( 3117) ,
1mol( ) , ,
( ) ,

( 3117) M x
( M )

T, p,

T, p,

= M
j

T, p,

+
j

T, p,

= 1, ( 3116)
j

M = M +

T, p,

( 3132)
j

m , M T p ( m - 1)
, x 1 , x 2 , , x - 1 , x , x + 1 , , x m
x , , , :
dM =

M
xk

dx k ( T , p )
T, p, x

, k , x l x x k
d , j ,
M

xk

T, p,

M
xk

T, p , x

xk

( 3133)
j

, x k = k / :
j

xk

= j

k
= 2

xk
( k )

( 3134)

( 3132) , ( 3133) ( 3134) , :

M = M -

x
k

M
xk

( 3135)
T, p , x

l k.

k l ( 3135) ( 3116) ,
( 3116) x ( ) ,
1 26

M ( M t ) ,
312 ( 3131) , M x 1 (
) M
[ ] ( 3135)
M1 = M -

x2

dM
dx 2

dM
dx 1

M1 = M + ( 1 - x 1)

( 3136a )

x 1 + x 2 = 1, dx 2 = - dx 1 , , ,
x 1 ,

dM

dx 1
M2 = M - x1

dM
dx 1

( 3136b)

dM

dx 1
, M I 2 ( x 1 = 0 ) I 1 ( x 1 = 1 ) ,
315 M x 1 , x 1

dM
:
dx 1
dM
M - I2
dM
=
,
= I1 - I 2
dx 1
x1
dx 2
I 1 I 2 :
I 1 = M + ( 1 - x 1)

dM
, I2 = M dx 1

x1

dM
dx 1

( 3136a ) ( 3136b) ,
I 1 = M1 , I 2 = M 2
, M , M x M
, 315 , , x 1 = 1 , M 1 = M 1 ,

315 M
x 1

316 M M

M x

12 7

 x 1 = 0( x 2 = 1) M 2 = M 2 316 ,
, M = M , 316 M
, M x 1 = 1( x 2 = 0) , M 2 = M 2 ,

x 1 = 0( x 2 = 1) , M 1 = M 1
317 25, 101. 33kPa
x = 0. 5 , vH 2 O v
, vH 2 O = 0. 963dm 3 / kg , v = 1. 235dm 3 / kg
v 318

317 318 v v H2 O x

3. 6
, , ,
( )

3. 6. 1
,
, ,
,
1.
,
dG = R T dln ^
f ( T , y )
lim
p 0

^f
= 1
y p

^ = ^fy p

1 28

( 3137)

, 3. 3
dG = R T dlnf ( T )
lim
p 0

f
= 1
p
f
p

( 3138)

, ,
dGm = R T dln f m ( T )
fm
= 1
p

lim
p 0
m

( 3139)

fm
p

2.
, p VT , ^

p VT

T , y , ( 3124)
dG = V dp

( 3140)

( 3137) ,
p V dp

RT
p

dln

dp
p

p V
= Z
RT

dln

( Z - 1)

dp
p

( Z 0

dp
p

^=

0 p ,
ln

^
=

1)

( 3141)

ln

^
=

V
dp RT

dp
p

Vt

RT ln

^
=

T, p ,

RT
p dp

( 3142)

V t
( 3142) , :
R T ln ^
=

T, V ,
t j

RT
V t dV t -

RT lnZ

( 3143)

Z p T ( 3143) ,
12 9

 p :
( 317) ,
Ft
Vt

T,

= -

F t - F
t = -

p dV t

V
t

, :

F t - F t= -

p dV t -

p dV t

V
t

p V , ,

, ,

F t - F
t = -

RT
dVt Vt

p -

RT ln

Vt
V
t

R T ln

Vt
V t

RT
dVt ,
Vt

T , Vt , j , ,
Ft

= -

T,V ,
t j

T, V ,
t j

F
t
T , V t , j

RT
V t dVt -

( 3144)

( 3108) ,
Ft

T, V ,
t j

Gt

F
t
=
T , Vt , j

T, p,

= G
j

Gt
= G
T , p , j

( 3144) ,

G - G = -

= R T ln

f^

T, V ,
t j

RT
Vt
dV
t R
T
ln
Vt
V t

= R T ln

^f
y p 0

Z RT
p
RT
p0

= RT lnZ + R T ln

^f

( 3145)

RT ln

Vt
= R T ln
V t

p0
p

( 3145) ,
R T ln

^f

py

= RT ln

^=

( 1)
1 30

T,V ,
t j

RT
Vt dV t -

RT lnZ

( 3146)

 ( 3142) , ( 376)
, ,

ln

1
=
RT

1
=
RT

RT
RT
+
- V dp
p
p

V 0

( V -

V ) dp

( 3147)

( 371) ( 3137)

^f
1
ln
=
y f
RT

p
0

( V -

V ) dp

( 3148)

, ,
, V = V ,
d
f^ = y f

( 3149)

( Lewis R andal ) ,
( 2)
,
, ; ,
,
, ( 215)
, ( 215)
2

RT
Bm
Vt =
+
p

( 3150)

Bm =

T , p j , V t ,
V =

Vt

T, p,

=
j

RT
+ ( 2 y B j p
j

Bm )

( 3142) ,
ln

^=

p
(2
y B j - B m )
RT
j

( 3151)

B j j
( 3151)
ln

^=

p
B +
RT

1
2

[ y y

( 2j - k ) ]

( 3152)

j = 2B j - B j j j k = 2B j k -

B j j - B kk

, ,
13 1


, ,
? , ^

1 ? ( 1) ( 2)

101. 33kPa [ 11] , ,

^

1, , ^

, ^

0. 6, ^

, ^

1. 5,

, ,
, ,
, ,
, , ,
, ,

[ 12 , 13]

( 3)
, ,
,
,
Redlich Kwong ( 2144) ( 2
148) ( 234) ,

T,V ,
t j

, ( 3

143) , :
2

bj
V
ln ^ = ln
+
V- b
V- b
+

y a
j

RT

ab
V+ b
ln
3/ 2 2
V
RT b

3/ 2

ln

V+ b
V

b
- lnZ
V+ b

( 3153)

a=

y y a

b=

y b

a , a j j , b, bj j R K , a j , 2. 7. 2

P rausnitz ( 3150) ( 1) CO 2 ( 2) ,

[ 14 ]

, 319 ,

k j ,
( 4) BWR
, BWR , ( 293) , ( 2. 7. 2 ) :
R T ln
1 32

^=

( B 0 + B 0 ) R T -

2( A 0 A 0 )

1
2

2( C 0 C 0 )
T2

1
2

1
V

 319 171. 1 0. 85( ) CO 2

: a k j = 0. 18 b kj = 0 c Lewis Ra nda ll

3
2
2 RT ( b b)
2

3( C C )
+
T 2 V2
-

1
3

2C r
T 2V 2 r

1
3

1
+
V2

1
3

exp( - r/ V2 )
r / V2

11
2

( a a )

3
2
5 a ( )

+ ( a a )

1
3

1
V5

exp( - r / V 2 )
2

1 - exp( - r / V )
r / V2

1
3

exp -

r
2
V

1 + r / V2
2

- R T lnZ

( 3154)

BW R ,
( ) ,
,
313 H 2 ( 1) - C 3 H 8 ( 2) , y 1 = 0. 208( ) ,
p = 3197. 26k Pa, T = 344. 75K R K
^1 1. 439
[ ] C 3 H 8 , :

T c/ K

pc / kP a

V c/ cm3 mol -

H2

42. 26

1923. 46

51. 5

C3 H 8

369. 8

4245. 52

203

0. 145

H 2 , 210
k j = 0. 07
2. 7. 2 , :
2

a 11
a 22

2. 5

0. 4278 ( 8314. 73) 42. 26

=
1923. 46

= 1. 7850 108 kPa cm 6 K 1/ 2 mol-

0. 4278 ( 8314. 73) 2 369. 82. 5

10
6
1/ 2
- 2
=
= 1. 8320 10 kP a cm K mol
4245. 52
13 3

b1 =

0. 0867 8314. 73 42. 26

3
= 15. 9385cm mol
1923. 46

b2 =

0. 0862 8314. 73 369. 8

= 62. 792cm 3 mol4245. 52

V c 12 =

1
1/ 3
1/ 3 3
3
( 51. 5 + 203 ) = 110. 51cm mol
8

w 12 =

0 + 0. 145
= 0. 0725
2

Z c 12 = 0. 291 -

0. 08 0. 0725 = 0. 285

0. 285 8314. 73 116. 26

= 2493. 0kPa
110. 51
2

a 12

0. 07) ( 369. 8 42. 26) 1/ 2 = 116. 26K

T c 12 = ( 1 -

p c 12 =

2. 5

0. 4278 ( 8314. 73) 116. 26

=
2493. 0

= 1. 729 10 kPa

- 1

cm K

1/ 2

mol

- 2

y 1 = 0. 208 y 2 = 1- 0. 208= 0. 798

2

10

a = 0. 208 1. 7850 10 + 0. 792 1. 8320 10

9

10

+ 2 0. 208 0. 792 1. 729 10 = 1. 207 10 kPa

b = 0. 208 15. 8385 + 0. 798 62. 79 = 53. 40cm 3 mol -

- 1

cm K

1/ 2

mol

- 2

( 234)
10

1. 207 10
3797. 26 +
(V 344. 8 1/ 2 V( V + 53. 40)

53. 40) = 8314. 73 344. 8

V = 554cm mol

- 1

( 3153) ,
ln

= ln

554
15. 94
+
554 - 53. 4
554 - 53. 4
2( 0. 208 1. 7939 108 + 0. 792 1. 729 10 9 )
554 + 53. 40
ln
1. 5
8314. 73 344. 8 53. 4
554

1. 207 10 10 15. 94
554 + 53. 40
+
ln
1. 5
2
8314. 73 344. 8 ( 53. 40)
554
- ln

3797. 26 554
= 0. 3567
8314. 73 344. 8

^=

1. 429

% =

1. 429 - 1. 439
100% = 1. 439

554
554 + 53. 40

0. 72%

3. 6. 2
,
1 34

, V, U , H S
, , , p VT
1.
, :
H =

y H

( 3155)

H
H

2.
: , ,
, ; ,

:
( H )

H=

T , p,

H =

y H

( 3156)

, ( 3156) H M , H ,
,
R K :
H
(H - H
)
=
= RT
RT
,

3 A2
ln( 1 + h) + Z 2 B

( 3157)

H
, T , p j , :
RT
H
H
H

=
+

RT T , p , j
RT
RT T , p , j

( 3158)

( 3157) ( 3158)
H H
=
+
RT
RT
=

H
+ RT
+

3 A
ln ( 1 + h) + Z 2
B

T, p,

T, p,

3
ln( 1 + h )
2

2
p
3 A
1

2
B 1+ h Z

A
B
B

T, p,

T, p,

Bp
2
Z

T, p ,

( 3159)
j

A B ,
13 5

, :
H
H
=
RT
RT

A
B
- 1 - N
A
B

( 3160)

2
h( 3 - Z + B p )
A 3ln( 1 + h) +
M=
2
A
B
3Z + h
- 1 - Bp - 2
B
2

N = -

3 A
ln( 1 + h) +
2 B

( 3161)

1 ( 1 + h) ( 1 - 2Z + 2B p ) ( 3 - Z + B p )
+ z
2
2
2
A
( 1 - h ) 3Z - h Z - 2 - h +
h
B
( 3162)

A
A
M , N RK , Bp h Z , h Z Bp
B
B

320 R K M

1 36

A
, M , N Bp E dmist er [ 1] ( 3162) ( 3163) , ( 3
B
20) ( 321)

321 RK N

314 255. 35K ( 1) ( 2) y 1 = 0. 742(

)
[ ] A 2 , A B

A2

0. 00450

0. 0671

0. 001412

0. 0139

0. 1179

0. 002148

A =

y A

= 0. 067 0. 742 + 0. 1179 0. 258

= 0. 0802at m
2

1
2

A = ( 0. 0802) = 0. 00643atm
B =

y B

- 1

= 0. 001412 0. 742 + 0. 002148 0. 258

= 0. 00160atm

- 1

A
0. 00643
=
= 4. 02
B
0. 00160
Bp = 0. 00160 64. 6 = 0. 1035
H
32
= - 1. 29
RT
13 7

 320 M = 6. 30
321 N = - 1. 30
( 3160)
H 1
= - 1. 29 RT
H 1 = ( -

0. 0671
0. 001412
- 1 + 1. 30
0. 0802
0. 00160

6. 30

0. 39) ( 8. 3196) ( 255. 35) J mol

H 2
= - 1. 29 RT
H 2 = ( -

- 1

= -

1 = -

849. 96J mol

0. 1179
0. 02148
- 1 + 1. 30
0. 0802
0. 00160

6. 30

3. 79) ( 8. 3196) ( 255. 35) = -

8059. 97J mol-

1 = -

0. 39

- 1

3. 79

( 3156)
H = 0. 742( -

849. 96) + 0. 258( - 8059. 97) = -

2698. 6J mol

- 1

A 2 / B Bp 32 H / RT = - 1. 29,
H = ( -

1. 29) ( 8. 3196) ( 255. 35) = -

2753J mol

- 1

,
, ,

31 :
( 1) U = -

( 2)

( 3)
( 4)

U
V
U
S
U
T

F
T
T

= T

p
T
T

= -

T
p
p

p2

= cV

ln T
lnV

;
V

32 Pit zer
Bp c
(0)
( 1)
= B + B
RT c
T r , p r Z , H
/ R T S
/ R

33 p 1 = 1atm ( = 101. 3k Pa ) , T 1 = 273. 2K p 2

= 200atm ( = 20265kP a) , T 2 = 473. 2K 1mol p VT (
) cp = 1. 1889+ 0. 00381T Jg
T = 473. 2 K
1 38

- 1

- 1

p / at m
V/ cm 3 mol T
V

V
T

10

40

60

100

140

160

180

200

3879

968

644. 7

388. 0

279. 2

245. 2

219. 2

198. 6

1. 016

1. 016

1. 088

1. 135

1. 171

1. 182

1. 191

1. 176

34 573. 2K 506. 63kP a( 5at m)

Z , H
S

T/ K
B/ cm 3 mol -

563. 2

573. 2

583. 2

- 125

- 119

- 113

35 1mol 1, 3 2533. 13kP a ( 25atm )

400K 12665. 63kPa( 125at m) 550K H , S , U V
36 1mol 410K 5471. 55 kPa V , U , S , F G
101. 33k Pa 0
37 , p V , lnp H , T S H S

( 1) ;
( 2) ;
( 3) ;
( 4)
38 505K ,
41. 70 cm 3 g - 1 , :
( 1) ;
( 2) ;
( 3)
39 , 241K 2026.
6kPa
310 101. 33k Pa , 0. 582( ) ( 1) 0. 418 ( 2)
354. 8 K , ,

y1

/ K

0. 582

354. 68

B 11 / cm 3 mol- 981

B 22 / cm 3 mol - 559

B 12 / cm 3 mol -

- 784

311 303. 2K 101. 33kPa , ( b ) ( c)

, V = 109. 4- 16. 8x b - 2. 64 x b2 , x b , V
3

cm . mol

- 1

, V b , V c V ( Lewis
13 9

R andal )
312 : 1
1
1 =

M - x 2M2
x1

x , M , M 2 2 T p

( 1) T , p , x 1 1 M 1 M 2
;
( 2) x 1 = 0, x 1 = 1
d1
: ( 1) M 1 = 1 + x 1 ( 1- x 1 )
dx 1
1
2 d
M 2 = M 2 - x 1 dx 1

( 2) x 1 = 0, M 1 = 1 ;

x 1 = 1, M 2 = M 2 -

1
x1

x = 1
1

313 20% ( ) A , 35% B 45% C

6079. 5kPa ( 60at m ) 348. 2K A , B C 0. 7,
0. 6 0. 9,
314 Prausnit z 323. 2 K 373. 2 K ( 1) ( 2)
:
5. 5 0

B 11 = -

1
3
8. 55
10
T

7. 3 50

B 12 = -

1
1. 74
103
T

1
3
21. 5
10
T

B 22 = -

T , K, B cm mol

- 1

3. 25

80k Pa 353. 2K

( 1) ( 2) , y 1 = 0. 3( ) ,

315 314 80kP a 353. 2K f^1

^f ( k Pa)
2

[ 1 ] Edmis ter W C .

A pplied H ydr ocarbon T hermodynamics . V ol . H oust on ,

Gulf P ublis hing

Company , 1974
[ 2] Vargaft ik N B. T ables on t he T hermophysical Pr opert ies of Liquids and G ases, 2d edit ion . N ew
yor k , Wiley , 1975
[ 3] Djordjevic B D et al . , Chem . E ng . Sci . , 32, 1103( 1977)

1 40

[ 4] K ordbachen R et al. , Can. J . Chem. E ng. , 1959, 37: 162

[ 5] Reid R C et al . , T he P ropert ies of G as es and Liquids , 2d edit ion . M cG raw H ill , 587, 1996
[ 6] Chao K C et al . , T hermodynamics of F luids an Int roduct ion t o Equilibriam T heory . M ar cel
Dekker, 1975
[ 7] P it zer K S et al , I . E . C . , 1958, 50: 265
[ 8] , . . , 1965: 14
[ 9] H ougen O A et al . , Chemical P roces s Principles , ls t edit ion . Wiley , 1947: 621
[ 10] Canjar L N et al. , T hermodynamic Propert ies and Reduced Cor relat ions for Gas es . H oust on,
T exas : Gulf P ublishing Company , 1967
[ 11] P rausnit z J M . phase E quilibr ia and F luid P roperties in t he Chem ical Indus try . A CS: Sym p. 60,
ed. St orvick T S. and S I Sandler , Was hingt on: ACS, 1977: 11
[ 12] , . . 1990, 41( 2) : 195
[ 13] , . . 1993, 22( 1) : 27
[ 14] Pr aus nitz J M et al . , Computer Calculat ions for H igh P res sure V apor Liquid Equilibria . P rentice
Hall Inc . , 1968
[ 15] . . , 1961

14 1

4 . 1
, :
, ,
;
; , , ; ,
; ,
( )
,
r =

p2
( p 1 , p 2 )
p1

:
: r = 1. 01. 1
: r = 1. 14. 0
: r 4. 0
, ( ) ,
,
, ,
,
,
, ,
r ,

, :
, , ;
; , ,
,

4. 1. 1
41 ,
, , , 2
1 42

, , ( , 1atm )
, 4 ,
, , 4 ,
, , 5,
, ,
, 4, ,

42

41
1 ; 2 ; 3 ; 4 ;

5 ; 6 ; 7

, ,
( ) ,
42
a 1 , a , ,
, , ,
, ( 12 ) ;
, , ( 12
)
p 2 , , 2b ;
, 2
b , a 12ba a 12
ba
a 12
ba a 12ba ,

: 1a 2_ b 2
b ,
( ) ,
, , , , a 1
, , 2 2
b
, 2 b 2
b ,
, ,
, a _ 1 2 b 2
b ,
14 3


, ,
, ,
, , ( )
, , ,
, , ,
, ,
, , ,
, ,
,
,
, 42 :
W a 1 = p 1 ( V1 -

W1 2 =

0) = p 1 V 1 , W 2b = p 2 ( 0 - V 2 ) = -

p 2 V2

p dV, W ba = 0

W = W a 1 + W 1 2 + W 2b + W ba = p 1 V 1 - p 2 V 2 +

p dV

d ( p V) = p 2 V2 -

p 1 V1 =

p dV +

Vdp

W= -

p
p

Vdp

( 41)

W ,
, ,
41 ,
, ,
, , , ,
, , 41
,
12
W= -

p 1 V 1 ln

p2
p1

( 42)

12
k
W=
p 1 V1 1 k- 1

p2
p1

m
W =
p 1 V1 1 m- 1

p2
p1

k- 1
k

( 43)

12

1 44

m- 1
m

( 44)

4. 1. 2
, ,
, ,

, ,
, 43 , ,
V 3 ,
, ,
,
,

43

( V 1 - V 4 ) , ( V 1

- V 3 ) V
= V 4 - V 3
43 , :
W 4_
W 1_
W 2_
W 3_

= p 1 ( V1 - V4 )

V
V

p dV

= p 2 ( V3 - V2 )

V
V

p dV

:
W = W 4 _ 1 + W 1_
= p 1 V1 -

= -

= -

+ W 2 _ 3 + W 3_

p 1 V4 +

Vdp -

1
2

p
p
p

Vdp +

V
V

p dV + p 2 V 3 - p 2 V 2 +

p dV

Vdp

Vdp

( 45)

43 , p 3 = p 2 , p 4 = p 1 , p

p
p

Vdp a 4123ba ,

Vdp a 43ba , 12341

12 34 ,
k
W=
p 1 V1 1 k- 1

p2
p1

k- 1
k

k
p 4 V4 1 k- 1

p3
p4

k- 1
k

p 1 p 2 ,
k
W=
p 1 ( V1 k- 1

V4 ) 1 -

p2
p1

k- 1
k

( 46)
14 5

 , :
( VE ) =

V1
=

V1 -

V4
V3

( 47)

( V 1 - V3 ) D , ( V 1 - V 4 ) = ( D )
( VE ) , 46
k
W =
p 1 ( D ) ( VE ) 1 k- 1

p2
p1

k- 1
k

( 48)

VE , C
C=

V3
=

V1 - V3

( 49)

, , 8% ,
1%
49 47
VE =

V1 - V4
( V1 - V3 ) + ( V3 - V4 )
=
= 1+ CV1 - V3
V1 - V 3

V4
V3

V4
=
V3

p2
p1

1
k

VE = 1 + C -

p2
C
p1

1
k

( 410)

p 2 / p 1 , 44

,
, , VE
410 ,
, VE ,
VE 50% 90%
41
( ) 24h
3

2830m , 1atm ( 101.

44

33k Pa ) 15. 6 50atm ( 5. 07 10 3 k Pa ) ,

pV
:
( 1) ;
( 2) ;
( 3)
1 46

1 . 15

: 228mm, 915mm, = 125rpm,

3. 2%
[ ] ( 1) 3. 2%
C = 0. 032
410
VE = 1 + 0. 032 -

50
0. 032
1

0. 1
1 . 15

= 0. 072

( )

( 0. 228) 2 ( 0. 915) = 3. 74 10 - 2 m 3
4
, ,
- 2

- 1

( 3. 74 10 m ) ( 125rpm) = 4. 68m min

( VE ) ( )
3
- 1
( 0. 072) ( 4. 68) = 0. 337m min
2830
118m 3 h - 1 , ,
= 1. 97m 3 min - 1 ,
24 60

1. 97
= 5. 85 6
0. 337
( 2) 6
WF = = -

1. 15
4
( 1. 0332 10 ) ( 1. 97)
1. 15 - 1
244kcal min -

50
1

0. 15
1. 15

1
1 427

= - 61. 5 106 J h - 1
( 3) ( )
Q = H + W F

Q = G cp dT + W F
G( kmolmin

- 1

) , cp 6. 9kcalkmol

T2 = T1

p2
p1

- 1

- 1

- 1

50
T 2 = 288. 8
1

0 . 15
1 . 15

= 481K

G=

2830
273
1

= 0. 083k mol min

22. 4
273 + 15. 6
60 24

14 7

Q = ( 0. 083) ( 6. 9) ( 481 = 110. 5 + ( -

288. 8) + ( -

244)

244) = - 133. 5kcal min

Q = - 8000kcal h

- 1

= - 33. 4 10 J h

- 1

- 1

4. 1. 3
, , T 1 ,
; ,
,

45, 7 , 5 6 , 3 4
, , 180
, 3 , 4 3 ,
9 1, 3 ,
p 2 T 2 , 3 , 10
8, , ,
4 ,
, 4 , p 3 , 12 ,

46

45
1, 2 ; 3, 4 ;

5, 6 ; 7 ; 8 ;

9, 11 ; 10, 12

46 a 122
3ca

, , 22
33
2
,

1 48

, , ,
, , ,

,
45 , 44,
m
W1 =
p 1 V1 1 m- 1

p2
p1

m
W2 =
p 2V 2 1 m- 1

m- 1
m

p3
p2

m- 1
m

, p 2
= p 2
p 1 V 1 = p 2 V 2

m
W = W1 + W2 =
p 1V 1 2 m- 1

p2
p1

m- 1
m

p3
p2

m- 1
m

p 2 ,
,

dW
= 0
dp 2

d
dp 2 2 -

p3
p2

m- 1
m

p4
p2

m- 1
m

= 0

p 1p 3

p 2 =

p2
p3
=
p1
p2

( 411)

W1 = W2
, ,
,
m , p 1 , p 2 , p 3 , , p m , p m+ 1 ,
, :
p2
p3
p4
pm
p m+ 1
=
=
= =
=
p1
p2
p3
p m- 1
pm

( 412)

, r ,
pm+ 1
p2 p3 p4
pm
p m+ 1
m
=

= r
p1
p1 p2 p3
p m- 1
pm
m :
m

r =

p m+
p1

( 413)

m
W= m

k
p 1 V1 1 k- 1

(r)

k- 1
k

( 414)
14 9

 , ,
:
W= m

k- 1
k
p 1 ( D ) ( VE ) 1 - r k
k- 1

( 415)

4. 1. 4
(
) N e ,
N e N F ; ,
N , , N
, 47
( 1)

G( kmolmin

- 1

kgmin

- 1

) ,

W ( kg m kmol- 1 ) ,
NT =

GW F
GW F
- 1
( kg m s ) =
( kW )
60
102 60
( 416)

( 2)

N=

N t( T )
( T )

( 417)

N=

N t( S)

( S )

( 418)

, ( T ) , ( S )

47

0. 65 0. 76, 0. 85
0. 97T S
,
p V
, 48 , f

( 3)
NF =

( 419)

, m , 0. 88 0. 92,
,
( 4)
1 50

48

 , ,

Ne =

NF
c

( 420)

: c , :

c = 0. 900. 94

c = 0. 920. 98

c = 0. 960. 99

c= 1

, N e
42 3D 22 ( ) 14. 5/ 320
, 0. 90, 0. 92,
:
3

( ) 14. 5m min

- 1

( ) 15k gf cm -

:
( ) 300mm

38

( ) 180mm

( ) 321kgf cm -

( ) 150mm

140

420mm

< 32

1669k W

380rpm

, ,
, ,
( 1) ;
( 2)
[ ] ( 1) , 413
3

r =

321
= 2. 78
15

, :
( p ) = 2. 78 15 = 41. 6kgf cm -

( p ) = 41. 6 2. 78 = 116kgf cm

- 2

( p ) = 116 2. 78 = 321kgf cm -

= 4079. 6kPa
= 11375. 7kPa

= 31479. 3kPa

125 , ,
:
( T ) = ( T ) = ( T ) = ( 38 + 273) ( 2. 78)

k- 1
k

1kgf cm - 2 = 98. 0665kP a

15 1

 k H 2 = 1. 408, kN 2 = 1. 400, N
2
H 2 = 1 3,
k = 0. 75 1. 408 + 0. 25 1. 400 = 1. 406
1. 40 6- 1
1. 406

( T ) = ( T ) = ( T ) = 311 2. 78

= 416K = 143

, 140
414 :
1. 406
15 14. 5 3
1. 406 - 1

NT = -

2. 78

( 1. 406 - 1 ) / 1 . 406

4
1 60 10

= -

4. 66 10 kg m h

- 1

= -

4. 66 10
1260kW
3 =
367. 1 10

418419
NF =

1260
1

= 0. 9
0. 92

1520kW

1669kW 149kW
0. 96, 1520/ 0. 96 =
1585k W
( 2) ,
:

N2

H2

N2

H2

0. 04

T e/ K

126. 2

33

p c / atm

33. 5

12. 8

6. 66+ 1. 20 10- 3 T

6. 947- 0. 1999 10 - 3 T

cp
/ calmol - 1 K-

T cM = 0. 75( 33. 3 + 8) + 0. 25( 126. 2) = 62. 5K

p cM = 0. 75( 12. 8 + 8) + 0. 25( 33. 5) = 23. 97at m = 2432. 1kPa

cp
M =

y c

- 3

0. 1999 10

= 0. 75( 6. 947 -

- 3

T ) + 0. 25( 6. 66 + 1. 02 10

T)

= 6. 87 + 0. 104 10- 3 T
M =

y =

0 + 0. 25 0. 04 = 0. 01

M ,
,

, 144,
,

384 :
( S 1_ 2 ) M
1 52

( H 1_ a ) M
( H b_ 2 ) M
=
+
+
T1
T2

T
T

2
1

cp
dT T

Rln

f
f

2
1

,
:
( pr) =

116
= 4. 67
24. 8

( T r) =

311
= 4. 98
62. 5

( pr) =

321
= 12. 9
24. 8

413
= 6. 61
62. 5

( T ) = 140= 413K , ( T r ) =
( H a- H 1 ) M
= Tc
f
P

0. 1,

( H b- H 2 ) M
= Tc

= 1. 06,

f
P

0. 3

= 1. 22

( S 1 _ 2 ) M =

62. 5 0. 1
62. 5 0. 3
+
311
413

+ 6. 87 2. 3lg
= - 0. 31cal mol -

1. 22 321
1. 06 116

1. 987 2. 3lg

413
- 3
+ 0. 104 10 ( 413 311
1

K -

311)

( T ) = 150, ( S 1_ 2 ) M = - 0. 10cal mol - 1 K ( T ) = 160, ( S 1_ 2 ) M = 0. 01calmol

- 1

- 1

( S 1_ 2 ) M T ( 49) , ( S 1_ 2 ) M = 0 ( T ) = 159,
140, , , r = 2. 5 p =
= 128. 3 kg cm - 2 , r r =

321
2. 5

321/ 15
= 8. 55, r = 3. 0, r = 2. 85
2. 5

, :

/ kgcm - 2 ( kPa)

/ kgcm - 2 ( kP a)

15( 1471. 0)

45( 4413. 0)

45( 4413. 0)

128. 3( 12581. 9)

128. 3( 12581. 9)

321( 31479. 3)

, , :
T = 153= 426K
( T r) =

426
45
= 6. 81, ( p r ) =
= 1. 82
62. 5
24. 8

( T r) =

311
15
= 4. 98, ( p r ) =
= 0. 6
62. 5
24. 8

:
15 3

H a- H 1
H b- H 2
0,
0
Tc
Tc
f
p

lg

( S 1_ 2 ) M = -

f
p

1. 0, lg

45
426
+ 6. 87 2. 3lg
15
311

1. 987 2. 3lg
- 3

+ 0. 104 10

1. 0

( 426 - 311) 0

T = 152 = 425K
( T r ) = 6. 8
( T r ) = 4. 98
128. 3
= 5. 16
24. 8

( p r ) =

( p r ) = 1. 82
:
( H a- H 1 ) M
0
Tc
( H b- H 2 ) M
= Tc
f
p
( S 1 _ 2 ) M = 0 +

0. 1

49

f
p

= 1. 02

62. 5 0. 1
425

+ 6. 87 2. 3lg

1. 987 2. 3lg

= 1. 08
1. 08 128. 3
1. 02 45

425
+ 0. 104 10- 3 ( 425 - 311) 0
311

T = 140= 413K
( T r ) = 6. 61, ( p r ) =

321
= 12. 9
24. 8

( T r ) = 4. 98, ( p r ) = 5. 16
:
( H a- H 1 ) M
= - 0. 1
Tc
f
p
( S 1 _ 2 ) M =

= 1. 27

f
p

0. 25 0. 1
62. 5 0. 4
+
311
413
+ 6. 87 2. 3lg

1 54

( H b- H 2 ) M
= Tc

0. 40

= 1. 14

1. 987 2. 3lg

321 1. 27
128. 3 1. 14

413
- 3
+ 0. 104 10 ( 413 - 311) = 0
311


, 136 , H
18 , , :
H 1_ 2 ) = -

WF = ( = = -

[ ( H

) + ( H a _ b ) + ( H b_ 2 ) ]

0. 104 10- 3
2
311) +
( 426 2

0 + 6. 87( 426 794cal mol -

1_ a

= -

3324. 5J mol -

311 ) + 0

WF = -

= -

+ 6. 25 0. 1 + 6. 87( 425 -

0. 104 10- 3
+
( 4252 2
794cal mol -

= -

WF = +

= -

= -

3112 )

3324. 5J mol-

62. 5 0. 1 + 62. 5 0. 4 + 6. 87 ( 413 -

0. 104 10- 3
( 4132 2
726cal mol -

= -

311)

3112 )

= 3039. 8J mol-

3D 22 ( ) 14. 5/ 320 15k g cm

3

14. 5m min

- 1

311)

- 2

( 1471kPa ) ,

, , ,

,
15
3
14. 5 10
pV
1. 033
=
=
= 8220mol min
RT
0. 08206 311

N 1 = [ ( W F ) + ( WF ) + ( WF ) ]
= - 8220( 794 + 794 + 726)
4

= - 1. 91 10 k cal min

- 1

= - 1. 91 10 4 60 1. 163 10 -

= - 1340kW
-

1340
1

= - 1620 kW , 1669kW
0. 9
0. 90

49kW
1620
= 1690kW
0. 96
,
,

41
, 1800kW 18
, 41
,
15 5

 4-1 3D22 ( ) -14. 5/ 320

/ /
/
kg cm - 2 kg cm - 2
kgcm - 2
( kP a )
( kP a )
/
( kP a)

15
44. 9
( 1471. 0) ( 4403. 2)

/
- 2

kg cm
( kP a)

/
kgcm
( kP a)

- 2

/
kgcm ( k Pa )

154

15
( 1471. 0)

41. 6
( 4079. 6)

143

15
( 1471. 0)

45
( 4413. 0)

153

149

41. 6

116

143

45

128. 3

152

( 4403. 2) ( 12621. 8)

( 4079. 6)

( 11376. 3)

( 4413. 0)

( 12582. 0)

128. 7
321
( 12621. 1) ( 31479. 3)

136

116
( 11375. 7)

321
( 31479. 3)

143

128. 3
( 12582. 0)

321
( 31479. 3)

140

44. 9

128. 7

4. 1. 5
42 , ,
,
, ,
:
Q = CT
147
Q = CV

mm-

k
( T2 1

T 1)

( 421)

,
, ,
,
, ,
:

Q=

C p dT

( 422)

,
:
Q = Cp m ( T - T 0 )

( 423)

, Cp m T T 0 ; T

410
T S

; T 0
, , C p ,
C p
410 T S 12, 2
3, 3
4
1 56

22
33

a 12 ba , b22
cb
43 3D 22 ( ) 14. 5/ 320 ,
5, ( 1) ( 2) ,
?
[ ] , ,

( 1) , , 143,

31 1

Q=

3 11

( 6. 87 + 0. 104 10- 3 T ) dT

C p dT =
41 6

4 16
- 3

= -

6. 87 ( 416 -

0. 104 10
311) +
2

= - [ 721 + 4] = - 725cal mol-

( 416 -

= 3023J mol-

311 )
1

= -

725 8220 60 2 = -

= 3 106 kJ h 1kcalkg

- 1

- 1

7. 15 105 kcal h -

715000
= 143t h 1 5

( 2) , ,
Q = H
, H , , ,
, , ,
H ,
Q= -

( 794 + 794) cal mol-

= -

= - 1588 8220 60 = =

1588cal mol -

= 6622J mol -

7. 86 10 kcal h

786000
= 157t h
1 5

- 1

= 6. 28kJ h

- 1

153t h - 1 , , ,

4. 1. 6
, ,
, ,
, , ; ,
, , , ,
15 7

, , ,
,
411 T S 411( b) 12
, 12
, , W p

:
W p= H 2- H 1

( 424)

, 411( b) 2
3462
,
, 62
256= 2
3462
23452
: , ;
,

411 ( a ) T S ( b)
1 ; 2 ; 3 ; 4 ; 5

, ;
, ,
, , ,
0 ,
W K S W K :
WK S
WK

( 425)

H2 - H1
H 2- H 1

( 426)

t2 - t1
t 2- t1

( 427)

0 =
, ,
0 =
, Cp = ,
0 =

0 H S T S ( )
1 58

426, ,
H 2 = H 1 +

H2 - H
0

H 2 p 2 , H S t 2
, 427
t2 = t 1 +

t2 - t1
0

?, ,
, , , ,

44 , V 2 =
3

400m h

- 1

, : p 1 = 1at ( 98. 1kPa) , t 1 = 17, 0 = 0. 85, p 2 =

4at ( 392. 3k Pa ) ,
[ ] ,
T2 = T1

k- 1
k

p2
p1

= 290 4

0. 28 6

= 430K

,
T 2= T 1 +

T2 - T1
430 - 290
= 290 +
= 455K
0
0. 85

W = G( H 2 - H 1 ) =

p 2V 2
Cp ( T 2 - T 1 )
RT 2

4 10 400
7
=

( 455 29. 27 455

28. 9
= 48000kcal h -

290)

= 55. 8kW

4. 2
, ,
, , , ,
, ,
, ,

4. 2. 1
1. 1. 3 17, u 2
15 9

:
2

u 2 = 91. 5

u1
- 1
( H 1 - H 2) +
( m s )
2g

( 428)

u 1 ,
u 2 = 91. 5

H1 -

H 2 ( m s - 1 )

( 429)

, H ( M ollier ) , 428 429

; ,
2

u2 - u1
k
=
p 1 V1 1 2g
k- 1

p2
p1

k- 1
k

( 430)

u 1 ,
u2 =

k
2g
p 1 V1 1 k- 1

p2
p1

k- 1
k

, p 1 , V 1 , kgm

( 431)
- 2

, m kg

- 1

p , u ,
u=

k
2g
p 1 V1 1 k- 1

p
p1

k- 1
k

( 432)

, ( F )
G :
G=

u1 F 1
uF
= =
V
V1

( 433)
1

p1 k
, , p , V = V1
( 124) , ,
p
G, , ,
, ,
, ,
,
( ) ,
412

, ,

, ,

412

:
, 124, p V k = = p 1 Vk1 , ,
:
V k dp + kp Vk - 1 dV = 0
1 60


dV
= V

1
dp
kp

( a)

, W F = 0, E p = 0, ,
110,

u 2 - u1
Vdp
=
p
2g
1
2

, ,
, :
- Vdp =

u
du
du
= g
u

gV
dp
u2

( b)

433, G ,
dF
du
+
F
u

dV
= 0
V

a , b ,
dF
kgp V - u 2
=
dp
F
u 2 kp

a=

kg p V

( c)

dF
a2 - u2
1
=
dp
2
F
u
kp

( 434)

, , , a =
kg RT ,
, u < a , ; u > a ,
, , dp < 0, dF < 0, dF > 0; dF =
0, u = a , , u 1 , , ,
,
, ,
p 2 / p 1 = k , ; k ,
k , , , k = 1. 4 , k = 0.
528; , k= 1. 3 , k = 0. 546

4. 2. 2
, (
) , , ,
,
( ) , ,
, , , ,
16 1

, ,
:
u < u ; H > H ; T > T
, , :
=

u
u

( 435)

, , 0. 920. 98
, ( )
u , u ,
u = u = ( 91. 5

H 1 - H 2)

( 436)

, :
u 2 / 2g

2
=
= 2
=

u / 2g

( 437)

0. 850. 95
45 p 1 = 6atm ( 608kPa ) , t 1 = 350,
p 2 = 4atm ( 405kPa ) 90% , , k = 1. 4
cp = 0. 24kcal kg - 1 K - 1 ,
[ ]
T2 = T1

p2
p1

k- 1
k

4
6

= ( 350 + 273)

1. 4- 1
1. 4

= 555K

u 1 , 429
u 2 = 91. 5
= 91. 5

H 1 - H 2 = 91. 5
0. 24 ( 623 -

Cp ( T 1 - T 2 )

555) = 369m s

- 1

c = = 0. 9, = 0. 947,
u2 =

u 2 = 0. 947 369 = 350m s

- 1

429,
0. 24( T 1 - T 2 ) =

u2
91. 5

= 14. 65

T 2 = 562K t 2 = 289

4. 2. 3
, ,
du> 0, dp < 0, ,
, , , ,
( ) , ,
1 62

du < 0, dp > 0 434, , ;

, , ,
, , , ,

4 . 3
( )
, ( )
, , , ,
, ,
, ,
, , ,
,
, , ,
, ,
,

413

, , ,

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

,
, 413 ,
,

16 3

G
( kgs

- 1

) p 1
( kPa) , p 23
( k Pa)

,
1 2 , ,
, 12
,
= ( 1 -

12
) ( H 1- H 2
)s

( 438)

, s
2 p 2
,
, p 2
= p 23; G
( k g s - 1 ) ,
, ,
2,
3

= ( 1 -

23
) ( H 1- H 2
)s

( 439)

:
= ( 2 -

12- 2
3 ) ( H 1
- H 2
)s

( 440)

3 , :
H 3= ( H 2
)s + (2-

12- 23
) ( H 1- H 2
)s

( 441)

G = G
+ G
, p 4 ,
, 34
,
2

( H 4 - H 3) s
u3 - u4
34 =
=

H4 - H3
2g ( H 4 - H 3 )

( 442)

H 4 , H 3 3
,
,
( G+ G
)(H

- H 3 ) = G
( H 1- H 3
)

G+ G H 1- H 2
=
G
H 4 - H 3

( 443)

1 kg
, ,

G
H 1+ G
H 1= ( G+ G
)H 4

( 444)

p 1
, p 23
p 4 , ( 442) ( 444) ,

H 3 , ( 442) H 4 , ( 443)

( G
+ G
) / G
, ( 442) H 4 , H 3 ( 442)

H 4 , ( 444) H 4 , H 4 ( 443)

46 , 785k Pa ,
0. 28kP a , 101kP a , ,
1kg k g ? , 12
= 0. 95, 23
= 0.
80, 34= 0. 90
1 64

[ ]
H 1
( p 1 785kPa ) = 661kcal kg
= 2763kJ kg -

- 1

S 1
( p 1 785kPa ) = 1. 59kcal kg = 6. 65kJ kg

- 1

K -

- 1

( H 2
) s( 0. 28bar ) = 536kcal kg

- 1

= 2240k J kg -

414 H S

414, ( 441)
H 3= 536 + ( 2 = 567kcal k g

0. 95 - 0. 80) ( 661 - 1

= 2370k J kg

536)

- 1

= H 1- H 3= 661 - 567 = 94kcal kg -

- 1

= 393kJ gk
0. 28bar H 3 = 587kcal kg - 1 = 2454k J kg - 1 ,
1. 03b ar H 4 = 635. 2k cal kg - 1 = 2655kJ kg - 1 ,
H 4 - H 3 = 635. 2 -

587 = 48. 2kcal kg

- 1

= 201. 5kJ k g

- 1

( 442)
H 4 - H 3 =

( H 4 - H 3) s
48. 2
=
= 53. 6kcal kg 34
0. 90

= 224kJ kg -

H 4 = 587 + 53. 6 = 640. 6kcal kg

- 1

= 2678kJ kg

- 1

( 443)
G+ G H 1- H 3
94
=
=
= 1. 75

G
H4 - H3
53. 6
16 5

G
= 0. 75
G
H 3 0. 28bar
H 1
= 625kcalkg

- 1

, ( 444)

1. 0 661 + 0. 75 625 = 1. 75H 4

= 642kcal kg

- 1

= 2684kJ kg

- 1

, H 3 , 1k g
0. 75kg , , 1kg 1. 33 kg
, ,
,
( ) ,
, ,
,
, ,
,
,
,
, 415

415
1 ; 2, 4, 6 ;
3, 5, 7

41 5, 150kPa 600kPa
, 3m 3 min - 1 ( 20 100kPa ) ,
:
( 1) ;
1 66

( 2)
42 100k Pa 60 420 kPa , 1kmol
( ) cp = 5. 42+ 0. 0414T kcal kmol- 1 K - 1
43 :
p V = R T + 30. 0p
3

p , V, T kP a, cm mol

- 1

: cp = 6. 66+ 1. 02 10 - 3 T ( k calk mol

K 100kPa kmol

- 1

- 1

25 100k Pa 15000kPa , , :
( 1) ;
( 2) ;
( 3) , k= 1. 394,
44 800 kPa ,
:
D = 30cm, S= 20cm, d = 6cm,
5% , = 300rpm
a b = 0. 78, [ :
, ( p 2 p 1 ) , ]
45 N 50/ 200 ,
:
= 125rpm
98% CO 2 , N 2 , H 2 , CH 4 , O 2
= 103kPa
= 880kW
= 3000m 3 h -

T DK100048( 1000kW )
:

103

330

330

960

960

3020

2960

7000

13

101

32

117

27

117

25

93

/ kP a
/

( ) 3950N m h

- 1

7000 20900
33

107

, 85A ,

1. 0
,
( 1) ;
( 2) ;
16 7

( 3)
46 , V 1 = 500 m 3 h - 1 , p 1 =
100kPa t 1 = 27, p 2 = 500kPa , 0. 95, 0. 75,
?
47 700k Pa, 16, 2800L ,
25. 4mm , :
( 1) ;
( 2) 150kP a
48 7. 6mm ,
1400k Pa 260, :
( 1) p 2 / p 1 ;
( 2) p 2 / p 1 ;
( 3) p 2 / p 1
49 , 700kPa , 304
30. 5ms

- 1

, 560, 490, 420, 350, 280, 210 140kP a

F / F 1 ( F , F 1 )

410 , p 1 = 1000kPa , t 1 = 300,

, p 2 = 100 kPa G= 0. lkg s

- 1

, ,
= 0. 94,

( : )
411 p 1 = 100 kPa , t 1 = 27 182k Pa ,
?

[ 1] Laby T H and Hercus E O Phil. T rans . Roy. Soc. , 1928, 277: 63
[ 2] Laby T H P roc . P hys . Soc. , ( L ondon ) , 1926, 38: 169
[ 3] Laby T H and Hercus E O . ibid , 1935, 47: 1003
[ 4] Os borne N S St ims on H F and Ginnings D C. J. Res . N at l. Bur. s td. , 1939, 23: 197
[ 5] laeger W and von Stein Wehr H . A nn . P hys ik , 1921, 369: 305
[ 6] C
B B. T ex

. M . , 1953
[ 7] Warner R E . Am . J. P hys. , 1961, 29: 124

1 68

5. 1
5. 1. 1
1.
51 ,
R ankine ( 52) , , 12 , ,
, W F ; 2_ 3 ,
, , , Q 2 , ; 34
, , , , , ,
W p ; 41 , , , Q1

51

52

1kg ,
, , , : , 1 ,
2 ; , 4 , 1 , ,
R ankine , , Q = H + W F
( W F = 0) ,
Q 1 = H = H 1 -

H4

( Q = 0) ,
W F = - H = H 1 -

H2

( W F = 0) , :
Q 2 = H = H 3 -

H2

( Q= 0) ,
16 9

Wp = -

H = H 4 -

H3

:
W = WF -

Wp = ( H 1 -

H 2) -

(H 4 -

H 3)

W = Q1 - Q2 = ( H 1 - H 4 ) - ( H 3 - H 2 )
R ankine :

t =

(H 1 W
=
Q1

H 2) H1 -

( H 4 - H 3)
H4

( 51)

, , , H 4 H 3 , ,

t =

H1 - H2
= 1H1 - H4

H2H1-

H3
H4

( 52)

, , ,
, , ( 51) ( 52)
,

51 Rank ine ,
6. 87bar, 49 16. 6,
49+ 16. 6= 65. 6

( 1)
( 2)
65. 6( a ) , 65. 6( b)
( 3) 1370 kPa ,
[ ] ( 1) , 53 ( 6) 7 ,
t = 164. 4, ,
, 25kPa ( 65. 6)
, 687kP a
, , 460,
( 460 - 164. 4) = 295. 6
,
, ,
- W = H 1_ 2 = H 2 - H 1

H 2 = 2605kJ kg

- 1

, H 1 = 3376kJ kg

- 1

W = 771k J kg

- 1

65. 6 , H 3 = 273kJ kg - 1
1 70

 53 Rankine

687kPa,

W = -

Vdp

, , V , :

W = - V

p
p

dp = -

V( p 4 - p 3 )

3
4

= -

10
0. 25)
= - 0. 672kJ kg 102

0. 00102( 6. 87 -

, ,
,
-

W = H 3 _ 4 = H 4 - H 3

H 4 = H 3 - W
H 3 = 273kJkg

- 1

,
H 4 = 273. 7k J kg

- 1

,
, :
H

4_ 1

= Q-

W = 0,
Q = H 4 _ 1 = H 1 -

H4

= 3376 - 273. 7 = 3102kJ k g -

W = W + W = 771 - 0. 672
= 770. 3kJ kg

- 1

= 7. 70 10 J kg

- 1

W
770. 3
=
= 24. 8%
Q
3102
17 1

 ( 2)
TH - TL
, , T = 437. 5 K T
TH
= 339K ,
( a ) , =

437. 5 - 339
100% = 22. 5%
437. 5

( b) 734K ,
=

734 - 339
100% = 53. 8%
734

, R ankine
, , R ankine
( 3) 1370kPa 687kPa ,
( 1) T S 54 ,
-

W = H 1_

= 2605. 4 -

3631. 2 = - 1025. 7kJ kg -

W = V( p 4 -

10
p 3 ) = 0. 00102( 13. 7 - 0. 25)
102

= 1. 347k J kg -

H4 = H3 -

W = 274. 4kJ kg

- 1

Q = H

4_ 1

= 3631. 0 -

274. 4 = 3. 36 106 J kg -

W = W + W = 1025. 7 - 1. 347 = 1. 024 10 J kg

- 1

W
1024. 4
=
100% = 30. 5%
Q
3356. 6

2. R ankine
51 , R ake ,
( 51 ( 3) , 1370kP a 371 )
R ankine , ,
, ( ) 51 ,
595 ,
1370kP a , Rank ine
?,
, 55 , ( 1)
, , ,
1 72

 55 Rankine

54 Rankine
: p , kP a ; t, ; H , kJ kg - 1 ;
S , kJ kg - 1 K - 1

, ( 2) ,

, , ,
( )

52 51 6180kPa 400
65. 6
( 1) Rankine ,
?
( 2) 6180kPa , : ( a )
? ( b) ? ( c) ? ( :
)
[ ] ( 1 ) 460 51
,
6870k Pa ,
,

, 51( 1)
, = 24. 8%
( 2) 6180kPa ,
56 , 6 6180kPa
,
460( 1)
( ) ,

56 Rankine
: p , kP a ; t , ; H , kJ kg - 1 ;
S , kJ kgK - 1

, 618kPa,
618kP a , 460 , 65. 5
17 3

 443. 3
, 65. 6, ,
56
, ;

( , ) ,
- W T = H

W T 1 = H 1 - H 2 = 3309. 4 -

2744. 2 = 565. 2kJ kg

- 1

2605. 4 = 736. 1kJ kg

- 1

,
W T 2 = H 1-

H 2 = 3341. 5 -

Wp = -

Vp = - 0. 00102( 61. 8 -

10
0. 255)
= 102

6. 15k J kg -

,
- 1

W = 565. 2 + 736. 1 -

6. 15 = 1295. 1kJ k g

= 1. 30 10 kJ kg

- 1

- W p = H = H 4 - H 3

H 4 = H 3 - W p = 273. 0 + 6. 15 = 279. 15kJ kg

- 1

,
,
QB _

= H B _

= H6-

H 4 = 3309. 2 -

279. 15 = 3030. 15kJ kg -

,
QR = H = H

H 2= 3341. 5 - 2744. 2 = 579. 3kJ kg

- 1

Q H = Q B _ S + QR ,
Q H = 3030. 15 + 579. 3 = 3609. 5kJ kg

- 1

= 3. 61 10 kJ kg

- 1

W
1. 30 106
=
100% = 36. 0%
QH
3. 61 106

, , Rank ine
, 50%
57 ,
( , ) ,
, ,
, ,
, 5 ,
3
1 74

: ( )
57, , ,
, ,
, 58

57

58

, ,
,

5. 1. 2
, ,
, , ;
, ,

, ,

, ,
, ,
, 59,
,
, ,
,
,
, , , ,

( , Brayton ) 510
17 5

 59

510

12 ( ) , p 1 p 2
, Q 23 , , p 4
, p 4 = p 1 ( 41) ,
,
=

W
W3 4 + W1 2
=
Q2 3
Q2 3

( 53)

1 kmol
[ ( 17) ] ,
,
-

W 12 = H 2 - H 1

,
- W 12 = H 2 -

H 1 = Cp ( T 2 - T 1 )

( 54)

,
-

W 34 = Cp ( T 4 -

T 3)

( 55)

Q 23 = C p ( T 3 - T 2 )

( 56)

,
= 1 -

T4 - T1
= 1T3 - T2

T1
T2

T4
T1
T3
T2

1
( 57)
1

12 34 ,
T2
=
T1

p2
p1

k- 1
k

T4
,
=
T3

p4
p3

k- 1
k

( 58)

p 2 = p 3 , p 4 = p 1 , ( 58)
T1
T4
T3
T4
=

=
T2
T3
T2
T1

( 59)

( 57)
= 1 1 76

T1
T2

( 510)

T1

=
T2

V2
V1

k- 1

1
,

k- 1

= 1 -

( 511)

k- 1

V1
,
V2
( 511) , ,

, , 12 ( 511) ,
, 23 14 T 4 = T 5 ,
T 2 = T 6 46 ,
, 25 ,
Q 2_ 5 = Cp ( T 5 - T 2 ) , Q 6_ 4 = Cp ( T 4 - T 6 ) Q 2 5 = Q 6_ 4 4
6 T 2 T 5 , Q 2 _ 5 , ,
Q 53 = Q 23 - Q 25 = C p ( T 3 - T 4 ) ,
=

(T3 -

T 2) T3 -

( T 4 - T 1)
= 1T4

T2 T3 -

T1
T4

( 512)

,
= 1 -

511 T S

T1
k- 1

T3

( 513)

512

512 ( 57) ( 512) ,

5. 1. 3
, , ,
,

, ,
17 7


, ,
, ,
,
,
513
, (
) , T S
( 514)

513

514 T S

W + W
Q 1 + Q 1

=
Q 1 + Q 1
Q1 + Q 1

=
=

+
1+

( 514)

Q 1
m( H 4 - H 3 )
=
Q 1
H8 - H7

, ; ; m
:
m=

( H 7 - H 0)
( H 6 - H 1)

, : ,
,
, R ankine , ,
, 4% 8%

1 78

5 . 2
:

5. 2. 1
, ,
, ,
, ( 515) , ,
, ,
, Q = 0,
, ,
,
H2 -

H1 = 0

515

H2 = H1

( 515)

,
:
T
p

( 516)
H

, , ,
, ,

, 20, 196kPa 98k Pa , = 0. 26,

, 0. 26, , = - 0. 03,
, ,
, p T :
H
T

dH =

H
p

dT +
p

dp
T

, dH = 0,
T
p

H
T

H
p
H
T

=
H

= Cp ,
p

T
p

=
H

H
p
Cp

( 517)
17 9

 H = U + p V, ( 517)
T
p

( U + p V)
p
Cp

= =
H

= -

1
Cp

U
p

1
Cp

( p V)
p

( 518)
T

, , , ( 518)
U
p
U
V

,
T

V
p

, ,
T

1
Cp

U
p

V
p

U
V

;
T

, ( 518)
T

, , T

1
Cp

( p V)
p Vp 516 , ,
p
T
( p V) T p ; ( p
) , p 1 V 1 < p 2 V 2 ,

1
Cp

( p V)
p

, , , ,
T

1
( p V)

Cp
p
T
( 518) , , ,
, ( p
) , p 1 V1 > p 2 V 2 , -

, ; , = 0, ;
, , , ,

516 p V p

1 80

517

( p V)
,
p
T
, , ,
516 ,

- 80, p V p , ,
, ( p V) T p , , ,

517 T , ; , ,
= 0
= 0 , ,
, , , ( 517) , = 0,
= 0 ,
517 , , , ,
, p T ,
, 518 , =
0, p = 0 p = 375at m ; , , p =
375atm , p , , ,
, p 375atm ,
, ,
( 518) 200K,
200 K - 73,

518

, , ,

, 10, :
= ( a -

273
bp )
T

( atm

- 1

( 519)

a b , a = 0. 268, b= 0. 00086; , a = 0. 313, b=

18 1

0. 00085
,
, dp , p ,
dT , T H T H , ,

T H =

p
p

dp

( 520)

, T ,
, ( 520)

T H =

2
1

1
T
Cp

V
T

V dp

( 521)

,
T H =

( H - H p 2 ) T ( ) - ( H - H p 1 ) T ( )
Cp ( )

( 522)

C p ( ) ( 522)
, , ( 521)
, , , T H
T H

273
= 0. 29p
T1

( 523)

, , ,
, ,
, ,
T H
1( p 1 , T 1 ) p 2 , T S 2,
T 1 - T 2 = T H p 3 , 4,
, T S T 3 - T 4 = T H , ,

5. 2. 2
,
, ;
, ( ) ,

, 519 T s = T 1 1 p 2 ,
T 2 , 2

:
( 1) : 519 ,
1 82

 20 , 10atm 1at m,
, 290. 7K , 2.
3K , , 153K,
140 K , 60
( 2) :
,
( H 2 , He) ,
,
( 3) : ,
, ;
,

519 T S

(
H ,
S )

( 4) : , , ,
, , ,
( 5) : , , , T H
, , , T S

5. 3
, ,
, ,
, , , ,

,
,

5. 3. 1
1.
, 5
20 , , ,
, , , ,

521 , :
12 , , , 23
, T ; 34 ,
, 41 , T 0
1 ,
18 3

 12 34 ,
, ,
;

520

521 522

522 , ,
, 34, , q0 ,
, , T 3
2.
q0 W F , ,
, , q0 k cal
k g -

q0 = H 1 -

H4

( 524)

Q 0 ( kcal h - 1 ) , ,
G=

Q0
( kg h - 1 )
q0

( 525)

,
W= H2 - H1

( 526)

q0
H1=
W
H2-

( 527)

H4
H1

N T = GW ( kcal h

- 1

G=

NT =

GW
( kW )
860

( 528)

NT =

Q0
( kW )
860

( 529)

Q0
q0

1 84

 , , ,
,
( 524) ( 526) ( 527) , H 1 , H 2 , H 3 H 4
( T S )
, G, N T ,
Q 0 , T , T 0 T 3
p 1 T 0 , p 2 T , T T 3 ,
, T 3 35,
T T 3 5 T , p 3
T 0 , p 1 , p 3 / p 1 , ,
, T 0 , - 30 ,
- 40
53 Q 0 = 40000kcal h - 1 , G,
, N T , :

12

30
30
30
30

/
-

15
35
35
15

25
25

25

[ ] ( 1) T S t 0 = - 15 H 1 = 397 kcal kg - 1 ,
522, , t = 30 H 2 = 452 kcal kg - 1 ,
p 2 = 11. 8at , t 3 = 25 3 H 3 = 128k cal
kg

- 1

, , H 4 = H 3 = 128kcal kg - 1

( 524)
q 0 = H 1 - H 4 = 397 -

128 = 269kcal kg

- 1

( 525)
Q0
40000
=
= 148. 7k g h q0
269

G=

( 527)
=

H1H2-

H4
269
=
= 4. 9
H1
452 - 397

( 529)
NT =

Q0
40000
=
= 9. 4kW
860 860 4. 9

pk
11. 8
=
= 4. 92
p0
2. 4
, p 0 t 0 = - 15
( 2) : H 1 = 390kcalkg

- 1

, H 2 = 483k calkg

- 1

, H 4 = H 3 ,
18 5

 128kcalkg

- 1

; p 0 = 0. 95at,
q0 = H 1 - H 4 = 390 -

128 = 262kcal kg -

G=

Q0
40000
=
= 153k g h q0
262

H1 H2 -

NT =

H4
262
262
=
=
= 2. 81
H1
483 - 390
93

Q
40000
=
= 16. 5kW
860 860 2. 81
pk
11. 8
=
= 12. 4
p0
0. 95

( 3) , H 1 = 390kcalkg

- 1

, H 2 = 483kcalkg

- 1

, t= 30

H 3 = 134 kcal kg - 1 , H 4 = H 3 = 134 kcal kg - 1 ,

q0 = H 1 - H 4 = 390 -

134 = 256kcal kg

G=

Q0
40000
=
= 156k g h q0
256

H1 H2 -

NT =

- 1

H4
256
=
= 2. 75
H1
483 - 390

Q0
40000
=
= 16. 9kW
860 860 2. 75
pk
= 12. 4
p0

( 4) , 12 T S , H 1 = 135. 2kcal kg - 1 ; H 2 = 141. 4

k calk g

- 1

: H 4 = H 3 = 105. 8kcalkg

- 1

q0 = H 1 - H 4 = 135. 2 G=
=
NT =

105. 8 = 29. 4kcal kg -

Q0
40000
=
= 1360kg h q0
29. 4
H1H2-

H4
29. 4
=
= 4. 75
H1
6. 2

Q0
40000
=
= 9. 8kW
860 860 4. 75

t = 30 t 0 = - 15, p k = 7. 59 at ( 744. 3k Pa ) p 0 = 1. 86at

( 182. 4k Pa ) ,
pk
7. 59
=
= 4. 08
p0
1. 86
( 1) ( 4) :
( 1) , , ,
;
( 2) , , ;
( 3) , ( 1) ( 4) ,
12 , , 10
1 86

5. 3. 2
,
: 1112 113
,
:
( 1) , , ,
, , ,
10
( 2) , , ,
, ,
, ,
, , , ( 30)
, 1471kP a, - 34, 98. 1kPa
, 30,
637kPa 882. 6kPa , , - 10,
- 23. 5, 98. 1 kPa
( 3) ,
, , ,
, ,
, ,
( 4) ,
( 5) ,
, , , ,
, 51

5. 3. 3
, ,
, , ,
, ,
,
, ,
, ,
, , - 21, - 18;
- 55, - 45
, ,
18 7

 1 88

5. 3. 4
,
( ) ,
, ,
,
, :
t 0 = - 15
t= + 30
t 3 = + 25( 5)
, ( 525)
Q 0 = Gq0

Q 0
G q0
=
Q0
Gq 0

( 530)

v 1 ( m 3 kg - 1 ) , qv ( k cal
m

- 3

),
q0 = q v v l

( 531)

, v 1 , qv
G( kgh

- 1

) :
G=

V ( m h

- 1

V
=
vl
vl

( 532)
3

) V ( m h

- 1

, , ,
( ) ,
( ) , , ,
, ,
, , ,
52 53
( 531) ( 532) ( 530) ,

V
( qv v l )
Q0
vl

qv
=
=
Q0

lqv
( qv v l )
vl

( 533)

Q 0 = Q0

qv
qv

( 534)
18 9

 52
t2 /

t1 /

53

15

20

25

30

t 2/

t 1/

35

15

20

25

30

35

- 5

0. 915 0. 899 0. 882 0. 862 0. 841

- 5 0. 843 0. 829 0. 813 0. 795 0. 775

- 10

0. 900 0. 885 0. 869 0. 850 0. 830

- 10 0. 814 0. 800 0. 784 0. 766 0. 746

- 15

0. 882 0. 867 0. 851 0. 832 0. 812

- 15 0. 786 0. 772 0. 756 0. 738 0. 718

- 20

0. 862 0. 848 0. 832 0. 812 0. 792

- 20 0. 758 0. 744 0. 728 0. 711 0. 691

- 25

0. 841 0. 827 0. 811 0. 793 0. 772

- 25 0. 732 0. 718 0. 702 0. 685 0. 665

- 30

0. 819 0. 805 0. 789 0. 711 0. 750

- 30 0. 707 0. 693 0. 677 0. 659 0. 639

, Q 0 Q 0
54 , t = 30, t3 = + 25,
t 0 = - 30, Q 0 = 40000k calh

- 1

[ ] T S , ( 522
4) H 4 = 128kcalkg

- 1

H 1 = 397. 5kcalkg

T S

- 1

, v 1 = 0. 5m kg

- 1

, H 4 = 128kcalkg

- 1

( 524)
q 0 = H 1 - H 4 = 393 -

128 = 265kcal kg

- 1

( 531)
qv =

q0
265
=
= 273kcal m
v1
0. 97

q0 = H 1 - H 4 = 397. 5 - 128 = 269. 5kcal kg

qv =

q0
269. 5
=
= 539kcal m
v1
0. 5

- 1

53
= 0. 659
= 0. 738, ( 530) ,

Q0 = Q0

qv
0. 738 539
= 40000
qv
0. 659 273

= 88800kcal h

- 1

, ,

=
w +
bt 1

w =

=
1 90

t 1 + 273
( )
t 2 + 299
t 1 + 273
( )
t 2 + 273

( 535)

b = 0. 002( )
= 0. 001( )
= 0. 0025( )

t 1 ( ) , t2 ( ) ,
NT

N =

( 536)

,
, , ,
V p f
36. 72

Nf =

( 537)

, N f ( kW ) ; p f , p f 0. 6k gcm
0. 30. 5kgcm

- 2

; V ( m h

- 1

- 2

N F N :
NF = N+ Nf

( 538)

55 12. 5 ( 12. 5 125mm )

, , 22 12
8S12. 5A :
: V
= 8
= 125mm
= 100mm
= 960rpm
, + 30, - 10,
5, 272000k cal
h

- 1

( 1)
( 2)
( 3)
[ ] , 523

523 p H

H 1 = 402 kcal kg -

p 1 = 2. 95 at m
S 1 = 2. 15 k cal k g3

v 1 = 0. 44 m kg

K -

- 1

H 2 = 452 kcal kg -

p 2 = 11. 95 atm
S 2 = S 1 = 2. 15 kcal kg -

K -

19 1

t 2 = 97
H 5 = 129kcal kg - 1 ( )
q0 = H 1 :

G=

H 6 = 402 - 129 = 273kcal kg

272000
= 996kg h 273

N = GW = G( H 2 - H 1 ) = 996( 452 = 49800kcal h

- 1

402)

- 1

( 1)
q0
273
=
= 5. 47
H2 - H1
50

( 2) , , : x =
0. 128, 87. 2% , :
- 1
- 1
H 6 = 89k cal k g , 397 kcal k g ,

H = H + H v ( 1 397 = 129 + ( 397

x)
129) ( 1 - x )

x = 12. 8%

( 3) ( 529)
NT =

GW
49800
=
= 57. 7kW
860
860

( 535)

=
w + bt 0 =
= 0. 868 -

- 10 + 273
+ 0. 001( 30 + 273

10)

0. 01 = 0. 858

N=

NT
57. 7
=
= 67. 3k W

0. 858
3

V = Gv1 = 996 0. 44m h

- 1

= 438m h

- 1

, 52, =

0. 850,
V =

V
438
3
=
= 516m h

0. 850

( 537)
Nf =

V p f
516 0. 6
=
= 8. 4k W
36. 72
36. 72

N p = N + N f = 67. 3 + 8. 4 = 75. 7kW

5. 4
, , ,
, , :
1 92

5. 4. 1
, ,
, ( 52 53) ;
, , ( 120 )
, , ,

, - 30, ; - 45,

524( a ) 524( b)
1 2,
, , ,
, ,
4,
5( ) , 6( ) ,
, ,
, , 1, ,

524

524, , ,

, , ,

19 3

5. 4. 2
, ,
1015kPa , p = 1015kPa,
: , - 65; 12, - 67; 22, - 75, ,
,
: ,
, ;
,
525, - 30, + 25,
13, - 25, - 90, T S ( 526) 12
3
341 , 56785 13 ,
13 ,
13 13 35

525 13

526

, ,
100kPa - 40( 527 1)
( ) , p 2 = 540kPa (
2) , ,
, - 20( 3) ,
( ) p 3 = 2160k Pa , (
4) , ,
, ,
- 35 ; ,

527

( 45 ) , ( ) ,
1 94

- 45( 6) , ,
- 100 ( , - 95
) , 1,
, , , ,
13 23

5 . 5
5. 5. 1
,
, , ,
0, 0
0. 61kP a , ,
, , , t 0 = 5, p 0 = 0. 87kPa ,
3

v
= 147. 2m kg

- 1

528,
1 p 1 ( 300 600kPa )
, , 2, 6
p 0 ( 4998P a) ,
, 3 ,
4 p k ( 294392Pa ) ,
4 :
5 , 6,
, , ;

528
1 ; 2 ; 3 ;

4 ; 5 ;

, 0

6 ; 7

, 0
,

,
=

Q0
Q

( 539)

, Q 0 ( kJ h - 1 ) ( ) , Q ( k J h - 1 )

5. 5. 2
, ,
, 529,
19 5

, , 1, 2, 3, 4 ,
, ,
, ,
( , ) ,
,
, ,
, ,
( 534) Q

529

530

1 ; 2 ; 3 ;

1 ; 2 ;

4 ; 5 ; 6 ;

3 ; 4 ; 5 ;

6 ; 7 ; 8 ;

9 ; 10 ; 11 ;

12 ; 13

0. 30. 5,

, ,
, , ,
, ,
, , ,
, ,
,
, , ,
( 530) ,
,
,

1 96

5. 6
5. 1
: , ,
, , ,
,
,
, , 531 ,
T 0 T 1

12 , T 1 T 0 ,
23 , ,
T 0 ( ) Q 0
3 34 ,
T 0 T 1 41
, , T 1
( ) Q 1

531

W,

T 0 Q0 T 1 ,
Q1
Q1 = Q0 + W

1 :

1 =

Q1
W

Q1 = Q0 + W ,
1 1,
1 = 5, 1J , 5J ,

,
, , ,
,
, , ,
, , , ,

532
2

, , , 6 10 kPa,
18 102 kPa , - 68 85, , , 0
, - 21, - 43- 36,
19 7

 532 ( 1 bar = 102 kP a )

- 43 - 32 , ,
, ,
, ,
, , ,
- 68 - 50 ,
, ,
, , , 532
( , , ,
) , , - 32,
,
, , ,
, ,
: , ,
,
, ,
, , ,

5 . 7
- 100, - 100( )
, , , ,
, ,
, ,

( ) , ;
1 98

, ,

5. 7. 1 ( Linde )
1.
533, 1( p 1 , T 1 ) p 2 , ,
T 1 2( p 2 , T 1 ) ( 3) ,
T 0 ( 4) , ( )
, ,
1

533

, , , ( x ) 12
345 , 5, ; ( 1- x ) 123
461 , ,

2.
534, ,
T 1 2 , a ,
,
, ( a )
2 ,
T 1 T b , T a
T 1 , 1 , b

534

c, T d ,
19 9

, , T 0 , ,
3.
1kg , x kg , ,
x kg , , q0 ( kJ kg

- 1

q0 = x ( H 1 - H 0 )

( 540)

, H 1 T 1 p 1 ; H 0 T 0 ,
H 5
533( a ) , 1kg 2 ,
x kg 5 , ( 1- x ) kg 1 ,
:
1 H 2 = x H 0 + ( 1 -

x)H 1

x=

H1 - H2
H1 - H0

( 541)

, H 2 T 1 p 2 , 2
( 540) ( 541) :
q 0 = H 1 - H 2 ( kcal kg - 1 )

( 542)

, 1, 2 , T 1 p 2 , p 1
p 1 , T 1 , q0 p 2
, ,
: , , , H
; , T 1 ,
, H

,
x =

H 1 - H 2 - H H1 - H0

( 543)

T 1 5, 5
, H = C p t = 0. 24 5 kcal kg - 1 = 1. 2 kcal kg - 1 = 5 kJ kg - 1
H , , 1 2kcal
kg

- 1

- 1

= 48kJ k g

4.
W , W
, ,
W =

p2
1
RT 1 ln

p1

0. 6 ;
1 kg , ,
2 00

( 544)

Wx =

W
1
p2
=
R T 1 ln
x
x
p1

( 545)

p2
p1
Wx =
3600 102 x
R T 1 ln

( 546)

, T 1 p 2 / p 1 ,
x p 2 , , x , x
( p 2 - p 1 ) , p 2 / p 1 , p 2 ,
p 2 20M Pa , ,
p 2 20M Pa

5. 7. 2 Heyla ndt
1.
52 :
,
, , ,
20 1000kPa 10kPa , 140,
2. 3, , , ,
, , ,
, 535( b) T S , 2
2a , 21
, T 1 ,
0 :
0 =

H 2 - H 1
H2 - Hd

( 547)

, ( H 2 - H d ) 1k g W p ; ( H 2 - H 1
) 1kg
W p

30, 0 = 0. 7 ; 30, 0 = 0. 65
, ,
, ; , ,
, , H eylandt
535 , 1kg ( , ) p 2 = 20M Pa
2, : M kg, C 1 , C 2 3,
4, xkg , ,
( M - x ) kg C 2 ; ( 1- M ) k g
, 21
W p
C 2 ,
C 1 , 1
1, 1(
T 1 3_ 5)
20 1

 535 Heylandt
A ; B ; C 1 , C 2 ;
D ; E ; F

2.
, H eylandt ( 5
40) ,
x =

H1H1-

H2
(1 +
H0

M ) ( H 2 - H 1
)
H1 - H0

( 548)

( 541) , , Heylandt ( 1- M ) k g
W p = H 2 - H 1

535, T S , ( p 2 , T 1 ) 2,
= 0 ( H 2 - H a )
T 0 a T S H 2 H a , H 2 - H 1

3.
1 kg , ( 1- M ) kg ( 1- M ) W p = ( H 2
- H 1
) ( 1- M ) , m = 90% 95% ,
( H 2 - H 1
) ( 1- M ) m , ( 544)
W :
W=

1
p2
R T 1 ln

p1

m(1 -

M) ( H 2 -

H 1
)

( 549)

, W K , ,
, ,
( 544) ,
2 02

,
56 536 11800 , :

536

p 2 = 200at , t 1 = 20; p 1
= 6. 5at; p 1 = 1. 6at ; M = 0. 6;
0 = 0. 65;
= 0. 60,
[ ] 536, H eylan dt , T S ,
:
- 1

p 2 = 200at T 1 = 293K , H 2 = 112k cal k g

p 1 = 1. 6at T 1 = 293K , H 1 = 121kcal kg - 1 , T S , :

H a = 65 kcal kg -

p 1 = 1. 6at , ( 536 8) :
H 0 = 25k cal k g-

:
x =
=

( H 1 - H 2) + ( 1 - M) ( H 2 H1 - H0

H 4)

( 121 - 112) + ( 1 - 0. 6) ( 112 121 - 25

65) 0. 65

kg = 0. 245kg

m = 0. 90, :
R T 1 ln
W=

p2
p1

- (1-

29. 3 293ln
=

0. 6

200
1. 6

M) ( H 2 -

- (1-

H 4 ) m

0. 6) 427 ( 112 - 65) 0. 65 0. 90

= 6. 32 104 kg m kg - 1 ( ) = 6. 2 105 J kg - 1 ( )

20 3


51 : 2500 kPa , 390;
: 2300kPa , 385; : 7kPa,
( 1) Rank ine ( )
( 2) ba = 0. 71kg( k Wh )
7000k calk g

- 1

- 1

, (

) a

52 , 17000kPa , 565;
3500k Pa, 570, 5kP a, :
( 1) ;
( 2) Rank ine ;
( 3) Rank ine ?
( 4)
53 , 3000k Pa, 400,
1200k Pa , , ,
6

, 10. 6 10 k calh

- 1

( 44. 3 10 k Jh

- 1

),

kW ?
54 :
( 1) 4500 kg 500 kPa , 175;
( 2) 900kg 140kP a ;
( 3) 1100kW
1200kP a, ,
500kPa 175,
, 255, ( 2) ,
900 kg 140 kPa ,
, ,
, ,

( 1) , T S ;
( 2) ;
( 3)
55 1500kW :
15; = 3. 5; 600, , :
( 1) ;
( 2) ( ) ;
( 3) ;
( 4) , ?
2 04

56 ,
51 , :
: p 1 = 100kPa , t1 = 20, t 3 =
800, t 1
= 120, = 8
: p 5 = 13000kP a, t 5 =
565, p 6 = p 7 = 3000 kPa , t 7 = 565, p 8 =
4kPa
t1 =
300, t 1
= 120,

57 ,
, - 25,

51

1180kP a, ,
40000 kcal ( 167000kJ ) ,
( 1) ;
( 2)
58 , 250000kcal h

- 1

( 1045000k J h - 1 ) , - 20, + 25, + 20

S/ D = 1. 2, = 200
N 0 / N = 0. 63,
59 Q 0 = 10000kcal h - 1 ( 41800kJ h - 1 ) ,
: t 0 = - 15, t k = + 25, t = + 20,
, :
( 1) ;
( 2) ;
( 3) ;
( 4) ;
( 5)
510 ,
79, 16,
21, - 12
( ) ,
( ) , :
( 1) ;
( 2) ;
( 3) ;
20 5

( 4)
511
( 52) ,
, 5 ,
13 ,
( 98% ) (
) , 32
750 kg ,
( 1) ;
( 2) ( k J h - 1 ) ;

52

( 3) ;
( 4)

512 Claude ( 53) , :

3500k Pa , 25; - 11, 80% ,
100kP a, 20% 50%
, 1kg

53
A B C 1 , C 2 , C 3
D E

[ 1] ( ) M M , H C . , , . , 1987
[ 2] ( ) J M , H C . , . , 1982

2 06

[ 3] . . , 1965
[ 4] , . , 1963
[ 5] Byk

. ,

3
, 1952
[ 6] ( ) . . , 1982
[ 7 ] Bet t K E et al, T her modynamics for Chemical E ngineer s. T H E A T H LO N E P RE SS of t he
O nivers it y of L ondon , 1975

20 7

6
, ,
, , (
) ,
, :
, ?

6 . 1
,
, ,
,
:
( 1) ;
( 2)
,
, ,
T 0
, ,

, T 0
T 0 , ,

Q = T 0 S

( 61)

, ,
,
W = Q - U

( 62)

W R = T 0 S - U

( 63)

( 61) Q ,
, W R , S U
, T 0
, ,
, ; , ,
, ( 61) ,
2 08

 p 0 V, , p 0 , V ,
W d = T 0 S -

U -

p 0 V

( 64)

, ,

T 0 p 0
, , 14. 2 ,
WF = Q -

H - E k -

E p

( 65)

, E k E p ( 61) Q ,
W d = T 0 S -

H -

E k -

E p

( 66)

,
,
( 64) ( 66) ,
, S , U V , , S , H , E k E p
, ( 64) ( 66)

, ( 66) ,
W d = T 0 S -

( 67)

61 1kmol 800K 3923kPa

, 298K
[ ] 1kmol ( 800K , 3923k Pa) ( 298K,
100kPa ) ( 67) , S H
,

H =

T
T

Cp
dT =

29 8
- 3

( 6. 50 + 1. 00 10 T ) dT = - 3538. 6kcal kmol

80 0

- 1

S =

0
1

C p
p0
dT - R ln
=
T
p1

= 0. 409kcal kmol-

2 98

( 6. 50/ T + 1. 00 10 - 3 ) dT 8 00

K -

H S ( 67)
W d = T 0 S -

1. 986ln

100
3923

H = 298( 0. 409) - ( -

= 3660kcal kmol-

3538. 6)

= 1. 53 10 7 J kmol -

, ,
:
( 1) , p 1 , T 1
p 0 = 1atm , T 2 ;
( 2) 1at m , T 2 T 0
,
Q = H + W F
20 9

 , Q= 0,
W F = - H = H 1 -

H2

, H 2 ( T 2 1at m )
, 2 ,
T 0
, ,
, W T 0
( 150) ,

W =

T -

T0
T

(-

Q)

61 61

, Q Q ( ) :

W = - Q + T 0

T
T

Q
T

, , , 1
, Q
, ( H 0 - H 2 ) ,
W = -

(H 0 -

H 2 ) + T 0 S

( ) W F W ,
W d = - ( H 2 - H 1 ) = H1-

(H 0 -

H 2 ) + T 0 S

H 0 - T 0( S1 - S0)

( 67) 61 T S ; 12
, 2O , 1bdO
1 ( H 1 - H 0 ) , abcOa
T 0 S, 1aOcdO
1

6 . 2
1 ,
W L = T 0 S T

( 68)

, T 0 , S T
, ,
, :

,
W L = W d -

WF

( 69)

W L = T 0 S - Q

( 610)

W d W F ( 66) ( 65) ,
, Q , S
2 10

, ( 69)
W L = T 0 S + Q 0
, Q 0 , - Q , S 0 Q 0 / T 0 ,
Q0 = T 0 S 0

W L = T 0 S + T 0 S 0 = T 0 ( S + S 0 )

W L = T 0 S T
, ,
, , S T 0, ( 610)
WL 0
, , , ; , , (
) ,
, , ,
62 , 1471kPa 480 ,
68. 6 kPa ,
85% , , 20
7. 11k Jkg

- 1

( ) ,

[ ]
H 1 = 3423kJ kg

- 1

, S 1 = 7. 511kJ k g

- 1

- 1

, 0. 7bar , 7. 511kJ
k g - 1 K - 1 , 2660kJ k g - 1 ,
3423 -

2660 = 763kJ kg

- 1

W F = 0. 85 763 = 648. 55kJ kg

- 1

, ,
H = Q -

WF

H2 = H1 + Q-

W F = 3423 - 7. 11 -

648. 55 = 2767. 3kJ kg

- 1

,
p 2 = 68. 6kPa
H 2 = 2767. 3 kJ kg
S 2 = 7. 766 kJ kg -

- 1

K -

( 610)
W L = T 0 S - Q = 293( 7. 766 -

7. 511) + 7. 11 = 8. 18 10 J kg

- 1

,
,
21 1

(
)
W d = T 0 S -

H = 293( 7. 766 - 7. 511) -

( 2767. 3 -

3423) = 730. 4kJ k g -

W L = W d - W F = [ 730. 4 = 8. 19 104 J kg -

648. 55] k J kg

- 1

6. 3
6. 3. 1
, ( 69)
, , ( 69)

W L = W d -

WF

( 611a )

, : ( 66) ( 67)
W d , ( 610) W L , W F
( 65)
, ( 611 a )
W d = W F + W L

( 611b)

, , W F ,
W L ,
, t

t =

WF
W d

( 612)

, ( 611a )
W L

W F = W d -

( 611c)

, ,
, ,
, ,

t =

W d
WF

( 613)

63 , 62 101k Pa
27, 6865 kPa , 27 101kPa ,
( 101kP a) , 24
5. 86kJ kg - 1 ( 1k g ) ,

2 12

 ,
,

[ ] , T 0
,
T 0 300 K
101kP a 6865kP a
,
27
75%
1022kJ kg

- 1

( ) ( 541 ) , x =
0. 0605k g
, 61 (

62

[ 1] ) , 1kg

61

t/

26. 7

101

952. 05

7. 060

26. 7

6865

885. 45

4. 712

- 66. 7

6865

518. 82

3. 229

- 161. 4

101

518. 82

4. 647

- 161. 4

101

41. 10

0. 367

- 161. 4

101

549. 67

4. 923

24

101

945. 97

7. 039

p / kP a

H / kJ kg-

S / kJkg- 1 K -

( 65) , E K E p
Q = H + W F = ( 885. 45 -

952. 25) -

1021 = 1087. 8kJ k g -

, ,
, ( 67)
W d = T 0 S -

H = 300( 0. 0605 0. 367 + 0. 9395 7. 039

( 0. 0605 41. 10 + 0. 9395 945. 97 -

7. 060) -

= 6. 64 104 J kg -

952. 25)

( 69)

W L = T 0 S -

Q = [ 300( 4. 712 -

= 3. 834 10 5 J kg -

7. 060) + 1087. 8] k J kg

- 1

21 3

W 2 = 300[ 0. 9375( 7. 039 = 1. 444 105 J kg -

4. 923) + ( 3. 229 -

4. 712) ] -

5. 8

W 2 = 300( 4. 467 -

3. 229) -

= 4. 25 105 J k g -

62
62 63
W/ J kg

W F / %

6. 64 104

6. 5( = t )

W L

3. 834 105

37. 6

W L

1. 444 105

14. 2

W L

4. 25 105

41. 7

100. 0

, W F

10. 188 10

( 611b) , , , ( 612) ,
( 6. 5% )
, ,
,
64 ,
: ( ) 20% ;
3432kP a , 480, 75% ( )
6. 86kP a , ,
,
260, 25,
[ ] 62 , 63
63 62

t/

p / kP a

- 1

H / kJ kg

- 1

S / kJ kg

K -

480

3432

3397. 9

7. 090

x = 0. 973

38. 7

6. 86

2500. 1

8. 053

38. 7

6. 86

161. 8

0. 554

38. 7

3432

161. 8

0. 554

, , ,
, ,
, H
S ,

2 14

C + O 2 CO 2
25
H = - 393129kJ kmol
S = 2. 947 kJ k mol

- 1

- 1

- 1

H 25 , S
( 67) ,
W d = T 0 S -

H = [ 298. 2( 2. 947) + 393129]

= 394000k J kmol

- 1

1kmol ,
1. 2k mol O 2 4. 51k mol
N 2 , 5. 71kmol
260

63

,
260 25 31. 35kJ kg - 1 K - 1 ,

Q = 5. 71 31. 35( 25 -

260) = -

42067kJ

260
,
393129 -

42067 = 351062k J

351062
= 108. 5k g
3397. 9 - 161. 8

W F = 108. 5( 3397. 9 -

2500. 1) = 97411. 3k J = 9. 741 10 7 J

( )
Q = 108. 5( 161. 8 -

2500. 1) = -

253705. 6kJ

, ,
W L = T 0 S - Q = 298. 2[ 108. 5( 7. 09 -

0. 554)

+ 2. 947] + 42067kJ = 2. 544 10 8 J

W L = 298. 2[ 108. 5( 8. 053 -

7. 090) - 0]

= 31157. 6kJ = 3. 12 10 7 J

W L = 298. 2 108. 5( 0. 554 -

8. 053) + 253705. 6

= 11077. 7kJ = 1. 11 10 7 J
, ( 611b) ,

21 5

W / J kmol -

W d

9. 741 10 7

24. 7%

W L

2. 544 10

64. 4%

W L
W L

3. 12 107

7. 9%

1. 11 107

2. 8%

W L

3. 941 10

100. 0%

, , ,
,
,
, , ,
,
, , ,
,

6. 3. 2
1.
,

, :
, ,
,

, ,

[ 5]

, 64 ,
, , 64

Q =

H1 +

H 2 + W 1, 2

( 614)

, H 1 ; H 2 ; W 1 , 2
2

, ,

Q =

H 1 + EK 1 + Ep1 +

2 16

H 2 + E K 2 + E p 2 + W 1, 2

( 615)

 64

65

, 65 ,

S1 +

Q
+ S V = S 2
T

( 616)

Q

1 T
T ; S V

, S 1 ; S 2 ;

( 615) ( 616) , ( - T 0 )
( 616) , , W 1, 2 ,
,
E k -

W 1, 2 = H 1 - H 2 - T 0 ( S 1 - S 2 ) -

E p -

T 0 S V +

2
1

T - T0
Q ( 617)
T

S V = 0, ( ,
T 0 ) , ( 617) ,
W 1, 2R = H 1 - H 2 - T 0 ( S 1 - S 2 ) -

E k -

E l

( 618)

( 618)
W 1, 2R =

u2
H - T 0S +
+ Z 2g

H -

u2
T 0S +
+ Z
2g

( 619)

( 618) 2 ( 0 ) ,
W 1 , 0R = H 1 - H 0 -

T 0( S1 -

u 21 - u 20
- ( Z1 2g

S0) -

Z0)

u2
H - T 0 S- Z = B, B ,
2g
,
W 1, 0R = B 1 -

B0

( 620)

W 1, 0R , ,
T 0 , , ,
,
, , B 0 = 0( 617)

W 1, 2 = B 1 -

B2 -

T 0 S V +

T - T0
Q
T

( 621)
21 7

 , B = H - T 0 S ,
Darries ( 621)
W1 , 2 = ( H 1 - T 0 S 1 ) -

(H 2 -

T 0S2) -

T 0 S V +

T - T0

Q
T

( 622)

, S V = 0,
W 1, 2R = ( H 1 -

T 0S 1 ) -

( H 2 - T 0S2) +

2
1

T - T0

Q
T

( 623)

:
,
W L = W 1 , 2R -

W1 , 2

( 622) ( 623) ,
W L = T 0 S V

( 624)

: ,
Gauy Stodola ( 68)
1
t =

W
=

, W / Q ,
: ,
, , , ( )

a v =
B1 -

W1 , 2
2
T -

B2 +

T0
T

= 1
Q

T 0 S V
2
T - T0
B1 - B2 + 1

Q
T

( 625)

a v =

W 1, 2
= 1B1 - B2

T 0 S V
B1 - B2

( 626)

a v , T 0 S V = 0, a v = 1;
, W 1, 2 = 0,
a v = 0
2. H - S T - S
66 , H 1 S 1 , H 0 S 0 ,
1 0 p 0 = 0 02,
S 1 = , 12 1
:
12 = 13 + 32 = 13 + 03tg
H
S

= T , 0
p

tg=
2 18

H
S

= T0
p= p

, 12
12 = H 1 -

H 0 + T 0( S 0 -

S1) = B 1 -

66 H S

B0

67 T S

T S , 67 , 1eca 1- bd cab= H 1
- H 0 , 20f e2= T 0 ( S 0 - S 1 ) , B 1 - B 0 = 120f d b1
65 1min 23kg,
1kg ( )
300 K

p / kP a

101. 3

206. 7

T/K

289

367

206. 1

261. 7

289. 7

367. 8

U/ kJ kg H / kJ kg-

[ ] ,
- W = WR = B 2 = (H 2 -

B1

T 0S2) -

= H2 - H1 =

367. 8 -

( H 1 - T 0S 1 )

T 0 cp ln
289. 7 -

= 6. 74 10 J k g
N =

T2
T1

Rln

p2
p1

300 1. 003ln

367
206. 7
- 0. 2863ln
289
101. 3

kJ kg -

- 1

67. 42 23 3600
0. 73 = 26k W
60 2641. 8

1kg
- WF = H 2 -

H 1 = 367. 8 -

289. 7 = 76. 1kJ kg -

NF =

78. 1 23 3600
= 30kW
60 3592
21 9

 N F - N = 30- 26= 4kW , ( 613) ,

t =

W
67. 42
=
= 86. 3%
WF
78. 10

66 ,
555K 555kcalkg

- 1

( ) 278K,

, ,
5% , T S
,
[ ] ( 1)
S =

555
= 1kcal kg
555

- 1

68 , 250k cal k g- 1 305kcal kg - 1 ,

S T = [ 1. 0 + 2( 0. 05 1. 0] kcal kg -

K -

= 1. 1kcal kg -

K -

( 2)
t =

Q1 - Q2
W
555 - 1. 1 278
=
=
100 = 45%
Q
Q1
555

3.
,
, ,
, ,

68

69

, Gras sman
69( a ) , ,
69( b) , 69( c) ,
2 20


1 K , 2, T
3, 4 , H 5
: 1 ,
2 , 3 ,
2
, ,
, , ,
,
,
, ,
, 4
,
, ,
, ,

6 . 4
, ,
, ,
( ) ( )
610 , ,
W Q ,
:
W = H - Q

H = dH d + bH b -

( 627)
fHf

, d , b, f ,
,

, Q T dS , ( 627)
-

W m = H -

T dS

610

( 628)

T , , T T 0 , , T T 0
, T , ,
, W
W m W ,
- W = -

Wm - W

( 629)

1 ,
22 1

 T -T T ( 0

W =

Q) = -

(T

T 0)
Q

( 630)

( 628) , ( 629) ( 630) ,

- W = H -

T 0 S

( 631)

d S d + bS b - f S f

( 632)

TQ =

S =

( 631) , ( 623) ( 630) ( 631)

T T 0 , , T
T 0 W W m , ( 629) , ( 631) ,

- W = B

( 633)

B = d B d + bB b -

f Bf

, , ,
[ 2 4]
=

- W

( 634)

, H x , Sx B x

611 T > T 0 ( T > T 0 )

612

, ( ) , H
S ( )
67 30% 15. 5 95% 5%
, 1at m 15. 5,
[ ] ,
B f = ( H f - H 0f ) , B f
2 22

T 0 ( S f - S 0f )

B f = ( H 1 x 1 + H 2 x 2 + H M ) - T 0[ ( S1x 1 + S2x 2) -

( H 0 1 x 1 + H 02 x 2 + H

0M

R( x 1 lnx 1 + x 2 lnx 2 ) + S E

- ( S 01 x 1 + S 0 2 x 2 ) + R ( x 1 lnx 1 + x 2 lnx 2 ) -

S 0 ]

, 0 T 0 ,
Bf = ( H 1 -

H 01 ) x 1 + ( H 2 - H 02 ) x 2 - T 0 [ ( S 1 -

S 01 ) x 1 + ( S 2 -

S 02 ) x 2 ]

,
B f = cp 1 ( T - T 0 ) x 1 + cp 2 ( T -

T 0 ) x 2 - T 0 cp 1 ln

T
T
x 1 + cp 2 ln
x2
T0
T0

B f = ( cp 1 x 1 + cp 2 x 2 ) T -

T 0 - T 0 ln

T
T0

75. 4kJ kmol K - 1 , 75. 2kJ kmol K - 1 , 15. 5

( 288. 7K ) , b 358K , d 313. 2K , B f , B d B b
B f = ( 75. 4 0. 3 + 76. 2 0. 70) ( 288. 7 -

288. 7 -

288. 7ln1. 0) = 0kJ kmol

- 1

B d = ( 75. 4 0. 95 + 76. 2 0. 05) ( 313. 2 - 288. 7 - 288. 7ln1. 085)

= 62. 8kJ kmol

- 1

B b = ( 75. 4 0. 05 + 76. 2 0. 95) ( 358. 0 - 288. 7 - 288. 7ln1. 24)

= 548. 5kJ kmol

- 1

d 0. 278, b 0. 722, 1kmol

- W = B = d B d + bB b -

f Bf

= 0. 278 62. 8 + 0. 722 548. 5

5

= 4. 14 10 J kmol

- 1

61 1kmol ( 1470kPa, 538, t 0 = 16)

62 1kg 100k Pa 20 ,
20;
63 62 260 ,
? ? 62

64 45kmol min

- 1

, 305K 278K

N , 305 K 29. 3kJ kmol- 1 - 1

65 100kPa 5 1000kPa,
, , , 100 kg kmol - 1 ( )
5, 145
22 3

 , cp =
29. 3k Jkmol

- 1

- 1

66
- 3

cp = 26. 377 + 7. 612 10

- 6

T - 1. 453 10

T cp K kJ kmol - 1 K - 1 1100
38, 16, ?
,
67 260,
1375 315, 27 1kg
- 1

, , 1kJkg

- 1

68 , 2100kPa 100kPa
,
69 , 21 - 7,
3

27, 25m ,
? : cp = 3. 5kJ k g - 1 - 1 ; = 1150k g m - 3
610 30% ( ) ,
38, 100kP a , 16, W

[ 1] M att hew s CS and H ur d C O . T rans . A m . Ins t . Chem . Engr s. , 1946 42 55
[ 2] Dodge B F and H ons um C. ibid, 1927, 19 117
[ 3] Benedict M . Chem . Eng . P rogr . , 1947, 43 41
[ 4] and Coull J. J. Ins t . P et rol , 1949, 35 770

2 24

7
, :
, ,
, , ,
, ,
,
, ,
,

7. 1
7. 1. 1
, ( Dalt on ) ,
( R aoult ) ,
:
f^

= x f

( 71)

f^ f ( 71)
( 3. 6. 1 )
6 :
id

id

G - G = RT lnx , V - V = 0
H id -

H = 0, U id - U = 0

id

id

Rlnx , F - F = R T lnx

S - S = -

id , , 6 ( 7
1)
d

G - G= RT lnx : ( 3138) , , p p ,
G - G0 = RT lnf^ / ( x p 0 )

( 72)

( 3139) , p 0 p ,
G -

G0 = R T lnf / p 0

( 73)

,
( G -

G ) -

( G0 - G0 ) = R T ln ( ^
f / x f )

( 74)
22 5

( 74)
f^ / x f = r

^f

( 75)

x f , ,

( 71) 1, , ( 74)
G id - G = G0 - G0
0

( 76)

( G - G ) = RT ln x T p , ( 31 38)
, f^ = x f f = p 0 ( ) ,
0

G - G = RT ln( x p ) - RT lnp = RT lnx

( 76) ,
id

G - G = R T lnx

( 77)

( G -

G ) = ( G - G ) ( )

id

V - V = 0: ( 71) , ,
ln ^
f
p

T,

lnf
p

( )

( 78)

( 3138) ( 3141) ,
lnf^
p

id

V
=
RT

T,

( 79)

,
lnf
p

=
T

V
RT

( 78) ( 79) ,
V id -

V = 0

( 710)

id

H - H = 0: ( 71) ,
T ,
lnf^
T

p,

lnf
T

( )

( 711)

R T ( 72) , T
,
0

G - G
T
RT

p,

ln ^
f
T

( 712)

p,

( 712) ,
0

G - G
T
RT

p,

= -

G - G
1
+
2
RT
RT

, ( 713) , G =
2 26

G
T

p,

G0
T

T, P,

p,

T ,
j

( 713)

G
T
Gt
T

p,

p,

G
T

T, p,

p,

= - S t , :
St

= -

p,

T, p,

= -

( 713) , H = G+ T S
:
0

G - G
T
RT

p,

G - G0
2
RT

= -

S - S 0
= RT

H - H 0
2
RT

( 714)

( 712) ( 714) ,
ln ^
f
T

p,

= -

H - H 0
2
RT

( 715)

,
lnf
T

H- H
RT 2

= p

( 716)

( 715) ( 716) ( 711) ( 715) ( 7

16) , ,
id

H - H= H - H

( 717)

p 0 , H 0 H 0 H H , ( 717) ( H
- H
) = 0( ) ,
:
H id -

H= 0

( 718)

id

U - U = 0: H = U + p V ( 311) H = U + p V ,
,
id

id

id

H - H = U - U + p V - V
( 718) ( 710) ,
U id -

U = 0

( 719)

S id - S = - R lnx : G= H - T S ( 3. 5. 2 ) G = H - T S ,
, ( 77) ( 718) ,
id

S - S = - R lnx

( 720)

id

F - F = R T lnx : , F = U - T S F = U - T S , ( 719)
( 720) ,
id

F - F = R T lnx

( 721)

,
N
id

V =

x V

( 722)

N
id

U =

x U

( 723)

22 7

id

x H

( 724)

N
id

S =

x (S

Rlnx )

( 725)

x ( F

id

F =

+ RT lnx )

( 726)

+ R T lnx )

( 727)

x ( G

id

G =

7. 1. 2 ,
, ,
f^ V = f V y
V
, ^
f ; f

( 728)

, ^
f = ^
f ,
L

f^ = f x

( 729)

f^ V = f L x

( 730)

, ,
, , ( 729)
a x a , , ,

^f

= f L a a = ^
f L / f

( 731)

, , a = x ,

id

= + R T ln x

( 732)

= 0 + R T lna

( 733)

,
0

, ,
, ,
,
( 732) ( 733) , a x
, :
= a / x = ^
f / ( f x )
L

( 734)

, :
( 1) 1
, ( 732) 0
2 28

( 733) , = , , a = 1, ( a ) x = 1 = 1
( a ) x = 1
=
( x ) x = 1

( ) x = 1 =

1
= 1
1

, x 1 , 1
( 2)
a = x , = a / x = 1
( 3) = a / x , a x ,
1:
> 1, ;
< 1,
, ,
,
, ( 735) ,
a =

^f
f

^f
f

p
p 0

( 735)

p
0
x p

( 736)

p y
0
p x

( 737)

( 736) ,

, ,
0

K = y / x = p / p

( 738)

,
0

K
y / x
p / p
p
= j =
=
=
=
0
0
Kj
yj / xj
j p j / p
j p j

( 739)

,
,
, ,

7. 1. 3 , Gibbs - Duhem
T , p x
:
E

M = M- M

id

M E = M - M id
E

( 740)
( 741)

M , M ,
22 9

x M

M = M -

( 742)

M , M V,
T p , M 0 V0 =
V , ( 742)

x V

V = V -

( 743a )

V T p , 1mol ,

x V

, ( 3119) , V =

, ( 743a )

V =

x ( V

- V )

( 743b)

x U

U = U -

H = H -

x H

x S

x ( H

x ( S

- H )

( 745)

S )

( 746)

x ( F

- F )

( 747)

G)

( 748)

x G

( 744)

x F

G = G -

- U )

F = F -

S = S -

x ( U

x ( G

x M

M = M -

( 749)

( 749) ( 741)
E

M = M -

x M

id

(M -

x M )

= M - M id
, , M E ,
E

M = M = M -

id

( 750)

V = V = V -

id

( 751)

, ( 722) , V = 0, U H C idp
id

id

id

, ,
, , ,
, ( 750) ( 727)
G = G - R T ( x lnx )
E

( 752)

( 742)
GE = G -

x G

2 30

- R T ( x lnx )

( 753)

 , ,
,
E

G = H

- TS

H
T

E
p

c =

( 754)

S
T

= T
p, x

( 755)
p, x

G
p

V =

GE
T

S = HE
= RT
E

( 756)
T, x

( 757)
p, x
E

G / RT
T

( 758)
p, x

, H = H , cp = cp V = V
, ,
E

id

M = M - M

( 759)

id

G = G - G

( 760)

x G

( 761)

= GE

( 760) , ( 761) ( 727) ( 733) ,

GE =

x G

x G

x G

- Gd

= ( x G -

x G )

RT x lnx

= R T x ln a

RT x lnx

a
x

= R T x ln

= R T x ln

( 762)

( 762) ,
d

G = G - G = R T ln = R T ln

a
x

( G )

RT ln = G =

T , p,

( 763)
j

( 3131) , ,
-

SdT + Vdp -

x dG

= 0

,
23 1

 x dG

S E dT + VE dp -

= 0

x d( R T ln)

- S dT + V dp -

= 0

( 764)

x d ( RT ln)

( Rln ) dT + R T dln

G
=
dT + RT x dln
T

( 764) , H E = GE + T S E ,
-

( H / RT ) dT + ( V / RT ) dp -

x dln =

( 765)

( 765) , ,

( 762) , G , ( 71) , ,
= 1,
GE = 0 ( )
E

( 766)
E

, S = 0 V = 0 , H = 0 , H

= U E + p V E ( 754) ,
E

G = U ( )

( 767)

( 768)

G = -

T S ( )

7. 2
, ( 737) :
=

p y
p 0 x

x ,
x ,
x ( van L aar ) ,
( M argules) , ( Wilson ) NR T L ( N onRandom T wo L iquids)
,
,
, ,

2 32

7. 2. 1 Scatchar d - H ildebr an d
Scatchard [ 3] H ildebrand [ 2]
U E :
UE =

x V C

( x x j V Vj C j )

( 769)

( 767) , , Cj = ( CC j ) 0. 5 ,

x V -

GE =

( x V ) 2

x V

( 770)

, V , = C 0. 5 , C = U / V , U

,
E

G = ( x 1 V 1 + x 2 V2 )

( 1 - 2 )

( 771)

1, 2 :

x 1 V1
,
x 1 V 1 + x 2 V2

x 2V 2
x 1V 1 + x 2 V 2

( 763) ( 771) , ,
V 1 ( 1 - 2 ) 2
ln1 =
RT

2
2

V 2 ( 1 - 2 ) 2
ln2 =
RT

2
1

( 772)

1, R aoult V
85
, ( 1k j ) ( C C j )

0. 5

( 769) C j , , k j

7. 2. 2 Wohl
W oh l 1946 W ohl

[ 4]

G / ( RT x q) =
E

Z Z a

Z Z Z

, q , Z = x q

a j k +

( 773)

x q
j

= q

q , a
j

, a j k

, j , j , k , a a 0
( 773) ,
,
, ; (
23 3

) , , W ohl ,
, van L aar , M argules ( 773)
,
E

G
= Z 1 Z 2 a 1 2 + Z 2 Z 1 a 21 + Z 1 Z 1 Z 2 a 112
RT ( q1 x 1 + q2 x 2 )
+ Z 1 Z 2 Z 1 a 121 + Z 2 Z 1 Z 1 a 21 1 + Z 1 Z 2 Z 2 a 1 22
+ Z 2 Z 1 Z 2 a 212 + Z 2 Z 2 Z 1 a 22 1

( 774a )

, a 1 2 = a 2 1 , a 112 = a 121 = a 211 , a 1 22 = a 212 = a 221 ,

GE
= 2Z 1 Z 2 a 12 + 3Z 21 Z 2 a 112 + 3Z 1 Z 22 a 12 2
R T ( q1 x 1 + q2 x 2 )

( 774b)

, 2Z 1 Z 2 a 12 ( Z 1 + Z 2 ) , Z 1 + Z 2 = 1,
E

G
=
RT

q2
x 2 Z 1 Z 2 Z 1 q1 ( 2a 12 + 3a 112 ) + Z 2 q1 ( 2a 1 2 + 3a 12 2 )
q1

x1 +

( 774c)

q1 ( 2a 1 2 + 3a 12 2 ) = A 12 , q2 ( 2a 12 + 3a 112 ) = A 2 1
( 774c) ,
E

G
=
RT

q2
q1
x 2 Z 1 Z 2 Z 1 A2 1
+ Z 2 A1 2
q1
q2

x1 +

( 774d )

x1 =
Z1 =

1
1
2
2
=
; x2 =
=

1 + 2

1 + 2

1 q1
1
2 q2 / q 1
=
, Z2 =
1 q1 + 2 q2
1 + 2 q2 / q1
1 + 2 q 2 / q1

( 774d ) ,
2
1

2 A 21 + 1

G
=
RT

2
2

q2
q1

q2
1 + 2
q1

A 12
2

( 774e)

( 763) ( 774e) , ,
ln1 = Z 22 A 1 2 + 2Z 1 A 2 1

q1
- A 12
q2

( 775a )

ln2 = Z 21 A 2 1 + 2Z 2 A 1 2

q2
- A 21
q1

( 775b)

( 775a ) ( 775b) A 12 , A 21 q 2 / q1 ,
, :
( 1) Scatch ardH amer
V 1 V 2 q1 q2 , ( 775a ) ( 7
75b)
2

ln1 = Z 2 [ A 12 + 2Z 1 ( A 2 1
2 34

V1
- A 12 ) ]
V2

( 776a )

ln2 = Z 1 [ A 21 + 2Z 2 ( A 1 2

V2
- A 21 ) ]
V1

( 776b)

( 2) van L aar
( 775a ) ( 775b) q2 / q1 = A 2 1 / A 12 ,
A1 2
ln 1 =
A 12 x 1 2
1+
A 21 x 2
A2 1
A 21 x 2
1+
A 12 x 1

ln 2 =

( 777a )

( 777b)

( 3) M argules
( 775a ) ( 775b) q2 / q1 = 1,
2

ln1 = x 2 [ A 1 2 + 2x 1 ( A 21 - A 1 2 ) ]

( 778a )

ln2 = x 21 [ A 2 1 + 2x 2 ( A 12 - A 2 1 ) ]

( 778b)

( 4)
A 1 2 = A 21 , van Laar Margules
ln 1 = A 12 x 2

( 779a )

ln 2 = A 21 x 21

( 779b)

, ( 779 a ) ( 779b) lnx

, W ohl ,
W ohl

723 Flor y- H uggins

[ 7]

F lory Huggins
S :

[ 8]

S = -

R x ln

( 780)

= x m

x m
j

E
m , S =

x ( S

S d ) ( 7

46) ( 720) ( 768) ,

GE = RT x ln( / x )

( 781)

( 763) , ,
ln = ln( / x ) + 1 -

/ x

( 782)

1, R aoult
, ( 782) ,
ln1 = ln(

/ x1 ) + 1 -

/ x1

( 783a )
23 5

ln2 = ln(
,

= x 1 V1 / ( x 1 V1 + x 2 V2 ) ,

/ x2 ) + 1 -

/ x2

( 783b)

= x 2 V 2 / ( x 1 V 1 + x 2 V 2 ) ( 772 ) , Flory

H uggins [ ( 782) ( 783) ]

, ,

724 Wilson

[ 5]

1964 , Wilson :
E

G / RT =

x 1 ln( x 1 + 1 2 x 2 ) - x 2 ln( x 2 + 21 x 1 )

( 784)

1 2 =

V2
exp V1

12
11
RT

( 785a )

2 1 =

V1
exp V2

21
22
RT

( 785b)

( 763) ( 784) , 1 2 :
ln1 = - ln x 1 + 12 x 2 + x 2

12
x 1 + 12 x 2

21
x 2 + 2 1 x 1

( 786a )

ln 2 = - ln( x 2 + 21 x 1 ) + x 1

21
x 2 + 2 1 x 1

1 2
x 1 + 12 x 2

( 786b)

12-
11 ) (
21 -
2 2 ) ,
W ils on (

, , W ils on
, ,
,
W ils on F loryHuggins , ( 781) ,

G / R T = x 1 ln (
,

/ x 1 ) + x 2 ln(

/ x 2)

( 787)

= x 1 V 1 / ( x 1 V 1 + x 2 V 2 ) , 2 = x 2 V 2 / ( x 1 V 1 + x 2 V 2 ) Wilson ( 787)
1 2 , 1 2
1

1 1 , x 1 1
, 1 2 , x 12
x 12
x 2 exp =
x 11
x 1 exp -

12 / R T

11 / R T

( 788a )

x 12 + x 11 = 1
11 1 1 , 12 1 2
x 1 x 2 , x 11 x 12 ,
2 2 , 1
x 21
x 1 exp =
x 22
x 2 exp
2 36

21 / R T

22 / R T

( 788b)

x 21 + x 22 = 1
W ils on 1 2 1 2

1 =

2 =

x 1 1V 1
=
x 1 1V 1 + x 1 2V 2

1
V 2 x 12
1+

V 1 x 11

1
V 2 x 2 exp 1+

V 1 x 1 exp x 2 2V 2
=
x 2 1V 1 + x 2 2V 2

( 789a )

12 / R T
11 / R T

1
V 1 x 21
1+

V 2 x 22

1
V 1 x 1 exp 1+

V 2 x 2 exp -

( 789b)

12 / R T
22 / R T

12 = 21 , 1 2 ( 787)

G / R T = x 1 ln( 1 / x 1 ) + x 2 ln( 2 / x 2 )

( 790)

( 789a ) ( 789b) ( 790) , , ( 784)

W ils on ,
, , T s uboka
K alayama ( 1975)

[6]

T K Wilson

E
x 1 + V 12 x 2
x 2 + V 21 x 1
G
= x 1 ln
+ x 2 ln
RT
x 1 + 12 x 2
x 2 + 2 1 x 1

( 791)

V j = Vj / V , Vj 1 , W ils on

ln1 = ln

x 1 + V 12 x 2
+ ( x 1 + 12 x 2

V ) x 2

( 792a )

ln2 = ln

x 2 + V 21 x 1
x 2 + 21 x 1

V ) x 1

( 792b)

V =
=

V 12
x 1 + V 12 x 2
1 2
x 1 + 12 x 2

( -

V 21
x 2 + V 21 x 1

( 793a )

21
x 2 + 21 x 1

( 793b)

V 12 = V 2 / V 1

( 794a )

V 21 = V 1 / V 2

( 794b)

T K W ilson ,

7. 2. 5 Ren on - P r ausn itz NRTL

R enon Prausnit z 1968

[9]

, Wilson ,
23 7


, R enon W ils on ( 788a ) ( 788 b)
x 21
x 2 exp - 1 2 g 21 / RT
=
x 11
x 1 exp - 1 2 g 11 / RT

( 795a )

x 12
x 1 exp - 1 2 g 12 / RT
=
x 22
x 2 exp - 1 2 g 22 / RT

( 795b)

g 12 ( = g 21 ) , g 11 g 22 12, 11 22
12
( = 21 ) 1 2 ( N on R an dom Paramet er )
GE , Scot t Scott
, 1 , 2 ,
, 71
( 1) ,
g

(1)

= x 11 g 11 + x 21 g 21

( 796a )

(2)

= x 22 g 22 + x 12 g 12

( 796b)

, ( 2)
g

, ( 1 mol )
U = x 1g
71 Scot t

( 1)

+ x2 g

(2)

( 797)

( 796a ) ( 796b) ( 797) ,

U = x 1 ( x 1 1 g 11 + x 21 g 2 1 ) + x 2 ( x 22 g 2 2 + x 12 g 12 )

, ,
( 1)

( 2)

g = g 11 , g = g 2 2
,
GE = U - x 1 U1 - x 2 U2
= x 1 ( x 11 g 1 1 + x 21 g 21 - g 11 ) + x 2 ( x 2 2 g 22 + x 12 g 1 2 - g 22 )
= x 1 x 21 ( g 2 1 -

g 11 ) + x 2 x 1 2 ( g 12 - g 2 2 )

( 798)

( 791a ) ( 791b)
x 21 =

x 2 exp - 12 ( g 2 1 - g 11 ) / RT
x 1 + x 2 exp - 12 ( g 2 1 - g 11 ) / RT

( 799a )

x 12 =

x 1 exp - 12 ( g 1 2 - g 22 ) / RT
x 2 + x 1 exp - 12 ( g 1 2 - g 22 ) / RT

( 799b)

( 799a ) ( 799b) ( 798) , ( g 2 1 - g 11 ) / R T =

2 1 , ( g 12 g 22 ) / RT =
12 , G1 2
= exp - 12 12 , G2 1 = exp - 12 21 ,
21 G21

1 2 G 12
GE / R T = x 1 x 2
+
x 1 + x 2 G21
x 2 + x 1 G 12

( 7100)

( 763) ( 7100) ,

2 38

ln 1 = x

2
2

21 G21

1 2 G 12
2 +
2
( x 1 + x 2 G21 )
( x 2 + x 1 G1 2 )

( 7101a )

ln 2 = x

2
1

12 G12

2 1 G 21
2 +
( x 2 + x 1 G12 )
( x 1 + x 2 G2 1 ) 2

( 7101b)

( 7101a ) ( 7101b) N R T L
12 ,
21
12
,
1 2 ,
, 12 NR T L
12 , ,
R enon

[ 9]

, 12 0. 20. 47, 7 ,
12

0. 2, 0. 3, 0. 4, 0. 47 , 71
7-1 Renon 12

12

0. 30

0. 30

0. 20

0. 40

0. 47

0. 47

0. 47

0. 30

0. 47

:
E

: ( ) , G

< 0. 35RT

:
a : , ,

b : , ,

c : , R aou lt ,
; Raoult ,
: , ,
, , 12
: ,
: ,
: ( ) , 12 ( 0. 47) ,
N R T L
: ( )
: ( )
71
1 2 ,
12 ,
12 , , N R T L

N R T L : Wilson ;
; W ilson ,

7. 2. 6 UNI QUAC ( )
U NIQ U A C( U niversal Q uasi Chemical A ctivity Coefficient ) ,
A brams Prausnit z 1975

[ 15]

, 3 :

( 1) :
23 9

, ,
E

G = G + G

( 7102)

( 2) Guggenheim ( Q uasiCrys tal) F loryHuggins

, Guggenheim
, U NIQU A C
, r q ,

1,
2 :
1

1 =

x 1r1
,
x 1 r 1 + x 2r 2

x 2r2
x 1 r 1 + x 2r 2

( 7103)

x 1 q1
x 2 q2
, 2 =
x 1 q1 + x 2 q2
x 1 q1 + x 2 q2

( 7104)

72 r q
7-2

2. 70

2. 34

3. 79

2. 84

1. 54

1. 48

3. 19

2. 40

1. 43

1. 43

3. 72

2. 83

1. 32

1. 28

3. 97

3. 01

2. 23

2. 04

4. 50

3. 86

1. 80

1. 70

3. 92

2. 97

2. 11

1. 97

5. 85

4. 94

2. 57

2. 34

7. 20

6. 02

2. 48

2. 24

0. 92

1. 40

3. 15

2. 78

1. 00

1. 00

3. 17

2. 48

3. 48

3. 12

3. 82

3. 31

5. 17

4. 40

( 3) , U NIQ U A C Wilson
, 4 ,
( local surface fraction )
11,
12 ,
22
2 1
, 4 :

11 +
21 = 1, 12 +
22 =
1
W ils on , :

21 =

1
1 + 2 exp -

12 =

U 21 - U 11
RT

2
2 + 1 exp -

U 12 - U 22
RT

U 1 2 , U 2 1 1 2 :
2 40

( 7105a )

( 7105b)

U 12 = U 21
U 11 , U 2 2 , 1 2
, U NIQU A C
:
E

G
1
2
Z

1
2
= x 1 ln
+ x 2 ln
+
q1 x 1 ln
+ q2 x 2 ln
RT
x1
x2
2
1
2

( 7106)

Z , Z = 10
E

U NIQ U A C G Wils on , 1 , 2
W ils on ,
GE
= R T ( x 1 q1 + x 2 q2 )

1 ln (
1 +
2
21 ) 2 ln(
2 +

1
12 )

GE
= - x 1 q1 ln ( 1 + 2
21 ) RT

x 2 q2 ln(
2 +

1
12 )

( 7107)

21 =
ex p -

U 21 - U 11
RT

( 7108a )

12 =
ex p -

U 12 - U 22
RT

( 7108b)

( 763) ( 7106) ,
C

ln1 = ln
= ln

x1
1

x1

Z
1
q1 ln
+
2
1

1
Z
q1 ln
+ l1 2
1

r1
l2
r2

l1 -

x1

x 1 l1 + x 2 l2

( 7109)

, ( 763) ( 7107) ,
ln R1 = -

q1 ln(
1 +

2
21 ) +
2 q 1

21

1 +
2
21

12

1
12 +
2

( 7110)

( 798) ,
ln1 = lnC1 + lnR1

( 7111a )

, 2
ln2 = lnC2 + lnR2
C

ln2 = ln

x2

Z
2
q2 ln
+ l2 2
2

R
2 +

1
12
1 q2
ln2 = - q2 ln
+

l1 =

Z
( r 1 - q1 ) 2

( 7111b)
2

x2

x 2l 2 + x 1l 1

12

2 +

1
12

( r 1 - 1) , l 2 =

( 7112)

21
2
21 +

Z
( r 2 - q2 ) 2

( r2 -

( 7113)
1)

7 . 3
, ,
24 1

, ,
,
,
, , ,
, ,
,

,
,
, :
,
, , , ,
,

7. 3. 1 Scatchar d - H ildebr an d
( 763) ( 770) ,
R T ln =
=

T, P,

V k

= V -

2
k

k V k k

2V

V
k

T, P,

k Vk k

+ V

= V ( -

k ) 2

( 7114)

= x V ( x j V j )
j

7. 3. 2 Wilson
( 784)

x ln x

G / RT = -

( 7115)

( 763) ( 7115) ,
ln = 1 - ln( x j j ) j

x k k
x j kj

( 7116)

Wilson
2 42

, Wilson
j j 73 Wilson
7-3 Wilson

Wils on

( 1) ( 2)

1 at m

12
0. 1692

( 1) ( 2)

1 atm

0. 0552

0. 3167

( 1) ( 2)

0. 7189

1. 1816

( 1) ( 2)

50
C
50
C

0. 5229

0. 5793

( 1) ( 2)

50
C

0. 5088

0. 9751

21
0. 4064

Wils on
12
0. 5374

21
1. 0934

1. 2162

1. 4989

( 1) ( 2)

( 1) ( 2)

1 atm
1 atm

( 1) ( 2)

1 atm

1. 1200

0. 1820

( 1) ( 2)

0. 0497

4. 1839

10

( 1) ( 2)

1 atm
1 atm

0. 5601

0. 9796

11

( 1) ( 2)

1 atm

0. 1160

0. 1260

12

( 1) ( 2)

0. 2500

0. 4140

13

( 1) DM F ( 2)

1 atm
1 atm

0. 3600

0. 3820

14

( 1) ( 2)

1 atm

1. 7216

0. 4629

15

( 1) ( 2)

1 atm

0. 9020

0. 7828

16

( 1) ( 2)

1 atm

0. 3046

1. 8958

17

( 1) ( 2)

1 atm

0. 5866

0. 5127

18

( 1) ( 2)

1 atm

0. 1796

2. 6244

19

( 1) ( 2)

0. 2390

0. 2379

20

( 1) 1, 2( 2)

1 atm
1 atm

1. 9303

0. 3671

1 at m = 101325 pa
7-1 50
C , ( 1) ( 2) ( 3) , x 1 = 0. 34,

x 2 = 0. 33, x 3 = 0. 33, 50
C :

/ kPa

81. 82

78. 05

55. 58

Wilson 73, 50
C

[ ] 73 W ils on :
12 = 0. 7189, 21 = 1. 1816, 13 = 0. 5088
24 3

31 = 0. 9751, 23 = 0. 5229, 32 = 0. 5793

( 7116) , ,
:
ln 1 = 1 = 1-

ln( x 1 + x 2 1 2 + x 3 13 ) x 2 21
x 1 2 1 + x 2 + x 3 23

x1
x 1 + x 2 12 + x 3 13

x 3 3 1
x 1 31 + x 2 32 + x 3

ln( 0. 34 + 0. 33 0. 7189 + 0. 33 0. 5088)

0. 34
0. 34 + 0. 33 0. 7189 + 0. 33 0. 5088

0. 33 1. 1816
0. 34 1. 1816 + 0. 33 + 0. 33 0. 5229

0. 33 0. 9751
= 0. 03
0. 34 0. 9751 + 0. 33 0. 5793 + 0. 33

1 = 1. 03
ln2 = 1 = 1-

ln ( x 1 21 + x 2 + x 3 23 ) x2
x 1 21 + x 2 + x 3 23

x 1 12
x 1 + x 2 12 + x 3 1 3

x 3 32
x 1 31 + x 2 3 2 + x 3

ln ( 0. 34 1. 1816 + 0. 33 + 0. 33 0. 5229)

0. 34 0. 7189
0. 34 + 0. 33 0. 7189 + 0. 33 0. 5088

0. 33
0. 34 1. 1816 + 0. 33 + 0. 33 0. 5229

0. 33 0. 5793
= 0. 183
0. 34 0. 9751 + 0. 33 0. 5793 + 0. 33

2 = 1. 20
ln3 = 1 = 1-

ln ( x 1 31 + x 2 32 + x 3 ) x 2 23
x 1 21 + x 2 + x 3 23

x 1 13
x 1 + x 2 12 + x 3 1 3

x3
x 1 31 + x 2 3 2 + x 3

ln ( 0. 34 0. 9751 + 0. 33 0. 5793 + 0. 33)

0. 34 0. 5088
0. 34 + 0. 33 0. 7189 + 0. 33 0. 5088

0. 33 0. 5229
0. 34 1. 1816 + 0. 33 + 0. 33 0. 5229

0. 33
= 0. 348
0. 34 0. 9751 + 0. 33 0. 5793 + 0. 33

3 = 1. 42
50
C p
p = 1 x 1 p 01 + 2 x 2 p 02 + 3 x 3 p 03
2 44

= ( 1. 03 0. 34 81. 82 + 1. 20 0. 33 78. 05 + 1. 42 0. 33 55. 58) k Pa

= 85. 59k Pa

1 p 1 x 1
1. 03 81. 82 0. 34
y1 =
=
= 0. 335
p
85. 59
0

2 p 2 x 2
1. 20 78. 05 0. 33
y2 =
=
= 0. 361
p
85. 59
3 p 03 x 3
1. 42 55. 58 0. 33
y3 =
=
= 0. 304
p
85. 59

7. 3. 3 NRTL
7. 25 NR T L
E

2 1 G 21

12 G1 2
G
= x 1x 2
+
RT
x 1 + x 2 G 21
x 2 + x 1 G1 2

( 7100)

( 7100) , :

G
j

G
=
RT

xj

( 7117)

Gkx k
k

j = (gj g ) / RT
Gj = exp( -

j )
j

=
rj =
0

G = Gj j = 1

j =
j
( 763) ( 7117)

G
j

ln =

xk

x G
l

x j Gj

j Gkj x k

lj

lj

kj

( 7118)
xk

, , NR T L

7. 3. 4 UNI QUAC
U NIQ U A C Wilson N RT L , ,
U NIQ U A C ,
, U N IQ U AC :
E

G / RT =

x ln x

x qln

x q ln

( 7119)

24 5

ln = ln
-

q ln

qln
+ l 2

x j lj

j
j

x
j

1+

( 7120)

kj

x r

= x r

x q

= x q

ln
j = u j / R T
u j u j
u = 0
l = ( Z / 2) ( r - q ) - r + 1
Z = 10 ( )
u j u j , r , q van der
W aals , Bondi

[ 1 7]

7. 3. 5
, , ,
A SOG

[ 13]

1. ASOG ( )
A SOG ( A nalyt ical Solutions of Groups )

, ,

A SOG :
FH

lg = lg + lg

( 7121)

lgF H , Flory Huggins

FH

lg = lg
+ 0. 4343 1 FH
x j j
FH

FH

FH
x j j

( 7122)

FH
FH
x

/ x j
j
Flory H uggins

FH
, 7. 2. 3

;
j

xj
j
FH

( 7121) lg , :
lgG =

( lg ( )
k

lgk )

( 7123)

( )

k
k , k k , k k
2 46

( )
A SOG Wilson k k :
X l Alk
lgk = - lg( X l A kl ) + 0. 4343 1 -
l
l
X m Alm

( 7124)

A kl A l k k l Wilson ,
A kl A l k , A kk = A l l = 1
X k k ,

x
x
k

Xk =

( 7125)

,
, ,
, , ASOG

2. UNIFAC
U NIF AC ( U nivers al Q uasichemical Function al Group Activity Coefficien t,
) A SOG U N IQ U AC ,

( 1)
ln = ln C + lnR
C

( 7126)

, , U N IQ U A C
, U N IF AC
U NIQU A C r q , U NIFA C
R k Q k :
r =

R
( )
k

( 7127)

q =

Q
( )
k

( 7128)

( )

k
k , ,
( 2) ln R , U N IF AC

A SOG ,
R

ln =

[ ln ( )
k

( )

lnk ]

( 7129)

( )

k k , U NIFA C
A SOG , ASOG ( 7124) ,
lgk = - lg( X l a kl ) + 0. 4343 1 +
l

X l al k
X m al m
m

24 7

 U N IF AC X , m
W ils on a kl , U NIFA C
ln k = Q k 1 - ln( m m k ) -

m km
m

( 7130a )

lnk = Qk [ 1 - lnE k -

F k]

( 7130b)

E k k

Ek =

mk

= 1 1k + 2 2k + 3 3k +

( 7131)

F k
m m k

Fk =

1 k1
2 k 2
3 k3
+
+
+
E1
E2
E3

( 7132)

m m ,
m =

Q mX m
Q X

( 7133)

Q m m ; X m m , ( 7119)

Xm =

m m m
m = exp -

U m - U
= exp RT

a m
T

( 7134a )

m = exp -

U m - U m m
= exp RT

a m
T

( 7134b)

U m , U m m , ; a m a m
, , a m n K , a m n a n m ,
,
7-2 U NIFA C , 345K, x 1 = 0. 2
[ ] 1 CH 3 , 1 CH 2 1 OH , 6
A rCH :

Rk

Qk

CH 3

1 0

0. 9011

0. 848

CH 2

1 0

0. 6744

0. 540

OH

1 0

1. 0000

1. 2000

A rCH

0 6

0. 5313

0. 4000

a 12 = 0, a 21 = 0
2 48

a 23 = a 1 3 = 986. 5, a 32 = a 31 = 156. 4
a 24 = a 1 4 = 61. 13, a 42 = a 41 = -

11. 12

a 34 = 89. 6, a 43 = 636. 1
12 = 1, 21 = 1
23 = 13 = 0. 0573, 3 2 = 3 1 = 0. 6355
24 = 14 = 0. 8376, 4 2 = 4 1 = 1. 0328
34 = 0. 7713, 4 3 = 0. 1582
r 1 = 0. 9011 + 0. 6744 + 1 = 2. 5755
r 2 = 6( 0. 5313) = 3. 1878
q1 = 0. 848 + 0. 540 + 1. 200 = 2. 588
q2 = 6( 0. 40) = 2. 40
0. 2( 2. 5755)
= 0. 1680
0. 2( 2. 5755) + 0. 8( 3. 1878)

= 0. 8320

1 =

0. 2( 2. 588)
= 0. 2123
0. 2( 2. 588) + 0. 8( 2. 40)

2 = 0. 7877
l 1 = 5( 2. 5755 - 2. 588) + 1 -

2. 5755 = - 1. 6380

l 2 = 5( 3. 1878 - 2. 40) + 1 - 3. 1878 = 1. 7512

lns1 = ln

0. 1680
0. 2123
+ 5( 2. 588) ln
+ 0. 8320 - 1. 6380 0. 2
0. 1680

2. 5755( 1. 7512)
3. 1878

= 0. 3141
s

ln2 = ln

0. 8320
0. 7877
+ 5( 2. 40) ln
+ 0. 1680 1. 7512 0. 8
0. 8320

3. 1878( - 1. 6380)
2. 5755

= 0. 0175
( 1)

( 2)

0. 2
m
+ 0. 8
m
Xm =
0. 2( 3) + 0. 8( 6)

Xm

CH3

X1

0. 037

1/ 3

CH2

X2

0. 037

1/ 3

OH

X3

0. 037

1/ 3

A rCH

X4

0. 889

m =

X m Qm
X m Qm
=
0. 037( 0. 848 + 0. 540 + 1. 200) + 0. 889( 0. 40)
0. 4513

0. 0695

0. 3277

0. 0443

0. 2087

0. 0984

0. 4637

0. 7879

24 9

E k = 1 1k + 2 2k +
3 3 k +
4 4k
Ek

E1

0. 9901

0. 8311

E2

0. 9901

0. 8311

E3

0. 2296

0. 4944

E4

0. 9591

Fk =

1
k1
2 k2
3 k3

4
k4
+
+
+
E1
E2
E3
E4

Fk

F1

0. 8276

0. 6992

F2

0. 8276

0. 6992

F3

1. 1352

1. 3481

F4

1. 0158

lnk = Q k ( 1 - lnE k - F k )
lnk

ln 1

0. 1546

0. 4120

ln 2

0. 0985

0. 2623

ln 3

1. 6035

0. 4276

ln 4

0. 0104

ln1 = 0. 3141 + 1 ( 0. 1546 - 0. 4120) + 1 ( 0. 0985 + 1 ( 1. 6035 -

0. 2623)

0. 4276) = 1. 0688

1 = 2. 9119
ln2 = 0. 0175 + 6( 0. 0104 - 0) = 0. 0799
2 = 1. 0832

7. 4
7. 4. 1
7. 2 ,
,
, van Laar A 1 2 A 21 :
ln 1 =
2 50

A1 2
A 12 x 1
1+
A 21 x 2

( 777a )

A2 1
A 21 x 2
1+
A 12 x 1

ln 2 =

( 777b)

,
lim
ln1 = xlim
x 0
0

A 12
A 12 x 1
1+
A 21 x 2

lim
ln2 = xlim
x 0
0

A 21
A 21 x 2
1+
A 12 x 1

= A 1 2 = ln 1

= A 2 1 = ln 2

( 7135a )

( 7135b)

, van Laar
A 12 A 21 , ,

1.
, ,

1 = xlim
1
0
1

= xlim
2
0
2

,
, ,
van Laar , ( 7135a ) ( 7135b) M argules,

2
ln 1 = xlim
x 2 [ A 1 2 + 2x 1 ( A 2 1 - A 12 ) ] = A 12
0

( 7136a )

ln 2 = xlim
x 1 [ A 2 1 + 2x 2 ( A 1 2 - A 21 ) ] = A 21
0

( 7136b)

van Laar M argules

W ils on ,
ln1 = lim
- ln( x 1 + 12 x 2 ) + x 2
x 0
1

ln2 = lim
- ln( x 2 + 21 x 1 ) + x 1
x 0
2

1 2
21
x 1 + 12 x 2 21 x 1 + x 2
2 1
12
x 2 + 21 x 1 12 x 2 + x 1

= 1- ln1 2 - 2 1 ( 7137a )
= 1- ln2 1 - 1 2 ( 7137b)

N RT L ,
2

2 1 G 21 x 2

12 G12 x 2
ln = xlim
2 +
2
0
( x 1 + G 21 x 2 )
( G12 x 1 + x 2 )
1

=
21 +

12 G1 2 =

21 +

1 2 exp( 2

12
12 )

( 7138a )

1 2 G 12 x 1

21 G21 x 1
ln = xlim
2 +
2
0
( x 2 + G 12 x 1 )
( G21 x 2 + x 1 )
2

=
12 +

21 G2 1 =

12 +

2 1 exp( -

12
21 )

( 7138b)
25 1

, , ln 1 , ln 2
, , ,

73 ( 1) ( 2)

ln 1 = 0. 59, ln2 = 1. 42
( 7133 a ) ( 7133b) 12 21
[ ] :

ln1 = 1- ln12 - 21 = 0. 59

( 1)

ln2 = 1- ln21 - 12 = 1. 42

( 2)

( 1) , 2 1 = 1,
ln12 = - 0. 59, 12 = 0. 554
1 2 = 0. 554 ( 2) ,
ln21 = 1 -

1. 42 -

0. 554 = -

0. 974, 21 = 0. 3775

2 1 = 0. 3775 ( 1) ,
ln12 = 1 - 0. 59 -

0. 3775 = 0. 0325, 12 = 1. 033

1 2 = 1. 033 ( 2) ,
ln21 = 1 - 1. 42 -

1. 033 = -

1. 453, 21 = 0. 234

, 12 , 2 1 12 , 2 1

12 = 1. 2475, 21 = 0. 1888
,
lgx ,
, 72 ,
,

2.
,
, ( 737) ,
72

1 2 ,
( 1)

van Laar , ( 777a ) ( 777b)

x 2 ln2
A 12 = ln1 1+
x 1 ln1

x 1 ln1
A 21 = ln2 1+
x 2 ln2

( 7139a )
( 7139b)

, x 1 x 2 , 1 2 , ( 7139a ) ( 7139 b)
A 1 2 A 21 , ,
2 52

74 ( 1) ( 2) 101. 33k pa
van L aar A 1 2 A 2 1 , lgx

/K

x1 y 1

/ kpa
p p
0
1

/ kpa

/k

x 1 y 1

p 01 p 02

0
2

331. 45 0. 280 0. 420

109. 19 77. 19

329. 25 0. 600 0. 656

101. 19 69. 99

330. 35 0. 400 0. 516

104. 79 73. 46

328. 25 0. 676 0. 710

97. 72 67. 06

[ ] ( 1)
1
2

1 =

py1
p y2
, 2 = 0
0
p 1 x1
p 2x 2

1 2 :
x1

x2

ln1

ln2

0. 280

0. 720

1. 392

1. 057

0. 3307

0. 0554

0. 400

0. 600

1. 248

1. 113

0. 2215

0. 1070

0. 600

0. 400

1. 095

1. 246

0. 0907

0. 2199

0. 676

0. 324

1. 089

1. 352

0. 0852

0. 3016

( 2) ( 7139a ) ( 7139b) A 12 A 21

x 2 lg2
A 12 = lg1 1 +
x 1 lg1

x 1 lg1
A 21 = lg2 1 +
x 2 lg2

0. 720 0. 0240
= 0. 1436 1 +
0. 280 0. 1436

0. 280 0. 1436
= 0. 0240 1 +
0. 720 0. 0240

= 0. 294
= 0. 266

, :
x1
0. 280
0. 400

x2
0. 720
0. 600

A 12
0. 294
0. 286

A21
0. 266
0. 263

x1
0. 600
0. 676

x2
0. 400
0. 324

A12
0. 270
0. 269

A 21
0. 250
0. 331

4 van Laar
A 12 =

0. 294 + 0. 286 + 0. 270 + 0. 269

= 0. 280
4

A 21 =

0. 266 + 0. 263 + 0. 250 + 0. 331

= 0. 278
4

( 3) van L aar ,
:
lg1 =

A 12
A 12 x 1
1+
A 21 x 2

0. 280
0. 280x 1
1+
0. 278x 2

25 3

A 21
A 21 x 2
1+
A 12 x 1

lg2 =

0. 278
0. 278x 2
1+
0. 280x 1

, :
x1
0. 1
0. 2
0. 3
0. 4
0. 5

x2
0. 9
0. 8
0. 7
0. 6
0. 5

lg1
0. 2265
0. 1787
0. 1366
0. 1002
0. 0695

lg2
0. 0028
0. 0112
0. 0253
0. 0449
0. 0700

x1
0. 6
0. 7
0. 8
0. 9

x2
0. 4
0. 3
0. 2
0. 1

lg1
0. 0444
0. 0249
0. 0111
0. 0028

lg2
0. 1006
0. 1368
0. 1784
0. 2255

( 4) van L aar
van Laar
,
M argules ( 778a ) ( 7
78b) , :
A 12 =

( x 2 - x 1)
2lg2
lg1 +
2
x1
x2
( 7140a )

A 21 =

( x 1 - x 2)
2lg1
lg2 +
2
x1
x2
( 7140b)

W ils on ,
( 786a ) ( 786b) , Wilson
,
, x 1 x 2 , 1 2 ,
73 lg1 x 1

( 786a ) ( 786b) ,
12 21 ,

,
?
, ,
,
( 762) :
GE =

x RT ln

( 762)

G = x 1 R T ln1 + x 2 RT ln2
M argules ( 778a ) ( 778b) ,
GE
2
= x 1 x 2 [ A 12 + 2x 1 ( A 2 1 RT
2 54

A1 2 ) ]

+ x 2 x 1 [ A 21 + 2x 2 ( A 12 - A 2 1 ) ]
= x 1 x 2 ( A 1 2 x 2 + A 21 x 1 )

GE
= ( A 12 x 2 + A 21 x 1 ) = [ A 1 2 + ( A 21 - A 12 ) x 1 ]
R T x 1x 2

( 7141)

, G / ( x 1 x 2 R T ) x 1 , , M argules

van Laar ( 777a ) ( 777b)

E

G
= x 1 ln1 + x 2 ln2 =
RT
=

x1

A 12
A 12 x 1
1+
A 21 x 2

+ x2

A2 1
A 21 x 1
1+
A 12 x 2

A 12 A 21 x 1 x 2
A 12 x 1 + A 21 x 2

A 12 x 1 + A 21 x 2
A 21 + ( A 12 - A 21 ) x 1
RT
=
E x 1x 2 =
G
A 12 A 21
A 1 2 A 21

( 7142)

, ( x 1 x 2 R T ) / G x 1 , , van L aar
GE / ( x 1 x 2 RT ) x 1 , ( x 1 x 2 R T ) / GE x 1 ,
, , Wilson , N R T L Wilson

( 2)
, ,
, ,
, ,
, ( ) ,
, van Laar Margules
, ,

van L aar
van Laar :
ln1 =

ln2 =

A 12
A 12 x 1
1+
A 21 x 2
A 21
A 21 x 2
1+
A 12 x 1

( 777a )

( 777b)

( 777a)
( ln1 )

- 0. 5

A 0.12 5 x 1
1
=
+

A 0.12 5
A 21 x 2

( 7143a )

, ( 777 b ) ,
25 5

0. 5

( ln2 )

- 0. 5

A 21
x2
1
=

0. 5 +
A 12 x 1
A 21

( 7143b)

, ( ln1 ) 0. 5 , x 1 / x 2 ,
1/ A 0.12 5 , A 01 .2 5 / A 21 , A 12 A 2 1
( ln2 ) -

0. 5

x 2 / x 1 , A 12 A 21

, , ,
,
van L aar :
( 777a ) x 1 , ( 777b) x 2
x 1 ln1 + x 2 ln2 =

A 12 A 2 1 x 1 x 2
A 12 x 1 + A 21 x 2

x1
x1
1
1
=
+
x 1 ln1 + x 2 ln2
A2 1 x2
A 12

( 7144a )

x2
1
x2
1
=
+
x 1 ln1 + x 2 ln2
A1 2 x1
A 21

( 7144b)

, x 1 / ( x 1 ln1 + x 2 ln2 ) x 1 / x 2 , ; 1/ A 1 2 ,
1/ A 2 1 ; x 2 / ( x 1 ln 1 + x 2 ln2 ) x 2 / x 1 , , 1/ A 2 1 , 1/
A 12 ,
, van L aar :
A 12
ln1
A 12 / ln1

0. 5

0. 5

1=

A 12 x 1
A 21 x 2

( 7145)

- 1 x 1 / x 2 , , A 12 / A 21

M argules
M argules ,
2

( 778a )

( 778b)

ln1 = x 2 [ A 1 2 + 2x 1 ( A 21 - A 1 2 ) ]
ln2 = x 1 [ A 2 1 + 2x 2 ( A 12 - A 2 1 ) ]

ln 1
= A 12 + 2( A 21 - A 12 ) x 1
x 22

( 7146a )

ln 2
= A 21 + 2( A 12 - A 21 ) x 2
2
x1

( 7146b)

, ( ln1 ) / x 2 x 1 , , A 12 , 2( A 2 1 2

A 12 ) ; ( ln2 ) / x 2 x 2 , A 21 , 2( A 1 2 - A 21 )
, A 12 A 21
75 ( 1) ( 2) 101. 33 kpa
van L aar , ,

2 56

t/
C

x
100 y
100
1
1

t/
C

x
100 y
100
1
1

81. 8

1. 000

36. 0

60. 0

86. 6

1. 356

1. 745

52. 8

10. 0

65. 9

3. 60

1. 020

34. 9

70. 0

87. 9

1. 230

2. 090

44. 3

20. 0

77. 0

2. 76

1. 070

34. 2

80. 0

90. 3

1. 128

2. 720

40. 6

30. 0

80. 8

2. 18

1. 184

33. 9

90. 0

93. 0

1. 045

3. 970

38. 5

40. 0

83. 2

1. 80

1. 315

34. 1

100. 0

100. 0

1. 000

37. 1

50. 0

85. 0

1. 541

1. 491

[ ] ( 1) van L aar

:
x1
1
x1
1
=
+
x 1 ln1 + x 2 ln2
A2 1 x2
A 12
x2
x2
1
1
=
+
x 1 ln1 + x 2 ln2
A1 2 x1
A 21
:
100
x
1

ln1

ln2

x1
x 1 ln1 + x 2 ln2

x1
x2

x2
x 1 ln1 + x 2 ln 2

x2
x1

10. 0

1. 2809

0. 0198

0. 6853

0. 111

6. 1678

9. 000

20. 0

1. 0152

0. 0676

0. 7778

0. 250

3. 1104

4. 000

30. 0

0. 7793

0. 1689

0. 8521

0. 429

1. 9877

2. 333

40. 0

0. 5878

0. 2738

1. 0015

0. 667

1. 5022

1. 500

50. 0

0. 4324

0. 3994

1. 2017

1. 000

1. 2017

1. 000

60. 0

0. 3045

0. 5567

1. 4840

1. 500

0. 9893

0. 667

70. 0

0. 2070

0. 7372

1. 9126

2. 333

0. 8195

0. 429

80. 0

0. 1204

1. 0006

2. 7000

4. 000

0. 6705

0. 250

90. 0

0. 0440

1. 3787

5. 0712

9. 000

0. 5637

0. 111

2. 3026x 1 / ( x 1 ln1 + x 2 ln2 ) x 1 / x 2 2. 3026x 2 / ( x 1 ln 1 +

x 2 lnx 2 ) x 2 / x 1 ( 74a ) 74a 1. 28, 1. 45;
74b 1. 45, 1. 28, , 2. 3026/ A 1 2 =
1. 28, 2. 3026/ A 21 = 1. 45, A 12 = 1. 5880, A 21 = 1. 7989
van Laar ,
ln 1 =

1. 5880
1. 5880x 1
1+
1. 7989x 2

ln 2 =

1. 7989
1. 7989x 2
1+
1. 5880x 1

( 2)
25 7

 74 ( a ) x 1 / ( x 1 lg1 + x 2 lg2 ) x 1 / x 2 ( b) x 2 / ( x 1 lg1 + x 2 lg2 ) x 2 / x 1

x 1 , x 2 1 2 , :
x
1
100

ln1

ln2

10. 0

1. 3172

1. 2809

3. 733

3. 60

0. 0178

0. 0198

1. 018

1. 020

20. 0

1. 0657

1. 0152

2. 903

2. 76

0. 0583

0. 0676

1. 060

1. 070

30. 0

0. 8351

0. 7793

2. 305

2. 18

0. 1354

0. 1689

1. 145

1. 184

40. 0

0. 6291

0. 5878

1. 876

1. 80

0. 2469

0. 2738

1. 280

1. 315

50. 0

0. 4479

0. 4324

1. 565

1. 541

0. 3961

0. 3994

1. 486

1. 491

60. 0

0. 2942

0. 3045

1. 342

1. 356

0. 5839

0. 5567

1. 793

1. 745

70. 0

0. 1697

0. 2070

1. 185

1. 230

0. 8149

0. 7371

2. 259

2. 090

80. 0

0. 0770

0. 1204

1. 080

1. 128

1. 0912

1. 0006

2. 978

2. 720

90. 0

0. 0198

0. 0440

1. 020

1. 045

1. 4197

1. 3788

4. 136

3. 970

ln1 x 1 ln2 x 1 , 75, , van L aar

3.
,
, : ,
1 =

y 1p
y 2p
2 =
0,
0
x1 p 1
x 2p 2

,
, van Laar M argules
2 58


,
,
,
,
(
)
( 0. 25< x 1 < 0. 75) ,
, ,

76 ( 1 ) ( 2) 101.

75 lg1 x 1 lg2 x 1

33k pa , 87. 8
C , x 1 = 0. 432,
van L aar , 87. 8
C
p s1a t = 69. 86 kpa , p s2 a t = 64. 39k pa
[ ] ( 1)
, x 1 = y 1 , x 2 = y 2 ,
1 =

p
101. 33
= 1. 451
sa t =
p1
69. 86

2 =

p
101. 33
= 1. 575
sa t =
p2
64. 39

( 2) van L aar
( 7139a ) ( 7139b) :
A 12

x 2 ln2
= ln1 1 +
x 1 ln1

0. 568ln1. 575
= ln1. 451 1 +
0. 432ln1. 451
A 21

x 1 ln1
= ln2 1 +
x 2 ln2

= 2. 525

0. 432ln1. 451
= ln1. 575 1 +
0. 568ln1. 575

= 1. 197

van Laar :
ln1 =

ln2 =

2. 525
2. 525x 1
1+
1. 197x 2
1. 197
1. 197x 2
1+
2. 525x 1

( 3) van L aar ,
s at

sa t

p 1 x 1 1
p 2 x 2 2
y1 =
, y2 =
p
p
25 9


p1
p sa1 t x 1 1
y1 =
=
=
p
p sa1 t x 1 1 + p s2 at x 2 2
sa t

1
p s2 at x 2 2
1 + s at
p 1 x 1 1

sa t

y 1 p 2 / p 1 ,
( ) , ,
sa t
s at
97. 8
C p 2 / p 1 = 0. 923, 87. 8
C

, , ,
:
x1

y 1 ( )

y 1 ( )

y 1

0. 10

5. 24

1. 04

0. 376

0. 372

0. 004

0. 20

2. 95

1. 15

0. 407

0. 392

0. 015

0. 30

2. 00

1. 31

0. 415

0. 404

0. 011

0. 40

1. 54

1. 51

0. 425

0. 424

0. 001

0. 432

1. 45

1. 58

0. 432

0. 432

0. 000

0. 50

1. 30

1. 74

0. 447

0. 452

- 0. 005

0. 60

1. 16

2. 00

0. 484

0. 492

- 0. 008

0. 70

1. 07

2. 29

0. 542

0. 551

- 0. 009

0. 80

1. 03

2. 61

0. 632

0. 641

- 0. 009

0. 90

1. 01

2. 94

0. 769

0. 778

- 0. 009

, , van L aar ,

4. ( p -x)
, ,
p x ,
,
, , ,
p x , p x ,
,
y1 p
( 1 - y2 ) p
p - x 2 2 p s2 at
1 =
=
sa t =
sa t
sa t
x 1p 1
x 1p 1
x 1p 1

( 7147a )

x 1 0, x 2 1, 2 1,
p - x 2 p sa2 t
lim
1 = =
x 0
x 1 p sa1 t

( 7148a )

,
2 =
x 2 0, x 1 1, 1 1,
2 60

p -

sa t

x 1 1 p 1
sa t
x 2p 2

( 7147b)

s at

p - x1 p 1
lim

2 = =
s at
x 0
x 2p 2
2

( 7148b)

x 1 , 2 1

s at

p - x 2p 2

1 =
x 1 p s1 at

( 7149a )

s at

p - x 1p 1

2 =
x 2 p s2 at

( 7149b)

1,
2 , ln

1 x 1 x 1 0 , ln

(
1)
ln
2 x 2 x 2 0 , ln (
2)

, p x :
( 1) p x 1 ( x 1 ) , ( 7149a ) x 1
1 ,
ln
1 x 1 , x 1 0, ln

1 A 1 2 , A
12
( 2) , ( 7149b) x 1
2 ( x 2 ) ln
2 x 1

, x 1 1, ln
2 A 21 , A
21
( 3) 1 = ( p - x 2 2 p s2 at ) / ( x 1 p s1 at ) x 1 1 ,
1
2 A
12 A
2 1 , van
2 , 1 ,

L aar , x 1 , x 2 , 2 1,
ln1 x 1 , x 1 0
ln1 A 1 2
( 4) 2 = ( p - x 1 1 p s1 at ) / ( x 2 p s2 at ) x 1 2
x 1 , 1 A
12 A
2 1 , ln
2 x 1
x 1 1 ln 2 A 21
( 5) A 12 A 2 1 , ,
x 1 y 1 ,
77 ( 1) ( 2) 80
C p x 1 :
x1

0. 10

0. 20

0. 30

0. 40

0. 60

0. 70

0. 80

0. 90

p / kpa

63. 46

70. 19

74. 13

76. 13

76. 73

75. 93

73. 33

66. 86

sa t

s at

80
C p 1 = 47. 34kpa p 2 = 51. 13k pa
van Laar
[ ] ( 1)
1

2
( 7149a ) ( 7149b)
1
2 (

1 x 1 ,

2
x 2 ) , :
x1

x2

t
x 1 p sa
1

x 2 p sat
2

ln
1

0. 10

0. 90

63. 46

4. 73

45. 99

3. 69

1. 3056

0. 20

0. 80

70. 19

9. 47

40. 93

3. 09

1. 1282

ln
2

26 1

0. 30

0. 70

74. 13

14. 27

35. 73

2. 70

0. 9932

0. 40

0. 60

76. 13

18. 93

30. 53

2. 40

0. 8755

0. 60

0. 40

76. 73

28. 40

20. 40

2. 36

0. 8587

0. 70

0. 30

75. 93

33. 06

15. 33

2. 79

1. 0260

0. 80

0. 20

73. 33

37. 86

10. 21

3. 47

1. 2442

0. 90

0. 10

66. 86

42. 53

5. 11

4. 75

1. 5581

ln
1 x 1 ln
2 x 1 ( 76) , 0.

4343A
12 = 0. 65 A
1 2 = 1. 497 0. 4343A
2 1 = 0. 88 A
21 = 2. 026
( 2) A
12 A
2 1 , van L aar
1 ( x 2 ) ,
1 2
ln1 =

ln2 =

1. 497
1. 497x 1
1+
2. 026x 2
2. 026
2. 026x 2
1+
1. 497x 1

( 3) ( 7147a ) ( 7147b) , 1 2 , :
x1

x2

ln1

ln2

0. 10

0. 90

3. 60

1. 2809

0. 20

0. 80

2. 88

1. 0578

0. 30

0. 70

2. 40

0. 8755

0. 40

0. 60

2. 01

0. 6981

0. 60

0. 40

1. 81

0. 5933

0. 70

0. 30

2. 32

0. 8416

0. 80

0. 20

3. 11

1. 1346

0. 90

0. 10

4. 61

1. 5282

76 , , 0. 4343A 1 2 = 0. 64 A 12 = 1. 4736
0. 4343A 2 1 = 0. 85 A 2 1 = 1. 9572,
:
ln 1 =

1. 4736
1. 4736x 1
1+
1. 9572x 2

ln 2 =

1. 9572
1. 9572x 2
1+
1. 4736x 1

( 4) x 1 ( x 2 )
sa t

sa t

1 2 , p = x 1 1 p 1 + x 2 2 p 2 ,
, , ,
, x 1 / ( x 1 ln1 + x 2 ln2 ) x 1 / x 2 x 2 / ( x 1 ln1 + x 2 ln 2 )
2 62

x 2 / x 1 A 12 A 2 1
5.
,
( 101. 33kpa ) ,
T x 1 , 4

( 1)
1

2
sa t

sa t

p - x 2p 2
p - x 1p 1

1 =

2 =
sa t
sa t
x 1p 1
x 2p 2
76 lg
x 1 lg
2 x 1

sa t

sa t

p1 p 2
A ntoine

( 2) ln
1 x 1 ln

2 x 1 A
12 A
21
( 3) 1
1 =

p -

sa t

x 2 2 p 2
sa t
x 1p 1

2 A
1 2 A
2 1 van L aar
( 4) 2
2 =

p -

sa t

x 1 1 p 1
x 2 p sa2 t

1 A
1 2 A
2 1 van L aar
( 5) ln1 x 1 ln2 x 1 A 12 A 21
,
,

7. 4. 2
,

1.
, , ,
ppm , ,

50 60 ,
,
, ,
, , , ,
26 3

 , , ,
,
,
, , ,
, , ,
, , , 1L ,
, ,
, ,

RT
M L p s a t . Vg

( 7150)

, , R , T
, M L , p s at Vg

VR - VR
( tR - tR) F C
Vg =
=
WL
WL

( 7151)

, W L , V R ,
V R = tR F C
0
V R ,
0

V R = tR F C
, t R , t 0R , F C

, (
)
,
2 3 L
, ( 7150)
77 ,

2 =

RT
RT

, 3 =
s at
M L p 2 ( Vg ) 2
M L p s3 a t ( Vg ) 3

:
2 p sa2 t
R T / M L ( Vg ) 2
( Vg ) 3
= sa t =
=
3 p 3
R T / M L ( Vg ) 3
( Vg ) 2

23

( 7152)

( V R ) 3 - VR
( VR ) 2 - VR
( Vg ) 3 =
, ( Vg ) 2 =
WL
WL

( Vg ) 3
( VR ) 3 =
=
( Vg ) 2
( VR ) 2
23

2 64

V0R
0
VR

( 7153)

( 7152) , 23 2 3 , W L

W L 23

23 ,

,
2 3
,

2.

, ,
, Flory
H uggins ,
N ull Flory Huggins
( 1)
:
V 1 ( 1 - 2 )
ln =
RT

( 7154a )

V 2 ( 1 - 2 ) 2
ln =
RT

( 7154b)

, 1 , 2 1, 2 , V 1 , V2 1
2 , 1 , 2 1 2
85 ,
:
1 =

U V1
V1

( 7155a )

2 =

U V2
V2

( 7155b)

U , U = H
- R T , ( 7154a ) ( 7154b)
( 2) Flory Huggins

FloryHuggins
, ( 783 a ) ( 783b ) :
ln1 = ln

ln2 = ln

V1
+ 1V2

V1
V2

( 7156a )

V2
+ 1V1

V2
V1

( 7156b)

( 3)
, ( 7155)
( 7156) ,
26 5

V1
ln = 1 + ln
V2

V1
V1 (
1
2)
+
V2
RT

V2
ln = 1 + ln
V1

V2
V 2 ( 1 - 2 )
+
V1
RT

( 7157a )
( 7157b)

, [ 23]

71 , ,
1, 1, 1,
1 1
72 45
C ( 1) ( 2)
:
x1

0. 0347

0. 1914

0. 3752

0. 4790

0. 6049

0. 8009

0. 9609

y1

0. 1801

0. 4603

0. 5429

0. 5684

0. 5936

0. 6470

0. 8001

p / kpa

33. 06

44. 80

48. 60

49. 27

49. 47

48. 36

41. 91

p 01 = 34. 50kpa, p 02 = 27. 50kpa

, ,

73 2 ^a 1 , GibbsDu hem ^a 2 ,
2
74 2 45
C ( 1) ( 2) :
x1
H / J mol -

0. 128

0. 317

0. 414

0. 631

0. 821

414

745

860

930

736

( 1) 45
C H mix , G, m ix T S mix x
( 2) GE , H E T S E , x
75
B =

y B

1
2

y y

j = 2B j -

B -

Bj j

:
Z=
:
2 66

pV
Bp
= 1+
RT
RT

( 1) V =
E

( 2) G =
E

( 3) S = E

( 4) H =

1
2

y y

p
y y j j

j
dj
p
y y j

2 j
dT
p
d j
y y j j - T

2 j
dT
E

76 Gibbs G = B x 1 x 2
E

40
C 101. 33kpa , G / RT , H / RT , S / R
101. 33kpa B
B = 0. 6186 -

0. 004t(
C)

77 ( 1) ( 2)
GE / RT = x 1 x 2
= 0. 735, :
t/
C

p 01 / kP a

p 02 / kP a

t/
C

p 01 / kP a

p 02 / kP a

34. 6

101. 33

46. 66

50

169. 98

81. 33

40

122. 66

56. 66

56. 1

204. 65

101. 33

45

145. 32

67. 99

101. 33kpa tx y
78 ( 1) ( 2) t =
45
C, p = 24. 4kpa, x 1 = 0. 300, y 1 = 0. 634, 1 2 45
C
0

p 1 = 23. 06kpa, p 2 = 10. 05kpa, ,

( 1) 1 2 ;
( 2) GE / RT ;
( 3) G/ R T ;
( 4) , ? ?

79 ( 1) ( 2) ln1 = 0. 59, ln2

= 1. 42, Wilson
ln1 = 1 - ln12 -

2 1

ln2 = 1 - ln21 -

1 2

W ils on 12 2 1
710 U NIFA C ( 1) ( 2) T = 307K
x 1 = 0. 047 1 2 1 = 4. 41 2 = 1. 11
711

E
x 1 x 2 C 21
x 1 x 2 C 12
G
=
+
RT
x 1 + D 21 x 2
x 2 + D 12 x 1

26 7


C 21 = ( g 21 -

g 1 1 ) / R T C 12 = ( g 12 - g 22 ) / R T

D 21 = exp( -

21 C 21 ) D 12 = exp( -

12 C 12 )

712 ( 1) ( 2) 77. 6
C x 1 = 0. 525 ,
sa t

sa t

101. 33kpa p 1 = 99. 3kpa p 2 = 98. 0

k pa
( 1)
77. 6
C
( 2) ( 1)

[ 1] Edmis ter W C et al. Applied H ydrocar bon T herm odynam ics ", vol. 1, 2d edit ion , Houst on, T exas:
Gulf P ublishing CO, 1984
[ 2] H ildebrand J H . J . A m. Chem. Soc. , 1929, 51: 66
[ 3] Scat chard G . Chem . Rev. , 1931, 8: 321
[ 4] Wohl K. T rans. A IChE , 1946, 42: 215
[ 5] Wils on G M . J . A m . Chem . Soc , 1964, 86: 127
[ 6] T s uboka T and T K at ayama . J. Chem . Eng . , J apan , 1975, 8( 3) : 181
[ 7] F lory P J. Chem. phy. , 1942, 9: 660; 1942, 10: 51
[ 8] H uggins M L . J. P hy . Chem . , 1941, 9: 440; Ann . NY A cad . Sci . , 1943, 43: 1
[ 9] Renon H and J M P rausnit z. A IChE J . , 1968, 14: 135
[ 10] Scot t R L . A nn . Rev. P hy. Chem . , 1956: 743
[ 11] K arr A E . Ind. E ng. Chem. , 1951, 43: 961
[ 12] N agat a I. J . Chem . Eng. Japan, 1973, 6 ( 1) : 18
[ 13] Deal C H and E L Derr . I . Chem . E . Symposium Series, 1969, 32: 340
[ 14] F redens lund A , R L Jones and J M P rausnit z. A IChE J . , 1975, 21: 1086
[ 15] A bram D S and J M P rausnit z. AIChE J . , 1975, 21: 116
[ 16] F redens lund A . Ind. Eng. Chem . P roces s Des . Dev. , 1977, 16 ( 4) : 450
[ 17] Bondi A . P hys ical P roper ties of Molecular Liquids , Cryst als , and Glas ses , N ew Y ork : John Wiley
& Sons, 1968
[ 18] , . , , 1985
[ 19] N ull H R . P hase E quilibrium in P rocess Design , N ew Y ork : Wiley , 1970
[ 20] . ( ) , 1970, 34 ( 7) : 730
[ 21] K orcats u , M iyahara . J . Chem . Eng . J apan , 1970, 3( 2) : 157
[ 22] Renon H and J M Praus nitz. Ind. Eng. Chem . Des. Dev. , 1969, 8: 413
[ 23] H elpins till J G et al. , I. E . C. P rocess Des ign & Development , 1968, 7, 2

2 68

8
, , (
)
;
;

8 . 1
8. 1. 1
( ) ,
, ; ,

, (
) , Gibbs
: , C
, P , :
= = = P ( = 1, 2, , c)

( 81)

P P
= G =

( G)

T, p,

Gibbs :
dG = R T dln ^
f ( T )

( 3138)

( 81) , :
G , P
( P ) , :

= R T ln( ^
f /^
f )
P

- = RT ln ( ^
f /^
f )
P

.....................
P- 1

= R T ln ( ^
f
P

P- 1

/^
f )
P

( 81)
26 9

^f
ln
^f

= ln

f^

P- 1

= = ln

f^ P

f^

f^ P

= 0

^f
^f

f^
f^

^f
^f

P- 1

= =

= 1

:
f^ = f^ = = ^
f P
( = 1, 2, , C)

( 82)

, , ,
( 82) , ,
, , , ( 82)

8. 1. 2
P C , T , p , [ P ( C - 1) +
2] , , ,
, ,
Gibbs 1875
:
F = C-

P + 2

( 83)

, ,
, ( )
, , ;
, ,
= -
= [P ( C = C( P -

1) + 2] -

[ C - P + 2]

1)

( 81) C ( P - 1)
,
8. 1 ,
[ ] = C ( P - 1) = 2( 2- 1) = 2
( 81) :

^f

V
1

= ^
f V1

^f

V
2

= ^
f 2

( 1)

L
0
0
Lewis R andall ^
f L = x f L , f L T , p

2 70

 f ,
f
f / f

sa t

0
L

= f= p

s at

f s a t
s at
p

f
= p sa t
sa t
f

s at

f
s at
f

( 2)

sa t

p p , ( 372) :
ln f / f

s at

p
p sa t

VL
dp
RT

, p p sa t , ,
f / f
sa t

= 1

= 1, ( 2)
f

^f

s at

0
L

sa t

= p

= x f

0
L

= x p

s at

( 3)

( 4)

V
, ^
f

f^ =
V

p y

^ = 1,
V

f^ V = p y

( 5)

( 3) ( 5 ) ( 1) ,
( R aoult )
p y 1 = p sa1 t x 1
sa t

p y2 = p 2 x 2

8 . 2
8. 2. 1

: : ; (
) ; ( )
,
, Dalton , R aoult
, R aoult ,
; , Henry
, Raoult
81
82( a ) 82( b) 82( b) y x ( ) 82( a )
, , y x
y x ,
27 1

 81 82

, R aoult , R aoult
Dalt on ,
s at

p y = p x
83
, 84
x 1 = 01 ( 85 86)
, CCl4 CS 2 ; ,
, ,
,
y , a z e = x , a z e

( 84)

y x y x y = x ( )

8. 2. 2
8. 1. 2

f^ V = f^ L ( = 1, 2, , C)
, :
2 72

( 85)

 83 ( A ) ( B)

84

^f
^f

= p y ^

= y f

^f

= p y ^ , ^
f = p x ^
V

( 86)

f^ V = y V f 0V , f^ L = x L f L0

( 87)
27 3

 85 ( E ) ( A )

^ , f
0

V L
( 86) ( 87) ( 85) , 4 ,
:
y ^ = x ^
V

p y ^ = x L f
V

( 88)
0
L

( 89)

( 88) ( 89) :
K = y / x =

/ ^ V

K = y / x = ( L f L0 ) / ( ^ V p )

( 88a )
( 89a )

K = y / x ,
( V aporization E quilibrium Rat io) K K > 1,
, ,
K
( 88) ( 89) ( 85) ,
,
,

L ,

f 0 T , p
2 74

 86 ( A ) ( C)

( T , p , y 1 , y 2 , , y - 1 )

( T , p , x 1 , x 2 , , x - 1 )

L = ( T , p , x 1 , x 2 , , x - 1 )
f

0
L

= f (T, p)

( N ) , [ P ( C - 1) + 2] = [ 2( N - 1) + 2]
= 2N , N N , N
( 88) ( 89) N ,
4 :
( 1) : p x 1 , x 2 , , x - 1 T y 1 , y 2 , , y - 1 ;
( 2) : T x 1 , x 2 , , x - 1 p y 1 , y 2 , , y - 1 ;
( 3) : p y 1 , y 2 , , y - 1 T x 1 , x 2 , , x - 1 ;
( 4) : T y 1 , y 2 , , y - 1 p x 1 , x 2 , , x - 1
, ( 88)
( 89)
,
,
27 5


: ,

8. 2. 3
( 89) , ( < 200k pa )
( 89) , f 0L , ( 373) ,
V
dp
RT

dln f =

( 373)

sa t

, p p
0

f L
ln sa t =
f L

V L
dp
RT

p sat

0
L

= f

sa t
L

exp

p
p sa t

VL
dp
RT

= f

sa t
L

(P F )

( 810)

( P F ) = exp

VL
dp
RT

p sa t

( 811)

Poynting
( 810) ( 89) ,
p y ^ = x f
V

s at
L

(P F )
sa t

= x p

f L
sa t ( P F )
p

s at

s at

sa t

= x p

( 812)

(P F)

s at

sa t

y
p ( P F )
K=
=
x
p ^ V

( 812a )

, , ( 812) ( 812a )
,
, p s at
,

sa t

= 1, VL / R T , ,

( P F ) = exp

p
p sa t

VL
dp = 1
RT

( 812)
sa t

p y = x p

2 76

( 813)

sa t

p
K = y / x =
p

( 813a )

, = 1, ( 813)
s at

p y = x p

( 814)

R aoult
s at

p , ,
,
, ,
,

8. 2. 4
( 15002000k pa) , ,
P oynting ( P F ) 1, , ( 812)
:
p y ^ = x p
V

s at

sa t

( 815)

, , :
sa t

p y = x p

( 813)

( V r 2)
( 815)

s at

ln

[ Z 0

ln ^ =
V

1]

dp
p

[ Z 0

1]

( 379)

dp
p

( 3142)

s at

ln

B p
=
RT

( 816)

ln ^

2 y j B j - B m
j= 1

p
RT

( 817)

Bm =

y y B

( 818)

B B j , ,
, Wilson , NR T L , A SOG , U NIQ U A C , U N IF AC ,
Scat chardHildebrand, Margules van Laar
, ; Scatchard H ildebrand
, , ;
, W ils on , N RT L ( ) ;
27 7

, ,
; Wilson , 3 ,
, NR T L
87 88 ( 815)
87 ( 1) ,

87

p , x 1 , x 2 , , x - 1 ( x = 1) 81

, p s a t

, ,

, ^ ,
V

= 1

, , :
( 1) B B j ;
sa t

( 2) p ;
( 3) ( 816)

sa t

( 4) ( W ils on )
2 78

 88

, ( 815) y , ,
y :
s at

y =

x p
p^

s at

( = 1, 2, , )

81

sat

sat

sa t
p = f (T)

p sat
( Ant oine ) )

T , p , y 1 , y 2 , , y -

T , VL, Z L ,
t
: p sa
, T ,

T
T , x 1 , x 2 , , x -

: VL ( VL = f ( T ) ) j j

, y y = 1 y

, y y , ^ y 1
V

^ V = 1, y ,

27 9

, y ,

, p sa t

sa t

, y y , ,

y ( 10-

10 - 4 ) , y 1 y = 1,

, y ,
y 1, y > 1, ,

, ,
^ = 1, ^ , y
V

1
88
82 ( 815) Wilson
, p = 101. 33kpa
,
8-2 ---( p = 101. 33kpa)

sat

y ( )

y ( )

x
0. 731

0. 610

0. 035

sa t

0. 597

/ kpa
82. 124

0. 9603

0. 9512

1. 0179

0. 212

0. 221

51. 686

0. 9831

0. 9664

11. 6742

0. 111

0. 085

0. 086

74. 646

0. 9678

0. 9565

1. 0300

0. 123

0. 093

0. 096

56. 377

0. 9779

0. 9602

1. 3351

82 , 1 01 . 3 3 kpa ,
0. 951. 0 , ^
V

1, ,

^
V

( 815) , ( 1
) , , 101. 33kpa ,
, ( 813)
, , , ( 813) ( 815)

8 . 3

10
2 80

, ,
, , H 2 CH 4

, 83 89
( 1) ( 2) ,
, 37. 8
C , y x

89 ( 1) ( 2) [ 10]

, 1. 0, ,
33
C, 4883. 87k pa ( 48. 2atm) ,
197
C , 3374. 12kpa ( 33. 3at m ) T c, C2 H 6 ,
, y x , y x
( ,
, , ) ,
C , , 171. 1
C
, 197
C , ,

28 1

( ) ( ,
) ; , ^

V
1

= 1

; , f 0

1961 K. C. Chao J . D. Seader

[1]

60 , ChaoSeader ,
,
,
Chao Seader , :
8-3 ( 1) -( 2) -

/ %

/
C

x 1

y 1

/ 101. 325kpa

0. 00

0. 00

0. 30

14. 32

91. 58

3. 4

28. 91

95. 04

6. 8

43. 16

96. 59

10. 2

4. 4

56. 59

97. 63

13. 6

69. 50

98. 38

17. 0

81. 41

99. 01

20. 4

92. 35

99. 60

23. 8

100. 00

100. 00

26. 18

0. 00

0. 00

1. 07

6. 24

68. 08

3. 4

15. 19

84. 48

6. 8

23. 71

88. 97

10. 2

32. 01

91. 34

13. 6

40. 02

92. 84

17. 0

37. 8

47. 74

93. 89

20. 4

55. 11

94. 72

23. 8

62. 19

95. 48

27. 2

68. 79

96. 09

30. 6

74. 65

96. 73

34. 0

85. 03

97. 82

40. 8

92. 74

98. 54

47. 6

97. 78

97. 78

51. 41

0. 00

0. 00

2. 89

7. 55

58. 55

6. 8

13. 23

70. 18

10. 2

19. 00

76. 92

13. 6

24. 43

81. 00

17. 0

71. 1

29. 82

83. 91

20. 4

35. 00

85. 92

23. 8

2 82

39. 91

87. 22

27. 2

44. 71

88. 23

30. 6

49. 40

89. 09

34. 0

58. 04

90. 32

40. 8

65. 79

90. 91

47. 6

/ %

/
C

x 1

y 1

/ 101. 325kpa

72. 95

91. 00

54. 4

80. 28

89. 08

61. 2

85. 02

85. 02

62. 79

0. 00

0. 00

6. 45

0. 48

4. 62

6. 8

5. 06

33. 50

10. 2

9. 47

48. 20

13. 6

13. 67

56. 98

17. 0

17. 96

63. 58

20. 4

22. 13

68. 37

23. 8

104. 4

26. 30

71. 88

27. 2

30. 32

74. 56

30. 6

34. 30

76. 61

34. 0

41. 88

79. 38

40. 8

48. 86

80. 02

47. 6

55. 67

80. 19

54. 4

62. 43

79. 71

61. 2

71. 89

71. 89

67. 32

0. 00

0. 00

12. 64

0. 84

4. 81

13. 6

4. 36

20. 42

17. 0

8. 21

32. 57

20. 4

11. 72

40. 50

23. 8

137. 8

15. 20

46. 12

27. 2

18. 59

50. 46

30. 6

21. 97

54. 02

34. 0

28. 42

58. 74

40. 8

34. 26

61. 07

47. 6

39. 88

61. 65

54. 4

47. 02

61. 39

61. 2

56. 30

56. 30

64. 4

0. 00

0. 00

22. 39

1. 32

3. 85

23. 8

4. 51

12. 74

27. 2

28 3

7. 62

20. 62

30. 6

171. 1

10. 70

26. 98

34. 0

16. 06

32. 99

40. 8

22. 16

33. 59

47. 6

29. 46

29. 46

50. 90

: : H H R eum er et al . J . Chem . E ng . Dat a , 1960, 5: 44;

1at m = 101. 325k pa .

A : ( mixed model type correlation)

[ 2]

( 89) , K
K = y / x =
0

f ,

( 819)

( ) , V L

0
f 0 / p =

, ^
van der Waals ( RK ) ,
Scat chardHildebrand ,
Chao Seader
B : ( EOS )

:
K = y / x =

/ ^ V

( 88a )

B ,
, ( T c , p c , ) , ,
( ) ,
, ,
, ,
, 84
[ 3]

P rausnitz

A, B
8-4 AB

p VT x ,

;
;

2 84

( ) ;
;

;

V ;

f V ,

8. 3. 1 Chao - Seader -
Chao Seader
^
0

,
0
, Chao Seader

,
0

K=

( 819)

:
1. ( ) ^ i
Redlich Kwong ( RK ) ( 3154) ( 2144) ( 2
148) ( 2149) , :
ln ^

2
B
A B
A
Bp
= ( Z - 1) - ln ( Z - Bp ) 2 1+
ln
B
B
Z
A B

( 820)

Z
B=

y B , B = 0. 0867

T c
p cT
2. 5

A=

y A ,

T c
0. 4278
2. 5
p c T

A =

A ( atm ) -

1
2

( 821)
0. 5

( 822)

, Bi atm - 1

2. i
R obins on Chao ( 1971)

[5]

M affiolo ( 1975)

[ 6]

Scat chardHildebrand :
= exp[ V ( -

) / R T + ln
+
1-

=
V / x V

( 823)
( 824)

, x , V

V 85 V
28 5

 , , , R T ln = , V
( 25
C) , H 2 , CH 4 ,
C 2 H 6 , V , 25
C ,

3. i
0

P tz er ,

85

/ ( J / cm 3 )
6. 65

1
2

V/ cm 3 / mol
31

11. 62

52

0. 1064

12. 38

68

0. 1538

13. 09

84

0. 1825

13. 77

105. 5

0. 1953

13. 77

101. 4

0. 2104

14. 36

117. 4

0. 2387

14. 36

116. 1

( 0. 195)

14. 36

123. 3

0. 2927

14. 87

131. 6

0. 3403

15. 20

147. 5

0. 3992

15. 45

163. 5

0. 4439

15. 65

179. 6

0. 4869

15. 80

196. 0

0. 5210

15. 94

212. 2

0. 5610

16. 04

228. 6

0. 6002

16. 14

244. 9

0. 6399

16. 20

261. 3

0. 6743

16. 29

277. 8

0. 7078

16. 35

294. 1

0. 7327

16. 43

310. 4

0. 0949

12. 44

61

0. 1451

13. 16

79

0. 2085

13. 83

95. 3

0. 2575

13. 83

91. 2

0. 2230

13. 83

93. 8

0. 1975

13. 83

95. 4

1, 3

0. 2028

14. 20

88. 0

0. 2198

14. 42

110. 4

( 0. 206)

14. 42

107. 8

( 0. 209)

14. 42

109. 0

2 86

21

( 0. 200)

14. 42

108. 7

31

( 0. 149)

14. 42

112. 8

22

( 0. 212)

14. 42

106. 7

0. 2463

( 15. 14)

125. 8

0. 2051

16. 59

94. 7

0. 2346

16. 06

113. 1

0. 2032

16. 78

108. 7

0. 2421

/ ( J / cm 3 )
16. 02

1
2

V/ cm 3 / mol
128. 3

0. 2130

18. 74

89. 4

0. 2591

18. 25

106. 8

0. 2904

18. 39

121. 2

0. 3045

18. 05

123. 5

0. 2969

17. 94

124. 0

0. 2936

17. 98

123. 1

1cal= 4. 1868J .
0
( 0)
( 1)
lg
= lg

+ lg

( 825)
(0)

, , , lg
( 1)
lg

, :
( 0)
lg

= A 0 + A 1 / T r + A 2 T r + A 3 T 2r + A 4 T 3r + ( A 5 + A 6 T r
2

+ A 7 T r ) p r + ( A 8 + A 9 T r ) p r - logp r
( 1)
lg

= -

( 826)

4. 23893 + 8. 65808T r - 1. 22060/ T r

3

3. 15224T r - 0. 025( p r -

0. 6)

( 827)

( 826) A 0 , A 1 , , A 9 86,
, 86 , = 0,
(1)

lg
( 0)
, lg

Gragson Streed

[ 4] , 86
86 ( 826)

( = 0)

A0

2. 05135

1. 36822

1. 50709

A1

- 2. 10899

- 1. 54831

2. 74283

A2

A3

- 0. 19396

0. 02889

A4

0. 02282

- 0. 01076

- 0. 02110
0. 00011
0

28 7

A5

0. 08852

0. 10486

0. 008585

A6

- 0. 02529

A7

- 0. 00872

A8

- 0. 00353

A9

0. 00203

Ch aoSeader ,
:
( 1) ( )
: 0. 5< T r < 1. 3( , 260
C )
: 6. 89M Pa , 80%
( 2)
: - 73260
C , 93%
: 55M Pa
( 3) ( ) < 0. 3, < 0. 2
( 4) K , < 0. 5, K
, > 0. 5
ChaoSeader , 810

810

ChaoSeader
2 88

8. 3. 2

,
..

[ 7]
Soave , Peng R obinson , BWR , BWR S Plocker L ee K es ler ,

^
BWR BWR S ,
,
Soave Pen g R obins on , ,
, ,
( N 2 , O 2 , CO CO 2 ) , Daubert , Grabos ki Danner ( 1978) [ 8] 9
, , Soave
K ChaoSeader ,
, BA SIC
8. 2 2026. 5kP a( 20at m) ( 1) ( 2)
, Soave ,
:

T c/ K

p c / kPa

C3 H 6

365

4620

iC4 H10

408. 1

3648

Vc / cm 3 . mol -

Zc

181

0. 275

0. 148

8. 4080

0. 0569

263

0. 285

0. 176

13. 3138 0. 0806

:
3

Z -

Z + ( A - B - B ) Z - AB = 0
2

( 1)

A = a
p/(R T )
B = bp / ( R T )
R = 0. 08205

1 = [ 1 +
0. 7113( 1 -

T / 365) ] 2

2 = [ 1 +
0. 7533( 1 -

T / 408. 1) ]

( a ) = ( y 1

a 1 1 + y 2

a 2 2 ) 2

b = y 1 b1 + y 2 b2
ln ^ =

b
(Z b
+

1) - ln Z 1 -

a b
bRT b -

b
V

a ln 1 + b
V
a

( 2)
28 9

 : p , x , y ; ( 1)
, ( y ) , ( x ) ; Z L Z V
( 2) , K =
y ;

/ ^ V y = K x ,

y -

= 1

1 >
,

x1

V
2

y1

ZV

ZL

T
373. 42

0. 6636

0. 1026

0. 9005

0. 7538

1. 5060

0. 7538

0. 1

367. 00

0. 1606

0. 6793

0. 0993

0. 8823

0. 7403

1. 4165

0. 6904

V
1

L
1

L
2

x1

y1

ZV

ZL

0. 2

T
360. 84

0. 3067

0. 6924

0. 0963

0. 8664

0. 7281

1. 3286

0. 6311

0. 3

354. 93

0. 4376

0. 7024

0. 0935

0. 8525

0. 7168

1. 2434

0. 5759

0. 4

349. 34

0. 5535

0. 7100

0. 0909

0. 8401

0. 7063

1. 1626

0. 5256

0. 5

344. 05

0. 6553

0. 7154

0. 0885

0. 8290

0. 6962

1. 0866

0. 4799

0. 6

339. 06

0. 7445

0. 7190

0. 0862

0. 8187

0. 6865

1. 0157

0. 4385

0. 7

334. 39

0. 8221

0. 7211

0. 0839

0. 8093

0. 6772

0. 9504

0. 4016

0. 8

330. 00

0. 8898

0. 7246

0. 0817

0. 8003

0. 6687

0. 8901

0. 3683

0. 9

325. 89

0. 9486

0. 7215

0. 0796

0. 7920

0. 6590

0. 8348

0. 3387

1. 0

322. 02

0. 7202

0. 0775

0. 7840

0. 6502

0. 7839

0. 3121

V
1

10 ! X Y DAT A WIT HSOAV E E Q N

20 O PT ION BASE 1
30 DIM X ( 2) , Y ( 2) , Z ( 2) , F ( 2) , G ( 2) , H ( 2)
40 DA T A . 8, . 2, . 9, . 1
50 M A T RE A D X, Y
60 R E A D P , R
70 DA T A 20, . 08205
72 DIM B( 2) , A( 2)
74 DA T A . 0569, . 0806
80 M A T RE A D B
90 INP U T T
100 A ( 1) = 8. 4078 ( 1+ . 7113 ( 1- ( T / 365) . 5) ) 2
110 A ( 2) = 13. 3125 ( 1+ . 7533 ( 1- ( T / 408. 4) . 5) ) 2
120 FOR I= 1 T O 2
130 Z( I) = X( I)
140 NE XT I
150 GOSU B 460
2 90

V
2

L
1

L
2

160 Z= . 05
170 GOSU B 500
180 DISPZL = ; Z
190 GOSU B 600
200 FOR I= 1 T O 2

210 G( I) = H ( I) !

L
i

220 Z( I) = Y ( I)
230 NE XT I
240 GOSU B 460
250 Z = 1
260 GOSU B 500
270 DISPZV= ; Z
280 GOSU B 600
290 FOR I = 1 T O 2
300 F ( I) = H ( I) !

V
i

310 K ( I ) = G ( I ) / F ( I )
320 Y ( I) = K ( I) X ( I)
330 NE XT I
340 S= Y ( 1) + Y ( 2)
350 DISPS = ; S
360 FOR I = 1 T O 2
370 Y( I) = Y( I) / S
380 NE XT I
390 DISP U SIN G 400; X ( 1) , Y ( 1) , T , F ( 1) , F ( 2) , G ( 1) , G ( 2)
400 IM A GE D. D , X . D . DDD , X , DDD . D. X , D . DDD, X , D . DDD , X , D . DDD , X ,
D. DDD
405 IF ABS( S - 1) < = 0. 0001 T HE N 420
410 GOT O 90
420 E ND
460 ! SR F OR SOA VE COE FFS
470 A = ( Z ( 1) A ( 1) . 5+ Z ( 2) A ( 2) . 5) 2
480 B = Z ( 1) B( 1) + Z ( 2) B( 2)
490 R E T U R N
500 ! SR F OR COM PR E SSIBIL IT Y Z
510 C= A P / R 2/ T 2
520 D = B P / R / T
530 F 1= Z 3- Z 2+ ( C - D - D 2) Z - C D
29 1

540 F 2= 3 Z2- 2 Z+ C- D- D2
550 H 1= F 1/ F 2
560 IF ABS ( H 1/ Z) < = . 0001 T H E N 590
570 Z = Z - H 1
580 GOT O 530
590 R E T U R N
600 ! SR F OR FU GACIT Y CO EF FS
610 FOR I= 1 T O 2
620 V = Z R T / P
630 H ( I ) = - L OG ( Z ( 1- B / V ) ) + B ( I ) / B ( Z - 1)
640 H ( I) = H ( I) + L OG( 1+ B/ V ) / B/ R / T ( A B( I) / B- 2 ( Z( 1) ( A ( I) A ( 1) ) . 5
+ Z ( 2) ( A ( I) A ( 2) ) . 5) )
650 H ( I) = E XP ( H ( I) )
660 NE XT 1
670 R E T U R N
680 E ND

8 . 4
, (
)
,
,
,
, , ,
,
,

Gibbs Duhem ,

8. 4. 1 Gibbs - Duhem
( 3131) , Gibb s , p , T ,

x dG

x d =

Gibbs Duhem , ,
dG = d = R T dlnf^
,
2 92

( 828)

 x dln ^f

= 0 ( T , p )

( 829)

0
0
0
a = ^
f / f , T , p , f , f^ = a f ( 829) ,

x dlna

= 0

( 830)

a = x , ( 830) ,

x dlna

x dln + x dlnx

= 0

x dlnx = 0,

x dln =

0 ( T , p )

( 831)

Gibbs Duhem :

ln
xj

= 0
T, p, x

( 832)

Gibbs Duhem , ,
Gibbs
Duhem :
x1

ln 1
x1

ln2
x1

+ x2
T, p

= 0

( 833)

T, p

, Gibbs Duh em
, F = C - P + 2, 2, T , p ,
, ,
( 833) ,
, ,

8. 4. 2
lg1 x 1 lg2 x 1 ,
,
( 1) ,
,
( 2) x 1 , ,

x1

ln1
x1

ln2
x1

+ x2
T

= 0
T

ln1
x1

= T

x2
x1

ln2
x1

x 1 = x 2 = 0. 5,
29 3

ln 1
x1

ln2
x1

= T

x 1 = 0. 5 , ,
( 3) , 1/ 4; ,
, van L aar : van L aar
:
A
Ax 1
1+
Bx 2

lg1 =

B
Bx2
1+
Ax 1

, lg2 =

x 1 = 0. 5 , x 1 = x 2 ,
2

lg1 =

A
1+
B

AB
=
2
( A + B)

B A2
=
( A + B) 2

lg2 =

B
1+
A

:
lg 1
lg2
AB
=
=
A
B
( A + B) 2
, A = B , 1/ 4 ,
, A= 2B , 2/ 9, ,
( x 1 = x 2 = 0. 5 ) , ,
( 4) lgx , ,
; ( ) ,
( ) x 1 ( ln1 / x 1 ) T + x 2 ( ln2 / x 1 ) T = 0, (
ln1 / x 1 ) T 0, ( ln2 / x 1 ) T 0( ) , ( ln1 / x 1 ) T
= 0, ( ln2 /

x 1 ) T = 0, , ( )

( 5) lgx van L aar , ( lg1 )

1/ 2

( lg2 )

1/ 2

, ;

van Laar , van L aar ,

( lg1 )
1

1
2

= A

1
2

1-

lg2 / B

1
2

1
2

= A -

A
B

1
2

( lg2 )

1
2

( 834)

( lg1 ) 2 ( lg2 ) 2 , van L aar ,

1

, ( lg1 ) 2 ( lg2 ) 2 ,
( 6) lgx
lg2 x 1 811 , lg1 x 1

x = 1
1

( lg1 ) dx 1

x = 0
1

d( x 1 lg1 ) = x 1 dlg1 + ( lg1 ) dx 1

2 94


( lg1 ) dx 1 = d( x 1 lg1 ) - x 1 dlg1

x = 1
1

x = 1
1

x1 = 0

x = 0
1

( lg1 ) dx 1 = x 1 lg1

x = 0
1

x1 = 1

x 1 dlg1

x 1 = 0, x 1 lg1 = 0; x 1 = 1 lg1 = 0,
x 1 lg1

x1 = 1

= 0,

x1 = 0

x = 1
1

x = 1
2

x = 0
1

x = 1
1

x = 1
2

( lg1 ) dx 1 = -

x = 0
1

x 1 dlg1

( 835a )

x 2 dlg2

( 835b)

lg2 x 2 ,
x

( lg2 ) dx 2 = = 0

x = 0
2

812

811 lg1 x 1

812 lg2 x 1

lgx ,

x = 1
1

( lg1 ) dx 1 -

x = 0
1

x = 1
1

( lg2 ) dx 1 = 0

x = 0
1

( 835)

x = 1
1

x = 1
1
x = 0
1

( lg1 ) dx 1 = -

( lg2 ) dx 1 = -

x = 0
1

x = 1
1

x = 1
1
x = 0
1

x 1 dlg1

( lg2 ) dx 2 =

x = 0
1

x = 1
1

x 2 dlg2

x = 0
1

x = 1
1
x = 0
1

( lg1 ) dx 1 -

x = 1
1
x = 0
1

( lg2 ) dx 1 = -

x = 1
1

( x 1 dlg1 + x 2 dlg2 )

x = 0
1

Gibbs Duhem ,
x jdlgj = 0, x 1 dlg1 + x 2 dlg2 = 0,
j
29 5

x = 1
1
x = 0
1

( lg1 ) dx 1 -

x = 1
1
x = 0
1

( lg2 ) dx 1 = 0

( 836)

8. 4. 3
8. 4. 2 ,
Gib bs Duhem ( 836)

x = 1
1
x = 0
1

lg

2
dx 1 = 0
1

( 837)

lg( 2 / 1 ) x 1 , 813 A B ,
( 837) ,

813 814 ( 1) ( 2) x 1 y 1

83 ( 1) ( 2) ; 25
C ,
39. 76
C 54. 81
C , 87

[ ] 814 39. 76
C 25
C 54. 81
C ,
54. 81
C 25
C 39. 76
C ,
, ( 837) ,
0

= py / p x , 25
C :
p y1
5572. 8 0. 474
1 = 0 =
= 2. 762
7839. 3 0. 122
p 1x 1
25
C 7839. 3Pa
2 =

p y2
5572. 28 0. 526
=
= 1. 057
0
p 2x 2
3159. 7 0. 878

25
C 3159. 7Pa
ln
2 96

2
1. 057
= ln
= 1
2. 762

0. 961

 , 88, 815 25
C 39. 76
C
ln 2 / 1 x 1 , 89
87 ( 1) ( 2)
t= 25
C
x1

y1

12. 2

t = 39. 76
C
x1

y1

47. 4

p / Pa
5572. 8

0. 00

16. 3

53. 1

6026. 1

22. 6

56. 2

32. 0

t = 54. 81
C
x1

y1

0. 00

p / Pa
7239. 4

0. 00

0. 00

p / Pa
15545. 3

6. 89

45. 6

1085. 9

9. 16

47. 53

25717. 8

6386. 1

8. 03

47. 30

11292. 4

11. 57

50. 36

27224. 3

58. 2

6759. 4

9. 94

49. 23

12065. 6

21. 20

57. 23

30517. 4

33. 7

58. 9

6799. 4

14. 52

54. 31

13252. 2

23. 75

58. 28

29850. 8

43. 7

62. 0

7026. 1

15. 48

55. 16

13492. 2

26. 71

58. 88

31637. 3

44. 0

61. 9

7039. 4

18. 31

57. 19

13918. 8

36. 98

61. 51

32997. 2

57. 9

68. 5

7306. 0

22. 08

58. 74

14305. 5

47. 88

65. 54

34210. 4

t = 25
C
84. 9

83. 0

7786. 0

23. 33

t = 39. 76
C
58. 76
14478. 8

61. 02

t = 54. 81
C
71. 02
35277. 0

26. 81

60. 30

14692. 1

91. 45

91. 45

36783. 5

36. 77

63. 41

15425. 3

100. 00

100. 00

36690. 2

44. 31

65. 83

15932. 0

48. 08

67. 26

16251. 9

60. 89

71. 89

16705. 2

77. 96

81. 29

17225. 2

93. 90

93. 97

17531. 8

95. 52

95. 52

17518. 5

100. 00

100. 00

17305. 2

88 ( 1) ( 2)
t = 25
C

t = 39. 76
C

0. 122

2
1
- 0. 961

0. 163

t = 54. 81
C

0. 0689

2
1
- 1. 556

0. 0916

2
1
- 1. 337

- 0. 852

0. 0803

- 1. 459

0. 1157

- 1. 187

0. 226

- 0. 572

0. 0994

- 1. 302

0. 2120

- 0. 747

0. 320

- 0. 176

0. 1452

- 0. 1074

0. 2375

- 0. 642

0. 337

- 0. 128

0. 1548

- 1. 033

0. 2671

- 0. 510

x1

ln

x1

ln

x1

ln

t = 25
C

t = 39. 76
C

t = 54. 81
C

x1

2
ln
1

x1

2
ln
1

x1

2
ln
1

0. 437

0. 116

0. 1831

- 0. 914

0. 3698

- 0. 143

29 7

 815 ( 1) ( 2) 816 lnx 1

0. 440

0. 425

0. 2208

- 0. 743

0. 4788

0. 131

0. 579

0. 450

0. 2333

- 0. 672

0. 6102

0. 411

0. 830

0. 767

0. 2681

- 0. 551

0. 9145

0. 859

0. 3700

- 0. 220

0. 4431

- 0. 013

0. 4808

0. 075

0. 6089

0. 375

0. 7796

0. 666

0. 9390

0. 859

0. 9552

0. 871

89
t/
C

ln
0

2
dx 1
1

ln
0

2
dx 1
1

25

0. 0856

0. 590

14. 5

39. 76

- 0. 0254

0. 620

- 4. 5

54. 81

- 0. 0299

0. 653

- 4. 6

89 25
C , 39. 76
C
54. 81
C 39. 76
C ln1 x 1 , 816, ln 2 x 1 = 0
, x 1 = 0 ln 2 , Raoult x 1
2 98

dln 2
= 0
dx 1
x 1 = 0. 05 , ln 1 x 1 ,
= 0. 05 , ln 2 x 1 , x 1 = 0. 05 ,

, , : 39. 76
C 25
C
39. 76
C ,
, x 1 = 00. 2 ,

8. 4. 4
,
, :

2
lg
dx 1 = 1

x = 1
1

x = 0
1

x = 1
1
x = 0
1

H S
dT
2. 303R T 2

( 838)

, H S , , J . mol - 1
2

H S = H -

x H

( 839)

= - 1

, H , H , J . mol

- 1

H S
2 dT = 0, ( 338)
x = 0 2. 303R T
1
( 337) , ,

( 838) , , dT = 0,

x = 1
1

( 837) , ( 838) ( 838) ,

H S , H erringt on

[ 9]

, :
lg

2
x 1 ( 813 ) , D ,
1

D=

( A) - ( B )
100
( A) + ( B )

( 840)

D , H errington D J , J

, ,

T 1- T 2

( 841)

T 1 T 2 1 2 ; , 817

T m ( K ) x 1 = 0 x 1 = 1 , J :
J = 150

Tm

( 842)

150 Herrington
29 9

 817

: ( D - J ) < 10,
H erringt on , ,

8. 5
8. 5. 1 Henr y
1803 W . Henry CO 2 , N 2 O , O 2 , N 2 H 2 S ,
, , Henry
,
p2 = H x2

( 843)

p 2
, x 2 , H
, Henry
H enry
,
; ,
25
C ,
818 ,
818 ( )
( 25
C)

x , Henry

H enry , H enry
H , 25
C , H
527. 6 10 5 Pa , p 2 = 1. 01325 105 Pa , ( 843) , ,
H
3 00

H enry , ,
,

8. 5. 2 H en r y
H enry ( 844) , p 2
f^ 2

^f

= H x2

( 844)

f^ 2 = H x 2 p 2 = H x 2 , Henry H
, H , H
819 , CO 2
, 25700 105 Pa
, Krit chevsky
K asarnovs ky Henry
ln

^f

x2

= lnK +

p V2
( T )
RT

( 845)

V 2 ; K Henry
Henry ,
ln ^
f 2 / x 2 p , , V 2 / R T , lnK
V 2 820 Henry

819 CO 2

820 CO 2

CO 2 ( 819) , ln ^
f 2 / x 2 p
V 2 H enry K : 50
C V 2 = 33.
3

4cm / mol , K = 2843. 7 10 P a ; 75

C V 2 = 31. 4cm / mol , K = 4085. 6 10 Pa
30 1


H enry

8. 5. 3
, 1at m 25
C
, ,
Prausnit zShair
, , yen
M cketta , ( )
1. P rausnitz-Shair

[ 10] , [ 11 ]

,
,
P rausnitz Sh air :
( ) ( ^f G2 = 1) , ;
( ) ,
, ( 100kPa )

G 2 , G 2 ,
L

G 2 f2 ( 3138) ( 3139) , ( 1)

G = G - G = RT ln
L
2

G
2

L
2

^f

G
2

= RT lnf L2

( 846)

( 733) , ( )
L

G = G2 - G2 = RT ln2 x 2

( 847)

2 G G2 = GL2 , G G ,

G + G = 0

( 848)

( 846) ( 847) ( 448) :

RT lnf

L
2

+ R T ln2 x 2 = 0

- lnx 2 = lnf

L
2

+ ln2

( 849)

( 772) ,

V 2 ( 1 - 2 )
- lnx 2 = ln f +
RT
L
2

3 02

2
2
1

( 850)

 x 2 T , 100kP a
L

; f 2 , V 2 2
; 1
;

x 2 0,

(
1

1)

L
2

T r 821
L

f2 / p c T r
:
f L / p c = 0. 827 + 6. 403lnT r 1 T r 2. 5
( 851a )
f L / p c = 0. 935T r 6. 5 T r < 1 ( 851b)
821 1 at n

, ,
( 850) ,
V L2
2 , 810

10
1 85 ( 7155) ( 850) ,

1
L
, V 2 ( 1 T
2
2 ) , 25
C V 2 , 2 , 1 ,
( 7114) ( 849) 2 , , ln2

810 ( 25
C)

H2

P rausnit zShair
3
2 / ( J/ cm )
6. 65

1
2

Y enM cket ta

VL2 / cm 3 / mol
31. 0

2 / ( J / cm )
7. 84

1
2

VL2 / cm 3 / m ol
37. 3

Ar

10. 9

57. 1

10. 23

55. 0

N2

5. 28

31. 0

7. 84

37. 3

O2

8. 18

57. 1

10. 2

55. 0

CO

6. 40

32. 4

6. 55

40. 0

Kr

13. 1

65. 0

12. 1

52. 0

Xe

12. 9

45. 8

Rn

14. 0

70. 0

13. 9

60. 0

CO 2

12. 3

55. 0

12. 3

62. 0

CH 4

11. 6

52. 0

10. 7

50. 7

C2 H 6

13. 5

70. 0

13. 0

70. 0

N 2O

12. 7

51. 0

C2 H 4

13. 5

65. 0

12. 9

50. 0

Cl 2

17. 8

74. 4

17. 6

55. 0

84 CO 2 25
C , p CO 2 = 101. 325 kPa CS2
50% ( ) CS 2 50% ( ) Henry
30 3

[ ] ( 850) ,
L

lnx 2 = lnf

V2 ( 2 - )
+
RT

L
2

CO 2 T r = 298. 2/ 304. 2= 0. 98 ( 851)

L

f2
6. 5
6. 5
= 0. 935T r = 0. 935( 0. 98) = 0. 82
pc

f 2 = 0. 82p c = 0. 82 74 10 = 60. 7 10 Pa
, CO 2 , , ,
CO 2 ,
3

= C S2 = 20. 5( J / cm )

1
2

( 2 -

) = 67J / cm

55 67
= 4. 0943 + 1. 4852
8. 314 298. 2

lnx 2 = ln60 +
= 5. 5795

- 3

x 2 = 3. 77 10
- 3

x 2 = 3. 28 10

H enry
H = p / x 2 = 1/ 3. 77 10-

= 268. 5 105 Pa

CO 2 :
3

T = 18. 25( J / cm )

1
2

(
2 -

) = 35. 4J / cm

55 35. 4
= 4. 0943 + 0. 7848
8. 317 298. 2

lnx 2 = ln60 +

= 4. 8749
- 3

x 2 = 7. 636 10

H = 132. 7 10 5 Pa
, CO 2 50% ( ) 50% ( ) CS2
:
VLm x = x CS 2 V LCS 2 + x T V LT = 0. 5 61 + 0. 5 107 = 84cm 3 / mol
CS

0. 5 61
= 0. 363,
84

0. 5 107
= 0. 637
84

= 0. 363 20. 46 + 0. 637 18. 25 = 19. 03( J/ cm 3 )

( 3 04

) = 45. 29J/ cm

1
2

lnx 2 = ln60 +

55 45. 29
= 4. 0943 + 1. 0050
8. 314 298. 2

= 5. 0993
- 3

x 2 = 6. 100 10

H = 166. 7P a
2. Yen -M ckett a
Y en M cketta , ( )
, Prausnit zShair ,
, ( 769)
:
E

G = ( x 1 V 1 + x 2 V 2 ) ( C 11 + C 22 -

2C 12 )

( 763)
L

ln 2 = V2 ( C 11 + C 22 -

2C 12 )

2
1

/ RT

7. 2. 1 ,
C 11 = 21 , C 2 2 = 22 , C 12 = 1 2
( ) , Yen M ckett a
2

C1 2 = 2 ( 1 + )

1
2

( 852)

, ( 1) ( ) ,
( 2) , 2
ln2 = V L2 21 + 22 -

2
1

22 ( 21 + ) 2

/ RT

( 853)

- lnx 2 = lnf

L
2

V 2 21 + 22 -

22 ( 1 + )
RT
L

1
2

2
1

( 854)

, f 2 V 2 , 2
1 , 1. 01325P a x 2 f

L
2

822

,
f L2
ln
= 0. 4551 + 1. 5077ln T r
pc
1. 5 T r 2. 5

( 855a )

f2
ln
= pc

0. 1891 + 2. 9866lnT r

( 855b)

1 < T r < 1. 5
L

V 2 , 2 ( 854)
L

14 2 V 2 810 , 811 10 ( )
1
30 5

[ 11]
8-11
1

/ J/ cm 3

- 5. 73

15. 24

3. 66

18. 21

15. 39

18. 82

17. 45

18. 93

11. 87

19. 44

15. 88

19. 44

14. 06

19. 74

1, 2

35. 60

21. 48

56. 27

21. 89

81. 02

23. 63

1 / ( J / cm )

1
2

85 Yen M cketta 25
C , 101. 325k Pa CH 4

CH 4 p c = 4. 64M Pa, T c = 190. 65K

[ ] CH 4 ( 2) , ( 2) ,
L

( 854) 25
C f 2 ,
T r = T / T c = ( 25 + 273. 15) / 190. 65 = 1. 56
( 855a )
L

f2
ln
= 0. 4551 + 1. 5077ln( 1. 56) = 1. 1256
pc

L
2

= 3. 082p c = 3. 082 4. 641M P a = 14. 30M P a

L

810 CH 4 2 V 2 :
3

2 = 10. 80( J/ cm ) 2 , V 2 = 50. 7cm / mol

811 25
C 1 :

1 = 19. 74( J / cm ) 2 , = 14. 06J/ cm

= 1,

- lnx 2 = ln141. 16 +

50. 7

( 19. 74) + ( 10. 80) - 2( 10. 80) [ ( 19. 74) + 14. 06]
8. 314 ( 25 + 273. 15)

1
2

= 6. 2678
- 4

x 2 = 18. 96 10
- 4

x 2 = 18. 35 10

E OS ,
, [ 12] , [ 13]
3 06

8 . 6
,
,

8. 6. 1
822 824 [ 10 ] , :
, ,
; , 40% (
) ( 125. 7
C ) ,
12. 7% ( ) , 59. 7% ( ) (
822)

822

:
N F = N + N = 1, 2,
I

( 856a )

N , N

N = x N

+ x N = 1, 2,

( 856b)

x , N
86 1mol 3mol , 80
C,

[ ] ( 822)

x = 0. 107, x = 0. 593

30 7

 823

x H 2 O = 1 -

1mol = x N

+ xN

= 0. 107N

+ 0. 593N

3molH 2 O = ( 1 - x ) N

+ (1 -

x)N

= 0. 893N

+ 0. 407N

= 2. 82mol, N

= 1. 18mol

, ( ) ,
,
;
; ,

f^ ( T , p , x ) = f^ ( T , p , x )
,

x ( T , p , x ) f ( T , p ) = x ( T , p , x ) f ( T , p )
,

x ( T , p , x ) = x ( T , p , x )

( 857)

: x 1 , x 2 , , x ; x 1 , x 2 , , x :

= 1

= 1

= 1

( 858)

= 1

( 857)
, ( 858) (
) ( 87) M argu les
, ( 857) :
3 08

A( 1 - x )
x exp
RT

A( 1 - x )
= x exp
RT

( 859a )

x exp

V (

) ( 1 RT

2 )

= x exp

V (

) ( 1 RT

2 )

( 859b)

87 van L aar 37. 8

C 10at m
van Laar
A = 2. 62, B = 3. 02
[ ]

Ax 1
1+
B ( 1 - x 1 )

B x2
1+

A(1 - x2 )

x = x exp

x = x exp

Ax 1
1+
B ( 1 - x 1 )

Bx 2
1+

A(1 - x2 )

= x exp

= x exp

x 1 + x 2 = 1

x1 + x2 = 1

= x 1 1

= x 2 2 ( 2)

( 1)

( 3)
( 4)

1, 2, :

( 1) x 1 ;

( 2) ( 1) x 1 , ( 3) x 2 ;

( 3) ( 2) x 2 ;
( 4) , x 1 x 2 ( 4) , x 1
,
, :

x 1 = 0. 118, x 1 = 0. 925
x 2 = 0. 882, x 2 = 0. 075
( 857) , ,
, Gibbs
, Gibbs GI M :
IM

= x 1 G1 + x 2 G2 + RT ( x 1 lnx 1 + x 2 lnx 2 )

( 860)

x 1 x 2 1, lnx 1 , lnx 2 0, ( 860) , ,

Gibbs Gibbs , 824
, Gibbs G:
IM

G= G

+ G

( 861)

Gibbs G , ,
M argules ,
E

G = Ax 1 x 2

( 862)

G = x 1 G1 + x 2 G2 + R T ( x 1 lnx 1 + x 2 lnx 2 ) + Ax 1 x 2

( 863)

A > 0, ,
30 9

 A b c, 824

824 ( ) ( )
( A = 0) ( A 0) Gibbs

Gibbs , c
x x , G ;
x , x Gibbs Gibbs
, 824 1 x x ,
, x x ( 857) ,
( 859a )
( )
,
2

d G > 0 ( M , T p )

( 864)
2

Gibbs ? ( G/ x ) T , p > 0,
2

, ; ( G/ x ) T , p < 0, T x 1 ,
;

G/ x 2 = 0 , G x 1 ,

T uc ,
= 0 T = T uc x 1

G
2
x1

T, p

> 0 T > T uc x 1

( 865a )

, T lc ,
= 0 T = T l c x 1

G
x 21

T, p

> 0 T > T l c x 1

( 865b)

M argules , ( 863) ,
2

G
x 21

T >
3 10

2A x 1 x 2
R

=
T, p

RT
x 1x 2

2A

( 866)
( 867a )

G
2
x1

> 0, ;
T, p

T <

2A x 1 x 2
R

( 867b)

G
x 21

< 0, ;
T, p

2Ax 1 ( 1 - x 1 )
R

T =

( 868)

( ) M argules ,
x 1 = x 2 = 0. 5 ,
T uc =

A
2R

( 869)

M argules ( , ( 865b) , ( 866)

) , M argules

E

( 866) ( 869) M argules G

,
, 1,
, ,

8. 6. 2
,
, van L aar M argules NR T L
, Wilson ,
( 1) van L aar
van L aar ,
, , van L aar ,
8
( )

( )

( )

( )

( )

( )

( )

( )

1 x 1 = 1 x 1
2 x 2 = 2 x 2
(
)

( )

x1 + x 2 = 1
x (1 ) + x (2 ) = 1
lg(1 ) =

( )

lg2 =

A
Ax (1 )
1+
B x (2 )
B
B x (2 )
1+
( )
Ax 1

, lg(1 ) =

, lg2 =

( )

A
Ax (1 )
1+
B x (2 )
B
B x (2 )
1+
( )
Ax 1

8 10 (1 ) , (1 ) , (2 ) , (2 ) , x (1 ) , x (1 ) , x (2 ) , x (2 ) , A B
31 1

( )

( )

x1 , x1

, 8 A B :
x (1 )
x (1 )
lg( x (1 ) / x (1 ) )
- 2
( ) +
( )
( )
( )
x2
x2
lg( x 2 / x 2 )
( )
( )
( )
( )
( )
(
)
x1
x1
2x 1 x 1 lg( x 1 / x 1 )
( ) +
( )
( )
( )
(
)
( )
x2
x2
x 2 x2
lg( x 2 / x 2 )

A
=
B

( 870a )

x (1 )
lg ( )
x1

A=

1
(
)
Ax 1
1+
( )
Bx 2

( 870b)

1
A x (1 )
1+
Bx (2 )

( 870a ) ( 870b) , x (1 ) x (1 ) , x (2 ) , x (2 ) , ( 8
70a ) , van L aar A/ B, ( 870b)
A , A , B
( 2) M argules
M argules , 8
( )

( )

( )

( )

( )

( )

( )

( )

1 x 1 = 1 x 1
2 x 2 = 2 x 2
(
)

( )

x1 + x 2 = 1
x (1 ) + x (2 ) = 1
lg(1 ) = [ x (2 ) ] 2 [ A + 2x (1 ) ( B - A ) ]
( )

( )

( )

( )

( )

( )

( )

( )

( )

lg1 = [ x 2 ] [ A + 2x 1 ( B - A ) ]
lg2 = [ x 1 ] [ B + 2x 2 ( A - B ) ]
lg2 = [ x 1 ] [ B + 2x 2 ( A -

B) ]

8 ,
( )

(
)
1

+ x

( )

x1
x2
( )
( )
lg ( ) + x 2 + x 2 lg ( )
x1
x2
( )
( )
3
x1 - x1

( )
1

B - A=

( 871a )

( )

x1
lg ( )
( ) 2
( )
( )
2 ( )
x1
( x 2 ) x 1 - ( x2 ) x 1
A=
2( B - A )
( )
2
( ) 2 ( ) 2
( ) 2
(x2 ) - (x2 )
(x2 ) - (x2 )

( 871b)

, ( 871a ) B - A , ( 871b) A ,
B
( 3) NR T L
N RT L , 8
(1 ) x (1 ) = (1 ) x (1 )
( )

( )

( )

( )

2 x 2 = 2 x 2
(
)

( )

( )

( )

x1 + x 2 = 1
x1 + x2 = 1
(
)
1

ln = ( x
3 12

( )
2

21

( )
1

G2 1
(
)
+ G2 1 x 2

(
)
2

1 2 G 12
( )
+ G12 x 1

( )
1

ln = ( x

( )
2

( )
2

(
)
1

( )
2

( )
1

ln = ( x
ln = ( x

21

(
)
2

G 12
+ G12 x (1 )

( )
2

G12
( )
+ G12 x 1

( )
1

G2 1
( )
+ G2 1 x 2

12

) [
12

+
+
+

( )
2

21 G1 2
+ G 12 x (1 )

(x

(
)
1

2 1 G 21
( ) 2
+ G21 x 2 )

(x

( )
1

2 1 G 21
( ) 2
+ G21 x 2 )

G 12 = exp( - 1 2
12 )
G 21 = exp( - 1 2
21 )
8 ,
( )

x1
ln ( ) =
x1

G21

21
( )
( )
( x 1 / x 2 ) + G21

( )

G12

12
( )
( )
( x 2 / x 1 ) + G12

12 G12
( )
( )
1 + ( x 1 / x 2 ) G 12

2 1 G 21
( )
( )
1 + ( x 2 / x 1 ) G2 1

+
2

G 12

12
( )
( )
( x 2 / x 1 ) + G 12

12 G1 2
(
)
( )
2
[ 1 + ( x 1 / x 2 ) G12 ]

G 21

21
( )
( x 1 / x (2 ) ) + G 21

x2
ln ( ) =
x2

( 872a )

( 872b)

21 G21
( )
( )
1 + ( x 2 / x 1 ) G 21

, x (1 ) , x (1 ) , x (2 ) , x (2 ) , 12 , ( 872a )
12,
21 ,
12
21
( 872b)
(
)
88 ( 1) ( 2) 70
C x 1 = 0. 0109,
( )

x 1 = 0. 7756, N RT L
12 ,
2 1 , NR T L
12 = 0. 2
[ ] x (1 ) = 0. 0109, x (1 ) = 0. 7756

x (2 ) = 1 - x (1 ) = 1 ( )

x2
x
x

( )
1
( )
1

( )

= 1 - x1

0. 0109 = 0. 9891

= 1 - 0. 7756 = 0. 2244
( )

x1
0. 7756
0. 7756
= 71. 15,
= 3. 456
( ) =
0. 0109
0. 2244
x2

x (2 )
x (2 )
0. 2244
0. 9891
= 9. 2269,
= 90. 74
( ) =
( ) =
0. 9891
0. 0109
x2
x1
x (1 )
x (2 )
0. 0109
0. 2244
= 0. 01102,
= 0. 2894
( ) =
( ) =
0. 9891
0. 7756
x2
x1
( 872a ) ( 872b) 12 = 0. 2,
exp( - 0. 2
21)

21
0. 01102 + exp( - 0. 2
21 )

ln 71. 15 =
ln0. 2269 =

12 exp ( - 0. 2
12 )
2
[ 1 + 0. 01102exp ( - 0. 2
12 ) ]

21 exp( 0. 2
12)
2
[ 1 + 3. 456exp( - 0. 2
12 ) ]

exp( - 0. 2 21 )
21
3. 456 + exp( - 0. 2 21 )
exp( - 0. 2
12 )

12
90. 74 + exp( - 0. 2
12 )

21 exp ( - 0. 2
21 )
[ 1 + 90. 74exp ( - 0. 2
21 ) ]
31 3

exp( - 0. 2
12)
12
0. 2894 + exp ( - 0. 2
12 )

21 exp( 0. 2 21 )
2
[ 1 + 0. 2894exp( - 0. 2
21 ) ]

12 =
0. 030,
21 =
4. 52
, NR T L 12 ,
21 ,
[ 14 ]

Renon Prausnit z

, ,

8. 7
( )
8. 7. 1

,
: , ( ) ;
, p VT
, ,
, ,
, , ,

, ,
f^ = f^
S

( 873)

f^ p p
S

p f p , ^
f f (
0

) ,
( RT dln f = Vdp ) T

( 373)

V S ,
0

f^

VS ( p - p )
= f exp
RT
S

( 874a )
4

Poynting 100at m( 10 kPa) , 1

f

^f

= p

VS ( p - p )
exp
RT

( 874b)

( 874b) , f^ S , ,
1
3 14

 ^
f y :
V

^f

y p = p

y p

( 86)

( 874b) ( 873) ,
0

VS( p - p )
exp
RT

( 875)

( 875) y
, y
^
V

:
y p
E =
=
p 0

V S ( p - p 0 )
exp
RT
( 876)

, 1, ,
,
1 ,

825 143
K

,^ V 1 ,

1 ,
825 143K ( )
,
( ) ,

( 877)

VS ( p - p )
exp
1
RT

( 878)

( 876)
p 0
y
p

( 879)

, , ,
, ^ ,
V

8. 7. 2 ( )
, , ,
31 5

,
, , ,
,

826( a ) ( d )

826
( a ) , CO 2 40
C ;
( b) : ;
( c ) ;
( d ) 75
C ( 1) ( 2) ( 3) ( 4)

,
f^ V2 = ^
f L2 = f

L
2

( 874) ( 875) ,
3 16

( 880)

y2 ^ 2 p =

0
2

V2 ( p - p 2 )
p exp
RT
0
2

( 881)

y2 = ( p / ^ 2
0
2

0
2

V2 ( p - p 2 )
p ) exp
RT

( 882)

P oynting , ,
, 89 , B
, 10. 13M Pa ( 100atm) ,
1020
100 , ,
Zhus e( 1955, 1960) ,
, ,

812
,

CO 2 ,

tc /
C

pc/ M P a

31. 0

7. 49

9. 2

5. 13

36. 5

7. 36

32. 3

4. 94

CClF 3 ( R 13, )
CH F 3 ( R 23, )

28. 9

3. 71

25. 9

4. 88

96. 8

4. 26

812

/
C

/ M pa

CO 2

40

30

CO 2

5070

6. 133. 4

CO 2

4555

31. 940. 5

CO 2

90

16. 222. 3

CO 2

40

40

CO 2

5060

35. 5

CO 2

40

60

CO 2

40

39

( )

CO 2

040

820

31 7

80150

50. 6

N 2O

50

30. 4

350

10

100

9. 111. 1

CO 2

3255

7. 455. 2

140

11. 112. 2

, ( 882)
, :
( 1) , ,
( 2) 827( d) ,
5. 13M pa ( 49. 7at m )
( 3) 827( b) , ,

, ,

[ 16 , 17]

89
[ ] 400 K

Tc

pc

Vc
3

/ cm 3 . mol -

/K

/ kpa

369. 8

4245. 5

203

0. 281 0. 152 - 0. 2069

748. 4

4053. 0

410

0. 267 0. 302

717. 0

1418. 6

828

878

2897. 9

594

526. 1

4069. 2

0. 227 - 0. 7044

514. 9

2487. 5

0. 430 - 1. 2222

3310. 3

0. 246 - 1. 1467

569. 8

/ cm . mol

Zc

- 1

pS

B j
1

VL
5

/ 1. 013 10 pa

- 2. 746

/ cm . mol-

0. 0717

132. 0

0. 236 0. 708 - 10. 060

0. 00437

294. 1

0. 228 0. 440 - 10. 369

0. 00153

151. 2

T s onopoulos 1, 2
, , , Poyntin g
, 827
B = y 21 B 11 + y 22 B 22 + 2y 1 y 2 B 12
ln ^ 2 =
y2 =

P
( 2y 1 B 12 + 2y 2 B 22 - B )
RT
0
2

V 2 ( P - P 02 )
exp
RT
P

p2

, p / p c > 0. 5T / T c , ,
2. 03M P a , , ,

3 18

( a ) ( b)
827 400K ( N ) ( H ) ( P )
( a ) ( b)

8. 8

, ,
, ,
, ,

, ,
, ,
,

8. 8. 1
, :
( dGt ) T , p = 0

( 883)

G t Gibbs :
d 1
d 2
dm
=
= =
= d

1
2

( 884)

, d d
31 9

, ( 884)
d =
d
( = 1, 2, , m)

( 885)

, ,
,

( dGt ) T , p =

= 0

( 886}

( 885) ( 886) ,
[
] d
= 0

( 887)

GT , p
GT , p =

( 888)

GT , p Gibbs ,
G T , p d= 0

( 889)

GT , p = 0

( 890)

d,

,
= 0 + R T ln( f^ 0 / f 0 )

( 891)

( 0) , (
) ( 891) ( 888) ,
GT , p = G + R T ln
( f^ / f )

( 892)

0
( i= 1, 2, , m ) G Gibbs

, ^
f / f , :
0

G T , p = G + R T ln
a

( 893)

G =

( 894)

, GT , p = 0,
0

(^
f / f ) = exp
0

( f^

G
RT

/ f 0 ) = K

( 895)

G0
RT

( 896)

G = - R T lnK

( 897)

K = exp 0

K , G K
E
, ^
f G

3 20

8. 8. 2
,
0

101. 325kPa , f = 101. 325kPa ( 895) :

^f

= K 101. 325

^
f ^
f = y ^ p ,

( y ^

p
101. 325

( 898)

, ^ = 1, ( 898) :

y =

p
101. 325

( 899)

8. 8. 3
, ,
( dGt ) T , p , ,
r , r ,

Gt ,
G t T p , T , p
, Gibbs , T , p ,
T , p , Gibbs ,
, T , p ,

Gibbs :
Gt =

, ,
, :
= + R T ln( f^ / f )
0

^f

( 891)

:
f^ = y ^ p

, 0 = G0f , ,
Gibbs , kPa , f 0 = 101. 325k Pa ,
32 1

, :
Gt =

0
f

+ ( ) R T ln

p
+ R T ln
101. 325

R T ln ( ) + R T ln ^

( 8100)

y
, G t ( )
{ } L agrange
G t ,
, A k
k a ik i
k k , a k = A k ,

( a

) - Ak = 0

k , k :

( a

) - Ak

= 0

, ( 8100) ,
Gt =

0
f

+ ( ) R T ln

R T ln ( ) + R T ln ^

p
+ R T ln
101. 325

k [ ( a k _
Ak ) ]

( 8101)

Gt

( 8101) n i ,

T , p,

, ,
j

:
0

Gf + RT ln

p
+ RT lny + RT ln ^ +
101. 325

a
k

= 0 ( = 1, 2, , m)

( 8102)
m , w :

y a

= A k / ( k = 1, 2, , w )

( 8103)

w , y

= 1

( 8104)

( m+ w + 1)
: y m ;
k w , ( m+ w

+ 1) ( 8102) ( 8103) ( 8104)

, ( 8102) ^ ,
3 22

^ 1 , ^ y , y ,
, , ^ 1
y , ,
y ^ , ( 8102 ) , y
, y
, ^

,
, ,
810 ( CH 4 ) , ( H 2 O ) , ( CO ) , ( CO 2 )
1000 K 101. 325k Pa , , 2 mol
CH 4 3mol H 2 O 1000K G0f
0

Gf CH 4 = 19300 J mol
0

- 1

Gf H 2 O = -

192720 J mol

G0f CO = -

200715 J mol -

Gf CO 2 = -

396110J mol

- 1

- 1

G0f H 2 = 0
[ ] A k , a k , :
k

A c= 2

k Ak
Ao = 3

CH 4

a CH 4 , C = 1

1mol a k
a CH 4 , O = 0

H 2O

a H 2 O, C= 0

a H 2 O, O = 1

a H 2 O, H = 2

CO
CO 2

a CO, C= 1
a CO2 , C = 1

a CO, O = 1
a CO2 , O = 2

a CO, H = 0
a CO2 , H = 0

H2

a H 2 , C= 0

a H 2, O = 0

a H 2, H = 2

A H = 14
a CH4 , H = 4

101. 325kPa 1000K , , ( 8102) ln ^

, ln ( p / 101. 325) , ( 8102) :
G0f + R T lny +

a
k

= 0

( 8102) 5 ( R T = 8314 J mol

- 1

CH 4 : 19300 + RT lny CH 4 +
C +
4H = 0
H 2O : -

192720 + R T lny H 2 O + 2
C +

0 =
0
32 3

CO : -

200715 + RT lny CO +
C +

0 =
0

CO 2 : - 396110 + RT lny CO 2 +
C +
20 = 0
H 2 : R T lny H 2 + 2
H =
0
( 8103) 3 :
C: y C H 4 + y CO + y C O 2 = 2/

H : 4y CH 4 + 2y H 2 O + 2y H 2 = 14/

O: y H 2 O + y CO + 2y CO 2 = 3/

, ( 8104)
y CH 4 + y H 2 O + y CO + y C O 2 + y H 2 = 1
:
y CH 4 = 0. 0199
y H 2 O = 0. 0995
y CO = 0. 1753
y CO 2 = 0. 0359
y H 2 = 0. 6694

= 1. 0000

= 8. 656

C / RT =
0. 797
0 / RT = 25. 1
H / R T = 0. 201
, ,

81 R aoult ( 1)
( 2) :
T/
C

p 01 / kP a

p 02 / kP a

T/
C

p 01 / kP a

p 02 / kP a

80. 1

101. 3

38. 9

98

170. 5

69. 8

84

114. 1

44. 5

100

180. 1

74. 2

88

128. 5

50. 8

104

200. 4

83. 6

90

136. 1

54. 2

108

222. 5

94. 0

94

152. 6

61. 6

110. 6

237. 8

101. 3

3 24

 90
C p x 101. 3kP a T x
82 ( 813)
2

ln1 = 0. 458x 2 ln 2 = 0. 458x 1

s at

sa t

40
C ( 1) ( 2) p x 40
C p 1 = 24. 6kpa, p 2 =
24. 4k pa ,
83 50
C , ( 1) ( 2)

s at

s at

( ) 2. 3 7. 0 50
C p 1 = 67. 50kpa, p 2 =
17. 63kpa , 50
C
84 , ( 1) ( 2) 101. 3kPa

t/
C
50

p 1 / kpa

p 2 / kpa

p 1 / kP a

p 2 / kP a

12. 40

t/
C
80

35. 86

100. 50

47. 32

60

51. 85

19. 86

90

135. 43

70. 11

70

72. 91

31. 06

100

179. 15

101. 33

75

85. 31

37. 99

110

233. 00

143. 30

85
:
ln1 = A + ( B -

A) x 1 -

Bx 21

ln2 = A + ( B -

A) x 22 -

Bx 22

A B , ,
?
86 50% ( ) 50% ( ) ,
65
C , 1722. 5kP a K :
( 1) , ;
( 2) , ;
( 3)
50% ( ) 50% ( ) , K ?
87 ,
y p = x p sa t

ln 1 = Bx 22 , ln2 = Bx 21
B , x a1 z ( = y a1 z ) B , p sa1 t
sa t

az

p 2 p
88 CH 4 , H enry 200K , 3040kPa
CH 4 ( ) H enry H i 20265kPa
95% ( ) CH 4 , 200K, 3040K pa, CH 4
3

200K CH 4 - 105cm / mol

32 5

89 CO 2 25
C, p CO 2 = 101. 325kPa CO 2
T c = 304. 2 K , p c = 7376. 46kPa
810 25
C 1 2 , ,
( )
x 2 = 0. 05 x 1 = 0. 05

s at

sa t

p 1 = 65. 86kPa, p 2 = 75. 99kPa

:
( 1) 1, 2 1 2 ;
( 2) ;
( 3) y 1
811 H 2 S H 2 O 1: 3, :
H 2 S + 2H 2 O = 3H 2 + SO 2

812 :
3H 2 + CO = CH 4 + H 2 O
, K
H 2 CO 4: 1
813 35
C, 101. 325kPa N 2 O 4 NO 2 0. 27,
( 1) K ;
( 2) 13. 33kP a
e;
( 3) 318K 298K , N 2 O 4 0. 664 0. 141,

814 CO H 2 :
CO( g) + 2H 2 ( g ) CH 3 OH ( g)
400K , 101. 325k Pa , , H 2
40% ( )
( 1) , CO CH 3 OH ;
( 2) 500K, 101. 325kP a , ( 1) ,
H 2 40% ? ( )
: 400K K = 1. 52, H 0 = - 94. 54kJ

[ 1] Chao K C and J D Seader . A ICh E . J . , 1961, 7: 598
[ 2] P raus nit z J M , W C E dm ist er and K C Chao . A ICh E J. , 1960, 6, 2: 214
[ 3] A CS Sympos ium Series 60, P hase Equilibr ium and F luid P ropert ies in t he Chemical Indust ry. 1977:
11

3 26

[ 4] Grayson H G and C W St reed. Sixth W orld Pet roleum Congress Pr oceeding, Sect . . 1963: 233
245
[ 5] Robins on R L and K C Chao . Ind . Eng . Chem . P rocess Des . Dev . , 1971, 10: 221229
[ 6] M affiolo G J Vidal and L A ss elineau. Chem . E ng. SCi. , 1975, 30: 625630
[ 7] P lo cker U . H . Knapp and J . M . Praus nitz . Ind. Eng . Chem . P rocess Des . Dev . , 1978, 17: 324
332
[ 8] Dauber t T E Chemical Engineering T hermodynamics . N ew Y ork : M cGraw Hill Book Company,
1985: 310
[ 9] H eringt on E F G . J . Inst . P etrol , 1951, 37: 457
[ 10] Sandler S I . Chemical and E ngineering T hermodynamics. New Y ork : John W iley & sons Inc . ,
1977: 434453
[ 11] , , 1977
[ 12] , , . , 1988, 28: 2832
[ 13] , . , 1988, 9: 307309
[ 14] Renon H and J M Praus nitz . Ind. Eng . Chem . P rocess Des . Dev . , 1969, 8: 413
[ 15] Chao K C and R A Gr eenkorn. T hermodynamics of F luids an int roduct ion t o E quilibrium T heory,
M arcel Dekker , Inc. 1975
[ 16] . . . , 1993, 18: 3538
[ 17] , . , 1990, 18: 2831
[ 18] W alas S M . Phas e Equilibr ia in Chem ical E ngineering. Bos ton: But terw ort h P ublis her s, 1985
[ 19] M M , H C . , , 1987

32 7

1m= 100cm

1kg= 103 g

1N = 1kg m s -

1bar = 105 pa = 105 kg m - 1 s - 2 = 105 N m -

= 0. 986923at m = 14. 5038psia= 750. 061mm Hg

1m 3 = 106 cm 3 = 103 L

1gcm - 3 = 103 kgm - 3 = 10 3 gL -

1J= 1kg m - 2 s- 2 = 1N m = 0. 239006cal

1kW = 10 3 kg m 2 s- 3 = 10 3 W = 103 J s - 1 = 103 V A = 1. 34102H P

K = + 273. 15

a t m ,

Vc /
Zc

99

0. 288

0. 008

4. 884

148

0. 285

0. 098

369. 8

4. 246

203

0. 281

0. 152

272. 7

425. 2

3. 800

255

0. 274

0. 193

58. 124

261. 3

408. 1

3. 648

263

0. 283

0. 176

72. 151

309. 2

469. 6

3. 374

304

0. 262

0. 251

72. 151

301. 0

460. 4

3. 384

306

0. 271

0. 227

72. 151

282. 6

433. 8

3. 202

303

0. 269

0. 197

86. 178

341. 9

507. 4

2. 969

370

0. 260

0. 296

100. 205

371. 6

540. 2

2. 736

432

0. 263

0. 351

114. 232

398. 8

568. 8

2. 482

492

0. 259

0. 394

T b/ K

T c/ K

P c/ M P a

16. 043

111. 7

190. 6

4. 600

30. 070

184. 5

305. 4

44. 097

231. 1

58. 124

cm 3 mol -

32 7

Vc /

Zc

129

0. 276

0. 085

4. 620

181

0. 275

0. 148

419. 6

4. 023

240

0. 277

0. 187

303. 1

464. 7

4. 053

300

0. 31

0. 245

60. 052

391. 1

594. 4

5. 786

171

0. 200

0. 454

58. 080

329. 4

508. 1

4. 701

209

0. 232

0. 309

41. 053

354. 8

548

4. 833

173

0. 184

0. 321

26. 038

189. 2

308. 3

6. 140

113

0. 271

0. 184

78. 114

353. 3

562. 1

4. 894

259

0. 271

0. 212

1, 3

54. 092

268. 7

425

4. 327

221

0. 270

0. 195

112. 559

404. 9

632. 4

4. 519

308

0. 265

0. 249

84. 162

353. 9

553. 4

4. 073

308

0. 273

0. 213

120. 914

243. 4

385. 0

4. 124

217

0. 280

0. 176

74. 123

307. 7

466. 7

3. 638

280

0. 262

0. 281

46. 069

351. 5

516. 2

6. 383

167

0. 248

0. 635

44. 054

283. 5

469

7. 194

140

0. 258

0. 200

32. 042

337. 8

512. 6

8. 096

118

0. 224

0. 559

50. 488

248. 9

416. 3

6. 677

139

0. 268

0. 156

72. 107

352. 8

535. 6

4. 154

267

0. 249

0. 329

92. 141

383. 8

591. 7

4. 114

316

0. 264

0. 257

137. 368

297. 0

471. 2

4. 408

248

0. 279

0. 188

187. 380

320. 7

487. 2

3. 415

304

0. 256

0. 252

39. 948

87. 3

150. 8

4. 874

74. 9

0. 291

- 0. 004

159. 808

331. 9

584

10. 335

127

0. 270

0. 132

70. 906

238. 7

417

7. 701

124

0. 275

0. 073

4. 003

4. 21

5. 19

0. 227

57. 3

0. 301

- 0. 387

2. 016

20. 4

33. 2

1. 297

65. 0

0. 305

- 0. 22

83. 800

119. 8

209. 4

5. 502

91. 2

0. 288

- 0. 002

20. 183

27. 0

44. 4

2. 756

41. 7

0. 311

0. 00

28. 031

77. 4

126. 2

3. 394

89. 5

0. 290

0. 040

31. 999

90. 2

154. 6

5. 046

73. 4

0. 288

0. 021

131. 300

165. 0

289. 7

5. 836

118

0. 286

0. 002

17. 031

239. 7

405. 6

11. 277

72. 5

0. 242

0. 250

44. 010

194. 7

304. 2

7. 376

94. 0

0. 274

0. 225

T b/ K

T c/ K

P c/ M P a

28. 054

161. 4

282. 4

5. 036

42. 081

225. 4

365. 0

56. 108

266. 9

70. 135

cm 3 mol -

3 28

Vc /

Zc

170

0. 293

0. 115

3. 496

93. 1

0. 295

0. 049

556. 4

4. 560

276

0. 272

0. 194

334. 3

536. 4

5. 472

239

0. 293

0. 216

32. 045

386. 7

653

14. 692

96. 1

0. 260

0. 328

36. 461

188. 1

324. 6

8. 309

81. 0

0. 249

0. 12

27. 026

298. 9

456. 8

5. 390

139

0. 197

0. 407

34. 080

212. 8

373. 2

8. 937

98. 5

0. 284

0. 100

30. 006

121. 4

180

6. 485

58

0. 25

0. 607

44. 013

184. 7

309. 6

7. 245

97. 4

0. 274

0. 160

32. 064

1314

11. 753

64. 063

263

430. 8

7. 883

122

0. 268

0. 251

80. 058

318

491. 0

8. 207

130

0. 26

0. 41

18. 015

373. 2

647. 3

22. 048

56. 0

0. 229

0. 344

T b/ K

T c/ K

P c/ M P a

76. 131

319. 4

552

7. 903

28. 010

81. 7

132. 9

153. 823

349. 7

119. 378

cm 3 mol -

0. 070

Ar

0. 0010

0. 0161

0. 00

C 2H 2

0. 0766

0. 1762

0. 00

Kr

0. 0100

0. 0249

0. 00

13

0. 0860

0. 1848

0. 0065

O2

0. 0111

0. 0364

0. 00

23

0. 0907

0. 2230

- 0. 005

N2

0. 0189

0. 0530

0. 00

C 6H 6

0. 0886

0. 2001

0. 00

CO

0. 0152

0. 0576

- 0. 006

0. 1185

0. 2474

0. 010

H2

- 0. 0994

- 0. 2185

0. 00

0. 1382

0. 2816

0. 0144

Cl 2

0. 0625

0. 1077

0. 0168

0. 0991

0. 1682

0. 0255

CO 2

0. 0783

0. 1954

- 0. 005

0. 1098

0. 2139

0. 0163

H 2S

0. 0422

0. 1142

- 0. 005

0. 0813

0. 1873

0. 00

S O2

0. 1101

0. 2375

0. 007

0. 0817

0. 1193

0. 0297

H 2O

0. 2558

0. 3638

0. 0887

NH3

0. 1951

0. 2740

0. 070

0. 1027

0. 2241

0. 0056

CS 2

0. 0210

0. 0738

- 0. 007

0. 1001

0. 2434

- 0. 005

F 11

0. 0676

0. 1747

- 0. 006

0. 1410

0. 2216

0. 042

F 12

0. 0656

0. 1794

- 0. 010

0. 1903

0. 2945

0. 057

F 13

0. 0575

0. 1604

- 0. 0096

0. 1945

0. 3281

0. 047

F 22

0. 1005

0. 2122

0. 0085

0. 1437

0. 2660

0. 026

F 113

0. 0822

0. 2241

- 0. 0133

0. 1549

0. 3088

0. 0185

CH 4

0. 0096

0. 0281

0. 00

0. 1659

0. 3274

0. 021

C2 H 6

0. 0445

0. 1103

0. 00

0. 1664

0. 3161

0. 026

32 9

C3 H 8

0. 0652

0. 1552

0. 00

0. 1615

0. 2920

0. 0316

n C4 H 10

0. 0790

0. 1897

0. 00

0. 1131

0. 2259

0. 0144

iC4 H 10

0. 0692

0. 1721

0. 00

0. 1075

0. 2533

0. 00

n C5 H 12

0. 0985

0. 2293

0. 00

0. 0757

0. 1792

0. 00

iC5 H 12

0. 0924

0. 2142

0. 00

0. 1191

0. 2478

0. 011

n C6 H 14

0. 1146

0. 2667

0. 00

0. 1165

0. 3461

- 0. 032

nC7 H 16

0. 1320

0. 2995

0. 00

0. 1521

0. 2879

0. 0246

n C8 H 18

0. 1454

0. 3306

0. 00

0. 2556

0. 4460

0. 0544

nC9 H 20

0. 1610

0. 3705

0. 00

0. 1739

0. 4295

- 0. 014

n C10 H 22

0. 1729

0. 3890

0. 00

0. 1783

0. 4566

- 0. 021

nC11 H 24

0. 1880

0. 4104

0. 00

0. 0744

0. 1606

0. 0059

n C12 H 26

0. 1971

0. 4354

0. 00

0. 0892

0. 2259

- 0. 0076

0. 0772

0. 1865

0. 00

0. 3033

0. 2366

0. 1853

0. 0860

0. 2077

0. 00

0. 1850

0. 2848

0. 0562

C2 H 4

0. 0345

0. 0878

0. 00

0. 4285

0. 4617

0. 2073

C3 H 6

0. 0600

0. 1471

0. 00

0. 3477

0. 4253

0. 1479

1C 4 H 8

0. 079

0. 1882

0. 00

103

10 2

: , , p
-3 BWR

A0

B0

1. 85500

0. 042600

4. 15556

C
10 0

c 10-

0. 02257

0. 49400

0. 00338004

0. 002545

0. 124359

0. 6000

0. 0627724

0. 179592

0. 345160

0. 0111220

0. 0327670

0. 243389

1. 18000

3. 33958

0. 0556833

0. 131140

0. 259000

0. 0086000

0. 021120

0. 178000

0. 923000

6. 87225

0. 0973130

0. 508256

0. 947700

0. 0225000

0. 129000

0. 607175

2. 20000

6. 11220

0. 0850647

0. 439182

0. 774056

0. 0187059

0. 102611

0. 455696

1. 82900

10. 0847

0. 124361

0. 992830

1. 88231

0. 0399983

0. 316400

1. 40132

3. 40000

10. 23264

0. 137544

0. 849943

1. 93763

0. 0424352

0. 286010

1. 07408

3. 40000

8. 95325

0. 116025

0. 927280

1. 69270

0. 0348156

0. 274920

0. 910889

2. 95945

12. 1794

0. 156751

2. 12121

4. 07480

0. 0668120

0. 824170

1. 81000

4. 75000

12. 7959

0. 160053

1. 74632

3. 75620

0. 0668120

0. 695000

1. 70000

4. 63000

14. 4373

0. 177813

3. 31935

7. 11671

0. 109131

1. 51276

2. 81086

6. 66849

17. 5206

0. 199005

4. 74574

10. 36475

0. 151954

2. 47000

4. 35611

9. 00000

25. 2325

- 0. 0645222

3. 88626

381. 637

0. 646261

5. 75722

5. 70791

15. 3030

6. 51013

0. 0503020

3. 43016

55. 7047

0. 0766343

1. 17652

0. 700159

2. 93016

17. 973

0. 17900

1. 8861

4. 3546

0. 08637

0. 89829

3. 0450

7. 2131

13. 828

0. 09209

1. 8670

5. 5238

0. 10994

0. 85505

2. 2759

6. 5044

11. 842

0. 19214

3. 3595

10. 108

0. 14000

1. 7483

2. 1890

5. 6500

1. 97575

0. 0338945

0. 0778086

1. 75020

0. 0698624

0. 460598

2, 3

2, 2

CO 2

3 30

0. 00527242 0. 00978903

C
10 0

103

10 2

0. 00358992 0. 00409736

0. 961331

0. 539386

0. 149013

0. 00198165 0. 000548110

0. 291569

0. 750042

0. 793879

8. 44395

0. 0146542

0. 113362

0. 0719604

0. 592390

0. 221172

0. 77460

0. 0068946

0. 031026

0. 538738

1. 90774

A0

B0

2. 46616

0. 0484030

0. 0841836

6. 32033

N2

1. 19257

0. 0458013

0. 0058894

SO 2

2. 12054

0. 0261827

H2 S

2. 78413

0. 0669750

c 10-

C O 2 CO 2 ;
C O 2 40% ( ) CO 2

- ( lg - ( lg

[ lg

[ lg

P r ) ( 0) P r ) ( 1)

( f / p ) ] ( 0)

( f / p ) ] ( 1)

S (0)

S ( 1)

1. 00 0. 000 0. 000
0. 99 0. 025 0. 021

- 0. 1642
- 0. 1680

- 0. 0332
- 0. 0273

0. 00
2. 57

0. 00
2. 83

0. 98 0. 050 0. 042

- 0. 1648

- 0. 0201

3. 38

3. 91

0. 47

0. 97 0. 076 0. 064

- 0. 1593

- 0. 0133

4. 00

4. 72

0. 96 0. 102 0. 086

- 0. 1540

- 0. 0074

4. 52

0. 95 0. 129 0. 109

- 0. 1488

- 0. 0023

0. 94 0. 156 0. 133

- 0. 1432

0. 92 0. 212 0. 180

Tr

z (0)

z ( 1)

z ( 0)

z ( 1)

0. 291
0. 202

- 0. 080
- 0. 090

0. 179

- 0. 093

0. 51 + 0. 020

0. 162

- 0. 095

5. 39

0. 54

0. 035

0. 148

- 0. 085

5. 00

5. 96

0. 565

0. 045

0. 136

- 0. 095

+ 0. 0027

5. 44

6. 51

0. 59

0. 055

0. 125

- 0. 094

- 0. 1329

+ 0. 0122

6. 23

7. 54

0. 63

0. 075

0. 108

- 0. 092

0. 90 0. 270 0. 230

- 0. 1221

0. 0213

6. 95

8. 53

0. 67

0. 095

0. 0925 - 0. 087

0. 88 0. 330 0. 285

- 0. 1127

0. 0290

7. 58

9. 39

0. 70

0. 110

0. 0790 - 0. 080

0. 86 0. 391 0. 345

- 0. 1031

0. 0361

8. 19

10. 3

0. 73

0. 125

0. 0680 - 0. 075

0. 84 0. 455 0. 405

- 0. 0943

0. 0418

8. 79

11. 2

0. 756

0. 135

0. 0585 - 0. 068

0. 82 0. 522 0. 475

- 0. 0856

0. 0459

9. 37

12. 1

0. 781

0. 140

0. 0498 - 0. 062

0. 80 0. 592 0. 545

- 0. 0774

0. 0493

9. 97

13. 0

0. 804

0. 144

0. 0422 - 0. 057

0. 78 0. 665 0. 620

- 0. 0695

0. 0512

10. 57

13. 9

0. 826

0. 144

0. 0360 - 0. 053

0. 76 0. 742 0. 705

- 0. 0620

0. 0522

11. 20

14. 9

0. 846

0. 142

0. 0300 - 0. 048

0. 74 0. 823 0. 800

- 0. 0551

0. 0520

11. 84

16. 0

0. 864

0. 137

0. 0250 - 0. 043

0. 72 0. 909 0. 895

- 0. 0485

0. 0510

12. 49

17. 0

0. 881

0. 131

0. 0210 - 0. 037

0. 70 1. 000 1. 00

- 0. 0422

0. 0489

13. 19

18. 1

0. 897

0. 122

0. 0172 - 0. 032

0. 68 1. 096 1. 12

- 0. 0366

0. 0463

13. 89

19. 3

0. 911

0. 113

0. 0138 - 0. 027

0. 66 1. 198 1. 25

- 0. 0317

0. 0432

14. 62

20. 5

0. 922

0. 104

0. 0111 - 0. 022

0. 64 1. 308 1. 39

- 0. 0273

0. 0402

15. 36

21. 8

0. 932

0. 097

0. 0088 - 0. 018

0. 62 1. 426 1. 54

- 0. 0234

0. 0369

16. 12

23. 2

0. 940

0. 090

0. 0068 - 0. 015

0. 60 1. 552 1. 70

- 0. 0200

0. 0333

16. 92

24. 6

0. 947

0. 083

0. 0052 - 0. 012

0. 58 1. 688 1. 88

- 0. 0170

0. 0300

17. 74

26. 2

0. 953

0. 077

0. 0039 - 0. 009

0. 56 1. 834 2. 08

- 0. 0142

0. 0262

18. 64

27. 8

0. 959

0. 070

0. 0028 - 0. 007

0. 54 1. 965 2. 370

19. 56

29. 84

0. 52 2. 130 2. 660

20. 55

32. 00

0. 291 - 0. 080
0. 43 - 0. 030
0. 000

33 1

Tr

- ( lg - ( lg

[ lg

[ lg

P r ) ( 0) P r ) ( 1)

( f / p ) ] ( 0)

( f / p ) ] ( 1)

S (0)

S ( 1)

0. 50 2. 315 2. 962

21. 60

34. 22

0. 48 2. 515 3. 310

22. 70

36. 48

0. 46 2. 730 3. 695

24. 05

38. 80

0. 44 2. 970 4. 100

25. 50

41. 14

0. 42 3. 240 4. 540

27. 05

43. 5

0. 40 3. 540 5. 010

28. 83

46. 0

0. 38 3. 870 5. 560

30. 70

49. 2

0. 36 4. 220 6. 240

32. 80

53. 0

0. 34 4. 600 7. 080

35. 10

57. 4

0. 32 5. 005 8. 300

37. 55

63. 6

0. 30 5. 450 9. 940

40. 20

71. 5

z (0)

z ( 1)

z ( 0)

z ( 1)

0. 28 5. 910 11. 960

0. 26 6. 380 14. 250

2 Z ( 0)
pr
Tr
0. 2

0. 4

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

2. 4

2. 6

0. 35
0. 40

0. 0557 0. 111 0. 167 0. 222 0. 277 0. 332 0. 387 0. 442 0. 497 0. 551 0. 606 0. 665 0. 714
0. 0500 0. 100 0. 150 0. 199 0. 249 0. 298 0. 348 0. 395 0. 446 0. 495 0. 544 0. 592 0. 641

0. 45

0. 0456 0.0912 0. 136 0. 182 0. 227 0. 272 0. 317 0. 362 0. 407 0. 451 0. 496 0. 540 0. 584

0. 50

0. 04230. 0844 0. 126 0. 168 0. 210 0. 252 0. 293 0. 335 0. 376 0. 417 0. 458 0. 499 0. 540

0. 55

0. 03960. 0791 0. 118 0. 158 0. 197 0. 235 0. 274 0. 313 0. 351 0. 390 0. 428 0. 466 0. 504

0. 60

0. 03750. 0748 0. 112 0. 149 0. 186 0. 222 0. 259 0. 295 0. 331 0. 368 0. 403 0. 439 0. 475

0. 65

0. 03590. 0715 0. 107 0. 142 0. 177 0. 212 0. 247 0. 281 0. 315 0. 350 0. 384 0. 417 0. 451

0. 70

0. 03460. 0690 0. 103 0. 137 0. 170 0. 204 0. 237 0. 270 0. 303 0. 335 0. 368 0. 400 0. 432

0. 75

0. 03380. 0673 0. 100 0. 133 0. 166 0. 198 0. 230 0. 261 0. 293 0. 324 0. 355 0. 386 0. 416

0. 80

0. 851 0. 066 0. 100 0. 133 0. 164 0. 192 0. 225 0. 258 0. 287 0. 318 0. 347 0. 376 0. 405

0. 85

0. 882 0. 067 0. 101 0. 134 0. 165 0. 194 0. 226 0. 258 0. 287 0. 316 0. 345 0. 374 0. 403

0. 90

0. 904 0. 778 0. 102 0. 135 0. 167 0. 198 0. 229 0. 25 0. 288 0. 316 0. 345 0. 373 0. 402

0. 95

0. 920 0. 819 0. 697 0. 145 0. 176 0. 205 0. 235 0. 262 0. 292 0. 321 0. 347 0. 375 0. 403

1. 00

0. 932 0. 849 0. 756 0. 638 0. 291 0. 231 0. 250 0. 278 0. 304 0. 329 0. 356 0. 381 0. 407

1. 05

0. 942 0. 874 0. 800 0. 714 0. 609 0. 470 0. 341 0. 320 0. 332 0. 350 0. 372 0. 393 0. 417

1. 10

0. 950 0. 893 0. 833 0. 767 0. 691 0. 607 0. 512 0. 442 0. 408 0. 402 0. 405 0. 420 0. 440

1. 15

0. 958 0. 908 0. 858 0. 805 0. 746 0. 684 0. 620 0. 562 0. 514 0. 484 0. 477 0. 478 0. 485

1. 20

0. 963 0. 921 0. 879 0. 835 0. 788 0. 737 0. 690 0. 640 0. 598 0. 568 0. 553 0. 545 0. 544

1. 25

0. 968 0. 930 0. 896 0. 858 0. 820 0. 778 0. 740 0. 702 0. 664 0. 636 0. 618 0. 606 0. 599

1. 30

0. 971 0. 940 0. 909 0. 878 0. 846 0. 811 0. 780 0. 749 0. 718 0. 691 0. 671 0. 657 0. 649

1. 4

0. 977 0. 952 0. 929 0. 908 0. 833 0. 859 0. 838 0. 817 0. 795 0. 777 0. 759 0. 745 0. 734

1. 5

0. 982 0. 963 0. 945 0. 927 0. 909 0. 892 0. 875 0. 859 0. 844 0. 831 0. 819 0. 808 0. 800

3 32


pr
Tr
0. 2

0. 4

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

2. 4

2. 6

1. 6

0. 985 0. 971 0. 957 0. 944 0. 930 0. 917 0. 904 0. 893 0. 882 0. 872 0. 863 0. 855 0. 848

1. 7

0. 988 0. 977 0. 966 0. 956 0. 946 0. 936 0. 926 0. 919 0. 911 0. 903 0. 896 0. 889 0. 883

1. 8

0. 991 0. 982 0. 974 0. 966 0. 958 0. 950 0. 944 0. 937 0. 931 0. 926 0. 921 0. 916 0. 913

1. 9

0. 993 0. 986 0. 980 0. 974 0. 968 0. 962 0. 958 0. 952 0. 948 0. 944 0. 940 0. 936 0. 933

2. 0

0. 995 0. 989 0. 984 0. 979 0. 975 0. 971 0. 968 0. 964 0. 961 0. 959 0. 956 0. 954 0. 953

2. 5

1. 000 0. 999 0. 999 0. 998 0. 998 0. 998 0. 998 0. 997 0. 999 1. 000 1. 001 1. 001 1. 002

3. 0

1. 001 1. 002 1. 003 1. 004 1. 005 1. 007 1. 008 1. 010 1. 012 1. 014 1. 016 1. 019 1. 022

3. 5

1. 002 1. 004 1. 006 1. 008 1. 011 1. 013 1. 015 1. 018 1. 020 1. 022 1. 024 1. 027 1. 030

4. 0

1. 003 1. 005 1. 008 1. 010 1. 013 1. 015 1. 017 1. 020 1. 022 1. 024 1. 024 1. 029 1. 032
pr

Tr
2. 8

3. 0

3. 2

3. 4

3. 6

3. 8

4. 0

4. 5

5. 0

6. 0

7. 0

8. 0

9. 0

1. 07

0. 35

0. 768 0. 822 0. 876 0. 930 0. 993 1. 04

1. 22

1. 36

1. 62

1. 88

2. 14

2. 39

0. 40

0. 690 0. 738 0. 787 0. 835 0. 883 0. 931 0. 979 1. 10

1. 22

1. 45

1. 69

1. 92

2. 15

0. 45

0. 629 0. 673 0. 717 0. 761 0. 805 0. 848 0. 892 1. 00

1. 11

1. 32

1. 54

1. 75

1. 96

0. 50

0. 581 0. 622 0. 662 0. 703 0. 743 0. 783 0. 824 0. 924 1. 02

1. 22

1. 42

1. 61

1. 80

0. 55

0. 542 0. 580 0. 618 0. 655 0. 693 0. 730 0. 767 0. 860 0. 952 1. 13

1. 31

1. 49

1. 67

0. 60

0. 510 0. 546 0. 581 0. 616 0. 651 0. 686 0. 721 0. 808 0. 893 1. 06

1. 23

1. 40

1. 56

0. 65

0. 485 0. 518 0. 551 0. 584 0. 617 0. 650 0. 683 0. 764 0. 845 1. 00

1. 16

1. 31

1. 47

0. 70

0. 464 0. 495 0. 527 0. 558 0. 589 0. 620 0. 651 0. 728 0. 804 0. 954 1. 10

1. 25

1. 39

0. 75

0. 447 0. 477 0. 507 0. 536 0. 566 0. 596 0. 625 0. 698 0. 769 0. 910 1. 05

1. 18

1. 32

0. 80

0. 433 0. 461 0. 490 0. 519 0. 547 0. 576 0. 605 0. 675 0. 746 0. 883 1. 017 1. 15

1. 28

0. 85

0. 431 0. 459 0. 487 0. 515 0. 542 0. 569 0. 597 0. 663 0. 730 0. 861 0. 990 1. 115 1. 24

0. 90

0. 430 0. 458 0. 485 0. 512 0. 538 0. 565 0. 591 0. 655 0. 718 0. 842 0. 966 1. 089 1. 21

0. 95

0. 430 0. 457 0. 484 0. 510 0. 536 0. 561 0. 587 0. 647 0. 709 0. 828 0. 947 1. 066 1. 185

1. 00

0. 433 0. 458 0. 484 0. 509 0. 534 0. 557 0. 582 0. 642 0. 702 0. 819 0. 932 1. 048 1. 166

1. 05

0. 441 0. 466 0. 489 0. 512 0. 535 0. 557 0. 580 0. 639 0. 700 0. 814 0. 923 1. 032 1. 147

1. 10

0. 462 0. 484 0. 504 0. 525 0. 547 0. 567 0. 589 0. 643 0. 699 0. 810 0. 916 1. 019 1. 129

1. 15

0. 498 0. 513 0. 529 0. 546 0. 563 0. 581 0. 600 0. 651 0. 705 0. 809 0. 911 1. 008 1. 113

1. 20

0. 548 0. 554 0. 563 0. 574 0. 587 0. 601 0. 618 0. 664 0. 714 0. 810 0. 907 1. 000 1. 100

1. 25

0. 597 0. 598 0. 602 0. 609 0. 618 0. 629 0. 643 0. 682 0. 726 0. 816 0. 907 0. 994 1. 088

1. 30

0. 644 0. 642 0. 642 0. 645 0. 651 0. 659 0. 668 0. 701 0. 740 0. 824 0. 910 0. 992 1. 078

1. 4

0. 725 0. 720 0. 718 0. 718 0. 722 0. 727 0. 734 0. 754 0. 781 0. 844 0. 921 0. 994 1. 071

1. 5

0. 794 0. 790 0. 785 0. 784 0. 784 0. 786 0. 790 0. 805 0. 826 0. 877 0. 934 1. 000 1. 070

1. 6

0. 843 0. 840 0. 836 0. 834 0. 833 0. 834 0. 835 0. 844 0. 860 0. 904 0. 953 1. 010 1. 075

1. 7

0. 879 0. 875 0. 873 0. 872 0. 872 0. 873 0. 874 0. 882 0. 895 0. 930 0. 972 1. 023 1. 082

1. 8

0. 910 0. 908 0. 907 0. 906 0. 906 0. 907 0. 908 0. 914 0. 925 0. 955 0. 993 1. 039 1. 091

1. 9

0. 931 0. 930 0. 929 0. 929 0. 930 0. 932 0. 934 0. 941 0. 950 0. 976 1. 010 1. 051 1. 097

2. 0

0. 953 0. 952 0. 952 0. 953 0. 954 0. 954 0. 956 0. 962 0. 972 0. 996 1. 027 1. 064 1. 106

2. 5

1. 004 1. 006 1. 008 1. 009 1. 012 1. 014 1. 018 1. 026 1. 035 1. 055 1. 079 1. 105 1. 136

33 3


pr
Tr
2. 8

3. 0

3. 2

3. 4

3. 6

3. 8

4. 0

4. 5

5. 0

6. 0

7. 0

8. 0

9. 0

3. 0

1. 025 1. 028 1. 030 1. 033 1. 036 1. 038 1. 041 1. 049 1. 058 1. 077 1. 10 1. 124 1. 150

3. 5

1. 033 1. 036 1. 039 1. 042 1. 045 1. 048 1. 051 1. 058 1. 067 1. 086 1. 105 1. 126 1. 148

4. 0

1. 035 1. 038 1. 041 1. 044 1. 047 1. 050 1. 053 1. 060 1. 068 1. 086 1. 104 1. 124 1. 143

-3 Z ( 1)
pr
Tr
0. 2

0. 4

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

0. 35

- 0. 027- 0. 048- 0. 073- 0. 100 - 0. 13 - 0. 15 - 0. 17 - 0. 20 - 0. 23 - 0. 26 - 0. 29

0. 40

- 0. 025- 0. 046- 0. 070- 0. 094 - 0. 12 - 0. 14 - 0. 16 - 0. 19 - 0. 22 - 0. 25 - 0. 28

0. 45

- 0. 024- 0. 044- 0. 067- 0. 089 - 0. 11 - 0. 13 - 0. 15 - 0. 18 - 0. 21 - 0. 24 - 0. 27

0. 50

- 0. 022- 0. 043- 0. 066- 0. 085 - 0. 11 - 0. 13 - 0. 15 - 0. 17 - 0. 20 - 0. 22 - 0. 25

0. 55

- 0. 021- 0. 041- 0. 060- 0. 080 - 0. 10 - 0. 12 - 0. 14 - 0. 16 - 0. 19 - 0. 21 - 0. 23

0. 60

- 0. 020- 0. 039- 0. 057- 0. 075- 0. 093 - 0. 11 - 0. 13 - 0. 15 - 0. 17 - 0. 19 - 0. 21

0. 65

- 0. 020- 0. 039- 0. 057- 0. 075- 0. 093 - 0. 11 - 0. 12 - 0. 14 - 0. 16 - 0. 17 - 0. 19

0. 70

- 0. 020- 0. 036- 0. 052- 0. 068- 0. 084 - 0. 10 - 0. 12 - 0. 13 - 0. 15 - 0. 16 - 0. 18

0. 75

- 0. 020- 0. 036- 0. 052- 0. 068- 0. 084 - 0. 10 - 0. 11 - 0. 12 - 0. 14 - 0. 15 - 0. 16

0. 80

- 0. 095- 0. 028- 0. 044- 0. 058 - 0. 07 - 0. 08 - 0. 10 - 0. 11 - 0. 12 - 0. 13 - 0. 14

0. 85

- 0. 067- 0. 031- 0. 049- 0. 064 - 0. 08 - 0. 09 - 0. 11 - 0. 12 - 0. 13 - 0. 14 - 0. 15

0. 90

- 0. 042 - 0. 09 - 0. 053- 0. 068- 0. 085 - 0. 10 - 0. 11 - 0. 12 - 0. 13 - 0. 14 - 0. 15

0. 95

- 0. 025- 0. 050 - 0. 10 - 0. 072- 0. 091 - 0. 10 - 0. 11 - 0. 12 - 0. 12 - 0. 13 - 0. 14

1. 00

- 0. 012- 0. 016- 0. 020 - 0. 05 - 0. 080- 0. 090- 0. 099- 0. 108- 0. 115- 0. 123 - 0. 13

1. 05

0. 000 + 0. 001+ 0. 005+ 0. 015 + 0. 02 + 0. 01 - 0. 01 - 0. 04 - 0. 06 - 0. 07 - 0. 08

1. 10

+ 0. 002 0. 008

0. 016

0. 030

0. 055

0. 082 + 0. 11 + 0. 082+ 0. 035 0. 000 - 0. 02

1. 15

0. 004

0. 012

0. 012

0. 040

0. 064

0. 093

0. 12

0. 140

0. 136 + 0. 100 + 0. 07

1. 20

0. 009

0. 018

0. 028

0. 044

0. 069

0. 10

0. 13

0. 16

0. 17

0. 17

0. 16

1. 25

0. 011

0. 023

0. 036

0. 050

0. 069

0. 10

0. 13

0. 16

0. 18

0. 19

0. 19

1. 30

0. 013

0. 027

0. 041

0. 055

0. 072

0. 10

0. 13

0. 16

0. 18

0. 20

0. 20

1. 4

0. 016

0. 032

0. 049

0. 065

0. 082

0. 10

0. 13

0. 16

0. 18

0. 19

0. 20

1. 5

0. 017

0. 035

0. 052

0. 070

0. 088

0. 10

0. 13

0. 15

0. 17

0. 18

0. 20

1. 6

0. 018

0. 036

0. 054

0. 07

0. 08

0. 10

0. 12

0. 14

0. 16

0. 17

0. 18

1. 7

0. 018

0. 036

0. 054

0. 07

0. 09

0. 10

0. 11

0. 13

0. 15

0. 16

0. 17

1. 8

0. 018

0. 036

0. 054

0. 07

0. 09

0. 10

0. 11

0. 13

0. 15

0. 16

0. 17

1. 9

0. 018

0. 035

0. 05

0. 07

0. 09

0. 10

0. 11

0. 13

0. 15

0. 16

0. 17

2. 0

0. 016

0. 031

0. 05

0. 07

0. 08

0. 10

0. 11

0. 13

0. 14

0. 15

0. 16

2. 5

0. 01

0. 02

0. 04

0. 05

0. 07

0. 08

0. 10

0. 11

0. 12

0. 13

0. 15

3. 0

0. 01

0. 02

0. 03

0. 05

0. 06

0. 07

0. 08

0. 09

0. 10

0. 11

0. 13

3. 5

0. 01

0. 02

0. 03

0. 04

0. 05

0. 06

0. 07

0. 08

0. 08

0. 09

0. 10

4. 0

0. 01

0. 02

0. 02

0. 03

0. 04

0. 05

0. 06

0. 06

0. 07

0. 08

0. 09

3 34


pr
Tr
2. 4

2. 6

2. 8

3. 0

4. 0

5. 0

6. 0

7. 0

8. 0

9. 0

0. 35

- 0. 32 - 0. 35 - 0. 37 ( - 0. 42) ( - 0. 53) ( - 0. 65) ( - 0. 78) ( - 0. 86) ( - 0. 95) ( - 1. 06)

0. 40

- 0. 30 - 0. 33 - 0. 35 ( - 0. 39) ( - 0. 49) ( - 0. 60) ( - 0. 72) ( - 0. 80) ( - 0. 88) ( - 0. 96)

0. 45

- 0. 28 - 0. 31 - 0. 33 ( - 0. 36) ( - 0. 45) ( - 0. 55) ( - 0. 67) ( - 0. 74) ( - 0. 82) ( - 0. 88)

0. 50

- 0. 27 - 0. 29 - 0. 31 ( - 0. 34) ( - 0. 42) ( - 0. 51) ( - 0. 61) ( - 0. 68) ( - 0. 75) ( - 0. 81)

0. 55

- 0. 25 - 0. 27 - 0. 29 - 0. 31

- 0. 39

- 0. 47

- 0. 55

- 0. 62

- 0. 68

- 0. 79

0. 60

- 0. 23 - 0. 25 - 0. 26 - 0. 28

- 0. 36

- 0. 43

- 0. 50

- 0. 56

- 0. 62

- 0. 67

0. 65

- 0. 21 - 0. 22 - 0. 24 - 0. 25

- 0. 32

- 0. 38

- 0. 43

- 0. 49

- 0. 54

- 0. 58

0. 70

- 0. 19 - 0. 20 - 0. 21 - 0. 23

- 0. 28

- 0. 33

- 0. 38

- 0. 42

- 0. 47

- 0. 51

0. 75

- 0. 17 - 0. 18 - 0. 19 - 0. 20

- 0. 25

- 0. 29

- 0. 33

- 0. 37

- 0. 40

- 0. 44

0. 80

- 0. 15 - 0. 16 - 0. 17 - 0. 18

- 0. 23

- 0. 26

- 0. 29

- 0. 32

- 0. 35

- 0. 39

0. 85

- 0. 16 - 0. 17 - 0. 18 - 0. 18

- 0. 22

- 0. 25

- 0. 28

- 0. 31

- 0. 34

- 0. 36

0. 90

- 0. 16 - 0. 17 - 0. 17 - 0. 18

- 0. 21

- 0. 24

- 0. 27

- 0. 30

- 0. 32

- 0. 35

0. 95

- 0. 15 - 0. 15 - 0. 16 - 0. 17

- 0. 20

- 0. 22

- 0. 25

- 0. 28

- 0. 31

- 0. 34

1. 00

- 0. 13 - 0. 14 - 0. 14 - 0. 15

- 0. 17

- 0. 20

- 0. 23

- 0. 26

- 0. 30

- 0. 33

1. 05

- 0. 09 - 0. 10 - 0. 10 - 0. 11

- 0. 14

- 0. 17

- 0. 20

- 0. 24

- 0. 28

- 0. 31

1. 10

- 0. 03 - 0. 05 - 0. 06 - 0. 07

- 0. 10

- 0. 13

- 0. 16

- 0. 21

- 0. 25

- 0. 28

1. 15

+ 0. 04 + 0. 02

- 0. 04

- 0. 08

- 0. 12

- 0. 16

- 0. 20

- 0. 24

0. 00

- 0. 04

- 0. 08

- 0. 12

- 0. 16

- 0. 19

0. 00

- 0. 01

1. 20

0. 14

0. 12

+ 0. 09 + 0. 07

1. 25

0. 18

0. 16

0. 14

0. 12

+ 0. 05

0. 00

- 0. 03

- 0. 07

- 0. 11

- 0. 13

1. 30

0. 20

0. 20

0. 19

0. 18

0. 10

+ 0. 04

0. 00

- 0. 04

- 0. 07

- 0. 09

1. 4

0. 21

0. 21

0. 21

0. 20

0. 15

0. 11

+ 0. 07

+ 0. 04

+ 0. 01

- 0. 01

1. 5

0. 20

0. 21

0. 21

0. 21

0. 20

0. 17

0. 14

0. 11

0. 09

+ 0. 07

1. 6

0. 19

0. 20

0. 20

0. 21

0. 22

0. 21

0. 19

0. 17

0. 15

0. 14

1. 7

0. 18

0. 19

0. 20

0. 21

0. 24

0. 25

0. 26

0. 25

0. 24

0. 22

1. 8

0. 18

0. 19

0. 20

0. 21

0. 26

0. 29

0. 31

0. 32

0. 32

0. 30

1. 9

0. 18

0. 19

0. 20

0. 21

0. 26

0. 30

0. 35

0. 38

0. 40

0. 40

2. 0

0. 17

0. 19

0. 20

0. 21

0. 26

0. 30

0. 35

0. 40

0. 43

0. 45

2. 5

0. 16

0. 18

0. 19

0. 20

0. 25

0. 30

0. 35

0. 40

0. 45

0. 50

3. 0

0. 14

0. 15

0. 16

0. 17

0. 23

0. 28

0. 34

0. 38

0. 45

0. 50

3. 5

0. 11

0. 12

0. 13

0. 14

0. 19

0. 24

0. 28

0. 33

0. 38

0. 42

4. 0

0. 10

0. 10

0. 11

0. 12

0. 16

0. 20

0. 23

0. 27

0. 31

0. 35

33 5

 3 36

 33 7

 3 38

-5 [ lg( f / p ) ] (1) = ( lg ) ( 1)
pr
Tr
0. 2

0. 4

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

0. 35

- 6. 65 - 6. 66 - 6. 68 - 6. 69 - 6. 70 - 6. 71 - 6. 72 - 6. 73 - 6. 74 - 6. 75 - 6. 76

0. 40

- 5. 02 - 5. 03 - 5. 04 - 5. 05 - 5. 06 - 5. 07 - 5. 08 - 5. 09 - 5. 10 - 5. 11 - 5. 12

0. 45

- 3. 90 - 3. 91 - 3. 92 - 3. 93 - 3. 94 - 3. 95 - 3. 96 - 3. 97 - 3. 98 - 3. 98 - 3. 99

0. 50

- 2. 96 - 2. 96 - 2. 97 - 2. 98 - 2. 99 - 3. 00 - 3. 01 - 3. 02 - 3. 03 - 3. 04 - 3. 05

0. 55

- 2. 22 - 2. 23 - 2. 24 - 2. 25 - 2. 26 - 2. 27 - 2. 28 - 2. 28 - 2. 29 - 2. 30 - 2. 31

0. 60

- 1. 68 - 1. 69 - 1. 70 - 1. 70 - 1. 71 - 1. 72 - 1. 73 - 1. 74 - 1. 74 - 1. 75 - 1. 76

0. 65

- 1. 28 - 1. 28 - 1. 29 - 1. 30 - 1. 31 - 1. 31 - 1. 32 - 1. 33 - 1. 34 - 1. 34 - 1. 35

0. 70

- 0. 94 - 0. 95 - 0. 96 - 0. 96 - 0. 97 - 0. 98 - 0. 99 - 0. 99 - 1. 00 - 1. 01 - 1. 01

0. 75

- 0. 69 - 0. 69 - 0. 70 - 0. 71 - 0. 71 - 0. 72 - 0. 73 - 0. 73 - 0. 74 - 0. 75 - 0. 75

0. 80

- 0. 04 - 0. 47 - 0. 48 - 0. 48 - 0. 48 - 0. 49 - 0. 50 - 0. 50 - 0. 51 - 0. 51 - 0. 52

0. 85

- 0. 03 - 0. 31 - 0. 31 - 0. 32 - 0. 33 - 0. 33 - 0. 34 - 0. 35 - 0. 35 - 0. 36 - 0. 37

0. 90

- 0. 02 - 0. 04 - 0. 18 - 0. 20 - 0. 20 - 0. 21 - 0. 21 - 0. 22 - 0. 23 - 0. 23 - 0. 24

0. 95

- 0. 01 - 0. 02 - 0. 03 - 0. 09 - 0. 10 - 0. 11 - 0. 12 - 0. 12 - 0. 13 - 0. 13 - 0. 14

1. 00

- 0. 01 - 0. 01 - 0. 01 - 0. 02 - 0. 03 - 0. 03 - 0. 04 - 0. 05 - 0. 05 - 0. 06 - 0. 06

1. 05

0. 00

0. 00

0. 00

0. 00

1. 10

0. 00

0. 00

0. 00

+ 0. 01

0. 01

0. 02

0. 02

0. 03

1. 15

0. 00

0. 00

0. 00

0. 01

0. 02

0. 02

0. 03

0. 04

0. 04

0. 05

0. 05

1. 20

0. 00

0. 01

0. 02

0. 03

0. 04

0. 05

0. 05

0. 06

0. 07

1. 25

0. 00

0. 01

0. 01

0. 02

0. 03

0. 03

0. 04

0. 05

0. 06

0. 07

0. 07

1. 3

+ 0. 01

0. 01

0. 02

0. 02

0. 03

0. 04

0. 04

0. 05

0. 06

0. 07

0. 08

1. 4

0. 01

0. 01

0. 02

0. 03

0. 04

0. 04

0. 05

0. 06

0. 07

0. 08

0. 08

1. 5

0. 01

0. 02

0. 02

0. 03

0. 04

0. 05

0. 05

0. 06

0. 06

0. 07

0. 08

1. 6

0. 01

0. 02

0. 02

0. 03

0. 04

0. 05

0. 05

0. 06

0. 06

0. 07

0. 08

1. 7

0. 01

0. 02

0. 02

0. 03

0. 04

0. 05

0. 05

0. 06

0. 06

0. 07

0. 08

1. 8

0. 01

0. 02

0. 02

0. 03

0. 04

0. 05

0. 05

0. 06

0. 06

0. 07

0. 08

1. 9

0. 01

0. 02

0. 02

0. 03

0. 04

0. 05

0. 05

0. 06

0. 06

0. 07

0. 08

2. 0

0. 01

0. 01

0. 02

0. 03

0. 04

0. 05

0. 05

0. 06

0. 07

0. 07

0. 08

2. 5

0. 01

0. 01

0. 02

0. 02

0. 03

0. 04

0. 04

0. 05

0. 06

0. 06

0. 07

3. 0

0. 00

0. 01

0. 01

0. 02

0. 02

0. 03

0. 04

0. 04

0. 05

0. 05

0. 05

3. 5

0. 00

0. 01

0. 01

0. 02

0. 02

0. 02

0. 03

0. 03

0. 04

0. 04

0. 04

4. 0

0. 00

0. 01

0. 01

0. 02

0. 02

0. 02

0. 02

0. 03

0. 03

0. 03

0. 04

+ 0. 01 + 0. 01

+ 0. 01 + 0. 01 + 0. 01 + 0. 01

0. 00

0. 00

0. 00

+ 0. 03 + 0. 03 + 0. 03

33 9


pr
Tr
2. 4

2. 6

2. 8

3. 0

4. 0

5. 0

6. 0

7. 0

8. 0

9. 0

0. 35

- 6. 78

- 6. 79

- 6. 80

- 6. 81

- 6. 86

- 6. 92

- 6. 96

- 7. 02

- 7. 06

- 7. 11

0. 40

- 5. 13

- 5. 14

- 5. 15

- 5. 16

- 5. 21

- 5. 26

- 5. 30

- 5. 34

- 5. 39

- 5. 43

0. 45

- 4. 00

- 4. 01

- 4. 02

- 4. 03

- 4. 07

- 4. 11

- 4. 15

- 4. 19

- 4. 23

- 4. 27

0. 50

- 3. 06

- 3. 07

- 3. 08

- 3. 09

- 3. 13

- 3. 17

- 3. 22

- 3. 26

- 3. 30

- 3. 34

0. 55

- 2. 32

- 2. 33

- 2. 34

- 2. 34

- 2. 38

- 2. 43

- 2. 46

- 2. 50

- 2. 53

- 2. 57

0. 60

- 1. 77

- 1. 77

- 1. 78

- 1. 79

- 1. 82

- 1. 86

- 1. 89

- 1. 93

- 1. 96

- 1. 99

0. 65

- 1. 36

- 1. 36

- 1. 37

- 1. 38

- 1. 41

- 1. 44

- 1. 47

- 1. 50

- 1. 53

- 1. 55

0. 70

- 1. 02

- 1. 03

- 1. 03

- 1. 04

- 1. 07

- 1. 09

- 1. 12

- 1. 15

- 1. 17

- 1. 19

0. 75

- 0. 76

- 0. 76

- 0. 76

- 0. 77

- 0. 80

- 0. 83

- 0. 85

- 0. 87

- 0. 89

- 0. 91

0. 80

- 0. 52

- 0. 53

- 0. 53

- 0. 54

- 0. 56

- 0. 59

- 0. 61

- 0. 63

- 0. 65

- 0. 67

0. 85

- 0. 37

- 0. 38

- 0. 38

- 0. 39

- 0. 41

- 0. 44

- 0. 46

- 0. 48

- 0. 50

- 0. 51

0. 90

- 0. 24

- 0. 25

- 0. 26

- 0. 26

- 0. 29

- 0. 31

- 0. 33

- 0. 35

- 0. 36

- 0. 38

0. 95

- 0. 15

- 0. 15

- 0. 16

- 0. 16

- 0. 18

- 0. 20

- 0. 22

- 0. 24

- 0. 26

- 0. 27

1. 00

- 0. 07

- 0. 07

- 0. 08

- 0. 08

- 0. 10

- 0. 12

- 0. 13

- 0. 15

- 0. 17

- 0. 18

1. 05

0. 00

- 0. 01

- 0. 01

- 0. 01

- 0. 03

- 0. 05

- 0. 06

- 0. 07

- 0. 09

- 0. 11

1. 10

+ 0. 03

+ 0. 03

+ 0. 03

+ 0. 03

+ 0. 02

0. 00

- 0. 01

- 0. 02

- 0. 03

- 0. 05

1. 15

0. 05

0. 06

0. 06

0. 06

0. 05

+ 0. 05

+ 0. 04

+ 0. 02

+ 0. 01

0. 00

1. 20

0. 07

0. 08

0. 08

0. 08

0. 09

0. 09

0. 08

0. 07

0. 07

+ 0. 06

1. 25

0. 08

0. 09

0. 09

0. 10

0. 11

0. 11

0. 11

0. 10

0. 10

0. 09

1. 3

0. 08

0. 09

0. 10

0. 10

0. 12

0. 13

0. 13

0. 13

0. 12

0. 12

1. 4

0. 09

0. 10

0. 11

0. 11

0. 13

0. 15

0. 15

0. 16

0. 16

0. 16

1. 5

0. 08

0. 09

0. 10

0. 11

0. 13

0. 15

0. 16

0. 17

0. 17

0. 18

1. 6

0. 08

0. 09

0. 10

0. 11

0. 14

0. 16

0. 18

0. 19

0. 20

0. 21

1. 7

0. 08

0. 09

0. 10

0. 11

0. 14

0. 16

0. 18

0. 20

0. 21

0. 23

1. 8

0. 08

0. 09

0. 10

0. 11

0. 14

0. 16

0. 19

0. 21

0. 23

0. 24

1. 9

0. 08

0. 09

0. 10

0. 11

0. 14

0. 16

0. 19

0. 21

0. 23

0. 25

2. 0

0. 08

0. 09

0. 09

0. 10

0. 13

0. 16

0. 19

0. 21

0. 23

0. 26

2. 5

0. 07

0. 08

0. 08

0. 09

0. 12

0. 14

0. 17

0. 19

0. 22

0. 24

3. 0

0. 06

0. 06

0. 07

0. 07

0. 10

0. 12

0. 15

0. 17

0. 20

0. 22

3. 5

0. 05

0. 05

0. 06

0. 06

0. 08

0. 10

0. 13

0. 15

0. 17

0. 19

4. 0

0. 04

0. 04

0. 05

0. 05

0. 07

0. 09

0. 10

0. 12

0. 14

0. 15

3 40

6 [ ( H
- H ) / RT c ] ( 0)
pr
Tr
0. 2

0. 4

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

2. 4

2. 6

0. 35

5. 81

5. 80

5. 79

5. 77

5. 75

5. 71

5. 69

5. 67

5. 65

5. 63

5. 61

5. 59

5. 57

0. 40

5. 63

5. 62

5. 61

5. 60

5. 58

5. 56

5. 54

5. 52

5. 50

5. 48

5. 46

5. 44

5. 42

0. 45

5. 48

5. 47

5. 45

5. 42

5. 40

5. 37

5. 35

5. 33

5. 31

5. 30

5. 28

5. 26

5. 25

0. 50

5. 31

5. 30

5. 29

5. 27

5. 25

5. 23

5. 21

5. 19

5. 17

5. 16

5. 14

5. 12

5. 10

0. 55

5. 18

5. 17

5. 15

5. 12

5. 10

5. 08

5. 06

5. 04

5. 02

5. 00

4. 98

4. 97

4. 95

0. 60

5. 05

5. 04

5. 03

5. 01

4. 98

4. 96

4. 94

4. 92

4. 90

4. 88

4. 86

4. 83

4. 82

0. 65

4. 91

4. 90

4. 90

4. 88

4. 86

4. 84

4. 82

4. 80

4. 78

4. 76

4. 75

4. 73

4. 72

0. 70

4. 81

4. 80

4. 78

4. 76

4. 75

4. 73

4. 71

4. 69

4. 68

4. 66

4. 65

4. 63

4. 62

0. 75

4. 69

4. 68

4. 67

4. 66

4. 64

4. 62

4. 61

4. 60

4. 58

4. 56

4. 55

4. 53

4. 52

0. 80

0. 37

4. 53

4. 52

4. 51

4. 50

4. 48

4. 47

4. 46

4. 44

4. 43

4. 42

4. 41

4. 40

0. 85

0. 32

4. 37

4. 36

4. 35

4. 34

4. 33

4. 33

4. 32

4. 31

4. 30

4. 29

4. 28

4. 28

0. 90

0. 27

0. 60

4. 06

4. 10

4. 14

4. 14

4. 15

4. 15

4. 14

4. 13

4. 13

4. 12

4. 12

0. 95

0. 23

0. 52

0. 86

3. 69

3. 80

3. 85

3. 87

3. 88

3. 89

3. 90

3. 90

3. 90

3. 90

1. 00

0. 21

0. 45

0. 76

1. 15

2. 3

3. 09

3. 32

3. 44

3. 52

3. 57

3. 60

3. 63

3. 65

1. 05

0. 19

0. 40

0. 64

0. 95

1. 35

1. 94

2. 54

2. 86

3. 07

3. 21

3. 30

3. 36

3. 39

1. 10

0. 17

0. 36

0. 57

0. 82

1. 10

1. 44

1. 83

2. 25

2. 55

2. 75

2. 89

3. 00

3. 08

1. 15

0. 14

0. 30

0. 49

0. 70

0. 93

1. 19

1. 48

1. 78

2. 07

2. 33

2. 52

2. 67

2. 78

1. 20

0. 13

0. 27

0. 44

0. 63

0. 83

1. 03

1. 25

1. 49

1. 73

1. 95

2. 13

2. 30

2. 44

1. 25

0. 12

0. 25

0. 39

0. 56

0. 73

0. 91

1. 09

1. 29

1. 50

1. 70

1. 87

2. 03

2. 17

1. 3

0. 11

0. 23

0. 36

0. 50

0. 66

0. 81

0. 97

1. 14

1. 32

1. 49

1. 64

1. 79

1. 93

1. 4

0. 09

0. 19

0. 31

0. 42

0. 54

0. 67

0. 80

0. 94

1. 08

1. 23

1. 36

1. 47

1. 59

1. 5

0. 09

0. 18

0. 29

0. 39

0. 49

0. 59

0. 70

0. 80

0. 93

1. 04

1. 15

1. 26

1. 36

1. 6

0. 09

0. 18

0. 27

0. 36

0. 45

0. 54

0. 62

0. 71

0. 81

0. 91

1. 00

1. 09

1. 18

1. 7

0. 08

0. 16

0. 25

0. 33

0. 41

0. 48

0. 56

0. 64

0. 71

0. 80

0. 87

0. 95

1. 02

1. 8

0. 07

0. 15

0. 23

0. 30

0. 37

0. 44

0. 51

0. 58

0. 64

0. 71

0. 78

0. 84

0. 90

1. 9

0. 06

0. 13

0. 19

0. 26

0. 33

0. 40

0. 46

0. 51

0. 57

0. 63

0. 68

0. 73

0. 78

2. 0

0. 06

0. 12

0. 18

0. 24

0. 30

0. 36

0. 42

0. 46

0. 51

0. 55

0. 59

0. 64

0. 69

2. 5

0. 04

0. 08

0. 12

0. 16

0. 19

0. 22

0. 25

0. 28

0. 31

0. 34

0. 37

0. 40

0. 43

3. 0

0. 03

0. 05

0. 07

0. 09

0. 11

0. 14

0. 16

0. 18

0. 20

0. 22

0. 24

0. 26

0. 28

3. 5

0. 02

0. 04

0. 05

0. 06

0. 07

0. 09

0. 10

0. 11

0. 12

0. 13

0. 15

0. 16

0. 17

4. 0

0. 01

0. 02

0. 03

0. 04

0. 04

0. 05

0. 06

0. 07

0. 08

0. 08

0. 09

0. 10

0. 10

34 1


pr
Tr
2. 8

3. 0

3. 2

3. 4

3. 6

3. 8

4. 0

4. 5

5. 0

6. 0

7. 0

8. 0

9. 0

0. 35

5. 55

5. 53

5. 51

5. 49

5. 47

5. 46

5. 44

5. 40

5. 36

5. 29

5. 21

5. 13

5. 05

0. 40

5. 40

5. 38

5. 37

5. 35

5. 34

5. 32

5. 30

5. 26

5. 22

5. 15

5. 07

5. 00

4. 92

0. 45

5. 23

5. 21

5. 20

5. 18

5. 17

5. 15

5. 13

5. 10

5. 05

4. 98

4. 90

4. 82

4. 73

0. 50

5. 09

5. 07

5. 06

5. 03

5. 02

5. 00

4. 98

4. 95

4. 91

4. 82

4. 74

4. 65

4. 55

0. 55

4. 93

4. 91

4. 90

4. 88

4. 87

4. 85

4. 83

4. 80

4. 76

4. 68

4. 60

4. 51

4. 42

0. 60

4. 81

4. 79

4. 77

4. 76

7. 74

4. 72

4. 71

4. 67

4. 63

4. 55

4. 47

4. 38

4. 29

0. 65

4. 70

4. 68

4. 67

4. 65

4. 64

4. 62

4. 60

4. 57

4. 53

4. 46

4. 38

4. 30

4. 21

0. 70

4. 60

4. 58

4. 57

4. 55

4. 54

4. 52

4. 51

4. 47

4. 43

4. 37

4. 29

4. 21

4. 12

0. 75

4. 51

4. 49

4. 48

4. 47

4. 45

4. 43

4. 42

4. 39

4. 35

4. 27

4. 20

4. 12

4. 03

0. 80

4. 39

4. 38

4. 36

4. 35

4. 34

4. 33

4. 32

4. 30

4. 23

4. 16

4. 10

4. 03

3. 95

0. 85

4. 27

4. 26

4. 25

4. 24

4. 23

4. 22

4. 21

4. 18

4. 11

4. 05

4. 00

3. 93

3. 85

0. 90

4. 12

4. 11

4. 10

4. 10

4. 10

4. 10

4. 10

4. 09

4. 05

3. 95

3. 89

3. 83

3. 76

0. 95

3. 90

3. 90

3. 90

3. 90

3. 89

3. 89

3. 89

3. 85

3. 85

3. 84

3. 77

3. 72

3. 67

1. 00

3. 68

3. 70

3. 71

3. 71

3. 70

3. 70

3. 70

3. 69

3. 68

3. 67

3. 64

3. 60

3. 57

1. 05

3. 42

3. 44

3. 46

3. 47

3. 49

3. 50

3. 51

3. 51

3. 50

3. 49

3. 48

3. 46

3. 45

1. 10

3. 15

3. 20

3. 24

3. 27

3. 29

3. 30

3. 32

3. 34

3. 34

3. 34

3. 33

3. 32

3. 32

1. 15

2. 86

2. 93

2. 98

3. 02

3. 05

3. 09

3. 12

3. 17

3. 18

3. 18

3. 19

3. 19

3. 20

1. 20

2. 56

2. 66

2. 73

2. 78

2. 82

2. 87

2. 91

2. 99

3. 02

3. 05

3. 07

3. 07

3. 08

1. 25

2. 29

2. 39

2. 48

2. 55

2. 61

2. 67

2. 72

2. 82

2. 87

2. 92

2. 93

2. 95

2. 98

1. 3

2. 05

2. 16

2. 24

2. 32

2. 39

2. 45

2. 52

2. 63

2. 72

2. 79

2. 81

2. 84

2. 88

1. 4

1. 70

1. 79

1. 88

1. 96

2. 04

2. 11

2. 18

2. 32

2. 43

2. 53

2. 58

2. 62

2. 65

1. 5

1. 45

1. 53

1. 61

1. 68

1. 75

1. 82

1. 88

2. 01

2. 12

2. 25

2. 33

2. 39

2. 41

1. 6

1. 26

1. 33

1. 39

1. 44

1. 51

1. 57

1. 64

1. 78

1. 87

2. 01

2. 12

2. 19

2. 21

1. 7

1. 08

1. 15

1. 21

1. 27

1. 33

1. 39

1. 45

1. 57

1. 66

1. 79

1. 91

2. 00

2. 03

1. 8

0. 95

1. 01

1. 06

1. 12

1. 18

1. 24

1. 31

1. 42

1. 50

1. 62

1. 74

1. 83

1. 86

1. 9

0. 82

0. 87

0. 92

0. 97

1. 02

1. 08

1. 13

1. 23

1. 32

1. 44

1. 54

1. 63

1. 67

2. 0

0. 74

0. 78

0. 82

0. 85

0. 89

0. 93

0. 97

1. 07

1. 14

1. 25

1. 33

1. 43

1. 46

2. 5

0. 45

0. 47

0. 50

0. 52

0. 54

0. 56

0. 58

0. 63

0. 67

0. 75

0. 81

0. 87

0. 91

3. 0

0. 30

0. 31

0. 33

0. 34

0. 36

0. 37

0. 38

0. 41

0. 44

0. 50

0. 53

0. 56

0. 58

3. 5

0. 18

0. 19

0. 20

0. 21

0. 22

0. 23

0. 23

0. 25

0. 26

0. 28

0. 30

0. 30

0. 29

4. 0

0. 11

0. 11

0. 11

0. 12

0. 12

0. 12

0. 13

0. 13

0. 14

0. 14

0. 14

0. 13

0. 12

3 42

7 [ ( H
- H ) / RT c ] ( 1)
pr
Tr
0. 2

0. 4

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

0. 35

10. 40

10. 46

10. 55

10. 61

10. 68

10. 74

10. 80

10. 85

10. 90

10. 94

10. 98

0. 40

9. 93

9. 98

10. 05

10. 11

10. 17

10. 22

10. 26

10. 30

10. 34

10. 37

10. 41

0. 45

9. 48

9. 51

9. 55

9. 59

9. 63

9. 67

9. 71

9. 74

9. 77

9. 80

9. 82

0. 50

8. 93

8. 97

9. 00

9. 04

9. 08

9. 10

9. 13

9. 15

9. 18

9. 20

9. 22

0. 55

8. 46

8. 50

8. 52

8. 55

8. 57

8. 58

8. 60

8. 61

8. 63

8. 65

8. 66

0. 60

7. 88

7. 91

7. 93

7. 95

7. 97

7. 99

8. 01

8. 02

8. 04

8. 05

8. 07

0. 65

7. 31

7. 34

7. 38

7. 42

7. 45

7. 48

7. 51

7. 54

7. 56

7. 59

7. 61

0. 70

6. 79

6. 81

6. 83

6. 87

6. 90

6. 94

6. 97

6. 99

7. 03

7. 06

7. 08

0. 75

6. 21

6. 24

6. 26

6. 28

6. 30

6. 32

6. 35

6. 37

6. 39

6. 41

6. 43

0. 80

0. 44

5. 60

5. 62

5. 65

5. 68

5. 70

5. 72

5. 75

5. 77

5. 80

5. 82

0. 85

0. 37

4. 74

4. 83

4. 92

5. 02

5. 06

5. 10

5. 13

5. 15

5. 17

5. 20

0. 90

0. 31

0. 71

4. 10

4. 21

4. 31

4. 37

4. 43

4. 48

4. 51

4. 54

4. 56

0. 95

0. 25

0. 55

1. 01

3. 83

3. 80

3. 81

3. 84

3. 84

3. 87

3. 87

3. 88

1. 00

0. 20

0. 41

0. 68

0. 95

2. 66

3. 17

3. 27

3. 33

3. 38

3. 41

3. 45

1. 05

0. 14

0. 27

0. 40

0. 54

0. 68

1. 22

1. 77

2. 19

2. 45

2. 59

2. 71

1. 10

0. 12

0. 22

0. 29

0. 36

0. 42

0. 52

0. 69

0. 92

1. 32

1. 71

1. 97

1. 15

0. 09

0. 17

0. 23

0. 28

0. 32

0. 36

0. 39

0. 45

0. 58

0. 81

1. 08

1. 20

0. 08

0. 14

0. 20

0. 24

0. 28

0. 29

0. 29

0. 32

0. 37

0. 47

0. 59

1. 25

0. 06

0. 13

0. 18

0. 21

0. 25

0. 25

0. 26

0. 28

0. 28

0. 30

0. 36

1. 3

0. 03

0. 06

0. 10

0. 13

0. 17

0. 19

0. 24

0. 23

0. 24

0. 25

0. 27

1. 4

0. 02

0. 04

0. 06

0. 08

0. 10

0. 11

0. 11

0. 12

0. 12

0. 12

0. 14

1. 5

0. 01

0. 01

0. 02

0. 03

0. 04

0. 04

0. 04

0. 04

0. 04

0. 04

0. 05

1. 6

0. 00

0. 00

0. 00

0. 00

0. 00

0. 00

0. 00

0. 00

- 0. 01 - 0. 01 - 0. 01

1. 7

- 0. 01 - 0. 01 - 0. 02 - 0. 03 - 0. 04 - 0. 04 - 0. 05 - 0. 05 - 0. 06 - 0. 06 - 0. 07

1. 8

- 0. 01 - 0. 02 - 0. 03 - 0. 04 - 0. 06 - 0. 07 - 0. 08 - 0. 09 - 0. 10 - 0. 10 - 0. 11

1. 9

- 0. 02 - 0. 03 - 0. 05 - 0. 07 - 0. 09 - 0. 11 - 0. 13 - 0. 15 - 0. 17 - 0. 19 - 0. 20

2. 0

- 0. 02 - 0. 04 - 0. 06 - 0. 08 - 0. 10 - 0. 13 - 0. 16 - 0. 19 - 0. 22 - 0. 25 - 0. 25

2. 5

- 0. 03 - 0. 06 - 0. 10 - 0. 13 - 0. 17 - 0. 20 - 0. 23 - 0. 26 - 0. 29 - 0. 32 - 0. 35

3. 0

- 0. 04 - 0. 08 - 0. 13 - 0. 17 - 0. 21 - 0. 25 - 0. 29 - 0. 33 - 0. 37 - 0. 41 - 0. 45

3. 5

- 0. 04 - 0. 08 - 0. 13 - 0. 17 - 0. 21 - 0. 25 - 0. 29 - 0. 34 - 0. 37 - 0. 42 - 0. 47

4. 0

- 0. 04 - 0. 08 - 0. 13 - 0. 17 - 0. 21 - 0. 25 - 0. 29 - 0. 34 - 0. 37 - 0. 42 - 0. 46

34 3


pr
Tr
2. 4

2. 6

2. 8

3. 0

4. 0

5. 0

6. 0

7. 0

8. 0

9. 0

0. 35

11. 02

11. 06

11. 09

11. 12

11. 27

11. 38

11. 47

11. 55

11. 61

11. 67

0. 40

10. 44

10. 47

10. 50

10. 52

10. 63

10. 72

10. 80

10. 86

10. 92

10. 97

0. 45

9. 85

9. 87

9. 89

9. 91

10. 00

10. 07

10. 13

10. 18

10. 23

10. 27

0. 50

9. 24

9. 26

9. 27

9. 29

9. 36

9. 42

9. 48

9. 52

9. 57

9. 61

0. 55

8. 67

8. 68

8. 70

8. 71

8. 77

8. 82

8. 88

8. 93

8. 98

9. 02

0. 60

8. 08

8. 10

8. 11

8. 13

8. 20

8. 27

8. 34

8. 41

8. 47

8. 52

0. 65

7. 63

7. 65

7. 68

7. 70

7. 78

7. 86

7. 92

7. 98

8. 04

8. 09

0. 70

7. 10

7. 11

7. 13

7. 15

7. 25

7. 33

7. 41

7. 48

7. 54

7. 60

0. 75

6. 45

6. 47

6. 49

6. 52

6. 65

6. 75

6. 85

6. 94

7. 02

7. 10

0. 80

5. 83

5. 86

5. 87

5. 90

6. 00

6. 13

6. 25

6. 36

6. 46

6. 56

0. 85

5. 22

5. 24

5. 26

5. 28

5. 39

5. 50

5. 59

5. 68

5. 75

5. 82

0. 90

4. 58

4. 60

4. 62

4. 64

4. 73

4. 82

4. 89

4. 96

5. 02

5. 10

0. 95

3. 90

3. 90

3. 93

3. 93

4. 04

4. 12

4. 19

4. 23

4. 28

4. 32

1. 00

3. 49

3. 53

3. 58

3. 61

3. 76

3. 88

3. 97

4. 02

4. 07

4. 10

1. 05

2. 79

2. 88

2. 94

2. 99

3. 26

3. 48

3. 57

3. 66

3. 75

3. 81

1. 10

2. 11

2. 24

2. 30

2. 39

2. 74

3. 01

3. 17

3. 30

3. 42

3. 53

1. 15

1. 32

1. 52

1. 67

1. 78

2. 24

2. 52

2. 73

2. 93

3. 09

3. 23

1. 20

0. 74

0. 91

1. 08

1. 21

1. 70

1. 98

2. 21

2. 41

2. 59

2. 79

1. 25

0. 43

0. 51

0. 63

0. 76

1. 26

1. 56

1. 79

1. 98

2. 15

2. 41

1. 3

0. 32

0. 39

0. 46

0. 53

0. 85

1. 11

1. 43

1. 60

1. 83

2. 10

1. 4

0. 16

0. 19

0. 22

0. 25

0. 45

0. 73

0. 98

1. 15

1. 40

1. 66

1. 5

0. 06

0. 07

0. 09

0. 09

0. 20

0. 47

0. 68

0. 86

1. 10

1. 36

1. 6

- 0. 01

- 0. 02

- 0. 02

- 0. 02

0. 05

0. 28

0. 45

0. 64

0. 88

1. 10

1. 7

- 0. 08

- 0. 09

- 0. 10

- 0. 10

- 0. 07

0. 11

0. 25

0. 43

0. 63

0. 85

1. 8

- 0. 12

- 0. 13

- 0. 14

- 0. 16

- 0. 16

- 0. 03

0. 08

0. 23

0. 42

0. 61

1. 9

- 0. 20

- 0. 21

- 0. 21

- 0. 21

- 0. 21

- 0. 15

- 0. 07

0. 06

0. 22

0. 39

2. 0

- 0. 25

- 0. 26

- 0. 26

- 0. 26

- 0. 28

- 0. 26

- 0. 19

- 0. 10

0. 03

0. 18

2. 5

- 0. 39

- 0. 43

- 0. 45

- 0. 48

- 0. 53

- 0. 55

- 0. 57

- 0. 59

- 0. 63

- 0. 61

3. 0

- 0. 49

- 0. 53

- 0. 57

- 0. 60

- 0. 74

- 0. 85

- 0. 95

- 1. 05

- 1. 14

- 1. 21

3. 5

- 0. 51

- 0. 55

- 0. 59

- 0. 63

- 0. 83

- 1. 02

- 1. 19

- 1. 37

- 1. 50

- 1. 67

4. 0

- 0. 50

- 0. 54

- 0. 58

- 0. 62

- 0. 84

- 1. 03

- 1. 25

- 1. 47

- 1. 66

- 1. 86

3 44

 T r , p r , Zc

Tr

P r = 1. 0

P r = 2. 0

Z c=

Zc =

Zc =

Zc =

Zc =

Zc =

Z c=

Z c=

Zc =

Zc =

Zc =

0. 23

0. 25

0. 27

0. 29

0. 23

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 30

3. 487

3. 287

3. 081

3. 490

3. 290

3. 084

3. 494

3. 294

3. 088

0. 32

3. 450

3. 253

3. 049

3. 454

3. 256

3. 052

3. 458

3. 260

3. 056

0. 34

3. 419

3. 223

3. 021

3. 423

3. 227

3. 025

3. 427

3. 231

3. 029

0. 36

3. 383

3. 189

2. 989

3. 387

3. 193

2. 993

3. 392

3. 198

2. 998

0. 38

3. 348

3. 156

2. 959

3. 354

3. 162

2. 964

3. 358

3. 170

2. 970

0. 40

3. 306

3. 118

2. 922

3. 313

3. 123

2. 928

3. 322

3. 132

2. 936

0. 42

3. 140

3. 271

3. 084

2. 891

3. 181

3. 278

3. 090

2. 897

3. 287

3. 099

2. 905

0. 44

3. 138

3. 234

3. 049

2. 858

3. 174

3. 239

3. 054

2. 863

3. 251

3. 065

2. 873

0. 46

3. 130

3. 195

3. 012

2. 824

3. 164

3. 203

3. 020

2. 831

3. 215

3. 031

2. 841

0. 48

3. 118

3. 156

2. 975

2. 789

3. 149

3. 165

2. 984

2. 797

3. 177

2. 995

2. 808

0. 50

3. 101

3. 115

2. 937

2. 753

3. 132

3. 126

2. 947

2. 763

3. 136

2. 957

2. 772

0. 52

3. 082

3. 076

2. 900

2. 719

3. 115

3. 088

2. 911

2. 729

3. 099

2. 922

2. 739

0. 54

3. 060

3. 036

2. 862

2. 683

3. 099

3. 050

2. 875

2. 696

3. 063

2. 888

2. 707

0. 56

3. 032

2. 996

2. 825

2. 648

3. 071

3. 012

2. 840

2. 622

3. 028

2. 855

2. 676

0. 58

3. 005

2. 956

2. 787

2. 613

3. 040

2. 974

2. 800

2. 630

2. 990

2. 823

2. 646

0. 60

2. 973

2. 913

2. 746

2. 574

3. 007

2. 932

2. 764

2. 591

2. 952

2. 783

2. 609

0. 61

2. 957

2. 893

2. 727

2. 556

2. 989

2. 913

2. 746

2. 574

2. 936

2. 768

2. 595

0. 62

2. 940

2. 868

2. 704

2. 535

2. 965

2. 888

2. 723

2. 553

2. 916

2. 749

2. 577

0. 63

2. 923

2. 849

2. 686

2. 518

2. 954

2. 868

2. 704

2. 535

2. 897

2. 731

2. 560

0. 64

2. 904

2. 825

2. 663

2. 496

2. 938

2. 845

2. 682

2. 514

2. 877

2. 712

2. 542

0. 65

2. 889

2. 800

2. 640

2. 475

2. 919

2. 824

2. 660

2. 494

2. 852

2. 689

2. 512

0. 66

2. 868

2. 781

2. 622

2. 458

2. 900

2. 800

2. 640

2. 475

2. 836

2. 674

2. 057

0. 67

2. 848

2. 757

2. 599

2. 436

2. 882

2. 784

2. 625

2. 461

2. 816

2. 655

2. 489

0. 68

2. 827

2. 733

2. 577

2. 416

2. 864

2. 761

2. 603

2. 440

2. 797

2. 637

2. 472

0. 69

2. 810

2. 709

2. 554

2. 394

2. 846

2. 737

2. 580

2. 419

2. 777

2. 618

2. 454

0. 70

2. 785

2. 686

2. 532

2. 374

2. 828

2. 718

2. 562

2. 402

2. 757

2. 599

2. 436

0. 71

2. 768

2. 661

2. 509

2. 352

2. 805

2. 693

2. 539

2. 380

2. 733

2. 577

2. 416

34 5

Tr

P r = 1. 0

P r = 2. 0

Z c=

Zc =

Zc =

Zc =

Zc =

Zc =

Z c=

Z c=

Zc =

Zc =

Zc =

0. 23

0. 25

0. 27

0. 29

0. 23

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 72

2. 741

2. 637

2. 486

2. 330

2. 782

2. 673

2. 520

2. 362

2. 711

2. 555

2. 395

0. 73

2. 717

2. 614

2. 460

2. 310

2. 759

2. 650

2. 498

2. 342

2. 687

2. 533

2. 376

0. 74

2. 693

2. 586

2. 438

2. 285

2. 736

2. 621

2. 471

2. 316

2. 662

2. 521

2. 351

0. 75

2. 667

2. 557

2. 411

2. 260

2. 714

2. 598

2. 449

2. 296

2. 640

2. 490

2. 333

0. 76

2. 643

2. 534

2. 389

2. 240

2. 690

2. 573

2. 426

2. 274

2. 620

2. 473

2. 317

0. 77

2. 617

2. 505

2. 363

2. 215

2. 668

2. 546

2. 400

2. 250

2. 594

2. 445

2. 292

0. 78

2. 593

2. 478

2. 336

2. 190

2. 644

2. 522

2. 378

2. 229

2. 571

2. 423

2. 271

0. 79

2. 566

2. 450

2. 310

2. 168

2. 621

2. 494

2. 351

2. 204

2. 546

2. 400

2. 250

0. 80

2. 535

2. 420

2. 284

2. 145

2. 597

2. 470

2. 329

2. 183

2. 524

2. 377

2. 230

0. 81

2. 502

2. 390

2. 257

2. 121

2. 577

2. 446

2. 306

2. 160

2. 500

2. 354

2. 206

0. 82

2. 478

2. 359

2. 231

2. 096

2. 553

2. 418

2. 280

2. 137

2. 472

2. 330

2. 183

0. 83

2. 442

2. 327

2. 201

2. 070

2. 526

2. 387

2. 250

2. 109

2. 447

2. 306

2. 161

0. 84

2. 407

2. 295

2. 171

2. 044

2. 498

2. 359

2. 224

2. 085

2. 420

2. 281

2. 137

0. 85

2. 370

2. 263

2. 141

2. 014

2. 468

2. 327

2. 194

2. 057

2. 394

2. 256

2. 114

0. 86

2. 340

2. 227

2. 107

1. 984

2. 436

2. 290

2. 161

2. 038

2. 358

2. 231

2. 098

0. 87

2. 297

2. 191

2. 077

1. 957

2. 402

2. 253

2. 131

2. 002

2. 330

2. 204

2. 070

0. 88

2. 256

2. 155

2. 043

1. 925

2. 364

2. 217

2. 098

1. 972

2. 302

2. 177

2. 049

0. 89

2. 216

2. 116

2. 006

1. 891

2. 324

2. 179

2. 063

1. 941

2. 274

2. 150

2. 022

0. 90

2. 191

2. 076

1. 969

1. 859

2. 285

2. 140

2. 027

1. 911

2. 243

2. 122

1. 998

0. 91

2. 131

2. 032

1. 932

1. 824

2. 232

2. 094

1. 990

1. 877

2. 211

2. 092

1. 970

0. 92

2. 077

1. 989

1. 890

1. 789

2. 174

2. 051

1. 948

1. 843

2. 180

2. 064

1. 943

0. 93

2. 020

1. 940

1. 846

1. 747

2. 113

2. 000

1. 904

1. 802

2. 145

2. 033

1. 913

0. 94

1. 965

1. 888

1. 797

1. 707

2. 057

1. 948

1. 855

1. 762

2. 104

2. 001

1. 887

0. 95

1. 898

1. 829

1. 745

1. 657

1. 994

1. 889

1. 803

1. 713

2. 063

1. 965

1. 856

0. 96

1. 784

1. 765

1. 685

1. 605

1. 920

1. 824

1. 743

1. 661

2. 028

1. 931

1. 825

0. 97

1. 729

1. 689

1. 617

1. 545

1. 850

1. 740

1. 667

1. 594

1. 988

1. 892

1. 790

0. 98

1. 628

1. 598

1. 535

1. 469

1. 748

1. 644

1. 580

1. 513

1. 946

1. 852

1. 755

0. 99

1. 475

1. 470

1. 420

1. 368

1. 624

1. 450

1. 450

1. 397

1. 902

1. 810

1. 719

1. 00

1. 000

1. 000

1. 000

1. 000

1. 000

1. 000

1. 000

1. 000

1. 854

1. 764

1. 676

3 46


p r = 4. 0
Tr

p r = 6. 0

p r = 10

p r = 15

Zc =

Z c=

Zc =

Zc =

Zc =

Z c=

Zc =

Zc =

Zc =

Z c=

Zc =

Zc =

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 30

3. 500 3. 300 3. 094 3. 506 3. 305 3. 098 3. 512 3. 320 3. 112 3. 527 3. 325 3. 116

0. 32

3. 465 3. 267 3. 063 3. 471 3. 272 3. 067 3. 484 3. 285 3. 079 3. 495 3. 295 3. 088

0. 34

3. 437 3. 240 3. 037 3. 442 3. 245 3. 041 3. 453 3. 255 3. 051 3. 463 3. 265 3. 060

0. 36

3. 402 3. 207 3. 006 3. 407 3. 212 3. 011 3. 421 3. 225 3. 028 3. 431 3. 235 3. 032

0. 38

3. 373 3. 180 2. 981 3. 378 3. 185 2. 986 3. 389 3. 195 2. 995 3. 401 3. 206 3. 005

0. 40

3. 334 3. 143 2. 946 3. 339 3. 148 2. 951 3. 357 3. 165 2. 967 3. 370 3. 177 2. 978

0. 42

3. 301 3. 112 2. 917 3. 306 3. 117 2. 922 3. 325 3. 135 2. 938 3. 340 3. 147 2. 950

0. 44

3. 267 3. 080 2. 887 3. 273 3. 086 2. 894 3. 292 3. 104 2. 909 3. 307 3. 118 2. 923

0. 46

3. 232 3. 047 2. 856 3. 239 3. 054 2. 863 3. 262 3. 075 2. 882 3. 278 3. 090 2. 896

0. 48

3. 195 3. 012 2. 824 3. 208 3. 024 2. 835 3. 230 3. 045 2. 854 3. 242 3. 068 2. 876

0. 50

3. 156 2. 975 2. 789 3. 171 2. 990 2. 803 3. 198 3. 015 2. 826 3. 214 3. 030 2. 840

0. 52

3. 120 2. 941 2. 757 3. 140 2. 960 2. 775 3. 166 2. 985 2. 798 3. 182 3. 000 2. 812

0. 54

3. 088 2. 911 2. 729 3. 104 2. 926 2. 743 3. 134 2. 955 2. 770 3. 153 2. 973 2. 787

0. 56

3. 056 2. 881 2. 701 3. 072 2. 896 2. 715 3. 103 2. 925 2. 742 3. 120 2. 949 2. 764

0. 58

3. 020 2. 847 2. 669 3. 040 2. 870 2. 691 3. 072 2. 896 2. 714 3. 093 2. 916 2. 733

0. 60

2. 984 2. 813 2. 637 3. 008 2. 836 2. 659 3. 044 2. 870 2. 690 3. 063 2. 888 2. 707

0. 61

2. 964 2. 794 2. 619 2. 996 2. 825 2. 649 3. 028 2. 855 2. 676 3. 050 2. 875 2. 695

0. 62

2. 945 2. 776 2. 602 2. 980 2. 809 2. 634 3. 013 2. 841 2. 663 3. 036 2. 862 2. 683

0. 63

2. 929 2. 761 2. 588 2. 964 2. 794 2. 620 2. 998 2. 828 2. 651 3. 022 2. 849 2. 670

0. 64

2. 913 2. 746 2. 574 2. 948 2. 779 2. 606 2. 985 2. 814 2. 638 3. 008 2. 836 2. 660

0. 65

2. 893 2. 727 2. 556 2. 932 2. 764 2. 591 2. 970 2. 800 2. 624 2. 995 2. 824 2. 647

0. 66

2. 877 2. 712 2. 542 2. 916 2. 749 2. 577 2. 951 2. 782 2. 602 2. 982 2. 811 2. 635

0. 67

2. 856 2. 693 2. 524 2. 900 2. 734 2. 563 2. 940 2. 772 2. 598 2. 968 2. 798 2. 623

0. 68

2. 836 2. 676 2. 507 2. 881 2. 716 2. 546 2. 918 2. 751 2. 579 2. 954 2. 785 2. 610

0. 69

2. 820 2. 660 2. 494 2. 865 2. 701 2. 532 2. 910 2. 743 2. 571 2. 940 2. 776 2. 602

0. 70

2. 802 2. 642 2. 477 2. 849 2. 686 2. 518 2. 890 2. 730 2. 560 2. 928 2. 760 2. 589

0. 71

2. 784 2. 625 2. 461 2. 833 2. 671 2. 500 2. 872 2. 716 2. 547 2. 915 2. 748 2. 577

0. 72

2. 765 2. 607 2. 444 2. 816 2. 655 2. 489 2. 860 2. 701 2. 533 2. 901 2. 735 2. 565

0. 73

2. 747 2. 590 2. 428 2. 799 2. 639 2. 474 2. 851 2. 688 2. 521 2. 894 2. 720 2. 559

0. 74

2. 729 2. 573 2. 412 2. 781 2. 622 2. 458 2. 837 2. 675 2. 509 2. 874 2. 710 2. 542

34 7


p r = 4. 0
Tr

p r = 6. 0

p r = 10

p r = 15

Zc =

Z c=

Zc =

Zc =

Zc =

Z c=

Zc =

Zc =

Zc =

Z c=

Zc =

Zc =

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 75

2. 709 2. 554 2. 394 2. 761 2. 603 2. 441 2. 812 2. 661 2. 495 2. 861 2. 697 2. 530

0. 76

2. 689 2. 535 2. 376 2. 745 2. 588 2. 426 2. 800 2. 646 2. 480 2. 848 2. 685 2. 518

0. 77

2. 672 2. 518 2. 360 2. 729 2. 573 2. 412 2. 784 2. 631 2. 468 2. 833 2. 671 2. 505

0. 78

2. 652 2. 500 2. 344 2. 709 2. 554 2. 394 2. 770 2. 617 2. 454 2. 820 2. 659 2. 494

0. 79

2. 631 2. 480 2. 325 2. 693 2. 539 2. 380 2. 750 2. 602 2. 440 2. 807 2. 646 2. 482

0. 80

2. 609 2. 460 2. 306 2. 673 2. 520 2. 362 2. 735 2. 587 2. 432 2. 790 2. 634 2. 476

0. 81

2. 588 2. 440 2. 287 2. 656 2. 504 2. 347 2. 719 2. 572 2. 418 2. 778 2. 621 2. 464

0. 82

2. 567 2. 420 2. 269 2. 638 2. 487 2. 331 2. 704 2. 558 2. 405 2. 762 2. 609 2. 452

0. 83

2. 546 2. 400 2. 250 2. 619 2. 470 2. 315 2. 687 2. 542 2. 389 2. 750 2. 595 2. 439

0. 84

2. 524 2. 380 2. 232 2. 660 2. 449 2. 295 2. 671 2. 527 2. 375 2. 740 2. 583 2. 428

0. 85

2. 503 2. 360 2. 214 2. 580 2. 433 2. 281 2. 655 2. 512 2. 361 2. 720 2. 571 2. 417

0. 86

2. 482 2. 340 2. 195 2. 562 2. 416 2. 265 2. 639 2. 496 2. 346 2. 708 2. 559 2. 405

0. 87

2. 461 2. 320 2. 176 2. 543 2. 398 2. 248 2. 621 2. 479 2. 330 2. 698 2. 545 2. 392

0. 88

2. 438 2. 299 2. 156 2. 524 2. 380 2. 232 2. 606 2. 465 2. 317 2. 682 2. 532 2. 380

0. 89

2. 415 2. 277 2. 136 2. 505 2. 362 2. 216 2. 590 2. 450 2. 303 2. 670 2. 519 2. 368

0. 90

2. 390 2. 257 2. 119 2. 486 2. 344 2. 200 2. 572 2. 434 2. 282 2. 658 2. 506 2. 349

0. 91

2. 365 2. 235 2. 100 2. 466 2. 325 2. 182 2. 560 2. 418 2. 267 2. 644 2. 493 2. 340

0. 92

2. 342 2. 214 2. 080 2. 440 2. 307 2. 165 2. 540 2. 402 2. 252 2. 632 2. 481 2. 330

0. 93

2. 316 2. 191 2. 060 2. 420 2. 288 2. 147 2. 532 2. 387 2. 238 2. 620 2. 470 2. 316

0. 94

2. 292 2. 168 2. 039 2. 400 2. 268 2. 129 2. 514 2. 370 2. 222 2. 606 2. 457 2. 303

0. 95

2. 267 2. 145 2. 018 2. 378 2. 249 2. 113 2. 498 2. 355 2. 208 2. 593 2. 445 2. 292

0. 96

2. 240 2. 120 1. 995 2. 356 2. 229 2. 096 2. 480 2. 338 2. 192 2. 581 2. 433 2. 281

0. 97

2. 211 2. 095 1. 973 2. 334 2. 208 2. 077 2. 463 2. 322 2. 177 2. 567 2. 420 2. 269

0. 98

2. 184 2. 072 1. 950 2. 313 2. 188 2. 059 2. 446 2. 306 2. 162 2. 555 2. 409 2. 258

0. 99

2. 155 2. 043 1. 925 2. 289 2. 165 2. 038 2. 429 2. 290 2. 147 2. 541 2. 396 2. 246

1. 00

2. 127 2. 016 1. 900 2. 266 2. 143 2. 018 2. 412 2. 274 2. 132 2. 532 2. 383 2. 234

3 48


p r = 20
Tr

p r = 25

p r = 30

Zc =

Zc =

Z c=

Zc =

Zc =

Z c=

Zc =

Zc =

Z c=

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 30

3. 535

3. 333

3. 124

3. 540

3. 337

3. 128

3. 546

3. 343

3. 133

0. 32

3. 506

3. 305

3. 098

3. 511

3. 310

3. 102

3. 517

3. 316

3. 108

0. 34

3. 474

3. 275

3. 070

3. 481

3. 282

3. 076

3. 489

3. 289

3. 083

0. 36

3. 442

3. 245

3. 042

3. 453

3. 255

3. 051

3. 459

3. 261

3. 057

0. 38

3. 410

3. 215

3. 013

3. 421

3. 225

3. 023

3. 430

3. 233

3. 030

0. 40

3. 378

3. 185

2. 985

3. 390

3. 196

2. 996

3. 400

3. 205

3. 004

0. 42

3. 350

3. 158

2. 960

3. 360

3. 168

2. 969

3. 370

3. 177

2. 978

0. 44

3. 319

3. 129

2. 933

3. 306

3. 140

2. 943

3. 341

3. 150

2. 952

0. 46

3. 288

3. 100

2. 906

3. 302

3. 113

2. 918

3. 310

3. 121

2. 925

0. 48

3. 257

3. 071

2. 878

3. 274

3. 085

2. 892

3. 282

3. 094

2. 900

0. 50

3. 226

3. 041

2. 850

3. 245

3. 059

2. 867

3. 252

3. 066

2. 874

0. 52

3. 197

3. 014

2. 825

3. 214

3. 030

2. 840

3. 225

3. 040

2. 849

0. 54

3. 167

2. 986

2. 799

3. 186

3. 004

2. 816

3. 198

3. 015

2. 826

0. 56

3. 139

2. 959

2. 773

3. 157

2. 976

2. 789

3. 170

2. 989

2. 802

0. 58

3. 109

2. 931

2. 750

3. 130

2. 951

2. 766

3. 145

2. 965

2. 779

0. 60

3. 081

2. 905

2. 723

3. 103

2. 925

2. 742

3. 120

2. 941

2. 757

0. 61

3. 070

2. 894

2. 713

3. 090

2. 913

2. 730

3. 108

2. 930

2. 746

0. 62

3. 056

2. 881

2. 700

3. 076

2. 900

2. 718

3. 096

2. 919

2. 736

0. 63

3. 044

2. 870

2. 690

3. 064

2. 889

2. 708

3. 082

2. 906

2. 724

0. 64

3. 031

2. 858

2. 679

3. 052

2. 877

2. 697

3. 065

2. 890

2. 709

0. 65

3. 018

2. 845

2. 667

3. 040

2. 866

2. 686

3. 060

2. 885

2. 704

0. 66

3. 005

2. 833

2. 655

3. 028

2. 855

2. 676

3. 050

2. 875

2. 695

0. 67

2. 991

2. 820

2. 643

3. 016

2. 843

2. 665

3. 038

2. 864

2. 684

0. 68

2. 980

2. 809

2. 633

3. 004

2. 832

2. 654

3. 027

2. 854

2. 675

0. 69

2. 967

2. 797

2. 622

2. 912

2. 820

2. 643

3. 016

2. 843

2. 665

0. 70

2. 955

2. 786

2. 613

2. 981

2. 810

2. 635

3. 005

2. 833

2. 657

0. 71

2. 943

2. 775

2. 600

2. 969

2. 799

2. 625

2. 994

2. 823

2. 648

0. 72

2. 931

2. 763

2. 591

2. 956

2. 787

2. 614

2. 985

2. 814

2. 639

0. 73

2. 917

2. 750

2. 579

2. 945

2. 776

2. 604

2. 974

2. 804

2. 630

0. 74

2. 906

2. 740

2. 570

2. 933

2. 765

2. 593

2. 964

2. 794

2. 620

34 9


p r = 20
Tr

p r = 25

p r = 30

Zc =

Zc =

Z c=

Zc =

Zc =

Z c=

Zc =

Zc =

Z c=

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 25

0. 27

0. 29

0. 75

2. 896

2. 730

2. 560

2. 921

2. 754

2. 583

2. 953

2. 784

2. 610

0. 76

2. 886

2. 721

2. 552

2. 911

2. 744

2. 574

2. 942

2. 774

2. 602

0. 77

2. 870

2. 706

2. 538

2. 899

2. 733

2. 563

2. 932

2. 764

2. 592

0. 78

2. 859

2. 695

2. 528

2. 887

2. 722

2. 553

2. 920

2. 753

2. 582

0. 79

2. 847

2. 684

2. 517

2. 877

2. 712

2. 544

2. 910

2. 743

2. 578

0. 80

2. 830

2. 673

2. 513

2. 864

2. 702

2. 540

2. 900

2. 734

2. 570

0. 81

2. 820

2. 661

2. 501

2. 852

2. 693

2. 531

2. 890

2. 725

2. 561

0. 82

2. 810

2. 650

2. 490

2. 844

2. 683

2. 522

2. 880

2. 715

2. 552

0. 83

2. 798

2. 639

2. 481

2. 832

2. 673

2. 513

2. 870

2. 706

2. 544

0. 84

2. 784

2. 628

2. 470

2. 820

2. 664

2. 504

2. 860

2. 698

2. 536

0. 85

2. 772

2. 616

2. 459

2. 810

2. 655

2. 496

2. 852

2. 689

2. 528

0. 86

2. 762

2. 605

2. 449

2. 800

2. 645

2. 486

2. 840

2. 680

2. 519

0. 87

2. 752

2. 595

2. 439

2. 792

2. 635

2. 477

2. 829

2. 672

2. 512

0. 88

2. 740

2. 585

2. 430

2. 780

2. 626

2. 468

2. 821

2. 669

2. 509

0. 89

2. 730

2. 574

2. 420

2. 770

2. 616

2. 459

2. 816

2. 655

2. 496

0. 90

2. 719

2. 563

2. 403

2. 760

2. 608

2. 445

2. 808

2. 647

2. 482

0. 91

2. 707

2. 552

2. 392

2. 756

2. 598

2. 435

2. 798

2. 638

2. 473

0. 92

2. 695

2. 541

2. 382

2. 745

2. 588

2. 426

2. 790

2. 630

2. 466

0. 93

2. 685

2. 531

2. 373

2. 736

2. 579

2. 418

2. 781

2. 622

2. 458

0. 94

2. 674

2. 521

2. 363

2. 726

2. 570

2. 409

2. 773

2. 614

2. 451

0. 95

2. 663

2. 511

2. 354

2. 717

2. 561

2. 400

2. 763

2. 605

2. 442

0. 96

2. 652

2. 500

2. 344

2. 706

2. 551

2. 391

2. 753

2. 596

2. 434

0. 97

2. 640

2. 489

2. 333

2. 696

2. 542

2. 383

2. 745

2. 588

2. 426

0. 98

2. 628

2. 480

2. 323

2. 686

2. 532

2. 373

2. 736

2. 580

2. 419

0. 99

2. 617

2. 467

2. 313

2. 676

2. 523

2. 365

2. 727

2. 571

2. 410

1. 00

2. 606

2. 457

2. 303

2. 667

2. 514

2. 357

2. 720

2. 563

2. 403

3 50

 U NIF AC
-1 UN IFAC

CH 2

CH 3

0. 9011

0. 848

: 2CH 3 , 4CH 2

CH 2

0. 6744

0. 540

2: 3CH 3 , 1CH

CH

0. 4469

0. 228

2, 2: 4CH 3 , 1C

0. 2195

0. 000

CH 2 = CH

1. 3454

1. 176

C= C

R k

Qk

1: 1CH3 , 3CH 2 ,
1CH 2 = CH

CH = CH

1. 1107

0. 867

2: 2CH3 , 2CH 2 ,
1CH = CH

CH 2 = C

1. 1173

0. 988

21: 2CH3
1CH 2 , 1CH 2 = C

CH = C

0. 8886

0. 676

22: 3CH3
1CH = C

C= C

0. 6605

0. 485

2, 32; 4CH 3 ,
1C= C

A CH

A CH

10

0. 5313

0. 400

: 6A CH

AC

11

0. 3652

0. 120

: 1CH 2 = CH ,
5ACH , 1A C

ACCH 2

ACCH 3

12

1. 2663

0. 968

: 5A CH , 1 ACCH 3

ACCH 2

13

1. 0396

0. 660

: 1CH 3 , 5A CH ,
1ACCH 2

ACCH

14

0. 8121

0. 348

: 2CH 3 , 5A CH ,
1ACCH

OH

OH

15

1. 000

1. 200

: 2CH 3 , 1CH ,
1OH

CH 3 O H

CH 3 O H

16

1. 4311

1. 432

: 1CH 3 O H

H 2O

H 2O

17

0. 92

1. 40

: 1H 2 O

A CO H

A CO H

18

0. 8952

0. 680

: 5A CH , 1ACOH

CH 2 CO

CH 3 CO

19

1. 6724

1. 488

2: 1CH3 , 1CH 2 ,
1CH 3 CO

CH 2 CO

20

1. 4457

1. 180

3: 2CH3 , 1CH 2 ,
1CH 2 CO

10

CH O

CH O

21

0. 9980

0. 948

: 1CH 3 , 1CH O

11

CCOO

CH 3 COO

22

1. 9031

1. 728

: 1CH 3 , 3CH 2 ,
1CH 3 CO O

CH 2 COO

23

1. 6764

1. 420

: 2CH 3 , 3CH 2 ,
1CH 2 CO O

35 1

12

H CO O

H CO O

R k
24

1. 2420

Qk

1. 188

: 1CH 3 , 1CH 2 ,
1HCOO

13

CH 2 O

CH 3 O

25

1. 1450

1. 088

: 1CH 3 , 1CH 3 O

CH 2 O

26

0. 9183

0. 780

: 2CH 3 , 1CH 2 ,
1CH 2 O

CH O

27

0. 6908

0. 468

: 4CH 3 , 1CH ,
1CH O

F CH 2 O

28

0. 9183

1. 1

: 3CH 2 ,
1F CH 2 O

14

CN H 2

CH 3 N H 2

29

1. 5959

1. 544

: 1CH 3 N H 2

CH 3 N H 2

30

1. 3692

1. 236

: 1CH 3 , 1CH 2
1CH 2 N H 2

15

CN H

CH N H2

31

1. 1417

0. 924

: 2CH 3 , 1CH N H 2

CH 3 N H

32

1. 4337

1. 244

, 1CH 3 , 1CH 3 N H

CH 2 N H

33

1. 2070

0. 936

: 2CH 3 , 1CH 2 ,
1CH 2 N H

CH N H

34

0. 9795

0. 624

: 4CH 3 , 1CH ,
1CH N H

16

( C) 3 N

CH 3 N

35

1. 1865

0. 940

: 2CH 3 , 1CH 3 N

CH 2 N

36

0. 9597

0. 632

: 3CH 3 , 2CH 2 ,
1CH 2 N

17

A CN H2

A CN H2

37

1. 0600

0. 816

: 5A CH , 1 ACNH 2

18

C 5H 5N

38

2. 9993

2. 113

: 1C5 H5 N

C 5H 4N

39

2. 8332

1. 833

3: 1CH 3 ,
1C5 H 4 N

C 5H 3N

40

2. 667

1. 553

2, 3: 2CH 3 ,
1C5 H 3 N

19

20

CCN

COO H

CCl

CH 3 CN

41

1. 8701

1. 724

: 1CH 3 CN

CH 2 CN

42

1. 6434

1. 416

: 1CH 3 , 1CH 2 CN

COOH

43

1. 3013

1. 224

: 1CH 3 , 1CO OH

H CO OH

44

1. 5280

1. 532

: 1H COO H

CH 2 Cl

45

1. 4654

1. 264

1: 1CH 3 , 2CH2 ,
1CH 2 Cl

CH Cl

46

1. 2380

0. 952

2: 2CH 3 , 1CHCl

CCl

47

1. 0060

0. 724

22: 3CH 3 ,
1CCl

22

CCl 2

CH 2 Cl 2

48

2. 2564

1. 988

: 1CH 2 Cl

CH Cl 2

49

2. 0606

1. 684

1, 1: 1CH 3 ,
1CH Cl 2

3 52

CCl 2

R k
50

1. 8016

Qk

1. 448

2, 2: 2CH 3 ,
1CCl 2

23

CCl 3

CH Cl 3

51

2. 8700

2. 410

: 1CH Cl 3

CCl 3

52

2. 6401

2. 184

1, 1, 1: 1 CH 3 ,
1CCl 3

24

CCl 4

CCl 4

53

3. 3900

2. 910

, 1CCl 4

25

ACCl

ACCl

54

1. 1562

0. 844

: 5A CH , 1 ACCl

26

CN O2

CH 3 N O2

55

2. 0086

1. 868

: 1CH 3 N O2

CH 2 N O2

56

1. 7818

1. 560

1: 1CH 3 , 1CH2 ,
1CH 2 N O2

CH N O2

57

1. 5544

1. 248

2: 2CH 3 ,
1CH N O2

27

A CN O2

A CN O2

58

1. 4199

1. 104

: 5A CH ,
1ACH NO 2

28

CS2

CS2

59

2. 057

1. 65

: CS2

29

CH3 SH

CH 3 S H

60

1. 8770

1. 676

: 1CH 3 SH

CH 2 S H

61

1. 6510

1. 368

: 1CH 3 , 1CH 2 , SH

30

62

3. 1680

2. 481

: 1

31

DOH

( CH 2 O H ) 2

63

2. 4088

2. 248

1, 2: 1CCH2
( OH ) 2

32

64

1. 2640

0. 992

1: 1CH 3 , 1CH2 ,
1I

33

Br

Br

65

0. 9492

0. 832

1: 1CH 3 , 1CH2 ,
1Br

34

C C

CH C

66

1. 2920

1. 088

1: 1CH3 , 3CH 2 ,
1CH C

C C

67

1. 0613

0. 784

2: 2CH3 , 2CH 2 ,
1CC

35

Me 2 S O

Me 2 SO

68

2. 8266

2. 472

: 1M e2 SO

36

A CRY

A CRY

69

2. 3144

2. 052

: 1A CRY

37

ClCC

Cl ( C = C )

70

0. 7910

0. 724

: 1CH = C,
3Cl( C= C)

38

ACF

ACF

71

0. 6948

0. 524

: 6A CF

39

DM F

DM F 1

72

3. 0856

2. 736

: 1DMF 1

DM F 2

73

2. 6322

2. 120

: 2CH 3 , 1DMF 2

CF 3

74

1. 4060

1. 380

: 2CF 3 , 4CF 2

CF 2

75

1. 0105

0. 920

CF

76

0. 6150

0. 460

40

CF 2

: 1 CH 3 ,
5CH 2 , 1CF

35 3

-2 UNIF AC- VLE a mn

0. 0 - 200. 0

76. 50 986. 5

CH2

C= C

2520. 0

ACH

- 11. 12 - 94. 78

A CCH 2

- 69. 70 - 269. 7

OH

CH 3 O H

H 2O

300. 0

692. 7

A COH

275. 8

1665. 0

CH 2 CO

10

CH O

505. 7

11

CCO O

114. 8

12

H COO

90. 49

91. 65

13

CH 2 O

83. 36

76. 44

52. 13

14

CNH 2

- 30. 48

79. 40

- 44. 85

15

CN H

65. 33 - 41. 32

- 22. 31

16

( C ) 3N

- 83. 98 - 188. 0

17

ACNH 2

5339. 0

18

- 101. 6

19

CCN

20

CO OH

21

CCl

91. 46 - 24. 36

22

CCl 2

34. 01 - 52. 71

121. 3

23

CCl 3

36. 70 - 185. 1

288. 5

24

CCl 4

- 78. 45 - 293. 7

25

A CCl

- 141. 3 - 203. 2

26

CN O2

27

ACNO 2

5541. 0

28

CS2

- 52. 65

29

CH 3 SH

30

- 25. 31

157. 3

404. 3

521. 6

31

DO H

140. 0

221. 4

150. 6

267. 6

32

128. 0

33

Br

- 31. 52

34

CC

35

M e 2 SO

36

A CRY

3 54

156. 4

0. 0

8694. 0

16. 51 - 52. 39

26. 76 - 82. 92

24. 82
315. 3

269. 3

61. 13

349. 2

- 32. 69 - 49. 92

- 7. 481

697. 2

1318. 01333. 0

4102. 0

693. 9

1509. 0

634. 2 547. 4

0. 0

167. 0

636. 1

637. 3

903. 81329. 0

- 146. 8

0. 0

803. 2

603. 2

5695. 0 884. 9

89. 60

25. 82

0. 0

- 137. 1

353. 5- 259. 7

- 50. 00

- 44. 50

249. 1

0. 0

- 181. 0- 101. 7

362. 3

377. 6

- 229. 1

289. 6

0. 0 324. 5

244. 2

- 451. 6

- 265. 2

365. 8

164. 5

108. 7

- 404. 8

- 340. 2

245. 4

249. 6

191. 2

155. 7

237. 7

339. 7

- 314. 7

- 164. 0

- 481. 7

- 330. 4

- 150. 0

- 500. 4

- 448. 2

28. 60 - 406. 8

- 598. 8

25. 34
140. 1

85. 84 - 170. 0

65. 69

223. 0

- 223. 9

109. 9

650. 4

979. 8

62. 32
4. 680

- 4. 700
- 237. 7
10. 38

21. 50

- 601. 8

232. 7
10000. 0- 36. 72

5. 182 - 339. 5
- 378. 2

- 332. 9- 341. 6

157. 8

242. 8

268. 2

- 151. 0

1020. 0

- 66. 17

122. 9

562. 2

529. 0

698. 2

747. 7

669. 9

708. 7

742. 1

649. 1

826. 7

134. 7

856. 3

860. 1

375. 5

246. 9

661. 6

920. 4

- 97. 05

341. 7

252. 6

417. 9

33. 61

- 127. 8
40. 68

58. 68

561. 6

1201. 010000

360. 7

823. 5

914. 2

461. 6

382. 8

1081. 0

23. 48
0. 0 838. 4

501. 3
291. 1

721. 9

- 72. 88 - 184. 4
50. 49
- 165. 9

- 2. 504- 143. 2

- 25. 87

0. 0

472. 5- 133. 1

185. 4

28. 41

155. 6

529. 0

49. 80 - 132. 3

- 22. 97 - 138. 4

1824. 0
16. 62

340. 7

31. 87
34. 78

695. 0

- 240. 0
386. 6

- 3. 167

- 75. 67

37

ClCC

41. 90

38

A CF

- 5. 132

39

DM F

31. 95

40

CF 2

147. 3

640. 9

726. 7

- 237. 2

- 157. 3

649. 7

645. 9

37. 70

133. 9

240. 2

64. 16

172. 2

287. 1

10

11

12

13

14

15

476. 4

677. 0

232. 1

741. 4

251. 5

391. 5

468. 7

289. 3

396. 0

273. 6

161. 7

122. 8

90. 49

- 49. 29

23. 50

CH2

C= C

ACH

A CCH 2

OH

84. 00

441. 8

101. 1

193. 1

CH 3 O H

23. 39

306. 4

- 10. 72

193. 4

H 2O

- 195. 4

- 257. 3

14. 42

A COH

- 356. 1

CH 2 CO

0. 0

10

CH O

128. 0

11

CCO O

372. 2

12

H COO

13

CH 2 O

14

CNH 2

15

CN H

16

( C ) 3N

17

ACNH 2

18

19

CCN

- 287. 5

- 266. 6

20

CO OH

- 297. 8

- 256. 3

21

CCl

286. 3

22

CCl 2

423. 2

- 132. 9

23

CCl 3

552. 1

176. 5

24

CCl 4

372. 0

129. 5

25

A CCl

128. 1

- 246. 3

26

CN O2

- 142. 6

27

ACNO 2

28

CS2

303. 7

29

CH 3 SH

160. 6

30

317. 5

524. 5

71. 23

25. 77

5. 994

- 52. 10

52. 38

16

32. 14

5688. 0

213. 1
28. 06
- 180. 6
540. 5

83. 02
359. 3
48. 89

255. 7 206. 6
658. 8

42. 70- 323. 0

266. 0
168. 0

53. 90
304. 0

- 449. 4
- 37. 36

213. 7

5. 202

0. 0

- 7. 838

304. 1
0. 0

372. 9

- 261. 1

0. 0

461. 3

- 235. 9

- 73. 50

0. 0

141. 7
0. 0

136. 0

- 49. 30

108. 8
38. 89

63. 72 - 41. 11
0. 0 - 189. 2
865. 9

0. 0

- 399. 1
- 51. 54

312. 5

- 47. 51

- 338. 5
225. 4
- 197. 7

488. 9

- 141. 4

- 20. 93
113. 9

- 293. 7
261. 1
203. 5

91. 13- 126. 0

- 108. 4

1088. 0

- 94. 49

243. 8

112. 4
239. 8

63. 71

106. 7

- 146. 3

35 5

10

11

12

152. 0

31

DO H

32

138. 0

33

Br

- 142. 6

34

CC

443. 6

35

M e 2 SO

110. 4

36

A CRY

37

ClCC

38

A CF

39

DM F

40

CF 2

13

14

15

16

22

23

24

9. 207

21. 92
736. 4

- 8. 671

41. 57

- 122. 1

- 18. 87

- 209. 3

97. 04

- 158. 2

17

18

1245. 0 287. 7

19

20

597. 0

663. 5

405. 9

730. 4

- 4. 449

212. 5

537. 4

52. 80

6096. 0

603. 8

CH 2

C= C

A CH

668. 2

A CCH2

764. 7

OH

- 348. 2

170. 0

CH 3 OH

- 335. 5

580. 5

H2 O

213. 0

459. 0

ACOH

CH2 CO

10

CH O

11

CCO O

12

6. 712

199. 0

36. 23 - 289. 5
112. 6

- 14. 09

21

35. 93 53. 76 24. 90 104. 3

99. 61

337. 1

4584. 0

- 18. 81 - 144. 4 - 231. 9

- 114. 1

- 98. 12

- 38. 32 - 102. 5 - 139. 4

370. 4

353. 7

- 305. 5
165. 1

143. 1
- 67. 80
497. 5
1827. 0

- 284. 0 - 354. 6

- 39. 20

660. 2

108. 9 - 209. 7

54. 47

H COO

- 356. 3

- 287. 2

13

CH 2 O

664. 6

14

CNH 2

- 99. 81

15

CNH

71. 23

16

( C) 3 N

17

A CN H 2

18

19

CCN

20

CO OH

21

CCl

22

CCl2

3 56

937. 9

3. 000

- 12. 14- 141. 3

75. 62 - 112. 1

325. 4

5831. 0

481. 7

669. 4

- 191. 7
751. 9

494. 6

301. 1

137. 8 - 154. 3

- 78. 85- 352. 9

0. 0

617. 1

- 216. 8
0. 0

- 169. 7

134. 3

0. 0

- 313. 5

- 8. 283
8455. 0

- 153. 7

- 351. 6 - 114. 7 - 165. 1

- 15. 62 - 54. 86

0. 0
326. 4

587. 3

47. 67

1821. 0

44. 42 - 183. 4
0. 0
- 84. 53

76. 75

212. 7

108. 3

249. 2

62. 42

0. 0

0. 0

56. 33

17

18

19

18. 98

74. 04

309. 2

492. 0

20

21

1346. 0 - 157. 1

23

CCl3

24

CCl4

1301. 0

25

A CCl

323. 3

26

CNO 2

27

ACNO 2

28

CS2

335. 7

73. 09

29

CH 3 SH

125. 7

- 27. 94

30

31

DO H

32

33

Br

34

CC

35

M e 2 SO

36

A CRY

- 42. 31

37

ClCC

298. 4

38

A CF

39

DM F

40

CF 2

689. 0

356. 9

11. 80

22
0. 0
17. 97

23

24

0. 0

- 30. 10

51. 90

- 314. 9

0. 0
- 255. 4
- 34. 68

5250. 0

514. 6
26. 06

60. 71

48. 48- 133. 1

164. 4
- 40. 82

21. 76

1169. 0

48. 49
225. 8

329. 1
- 215. 0

2344. 0

201. 7

- 343. 6

- 58. 43

85. 32- 143. 2

- 124. 6

335. 6

- 186. 7

25

26

27

321. 5

661. 5

C= C

959. 7

542. 1

A CH

538. 2

168. 0

194. 9

52. 07

A CCH2

- 126. 9

3629. 0

4448. 0

- 9. 451

OH

CH 3 OH

H2 O

ACOH

CH2 CO

10

CH O

11

CCO O

12

H COO

13

CH 2 O

14

CNH 2

CH 2

287. 8
17. 12
678. 2

61. 11

543. 0

28

184. 4

30
354. 5

31

32

3025. 0 335. 8

76. 30

157. 1

75. 14
220. 6

153. 0

29

477. 0
- 31. 09

399. 5

- 10. 43

147. 5

- 64. 69

210. 4

- 20. 36

4975. 0

- 120. 5

- 318. 9

188. 0

0. 0

113. 3

313. 5

37. 84

887. 1

- 687. 1
174. 5

137. 5

629. 0

216. 1

- 46. 28 - 163. 7

183. 0

202. 3

53. 59

- 101. 7

148. 3

4. 339
95. 18
68. 81

140. 9

- 8. 538

- 20. 11- 149. 5

- 70. 14

35 7

25

26

27

28

29

30

31

32

4350. 0

15

CNH

16

( C) 3 N

- 86. 36

17

A CN H 2

699. 1

18

19

CCN

20

CO OH

21

CCl

22

CCl2

23

CCl3

24

CCl4

25

A CCl

26

CNO 2

27

ACNO 2

28

CS2

29

CH 3 SH

30

31

DO H

32

33

Br

34

C C

35

M e 2 SO

36

A CRY

37

ClCC

38

A CF

39

DM F

40

CF 2

125. 3

- 62. 73

52. 31

464. 4

230. 9

21. 37

450. 1

59. 02
177. 6

475. 8 490. 9

534. 7

116. 6

- 64. 38

132. 2

546. 7

86. 40
247. 8

0. 0 - 154. 5
794. 4

0. 0
- 85. 12

533. 2

139. 8 304. 3

0. 0
0. 0
0. 0
0. 0

481. 3

0. 0

64. 28
224. 0

0. 0

125. 3
174. 4

313. 8

85. 07

535. 8

- 71. 00

- 191. 7

167. 9

33

m
1

CH 2

C= C

A CH

A CCH2

OH

6
7

479. 5

34
298. 9

35
526. 5

36
689. 0

523. 6
- 13. 59

37

- 0. 505 125. 8
237. 3

169. 9

69. 11

- 171. 3

4284. 0

133. 4

- 202. 1

253. 9

CH 3 OH

- 399. 3

- 21. 22

H2 O

- 139. 0

3 58

38

160. 8

39

40

485. 3 - 2. 859
320. 4

389. 3

245. 6

101. 4

5629. 0

44. 78 - 143. 9
- 48. 25 - 172. 4
319. 0

33

34

35

36

37

ACOH

CH2 CO

10

CH O

11

CCO O

12

H COO

13

CH 2 O

14

CNH 2

15

CNH

16

( C ) 3N

17

A CN H 2

18

19

CCN

20

CO OH

21

CCl

22

CCl2

215. 0

23

CCl3

363. 7

- 79. 54

24

CCl4

337. 7

- 86. 85

25

A CCl

- 60. 70

26

CNO 2

10. 17

27

ACNO 2

28

CS2

29

CH 3 SH

30

31

DO H

32

33

Br

34

CC

35

M e 2 SO

36

A CRY

37

ClCC

38

A CF

39

DM F

40

CF 2

245. 2

- 246. 6

- 202. 3

- 44. 58

- 44. 42

52. 08

- 23. 30

172. 1

38

39

40

- 61. 70

145. 6

254. 8

- 293. 1

- 203. 0

81. 57

- 19. 14
- 90. 87

- 125. 9

- 58. 77

41. 94

- 27. 70

215. 2

498. 6

48. 40
- 47. 37

31. 66

78. 92

- 417. 2

302. 2

0. 0

- 119. 8

0. 0
0. 0

0. 0

- 97. 71
0. 0
0. 0

6. 699

136. 6

0. 0
0. 0

35 9

 F - 12 T - S
A ( )
( v/ cm 3 / g, u / kJ / kg , h / kJ / kg , s/ kJ / ( kg K ) )

T/

p 10-

/ Pa

vf

vg

uf

ug

hf

hf g

hg

sf

sg

0. 00611 1. 0002

206278

- 0. 03

2375. 4

- 0. 02

2501. 4

2501. 3 - 0. 0001 9. 1565

0. 00872 1. 0001

147120

20. 97

2382. 3

20. 98

2489. 6

2510. 6

0. 0761

9. 0257

10

0. 01228 1. 0004

106379

42. 00

2389. 2

42. 01

2477. 7

2519. 8

0. 1510

8. 9008

15

0. 01705 1. 0009

77926

62. 99

2396. 1

62. 99

2465. 9

2528. 9

0. 2245

8. 7814

20

0. 02339 1. 0018

57791

83. 95

2402. 9

83. 96

2454. 1

2538. 1

0. 2966

8. 6672

25

0. 03169 1. 0029

43360

104. 88

2409. 8

104. 89

2442. 3

2547. 2

0. 3674

8. 5580

30

0. 04246 1. 0043

32894

125. 78

2416. 6

125. 79

2430. 5

2556. 3

0. 4369

8. 4533

35

0. 05628 1. 0060

25216

146. 67

2423. 4

146. 68

2418. 6

2565. 3

0. 5053

8. 3531

40

0. 07384 1. 0078

19523

167. 56

2430. 1

167. 57

2406. 7

2574. 3

0. 5725

8. 2570

45

0. 09593 1. 0099

15258

188. 44

2436. 8

188. 45

2394. 8

2583. 2

0. 6387

8. 1648

50

0. 1235

1. 0121

12032

209. 32

2443. 5

209. 33

2382. 7

2592. 1

0. 7038

8. 0763

55

0. 1576

1. 0146

9568

230. 21

2450. 1

230. 23

2370. 7

2600. 9

0. 7679

7. 9913

60

0. 1994

1. 0172

7671

251. 11

2456. 6

251. 13

2358. 5

2609. 6

0. 8312

7. 9096

65

0. 2503

1. 0199

6197

272. 02

2463. 1

272. 06

2346. 2

2618. 3

0. 8935

7. 8310

70

0. 3119

1. 0228

5042

292. 95

2469. 6

292. 98

2333. 8

2626. 8

0. 9549

7. 7553

75

0. 3858

1. 0259

4131

313. 90

2475. 9

313. 93

2321. 4

2635. 3

1. 0155

7. 6824

80

0. 4739

1. 0291

3407

334. 86

2482. 2

334. 91

2308. 8

2643. 7

1. 0753

7. 6122

85

0. 5783

1. 0325

2828

355. 84

2488. 4

355. 90

2296. 0

2651. 9

1. 1343

7. 5445

90

0. 7014

1. 0360

2361

376. 85

2494. 5

376. 92

2283. 2

2660. 1

1. 1925

7. 4791

95

0. 8455

1. 0397

1982

397. 88

2500. 6

397. 96

2270. 2

2668. 1

1. 2500

7. 4159

100

1. 014

1. 0435

1673.

418. 94

2506. 5

419. 04

2257. 0

2676. 1

1. 3069

7. 3549

110

1. 433

1. 0516

1210.

461. 14

2518. 1

461. 30

2230. 2

2691. 5

1. 4185

7. 2387

120

1. 985

1. 0603

891. 9

503. 50

2529. 3

503. 71

2202. 6

2706. 3

1. 5276

7. 1296

130

2. 701

1. 0697

668. 5

546. 02

2539. 9

546. 31

2174. 2

2720. 5

1. 6344

7. 0269

140

3. 613

1. 0797

508. 9

588. 74

2550. 0

589. 13

2144. 7

2733. 9

1. 7391

6. 9299

150

4. 758

1. 0905

392. 8

631. 68

2559. 5

632. 20

2114. 3

2764. 5

1. 8418

6. 8379

160

6. 178

1. 1020

307. 1

674. 86

2568. 4

675. 55

2082. 6

2758. 1

1. 9427

6. 7502

3 60


p 10-

T/

/ Pa

vf

vg

uf

ug

hf

hf g

hg

sf

sg

170

7. 917

1. 1143

242. 8

718. 33

2576. 5

719. 21

2049. 5

2768. 7

2. 0419

6. 6663

180

10. 02

1. 1274

194. 1

762. 09

2583. 7

763. 22

2015. 0

2778. 2

2. 1396

6. 5857

190

12. 54

1. 1414

156. 5

806. 19

2590. 0

807. 62

1978. 8

2786. 4

2. 2359

6. 5079

200

15. 54

1. 1565

127. 4

850. 65

2595. 3

852. 45

1940. 7

2793. 2

2. 3309

6. 4323

210

19. 06

1. 1726

104. 4

895. 53

2599. 5

897. 76

1900. 7

2798. 5

2. 4248

6. 3585

220

23. 18

1. 1900

86. 19

940. 87

2602. 4

943. 62

1858. 5

2802. 1

2. 5178

6. 2861

230

27. 95

1. 2088

71. 58

986. 74

2603. 9

990. 12

1813. 8

2804. 0

2. 6099

6. 2146

240

33. 44

1. 2291

59. 76

1033. 2

2604. 0

1037. 3

1766. 5

2803. 8

2. 7015

6. 1437

250

39. 73

1. 2512

50. 13

1080. 4

2602. 4

1085. 4

1716. 2

2801. 5

2. 7927

6. 0730

260

46. 88

1. 2755

42. 21

1128. 4

2599. 0

1134. 4

1662. 5

2796. 9

2. 8838

6. 0019

270

54. 99

1. 3023

35. 64

1177. 4

2593. 7

1184. 5

1605. 2

2789. 7

2. 9751

5. 9301

280

64. 12

1. 3321

30. 17

1227. 5

2586. 1

1236. 0

1543. 6

2779. 6

3. 0668

5. 8571

290

74. 36

1. 3656

25. 57

1278. 9

2576. 0

1289. 1

1477. 1

2766. 2

3. 1594

5. 7821

300

85. 81

1. 4036

21. 67

1332. 0

2563. 0

1344. 0

1404. 9

2749. 0

3. 2534

5. 7045

320

112. 7

1. 4988

15. 49

1444. 6

2525. 5

1461. 5

1238. 6

2700. 1

3. 4480

5. 5362

340

145. 9

1. 6379

10. 80

1570. 3

2464. 6

1594. 2

1027. 9

2622. 0

3. 6594

5. 3357

360

186. 5

1. 8925

6. 945

1725. 2

2351. 5

1760. 5

720. 5

2481. 0

3. 9147

5. 0526

374. 14

220. 9

3. 155

3. 155

2029. 6

2029. 6

2090. 3

2099. 3

4. 4298

4. 4298

: Keenan, J . H . , F . G . Keyes , P . G. Hil l, and J . G. M oore. St eam T ables . New Y or k: W iley, 1969

B ( )
( v/ cm 3 / g, u / kJ / kg , h / kJ / kg , s/ kJ / ( kg K ) )
p 10/ Pa

T/ C

vf

vg

uf

ug

hf

hf g

hg

sf

sg

0. 040

28. 96

1. 0040

34800

121. 45

2415. 2

121. 46

2432. 9

2554. 4

0. 4226

8. 4746

0. 060

36. 16

1. 0064

23739

151. 53

2425. 0

151. 53

2415. 9

2567. 4

0. 5210

8. 3304

0. 080

41. 51

1. 0084

18103

173. 87

2432. 2

173. 88

2403. 1

2577. 0

0. 5926

8. 2287

0. 10

45. 81

1. 0102

14674

191. 82

2437. 9

191. 83

2392. 8

2584. 7

0. 6493

8. 1502

0. 20

60. 06

1. 0172

7649. 0

251. 88

2456. 7

251. 40

2358. 3

2609. 7

0. 8320

7. 9085

0. 30

69. 10

1. 0223

5229. 0

289. 20

2468. 4

289. 23

2336. 1

2625. 3

0. 9439

7. 7686

0. 40

75. 87

1. 0265

3993. 0

317. 53

2477. 0

317. 58

2319. 2

2636. 8

1. 0259

7. 6700

36 1


p 10-

T/ C

/ Pa

vf

vg

uf

ug

hf

hf g

hg

sf

sg

0. 50

81. 33

1. 0300

3240. 0

340. 44

2483. 9

340. 49

2305. 4

2645. 9

1. 0910

7. 5939

0. 60

85. 94

1. 0331

2732. 0

359. 79

2489. 6

359. 86

2293. 6

2653. 5

1. 1453

7. 5320

0. 70

89. 95

1. 0360

2365. 0

376. 63

2494. 5

376. 70

2283. 3

2660. 0

1. 1919

7. 4797

0. 80

93. 50

1. 0380

2087. 0

391. 58

2498. 8

391. 66

2274. 1

2665. 8

1. 2329

7. 4346

0. 90

96. 71

1. 0410

1869. 0

405. 06

2502. 6

405. 15

2265. 7

2670. 9

1. 2695

7. 3949

1. 00

99. 63

1. 0432

1694. 0

417. 36

2506. 1

417. 46

2258. 0

2675. 5

1. 3026

7. 3594

1. 50

111. 4

1. 0528

1159. 0

466. 94

2519. 7

467. 11

2226. 5

2693. 6

1. 4336

7. 2233

2. 00

120. 2

1. 0605

885. 7

504. 49

2529. 5

504. 70

2201. 9

2706. 7

1. 5301

7. 1271

2. 50

127. 4

1. 0672

718. 7

535. 10

2537. 2

535. 37

2181. 5

2716. 9

1. 6072

7. 0527

3. 00

133. 6

1. 0732

605. 8

561. 15

2543. 6

561. 47

2163. 8

2725. 3

1. 6718

6. 9919

3. 50

138. 9

1. 0786

524. 3

583. 95

2548. 9

584. 33

2148. 1

2732. 4

1. 7275

6. 9405

4. 00

143. 6

1. 0836

462. 5

604. 31

2553. 6

604. 74

2133. 8

2738. 6

1. 7766

6. 8959

4. 50

147. 9

1. 0882

414. 0

622. 77

2557. 6

623. 25

2120. 7

2743. 9

1. 8207

6. 8565

5. 00

151. 9

1. 0926

374. 9

639. 68

2561. 2

640. 23

2108. 5

2748. 7

1. 8607

6. 8213

6. 00

158. 9

1. 1006

315. 7

669. 90

2567. 4

670. 56

2086. 3

2756. 8

1. 9312

6. 7600

7. 00

165. 0

1. 1080

272. 9

696. 44

2572. 5

697. 21

2066. 3

2763. 5

1. 9922

6. 7080

8. 00

170. 4

1. 1148

240. 4

720. 22

2576. 8

721. 11

2048. 0

2769. 1

2. 0462

6. 6628

9. 00

175. 4

1. 1212

215. 0

741. 83

2580. 5

742. 83

2031. 1

2773. 9

2. 0946

6. 6226

10. 0

179. 9

1. 1273

194. 4

761. 68

2583. 6

762. 81

2015. 3

2778. 1

2. 1387

6. 5863

15. 0

198. 3

1. 1539

131. 8

843. 16

2594. 5

844. 89

1947. 3

2792. 2

2. 3150

6. 4448

20. 0

212. 4

1. 1767

99. 63

906. 44

2600. 3

908. 79

1890. 7

2799. 5

2. 4474

6. 3409

25. 0

224. 0

1. 1973

79. 98

959. 11

2603. 1

962. 11

1841. 0

2803. 1

2. 5547

6. 2575

30. 0

233. 9

1. 2165

66. 68

1004. 8

2604. 1

1008. 4

1795. 7

2804. 2

2. 6457

6. 1869

3 62


p 10/ Pa

T/ C

vf

vg

uf

ug

hf

hf g

hg

sf

sg

35. 0

242. 6

1. 2347

57. 07

1045. 4

2603. 7

1049. 8

1753. 7

2803. 4

2. 7253

6. 1253

40. 0

250. 4

1. 2522

49. 78

1082. 3

2602. 3

1087. 3

1714. 1

2801. 4

2. 7964

6. 0701

45. 0

257. 5

1. 2692

44. 06

1116. 2

2600. 1

1121. 9

1676. 4

2798. 3

2. 8610

6. 0199

50. 0

264. 0

1. 2859

39. 44

1147. 8

2597. 1

1154. 2

1640. 1

2794. 3

2. 9202

5. 9734

60. 0

275. 6

1. 3181

32. 44

1205. 4

2589. 7

1213. 4

1571. 0

2784. 3

3. 0267

5. 8892

70. 0

285. 9

1. 3513

27. 37

1257. 6

2580. 5

1267. 0

1505. 1

2772. 1

3. 1211

5. 8133

80. 0

295. 1

1. 3842

23. 52

1305. 6

2569. 8

1316. 6

1441. 3

2758. 0

3. 2068

5. 7432

90. 0

303. 4

1. 4178

20. 48

1350. 5

2557. 8

1363. 3

1378. 9

2742. 1

3. 2858

5. 6772

100

311. 1

1. 4524

18. 03

1393. 0

2544. 4

1407. 6

1317. 1

2724. 7

3. 3596

5. 6141

110

318. 2

1. 4886

15. 99

1433. 7

2529. 8

1450. 1

1255. 5

2705. 6

3. 4295

5. 5527

120

324. 8

1. 5267

14. 26

1473. 0

2513. 7

1491. 3

1193. 6

2684. 9

3. 4962

5. 4924

130

330. 9

1. 5671

12. 78

1511. 1

2496. 1

1531. 5

1130. 7

2662. 2

3. 5606

5. 4323

140

336. 8

1. 6107

11. 49

1548. 6

2476. 8

1571. 1

1066. 5

2637. 6

3. 6232

5. 3717

150

342. 2

1. 6581

10. 34

1585. 6

2455. 5

1610. 5

1000. 0

2610. 5

3. 6848

5. 3098

160

347. 4

1. 7107

9. 306

1622. 7

2431. 7

1650. 1

930. 6

2580. 6

3. 7461

5. 2455

170

352. 4

1. 7702

8. 364

1660. 2

2405. 0

1690. 3

856. 9

2547. 2

3. 8079

5. 1777

180

357. 1

1. 8397

7. 489

1698. 9

2374. 3

1732. 0

777. 1

2509. 1

3. 8715

5. 1044

190

361. 5

1. 9243

6. 657

1739. 9

2338. 1

1776. 5

688. 0

2464. 5

3. 9388

5. 0228

200

365. 8

2. 036

5. 834

1785. 6

2293. 0

1826. 3

583. 4

2409. 7

4. 0139

4. 9269

220. 9

374. 1

3. 155

3. 155

2029. 6

2029. 6

2099. 3

2099. 3

4. 4298

4. 4298

: Keenan , et a l. , St ea m T abl es . N ew York : W iley , 1969

36 3

 C
( v/ cm 3 / g, u / kJ / kg , h / kJ / kg , s/ kJ / ( kg K ) )
T/

0. 06 105 P a ( 36. 16)

0. 35 105 Pa ( 72. 69)

23739

2425. 0

2546. 4

8. 3304

4526

2473. 0

2631. 4

7. 7153

80

27132

2487. 3

2650. 1

8. 5804

4625

2483. 7

2645. 6

7. 7564

120

30219

2544. 7

2726. 0

8. 7840

5163

2542. 4

2723. 1

7. 9644

160

33302

2602. 7

2802. 5

8. 9693

5696

2601. 2

2800. 6

8. 1519

200

36383

2661. 4

2879. 7

9. 1398

6228

2660. 4

2878. 4

8. 3237

240

39462

2721. 0

2957. 8

9. 2982

6758

2720. 3

2956. 8

8. 4828

280

42540

2781. 5

3036. 8

9. 4464

7287

2780. 9

3036. 0

8. 6314

320

45618

2843. 0

3116. 7

9. 5859

7815

2842. 5

3116. 1

8. 7712

360

48696

2905. 5

3197. 7

9. 7180

8344

2905. 1

3197. 1

8. 9034

400

51774

2969. 0

3279. 6

9. 8435

8872

2968. 6

3270. 2

9. 0291

440

54851

3033. 5

3362. 6

9. 9633

9400

3033. 2

3362. 2

9. 1490

500

59467

3132. 3

3489. 1

10. 134

10192

3132. 1

3488. 8

9. 3194

0. 70 105 P a( 89. 95)

1. 0 105 P a( 99. 63)

2365

2494. 5

2660. 0

7. 4797

1694

2506. 1

2675. 5

7. 3594

100

2434

3509. 7

2680. 0

7. 5341

1696

2506. 7

2676. 2

7. 3614

120

2571

2539. 7

2719. 6

7. 6375

1793

2537. 3

2716. 6

7. 4668

160

2841

2599. 4

2798. 2

7. 8279

1984

2597. 8

2796. 2

7. 6597

200

3108

2659. 1

2876. 7

8. 0012

2172

2658. 1

2875. 3

7. 8343

240

3374

2719. 3

2955. 5

8. 1611

2359

2718. 5

2954. 5

7. 9949

280

3640

2780. 2

3035. 0

8. 3162

2546

2779. 6

3034. 2

8. 1445

320

3005

2842. 0

3115. 3

8. 4504

2732

2841. 5

3114. 6

8. 2849

360

4170

2904. 6

3196. 5

8. 5828

2917

2904. 2

3195. 9

8. 4175

400

4434

2968. 2

3278. 6

8. 7086

3103

2967. 9

3278. 2

8. 5435

440

4698

3032. 9

3361. 8

8. 8286

3288

3032. 6

3361. 4

8. 6636

500

5095

3131. 8

3488. 5

8. 9991

3565

3131. 6

3488. 1

8. 8342

1. 5 10 5 P a( 111. 37)

3. 0 105 P a( 133. 55)

1159

2519. 7

2693. 6

7. 2233

120

1188

2533. 3

2711. 4

7. 2693

160

1317

2595. 2

2792. 8

200

1444

2656. 2

240

1570

280

606

2543. 6

2725. 3

6. 9919

7. 4665

651

2587. 1

2782. 3

7. 1276

2872. 9

7. 6433

716

2650. 7

2865. 5

7. 3115

2717. 2

2952. 7

7. 8052

781

2713. 1

2947. 3

7. 4774

1695

2778. 6

3032. 8

7. 9555

844

2775. 4

3028. 6

7. 6299

320

1819

2840. 6

3113. 5

8. 0964

907

2838. 1

3110. 1

7. 7722

360

1943

2903. 5

3195. 0

8. 2293

969

2901. 4

3192. 2

7. 9061

400

2067

2967. 3

3277. 4

8. 3555

1032

2965. 6

3275. 0

8. 0330

440

2191

3032. 1

3360. 7

8. 4757

1094

3030. 6

3358. 7

8. 1538

500

2376

3131. 2

3487. 6

8. 6466

1187

3130. 0

3486. 0

8. 3251

600

2685

3301. 7

3704. 3

8. 9101

1341

3300. 8

3703. 2

8. 5892

3 64


T/

5. 0 10 5 P a( 151. 86)

7. 0 105 P a( 164. 97)

374. 9

2561. 2

2748. 7

6. 8213

272. 9

2572. 5

2763. 5

6. 7080

180

404. 5

2609. 7

2812. 0

6. 9656

284. 7

2599. 8

2799. 1

6. 7880

200

424. 9

2642. 9

2855. 4

7. 0592

299. 9

2634. 8

2844. 8

6. 8865

240

464. 6

2707. 6

2939. 9

7. 2307

329. 2

2701. 8

2932. 2

7. 0641

280

503. 4

2771. 2

3022. 9

7. 3865

357. 4

2766. 9

3017. 1

7. 2233

320

541. 6

2834. 7

3105. 6

7. 5308

385. 2

2831. 3

3100. 9

7. 3697

360

579. 6

2898. 7

3188. 4

7. 6660

412. 6

2895. 8

3184. 7

7. 5063

400

617. 3

2963. 2

3271. 9

7. 7938

439. 7

2960. 9

3268. 7

7. 6350

440

654. 8

3028. 6

3356. 0

7. 9152

466. 7

3026. 6

3353. 3

7. 7571

500

710. 9

3128. 4

3483. 9

8. 0873

507. 0

3126. 8

3481. 7

7. 9299

600

804. 1

3299. 6

3701. 7

8. 3522

573. 8

3298. 5

3700. 2

8. 1956

700

896. 9

3477. 5

3925. 9

8. 5952

640. 3

3476. 6

3924. 8

8. 4391

10. 0 105 P a( 179. 91)

15 105 P a( 198. 32)

194. 4

2583. 6

2778. 1

6. 5865

131. 8

2594. 5

2792. 2

6. 4448

200

206. 6

2621. 9

2827. 9

6. 6940

132. 5

2598. 1

2796. 8

6. 4546

240

227. 5

2692. 9

2920. 4

6. 8817

148. 3

2676. 9

2899. 3

6. 6628

280

248. 0

2760. 2

3008. 2

7. 0465

162. 7

2748. 6

2992. 7

6. 8381

320

267. 8

2826. 1

3093. 9

7. 1962

176. 5

2817. 1

3081. 9

6. 9938

360

287. 3

2891. 6

3178. 9

7. 3349

189. 9

2884. 4

3169. 2

7. 1363

400

306. 6

2957. 3

3263. 9

7. 4651

203. 0

2951. 3

3255. 8

7. 2690

440

325. 7

3023. 6

3349. 3

7. 5883

216. 0

3018. 5

3342. 5

7. 3940

500

354. 1

3124. 4

3478. 5

7. 7622

235. 2

3120. 3

3473. 1

7. 5698

540

372. 9

3192. 6

3565. 6

7. 8720

247. 8

3189. 1

3560. 9

7. 6805

600

401. 1

3296. 8

3697. 9

8. 0290

266. 8

3293. 9

3694. 0

7. 8385

640

419. 8

3367. 4

3787. 2

8. 1290

279. 3

3364. 8

3783. 8

7. 9391

20. 0 10 P a( 212. 42)

30. 0 10 P a( 233. 90)

99. 6

2600. 3

2799. 5

6. 3409

66. 7

2604. 1

2804. 2

6. 1869

240

108. 5

2659. 6

2876. 5

6. 4952

68. 2

2619. 7

2824. 3

6. 2265

280

120. 0

2736. 4

2976. 4

6. 6828

77. 1

2709. 9

2941. 3

6. 4462

320

130. 8

2807. 9

3069. 5

6. 8452

85. 0

2788. 4

3043. 4

6. 6245

360

141. 1

2877. 0

3159. 3

6. 9917

92. 3

2861. 7

3138. 7

6. 7801

400

151. 2

2945. 2

3247. 6

7. 1271

99. 4

2932. 8

3230. 9

6. 9212

440

161. 1

3013. 4

3335. 5

7. 2540

106. 2

3002. 9

3321. 5

7. 0520

500

175. 7

3116. 2

3467. 6

7. 4317

116. 2

3108. 0

3456. 5

7. 2338

540

185. 3

3185. 6

3556. 1

7. 5434

122. 7

3178. 4

3546. 6

7. 3474

600

199. 6

3290. 9

3690. 1

7. 7024

132. 4

3285. 0

3682. 3

7. 5085

640

209. 1

3262. 2

3780. 4

7. 8035

138. 8

3357. 0

3773. 5

7. 6106

700

223. 2

3470. 9

3917. 4

7. 9487

148. 4

3466. 5

3911. 7

7. 7571

36 5


T/

40 105 Pa ( 250. 40)

60 105 P a( 275. 64)

49. 78

2602. 3

2801. 4

6. 0701

32. 44

2589. 7

2784. 3

5. 8892

280

55. 46

2680. 0

2901. 8

6. 2568

33. 17

2605. 2

2804. 2

5. 9252

320

61. 99

2767. 4

3015. 4

6. 4553

38. 76

2720. 0

2952. 6

6. 1846

360

67. 88

2845. 7

3117. 2

6. 6215

43. 31

2811. 2

3071. 1

6. 3782

400

73. 41

2919. 9

3213. 6

6. 7690

47. 39

2892. 9

3177. 2

6. 5408

440

78. 72

2992. 2

3307. 1

6. 9041

51. 22

2970. 0

3277. 3

6. 6853

500

86. 43

3099. 5

3445. 3

7. 0901

56. 65

3082. 2

3422. 2

6. 8803

540

91. 45

3171. 1

3536. 9

7. 2056

60. 15

3156. 1

3517. 0

6. 9999

600

98. 85

3279. 1

3674. 4

7. 3688

65. 25

3266. 9

3658. 4

7. 1677

640

103. 7

3351. 8

3766. 6

7. 4720

68. 59

3341. 0

3752. 6

7. 2731

700

111. 0

3462. 1

3905. 9

7. 6198

73. 52

3453. 1

3894. 1

7. 4234

740

115. 7

3536. 6

3999. 6

7. 7141

76. 77

3528. 3

3989. 2

7. 5190

80 105 Pa ( 295. 06)

100 105 P a( 311. 06)

23. 52

2569. 8

2758. 0

5. 7432

18. 03

2544. 4

2724. 7

5. 6141

320

26. 82

2662. 7

2877. 2

5. 9489

19. 25

2588. 8

2781. 3

5. 7103

360

30. 89

2772. 7

3019. 8

6. 1819

23. 31

2729. 1

2962. 1

6. 0060

400

34. 32

2863. 8

3138. 3

6. 3634

26. 41

2832. 4

3096. 5

6. 2120

440

37. 42

2946. 7

3246. 1

6. 5190

29. 11

2922. 1

3213. 2

6. 3805

480

40. 34

3025. 7

3348. 4

6. 6586

31. 60

3005. 4

3321. 4

6. 5282

520

43. 13

3102. 7

3447. 7

6. 7871

33. 94

3085. 6

3425. 1

6. 6622

560

45. 82

3178. 7

3545. 3

6. 9072

36. 19

3164. 1

3526. 0

6. 7864

600

48. 45

3254. 4

3642. 0

7. 0206

38. 37

3241. 7

3625. 3

6. 9029

640

51. 02

3330. 1

3738. 3

7. 1283

40. 48

3318. 9

3723. 7

7. 0131

700

54. 81

3443. 9

3882. 4

7. 2812

43. 58

3434. 7

3870. 5

7. 1687

740

57. 29

3520. 4

3978. 7

7. 3782

45. 60

3512. 1

3968. 1

7. 2670

120 10 P a( 324. 75)

140 10 P a( 336. 75)

14. 26

2513. 7

2684. 9

5. 4924

11. 49

2476. 8

2637. 6

5. 3717

360

18. 11

2678. 4

2895. 7

5. 8361

14. 22

2617. 4

2816. 5

5. 6602

400

21. 08

2798. 3

3051. 3

6. 0747

17. 22

2760. 9

3001. 9

5. 9448

440

23. 55

2896. 1

3178. 7

6. 2586

19. 54

2868. 6

3142. 2

6. 1474

480

25. 76

2984. 4

3293. 5

6. 4154

21. 57

2962. 5

3264. 5

6. 3143

520

27. 81

3068. 0

3401. 8

6. 5555

23. 43

3049. 8

3377. 8

6. 4610

560

29. 77

3149. 0

3506. 2

6. 6840

25. 17

3133. 6

3486. 0

6. 5941

600

31. 64

3228. 7

3608. 3

6. 8037

26. 83

3215. 4

3591. 1

6. 7172

640

33. 45

3307. 5

3709. 0

6. 9164

28. 43

3296. 0

3694. 1

6. 8326

700

36. 10

3425. 2

3858. 4

7. 0749

30. 75

3415. 7

3846. 2

6. 9939

740

37. 81

3503. 7

3957. 4

7. 1746

35. 25

3495. 2

3946. 7

7. 0952

3 66


T/

160 10 5 P a( 347. 44)

180 105 P a( 357. 06)

9. 31

2431. 7

2580. 6

5. 2455

7. 49

2374. 3

2509. 1

5. 1044

360

11. 05

2539. 0

2715. 8

5. 4614

8. 09

2418. 9

2564. 5

5. 1922

400

14. 26

2719. 4

2947. 6

5. 8175

11. 90

2672. 8

2887. 0

5. 6887

440

16. 52

2839. 4

3103. 7

6. 0429

14. 14

2808. 2

3062. 8

5. 9428

480

18. 42

2939. 7

3234. 4

6. 2215

15. 96

2915. 9

3203. 2

6. 1345

520

20. 13

3031. 1

3353. 3

6. 3752

17. 57

3011. 8

3378. 0

6. 2960

560

21. 72

3117. 8

3465. 4

6. 5132

19. 04

3101. 7

3444. 4

6. 4392

600

23. 23

3201. 8

3573. 5

6. 6399

20. 42

3188. 0

3555. 6

6. 5696

640

24. 67

3284. 2

3678. 9

6. 7580

21. 74

3272. 3

3663. 6

6. 6905

700

26. 74

3406. 0

3833. 9

6. 9224

23. 62

3396. 3

3821. 5

6. 8580

740

28. 08

3486. 7

3935. 9

7. 0251

24. 83

3478. 0

3925. 0

6. 9623

200 10 5 P a ( 365. 81)

240 105 P a

400

5. 83

2293. 0

2409. 7

4. 9269

440

9. 94

2619. 3

2818. 1

5. 5540

6. 73

2477. 8

2639. 4

5. 2393

480

12. 22

2774. 9

3019. 4

5. 8450

9. 29

2700. 6

2923. 4

5. 6506

520

13. 99

2891. 2

3170. 8

6. 0518

11. 00

2838. 3

3102. 3

5. 8950

560

15. 51

2992. 0

3302. 2

6. 2218

12. 41

2950. 5

3248. 5

6. 0842

600

16. 89

3085. 2

3423. 0

6. 3705

13. 66

3051. 1

3379. 0

6. 2448

640

18. 18

3174. 0

3537. 6

6. 5048

14. 81

3145. 2

3500. 7

6. 3875

700

19. 40

3260. 2

3648. 1

6. 6286

15. 88

3235. 5

2616. 7

6. 5174

740

21. 13

3386. 4

3809. 0

6. 7993

17. 39

3366. 4

3783. 8

6. 6947

800

22. 24

3469. 3

3914. 1

6. 9052

18. 35

3451. 7

3892. 1

6. 8038

23. 85

3592. 7

4069. 7

7. 0544

19. 74

3578. 0

4051. 6

6. 9567

280 10 5 P a

400

320 105 P a

440

3. 83

2223. 5

2330. 7

4. 7494

2. 36

1980. 4

2055. 9

4. 3239

480

7. 12

2613. 2

2812. 6

5. 4494

5. 44

2509. 0

2683. 0

5. 2327

520

8. 35

2780. 8

3028. 5

5. 7446

7. 22

2718. 1

2949. 2

5. 5968

560

10. 20

2906. 8

3192. 3

5. 9566

8. 53

2860. 7

3133. 7

5. 8357

600

11. 36

3015. 7

3333. 7

6. 1307

9. 63

2979. 0

3287. 2

6. 0246

640

12. 41

3115. 6

3463. 0

6. 2823

10. 01

3085. 3

3424. 6

6. 1858

700

13. 38

3210. 3

3584. 8

6. 4187

11. 50

3184. 5

3552. 5

6. 3290

740

14. 73

3346. 1

3758. 4

6. 6029

12. 73

3325. 4

3732. 8

6. 5203

800

15. 58

3433. 9

3870. 0

6. 7153

13. 50

3415. 9

3847. 8

6. 6361

900

16. 80

3563. 1

4033. 4

6. 8720

14. 60

3548. 0

4015. 1

6. 7966

18. 73

3774. 3

4298. 8

7. 1084

16. 33

3762. 7

4285. 1

7. 0372

: keenan J H , F G keyes , P G Hill and J G M oor e . St eam T abl es . N ew Yor k : W il ey, 1969.

36 7

 D
( v/ cm 2 / g, u / kJ / kg , h / kJ / kg , s/ kJ / ( kg K ) )
v

T/

25 105 Pa ( 223. 99)

50 105 P a ( 263. 99)

20

1. 0006

83. 80

86. 30

0. 2961

0. 9995

83. 65

88. 65

0. 2956

40

1. 0067

167. 25

169. 77

0. 5715

1. 0056

166. 95

171. 97

0. 5705

80

1. 0280

334. 29

336. 86

1. 0737

1. 0268

333. 72

338. 85

1. 0720

120

1. 0590

502. 68

505. 33

1. 5255

1. 0576

501. 80

507. 09

1. 5233

160

1. 1006

673. 90

676. 65

1. 9404

1. 0988

672. 62

678. 12

1. 9375

200

1. 1555

859. 9

852. 8

2. 3294

1. 1530

848. 1

848. 1

2. 3255

220

1. 1898

940. 7

943. 7

2. 5174

1. 1866

938. 4

944. 4

2. 5128

1. 1973

959. 1

962. 1

2. 5546

1. 2859

1147. 8

1154. 2

2. 9202

75 105 Pa ( 290. 59)

100 105 P a ( 311. 06)

20

0. 9984

83. 50

90. 99

0. 2950

0. 9972

83. 36

93. 33

0. 2945

40

1. 0045

166. 64

174. 18

0. 5696

1. 0034

166. 35

176. 38

0. 5686

80

1. 0256

333. 15

340. 84

1. 0704

1. 0245

332. 59

342. 83

1. 0688

100

1. 0397

416. 81

424. 62

1. 3011

1. 0385

416. 12

426. 50

1. 2992

140

1. 0752

585. 72

593. 78

1. 7317

1. 0737

584. 68

595. 42

1. 7292

180

1. 1219

758. 13

766. 55

2. 1308

1. 1199

756. 65

767. 84

2. 1275

220

1. 1835

936. 2

945. 1

2. 5083

1. 1805

934. 1

945. 9

2. 5039

260

1. 2696

1124. 4

1134. 0

2. 8763

1. 2645

1121. 1

1133. 7

2. 8699

1. 3677

1282. 0

1292. 2

3. 1649

1. 4524

1393. 0

1407. 6

3. 3596

150 10 5 P a ( 342. 24)

200 105 P a ( 365. 81)

20

0. 9950

83. 06

97. 99

0. 2934

0. 9928

82. 77

102. 62

0. 2923

40

1. 0013

165. 76

180. 78

0. 5666

0. 9992

165. 17

185. 16

0. 5646

100

1. 0361

414. 75

430. 28

1. 2955

1. 0337

413. 39

434. 06

1. 2917

180

1. 1159

753. 76

770. 50

2. 1210

1. 1120

750. 95

773. 20

2. 1147

220

1. 1748

929. 9

947. 5

2. 4953

1. 1693

925. 9

949. 3

2. 4870

260

1. 2550

1114. 6

1133. 4

2. 8576

1. 2462

1108. 6

1133. 5

2. 8459

300

1. 3770

1316. 6

1337. 3

3. 2260

1. 3596

1306. 1

1333. 3

3. 2071

1. 6581

1585. 6

1610. 5

3. 6848

2. 036

1785. 6

1826. 3

4. 0139

20

0. 9907

250 10 P a
82. 47
107. 24

0. 2911

0. 9886

300 10 P a
82. 17
111. 84

0. 2899

40

0. 9971

164. 60

189. 52

0. 5626

0. 9951

164. 04

193. 89

0. 5607

100

1. 0313

412. 08

437. 85

1. 2881

1. 0290

410. 78

441. 66

1. 2844

200

1. 1344

834. 5

862. 8

2. 2961

1. 1302

831. 4

865. 3

2. 2893

300

1. 3442

1296. 6

1330. 2

3. 1900

1. 3304

1287. 9

1327. 8

3. 1741

: Keenan J H , F G K eyes , P G H ill and J G M oore . St eam T ables . New Y or k : W iley , 1969

3 68

 1 T S

36 9

 2 F 12 T S

3 70

 3 T S

van Laar ; Margules

A kl , A lk

k l W ils on ( A SOG )

van der W aals ; RK

van Laar ; Margules

, Jmol

van der W aals ; RK

( )

, Jmol

- 1

- 1

, calmol

- 1

- 1

, calmol

- 1

- 1

37 1

cV

, Jmol

- 1

- 1

, calmol

- 1

- 1

cp

, Jmol

- 1

- 1

, calmol

- 1

- 1

, mol m

Ep

, Jkg

- 1

, Jmol

- 1

, kcalkg

- 1

Ek

, Jkg

- 1

, Jmol

- 1

, kcalkg

- 1

, N , Kgf

( H elmoltz ) , J mol -

( )

- 3

, kPa at m

, kPa at m

( Gib bs ) , Jmol

G j

N RT L

, m s -

, J mol
, J mol - 1 , cal mol -

- 1

2
- 1

H enry

, kg

, kW

( )

, kPa , at m

p cm

, kPa, at m

, J, cal

Qk

Q0

, Jh

q0

, Jkg

3 72

- 1

kcalh

- 1
- 1

- 1

k calk g

- 1

, m Pakmol

Rk

, Jmol

, K

T0

, K

T cm

, K

, J mol - 1 , cal mol -

U j

U N IQ U AC

, m s -

, m mol

V cm

, cm 3 mol -

, J

WF

, J

WL

, J

W d

, J

Xk

k ( ASO G )

, kg

Z cm

- 1

- 1

, calmol

- 1

- 1

, cm atmmol

- 1

- 1

- 1

1
3

- 1
1

N RT L

37 3

Bolt zmann ,

W ils on

, J mol -

FH

( A SOG )

( )

, molm

N RT L ; U N IQ U AC

- 3

3 74

, j , k

[ 1] Smith J M and Van Nes s H C. Int roduct ion t o Chemical E ngineering T hermodynam ics , 3rd, Ed. ,
M cG raw H ill , 1976
[ 2] Edmis ter W C. A pplied H ydrocarbon T hermodynam ics , Vol 1 and 2. Gulf Pub . Co . 1961. 1974,
1984
[ 3] Sandler S I . Chemical and Engineering T hermodynam ics . J ohn Wiley & Sons, Inc . , 1977
[ 4] Lay J E . T herm odynamics . Charles E . M errill Books, Inc. , Columbus, Ohio. 1963
[ 5] Bet t K E et al . T hermodynamics for Chemical E ngineers . T H E A T H LO NE P RE SS of U nivers it y of
London, 1975
[ 6] Balzhiser R E et al . Chem ical E ngineering T hermodynamics. P rent ice H all , Inc . , 1972
[ 7] H uang F F . Engineering T hermodynamics . M acmillan P ub . Co. Inc . , 1976
[ 8] Coull J and St uart E B. E quilibrium T her modynamics. John W iley & Sons , Inc. , 1964
[ 9] , , : , 1964
[ 10] N ull H R. P hase E quilibrium in P rocess Design. W ileyInt ers cience, 1970
[ 11] H ala E et al . V apour Liquid Equilibrium , 2nd Ed . , P er gamon Pres s, 1967
[ 12] : , , 1977
[ 13] , . , 1963
[ 14] , , , 1965
[ 15]

, 1952

37 5

4 [ lg ( f / p ) ] ( 0) = [ lg] (0)
pr
Tr
0. 2

0. 4

0. 35

- 3. 687

- 3. 964

0. 40

- 2. 820

0. 45

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

2. 4

2. 6

- 4. 116 - 4. 2165 - 4. 279

- 4. 344

- 4. 382

- 4. 421

- 4. 436

- 4. 451

- 4. 488

- 4. 501

- 4. 513

- 3. 100

- 3. 254

- 3. 357

- 3. 432

- 3. 490

- 3. 535

- 3. 572

- 3. 601

- 3. 626

- 3. 646

- 3. 662

- 3. 675

- 2. 134

- 2. 415

- 2. 571

- 2. 676

- 2. 754

- 2. 813

- 2. 860

- 2. 891

- 2. 930

- 2. 956

- 2. 978

- 2. 996

- 3. 011

0. 50

- 1. 604

- 1. 886

- 2. 044

- 2. 151

- 2. 229

- 2. 290

- 2. 339

- 2. 379

- 2. 412

- 2. 439

- 2. 463

- 2. 482

- 2. 499

0. 55

- 1. 186

- 1. 470

- 1. 629

- 1. 736

- 1. 816

- 1. 878

- 1. 928

- 1. 969

- 2. 004

- 2. 032

- 2. 057

- 2. 078

- 2. 096

0. 60

- 0. 851

- 1. 136

- 1. 296

- 1. 404

- 1. 485

- 1. 548

- 1. 599

- 1. 641

- 1. 676

- 1. 706

- 1. 731

- 1. 753

- 1. 772

0. 65

- 0. 569

- 0. 855

- 1. 015

- 1. 125

- 1. 206

- 1. 270

- 1. 322

- 1. 364

- 1. 400

- 1. 431

- 1. 457

- 1. 480

- 1. 499

0. 70

- 0. 336

- 0. 622

- 0. 783

- 0. 893

- 0. 975

- 1. 039

- 1. 092

- 1. 135

- 1. 171

- 1. 203

- 1. 229

- 1. 253

- 1. 273

0. 75

- 0. 140

- 0. 426

- 0. 587

- 0. 698

- 0. 780

- 0. 846

- 0. 897

- 0. 942

- 0. 978

- 1. 010

- 1. 038

- 1. 061

- 1. 083

0. 80

- 0. 060

- 0. 262

- 0. 425

- 0. 535

- 0. 618

- 0. 683

- 0. 736

- 0. 780

- 0. 817

- 0. 849

- 0. 877

- 0. 901

- 0. 922

0. 85

- 0. 046

- 0. 120

- 0. 281

- 0. 392

- 0. 474

- 0. 539

- 0. 592

- 0. 636

- 0. 673

- 0. 705

- 0. 733

- 0. 757

- 0. 779

0. 90

- 0. 042

- 0. 087

- 0. 163

- 0. 273

- 0. 356

- 0. 421

- 0. 474

- 0. 517

- 0. 554

- 0. 587

- 0. 614

- 0. 639

- 0. 680

0. 95

- 0. 033

- 0. 070

- 0. 112

- 0. 173

- 0. 255

- 0. 319

- 0. 372

- 0. 415

- 0. 452

- 0. 483

- 0. 511

- 0. 535

- 0. 557

1. 00

- 0. 028

- 0. 059

- 0. 094

- 0. 131

- 0. 175

- 0. 237

- 0. 287

- 0. 330

- 0. 367

- 0. 398

- 0. 425

- 0. 449

- 0. 470

1. 05

- 0. 024

- 0. 051

- 0. 079

- 0. 109

- 0. 142

- 0. 178

- 0. 218

- 0. 257

- 0. 292

- 0. 322

- 0. 349

- 0. 372

- 0. 393

1. 10

- 0. 021

- 0. 044

- 0. 067

- 0. 093

- 0. 120

- 0. 147

- 0. 177

- 0. 207

- 0. 237

- 0. 264

- 0. 289

- 0. 311

- 0. 331

1. 15

- 0. 018

- 0. 037

- 0. 058

- 0. 079

- 0. 101

- 0. 123

- 0. 146

- 0. 170

- 0. 194

- 0. 217

- 0. 238

- 0. 258

- 0. 276

1. 20

- 0. 016

- 0. 032

- 0. 050

- 0. 067

- 0. 086

- 0. 104

- 0. 124

- 0. 143

- 0. 163

- 0. 182

- 0. 200

- 0. 217

- 0. 233

1. 25

- 0. 014

- 0. 029

- 0. 044

- 0. 059

- 0. 075

- 0. 091

- 0. 107

- 0. 123

- 0. 139

- 0. 155

- 0. 171

- 0. 186

- 0. 199

1. 3

- 0. 012

- 0. 025

- 0. 038

- 0. 051

- 0. 065

- 0. 078

- 0. 092

- 0. 106

- 0. 119

- 0. 133

- 0. 146

- 0. 159

- 0. 171

1. 4

- 0. 010

- 0. 021

- 0. 031

- 0. 041

- 0. 052

- 0. 062

- 0. 072

- 0. 082

- 0. 092

- 0. 102

- 0. 111

- 0. 120

- 0. 130


pr
Tr
0. 2

0. 4

0. 6

0. 8

1. 0

1. 2

1. 4

1. 6

1. 8

2. 0

2. 2

2. 4

2. 6

1. 5

- 0. 008

- 0. 016

- 0. 024

- 0. 032

- 0. 040

- 0. 047

- 0. 055

- 0. 063

- 0. 070

- 0. 078

- 0. 085

- 0. 092

- 0. 099

1. 6

- 0. 007

- 0. 013

- 0. 019

- 0. 026

- 0. 032

- 0. 038

- 0. 044

- 0. 050

- 0. 056

- 0. 062

- 0. 067

- 0. 072

- 0. 077

1. 7

- 0. 005

- 0. 010

- 0. 015

- 0. 020

- 0. 025

- 0. 030

- 0. 034

- 0. 039

- 0. 043

- 0. 047

- 0. 051

- 0. 056

- 0. 059

1. 8

- 0. 004

- 0. 008

- 0. 012

- 0. 015

- 0. 019

- 0. 022

- 0. 026

- 0. 030

- 0. 033

- 0. 036

- 0. 039

- 0. 042

- 0. 045

1. 9

- 0. 003

- 0. 006

- 0. 009

- 0. 012

- 0. 015

- 0. 018

- 0. 020

- 0. 023

- 0. 025

- 0. 028

- 0. 030

- 0. 033

- 0. 035

2. 0

- 0. 002

- 0. 004

- 0. 007

- 0. 009

- 0. 011

- 0. 013

- 0. 015

- 0. 017

- 0. 019

- 0. 021

- 0. 023

- 0. 025

- 0. 026

2. 5

0. 000

0. 000

0. 000

0. 000

- 0. 001

- 0. 001

- 0. 001

- 0. 001

- 0. 001

- 0. 001

- 0. 001

- 0. 001

- 0. 001

3. 0

0. 000

+ 0. 001

+ 0. 001

+ 0. 002

+ 0. 002

+ 0. 003

+ 0. 003

+ 0. 004

+ 0. 004

+ 0. 005

+ 0. 005

+ 0. 006

+ 0. 007

3. 5

+ 0. 001

0. 002

0. 003

0. 003

0. 004

0. 005

0. 006

0. 007

0. 008

0. 009

0. 010

0. 011

0. 012

4. 0

0. 001

0. 002

0. 003

0. 005

0. 006

0. 007

0. 008

0. 009

0. 010

0. 011

0. 012

0. 013

0. 014

pr
Tr
2. 8

3. 0

3. 2

3. 4

3. 6

3. 8

4. 0

4. 5

5. 0

6. 0

7. 0

8. 0

9. 0

0. 35

- 4. 521

- 4. 527

- 4. 531

- 4. 534

- 4. 534

- 4. 534

- 4. 534

- 4. 525

- 4. 513

- 4. 474

- 4. 424

- 4. 366

- 4. 296

0. 40

- 3. 686

- 3. 695

- 3. 701

- 3. 706

- 3. 710

- 3. 712

- 3. 713

- 3. 711

- 3. 704

- 3. 678

- 3. 640

- 3. 593

- 3. 540

0. 45

- 3. 024

- 3. 035

- 3. 043

- 3. 050

- 3. 055

- 3. 060

- 3. 062

- 3. 065

- 3. 063

- 3. 046

- 3. 017

- 2. 980

- 2. 937

0. 50

- 2. 513

- 2. 525

- 2. 535

- 2. 544

- 2. 550

- 2. 556

- 2. 560

- 2. 567

- 2. 568

- 2. 559

- 2. 538

- 2. 508

- 2. 472

0. 55

- 2. 111

- 2. 124

- 2. 135

- 2. 145

- 2. 153

- 2. 160

- 2. 165

- 2. 175

- 2. 179

- 2. 176

- 2. 162

- 2. 138

- 2. 108

0. 60

- 1. 788

- 1. 803

- 1. 815

- 1. 826

- 1. 835

- 1. 842

- 1. 849

- 1. 861

- 1. 868

- 1. 870

- 1. 860

- 1. 842

- 1. 818

0. 65

- 1. 517

- 1. 532

- 1. 545

- 1. 556

- 1. 566

- 1. 574

- 1. 582 - 1. 5961 - 1. 605

- 1. 611

- 1. 606

- 1. 592

- 1. 572

0. 70

- 1. 291

- 1. 306

- 1. 320

- 1. 332

- 1. 343

- 1. 352

- 1. 360

- 1. 376

- 1. 387

- 1. 397

- 1. 395

- 1. 385

- 1. 369

0. 75

- 1. 100

- 1. 116

- 1. 131

- 1. 144

- 1. 155

- 1. 165

- 1. 174

- 1. 190

- 1. 202

- 1. 215

- 1. 217

- 1. 210

- 1. 197


pr
Tr
2. 8

3. 0

3. 2

3. 4

3. 6

3. 8

4. 0

4. 5

5. 0

6. 0

7. 0

8. 0

9. 0

0. 80

- 0. 941

- 0. 957

- 0. 972

- 0. 985

- 0. 997

- 1. 007

- 1. 016

- 1. 035

- 1. 048

- 1. 064

- 1. 067

- 1. 063

- 1. 052

0. 85

- 0. 797

- 0. 814

- 0. 829

- 0. 842

- 0. 854

- 0. 864

- 0. 874

- 0. 893

- 0. 907

- 0. 924

- 0. 929

- 0. 926

- 0. 917

0. 90

- 0. 679

- 0. 696

- 0. 710

- 0. 724

- 0. 736

- 0. 746

- 0. 756

- 0. 775

- 0. 789

- 0. 807

- 0. 814

- 0. 813

- 0. 805

0. 95

- 0. 575

- 0. 592

- 0. 607

- 0. 621

- 0. 632

- 0. 643

- 0. 652

- 0. 672

- 0. 687

- 0. 706

- 0. 713

- 0. 713

- 0. 707

1. 00

- 0. 489

- 0. 505

- 0. 520

- 0. 534

- 0. 545

- 0. 556

- 0. 566

- 0. 586

- 0. 601

- 0. 620

- 0. 629

- 0. 630

- 0. 624

1. 05

- 0. 411

- 0. 428

- 0. 442

- 0. 455

- 0. 467

- 0. 478

- 0. 488

- 0. 508

- 0. 523

- 0. 543

- 0. 552

- 0. 553

- 0. 549

1. 10

- 0. 348

- 0. 364

- 0. 378

- 0. 391

- 0. 403

- 0. 413

- 0. 422

- 0. 442

- 0. 457

- 0. 477

- 0. 487

- 0. 489

- 0. 486

1. 15

- 0. 293

- 0. 307

- 0. 321

- 0. 333

- 0. 344

- 0. 354

- 0. 363

- 0. 383

- 0. 397

- 0. 417

- 0. 427

- 0. 429

- 0. 426

1. 20

- 0. 247

- 0. 261

- 0. 273

- 0. 285

- 0. 295

- 0. 305

- 0. 314

- 0. 332

- 0. 346

- 0. 366

- 0. 375

- 0. 378

- 0. 376

1. 25

- 0. 212

- 0. 224

- 0. 236

- 0. 246

- 0. 256

- 0. 264

- 0. 273

- 0. 290

- 0. 304

- 0. 322

- 0. 331

- 0. 334

- 0. 332

1. 3

- 0. 182

- 0. 193

- 0. 203

- 0. 212

- 0. 221

- 0. 229

- 0. 237

- 0. 253

- 0. 266

- 0. 283

- 0. 292

- 0. 295

- 0. 294

1. 4

- 0. 138

- 0. 146

- 0. 154

- 0. 162

- 0. 169

- 0. 175

- 0. 181

- 0. 194

- 0. 205

- 0. 220

- 0. 228

- 0. 231

- 0. 229

1. 5

- 0. 104

- 0. 112

- 0. 117

- 0. 124

- 0. 129

- 0. 134

- 0. 139

- 0. 149

- 0. 158

- 0. 170

- 0. 176

- 0. 178

- 0. 176

1. 6

- 0. 082

- 0. 087

- 0. 092

- 0. 096

- 0. 100

- 0. 104

- 0. 108

- 0. 116

- 0. 123

- 0. 132

- 0. 137

- 0. 138

- 0. 136

1. 7

- 0. 063

- 0. 067

- 0. 071

- 0. 074

- 0. 077

- 0. 080

- 0. 083

- 0. 089

- 0. 094

- 0. 101

- 0. 105

- 0. 105

- 0. 102

1. 8

- 0. 048

- 0. 051

- 0. 053

- 0. 056

- 0. 058

- 0. 060

- 0. 063

- 0. 067

- 0. 071

- 0. 076

- 0. 078

- 0. 077

- 0. 074

1. 9

- 0. 037

- 0. 039

- 0. 041

- 0. 043

- 0. 045

- 0. 046

- 0. 048

- 0. 051

- 0. 054

- 0. 057

- 0. 057

- 0. 055

- 0. 051

2. 0

- 0. 028

- 0. 029

- 0. 031

- 0. 032

- 0. 033

- 0. 034

- 0. 035

- 0. 037

- 0. 039

- 0. 040

- 0. 039

- 0. 038

- 0. 034

2. 5

- 0. 001

- 0. 001

- 0. 001

- 0. 001

- 0. 000

0. 000

0. 000

+ 0. 001

+ 0. 003

+ 0. 006

+ 0. 011

+ 0. 016

+ 0. 022

3. 0

+ 0. 007

+ 0. 008

+ 0. 009

+ 0. 010

+ 0. 011

+ 0. 012

+ 0. 012

0. 015

0. 017

0. 023

0. 028

0. 035

0. 042

3. 5

0. 013

0. 014

0. 015

0. 016

0. 017

0. 018

0. 020

0. 022

0. 025

0. 031

0. 038

0. 044

0. 051

4. 0

0. 015

0. 016

0. 017

0. 019

0. 020

0. 021

0. 022

0. 025

0. 028

0. 034

0. 040

0. 047

0. 054