:

.
, ,
,
- ,
711 10,
http://tccc.iesl.forth.gr/education/local.html


di S
0
dt

1 ----
1.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.5 . . . . . . . . . . . . . . . . . . . . .
1.6 . . . . . . . . . . . . . . . . . . .
1.6.1 :
. . . . . . . . . . . . . . . . . . . . . . . . . . .
1.6.2 :
1.6.3 .
1.6.4 . . . . . . . . . . . . . . .
1.7 . . . . . . . . . . . .
1.8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.9 LEGENDRE . . . . . . . . . . . . . . . . .
1.10 MAXWELL . . . . . . . . . . . . . . . . . . . . . . .
1.11 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.12 GIBBS-DUHEM . . . . . . . . . . . . . . . . . . . . . .
1.13 . . . . . . . . . . . . . . . . . . . .
1.14 . . . . . . . . . . . . . . . . . . . . . . . .
1.15 DUHEM . . . . . . . . . . . . . . . . . . . . . . . . .

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14
15
15
16
16

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19
20
23
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24
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27
28

2
2.1 . . . . . . . . . . . . . . . . . . .
2.2 . . . . . . . . . . . . . . . . .
2.3 . . . . . . . . . . .
2.4 - . . . . . . . . . . .
2.5 . . . . . . . . . . . . . . . . .
2.6 . . . . . . . . . . . .
2.7 . . . . . . . . . . . . . . . . . . .
2.8 --

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29
29
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30
30
31
32
34
39

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1
. 1
. 7
. 9
. 11
. 13
. 14

ii

2.9 . . . . . . . . . . . . .
2.10 . . . . . . . .
2.11 . . . . . . . . . . . . . . . . . . . . . . . . .
2.12 . . . . .
2.13 LEGENDRE . . . . . . . . . . . . .
2.14 . . . . . . . . . . . . . . . . . . . . . . . . .
2.15 Gibbs-Duhem . . . . . . . . . . . . . . . . . . .
2.16 . . . . . . . . . . . . . . . .
2.17 . . . . . . . . . . . . . . . . . . . .
2.18 DUHEM . . . . . . . . . . . . . . . . . . . . .
2.19

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3
3.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1 . . . . . . . . . . . . . . . . . . . . .
3.1.2 . . . . . . . . . . .
3.1.3 . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.4 . . . . . . . . . . . . . . . . . . . .
3.1.5 - . . . . . . . . . .
3.1.6 . . . . . . . . . . . .
3.1.7 . . . . . . . . . . . . .
3.1.8 ,
. . . . . . . . . . . . . .
3.1.9 . . . . . . . . . . . . . . . . . . . . . .
3.1.10 Clausius-Clapeyron
()- . . . . . . . . . . . . . . . . . . . . . .
3.1.11 xi
. . . . . .
3.1.12
. . . . . . . . . . . . . . . . . . .
3.2 . . . . . . . . . . . . . .
3.2.1 van der Waals . . . . . . . . . . .
3.2.2 Hess . . . . . .
3.2.3 Kirchhoff . . . . . . . . . . . . . . . . . . . .
3.2.4 Gibbs
. . . . .
3.2.5 Gibbs-Helmholtz . . . . . . . . . . . . . . . . .
3.2.6 Gibbs .
3.2.7 Raoult . . . . . . . .
3.2.8 . . . . . . . . . . . . . . . . . . .
3.2.9 :
3.2.10 : . . . . . . . . . . .
3.2.11 : ,
vant Hoff . . . . . . . . . . . . . . . . . . . . .
3.2.12 . . . . . . . . . . . . . . . . . . . .
3.2.13 vant Hoff: . . . . . . . . . . . . . . . . . . . . .

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44
44
51
52
56
65
68
69
75
85
86

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89
89
89
89
90
90
91
91
92

. 92
. 93
. 93
. 94
. 97
. 99
. 99
. 100
. 100
. 101
. 101
. 102
. 103
. 103
. 103
. 104
. 104
. 104
. 105

iii

107

LEGENDRE

109

111

LAGRANGE

113

115

117

119

BOLTZMANN

133

-
135
.1 . . 142

145

147

iv

- -
- -
1.1

.
,
. ,
Avogadro (NA 1023 ),
.
() .
.


, .
Avogadro.
, ,
.

.
; .

[1, 2] 1

1. ----

.
.
.
, ,
.
. (
) .
( 1.1), , ()
() .

.
.
Euler.

,
, ,
.

.
. 1012
.

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

,
. .
(O )

(T ), (<>) -

1.1.

1.1:

Ui , i = 1, 2, . . . , Vi , i = 1, 2, . . . Ni , i = 1, 2, . . . .
.

U 2, V2, N2

U1, V1, N1
U3, V3, N3

U i , Vi , Ni

U 4, V4, N4

=
O

1
T

O(t)dt =< O > .

(1.1)

.
.
.
,
.
. ,
.

. ( ), .

. () ( ).
,

1. ----

(, ) ,
( 1.2).
( ) 1 . ,
, P ,
(P = f (V )).
.
,
. 1.3
(
) .
.

.
.
, (
1.2), , ,
,
.
;
.
.

,
. .
. ,
.
- ,
.
,
, .
- .
. ;
1

() (differential manifold)
k- (k f orms). k = 0
k = 1 .

1.1.

1.2:
Ei i. (, , )
.

.

.

F(Ei)

Ei

.
. ,
, ,
.
.

. .
;
.
Taylor:

F (x) = F (x0 ) +



dF (x) 
1 d2 F (x) 
(x

x
)
+
(x x0 )2 + . . .
x=x0
0
dx 
2 dx2 x=x0

(1.2)
,
.
.
;
-

1. ----

1.3: . (, , )
.

.

;
, ,
.
;
;
E ,
,
;

,
,
.
,
. .

1.2.

,
.
,
.
,
.
:
, ,
,
,

, , .
.

.

.

.

.

.

1.2

1. ----

1.3.

1.3

(1.3)

- :

(1.4)

(1.5)

(1.6)

():

(1.7)

():

(1.8)

(Gradient):
(Hessian):


d~
x=
d~
xT =

dx1
dx2

f (x1 , x2 ) =

f (x1 , x2 ) =

2 f (x1 , x2 ) =

(1.9)

dx1 dx2

f
x1
f
x2

(1.10)

(1.11)

f ~
f ~
i+
j
x1
x2
f 2
x2
1

f 2
x1 x2
2

f
x2 x1

f
x2
2

(1.12)

(1.13)

TAYLOR

df (x1 , x2 )

f (x1 + dx1 , x2 + dx2 ) f (x1 , x2 )

(1.14)
1
(f )T (d~
x) + (d~
x)T ( 2 f ) (d~
x) + . . .
(1.15)
2
f
f
dx1 +
dx2 +
(1.16)
x1
x2
1 2f 2
1 2f 2
2f
dx
+
dx
+
dx1 dx2 + . . .
1
2
2 x21
2 x22
x1 x2

10

1. ----

= f (x1 + x1 , x2 + x2 ) f (x1 , x2 )
(1.17)
1
x)T ( 2 f )(~
x) + . . .
(1.18)
(f )T (~
x) + (~
2
f
f

x1 +
x2 +
(1.19)
x1
x2
1 2f 2
1 2f 2
2f
+
+
x
x
x1 x2 + . . .
2 x21 1
2 x22 2
x1 x2

f (x1 , x2 )

f (x1 , x2 )

f (x1 + x1 , x2 + x2 ) f (x1 , x2 )
(1.20)
1
(f )T (~
x) + (~
x)T ( 2 f ) (~
x) + . . . (1.21)
2
f
f
x1 +
x2 +
(1.22)
x1
x2
1 2f
2f
1 2f
x21 +
x22 +
x1 x2 + . . .
2
2
2 x1
2 x2
x1 x2

( )

Z


f (x1 , x2 )dx1 dx2

Z
=

f (x1 , x2 )dx1 dx2

(1.23)

( )


=

x1


f (x1 , x2 )

f (x1 , x2 )
x2


=

f (x1 , x2 )
x1
f (x1 , x2 )
x2

(1.24)

(1.25)

1.4.

1.4

11

) , (N, V
, = N/V ).

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

)
, N1 , N2 , . . . , Nr , ,
U , , V . U
.
N1 , N2 , . . . , Nr , U V .
p , Nij , i = 1, . . . , r ,
Vj Uj , j = 1, . . . , p. :
p
X
j=1
p
X
j=1
p
X

Uj

= U = UT ()

(1.26)

Vj

= V = VT ()

(1.27)

= Ni = NiT , i = 1, . . . , r, ().

(1.28)

Nij

j=1

,
. .
.
.

)
, ,

12

1. ----
(U, U + dU ).
( ):

S(U ) = kB ln .
kB = 1, 38066 10

23

JK

(1.29)

Boltzmann.

S(U ) , U (S). ( )
, n1 , n2 , . . . , nr ,

S(U, V, n1 , n2 , . . . , nr ),

U (S, V, n1 , n2 , . . . , nr ).

(1.30)

p =

p = 1,

(1.31)

V , ~
n = (n1 , n2 , . . . , nr )T
(U, U + dU ) ( )
(Gibbs)

S(U, V, ~
n) = kB ln = kB

X 1


ln

= kB

p ln p .

(1.32)

) ( )
(
( )) ( ).
, U, S, V, n1 , n2 , . . . , nr .
(, p = 1)
( ). ,
(, p = 0)
.
n
p- (p) ( ):

f (x1 , x2 , . . . , xn ) =

1
p

f (x1 , x2 , . . . , xn ).

(1.33)

EULER ( ):

f (x1 , x2 , . . . , xn ) =

n
X
f
i=1

xi

xi .

(1.34)

1.5.

13

. -.
(
-) , . (q ) , [q = 0.

1.5

EULER :


U (S, V, n1 , n2 , . . . , nr ) =


S+


V+

V,ni

S,ni


r 
X
U
ni

i=1

ni .
S,V,nj6=i

(1.35)
:


:
:
:

(xi ,

f
)
xi


(1.36)

S V,ni


U
V S,ni


U
ni

(1.37)

(1.38)

S,V,nj6=i

. ,

(S, T ), (V, P ), (ni , i ), .

,
( ), :

U (S, V, ni ) = T S P V +

r
X

i ni

(1.39)

i=1

dU = T dS P dV +

r
X

i dni

(1.40)

i=1

, (
)

S(U, V, ni ) =

1
T

U+

P
T

r
X
i
i=1

ni

(1.41)

14

1. ----

dS =

1.6
1.6.1

1
T

dU +

P
T

dV

r
X
i
i=1

dni

(1.42)

dU = 0.

(1.43)

dU = [q + [w +

r
X

i dni .

(1.44)

i=1

[q [w
. (P, V ),
dU = [q P dV +

r
X

i dni .

(1.45)

i=1

U = q + w +

r
X

i ni .

(1.46)

i=1

,
-.

.

[q [w ( [). , dU dS
U S
. U S
P.
r

i=1 i dni

dU = [q + [w

(1.47)

1.6.

1.6.2

15

[t, t + dt]
( ) . - ,
.
dST
dt

UT ,VT ,nT
i

(1.48)

,
( )
- ( unconstrained)
( ). ,
ST (Ul , Vl , nil ; UT , VT , nT
i )

(Gradient) (ST )UT ,VT ,nTi = 0 (), .,

(1.49)

ST ~
ST ~
ST ~
i+
j+
k = 0,
Ul
Vl
nil

(1.50)

(Hessian) ( 2 ST )UT ,VT ,nTi 0.

(1.51)

( ) ( )

"

2 ST
Ul2

1.6.3


0,

2 ST 2 ST
Ul2 Vl2

2 ST
Ul Vl

2

#
0

(1.52)

(de S) - (di S)

dS = de S + di S.

(1.53)

di S
dt

0,

(1.54)

16

1. ----

-. p
l

di Sl
dt

0,

di Sl 0,

l = 1, . . . p

(1.55)

de S =

dq
T

dU dw
T

dU + P dV

Pr

i=1

i de ni

(1.56)

- di S -
.

1.6.4

(T = 0)
(S = 0).

( = 1).

1.7

(U, S, T, V, P, i , ni )
(U 0 , S 0 , T 0 , V 0 , P 0 , 0i , n0i ) ,
, , ST = S + S 0 (+), ((ST )UT ,VT ,nT = 0) ,
i

U + U0
V +V
ni +

n0i

UT

(1.57)

= VT

(1.58)

nT
i ,

i = 1, . . . , r

(1.59)

U + U 0

(1.60)

(1.61)

n0i

0, i = 1, . . . , r

(1.62)

V + V
ni +

T0

0i , i = 1, . . . , r

( )
( )
( ).

(1.63)
(1.64)
(1.65)

1.7.

17

( )
Lagrange ( ).
,
dS = de S + di S de S.
(1.66)
1.56 ( CLAUSIUS)

T dS [q

(1.67)

T S q

(1.68)

T S = q .
U T S P V +

r
X

i ni .

(1.69)

i dni .

(1.70)

i=1

dU = T dS P dV +

r
X
i=1

, , - ( unconstrained)
, U (Sl , Vl , nil ; ST , VT , nT
i ) ( l, T )

(Gradient) (U )S,V,ni = 0 (),

(1.71)

(Hessian) ( 2 U )S,V,ni 0 ().

(1.72)

U (
) ( )

"

2U
S 2


0,

2U 2U
S 2 V 2

2U
SV

2

#
0.

(1.73)

(dU/dt)S,V,ni 0.

(1.74)

18

1. ----

1.67 .
( )
!
1.52 ( 2 S < 0) 1.73
( 2 U > 0), :


V kT =
CV

T


0,

(P )


S

ni

T


0,

(1.76)

V,ni

0.

(1.75)

T ,ni

(1.77)

T ,V,j


CP = T


,

(1.78)

P,ni

CP CV > 0.

(1.79)

[q = CV dT.

(1.80)


CV =


(1.81)

V,ni

[q = CP dT

(1.82)

(1.83)
P,ni

T =


(1.84)

T ,ni

S =

1
V

V
P


(1.85)
S,ni

1.8. 19

1.8

, /
, (Ueq , Veq , nieq ).
Taylor

S(Ueq + U, Veq + V, nieq + ni )

Seq (Ueq , Veq , nieq )

S(U, V, ni )
1 2
+
S(U, V, ni )
2
+ .
(1.86)


S(U, V, ni ) =

1
T

1
Teq

U +

Peq

Teq

r 
X
i
i=1

eqi
Teq


ni .

(1.87)

Teq

Peq

eqi ,

i = 1, , r,
(1.88)

S = 0.

"
2

S(T, V, ni ) =

2
Teq

CV

#
(T )2
1

(< 0)

(1.89)

(V )2 (< 0)
(1.90)
Teq Veq T
X   i 
(ni nj ) (< 0), (1.91)
nj Teq
ij

(U = CV T ).
S = 0

S Seq = 1/2 2 S < 0.

(1.92)

, -
di S = Seq S = 1/2 2 S > 0, . . 2 S 0,

20

1. ----

.
, -
( 2 S ) ,
, .
(Seq )
:
Lyapunov

L(T, V, ni ) =

1
2

2 S(T, V, ni ) < 0,

(1.93)

dL(T, V, ni )
dt

2 S(T, V, ni )

dt

> 0.

(1.94)

- .

1.9

Legendre

,
. Legendre .
.
) (S, P, ni ). .

H(S, P, ni ) = U (P )V

dH = T dS + V dP +

r
X

(1.95)

i dni

(1.96)

i=1

H
S


= T,

P,ni

H
P


=V
S,ni

H
ni


= i .
S,P,nj

(1.97)

1.9. LEGENDRE

21

( ( unconstrained) )
.

2H

(H)S,P,ni = 0 (),
(1.98)
 2 
 2 
H
H
0. (1.99)
0,

0,
P 2 S,ni
n2i S,P,nj

S 2

P,ni

dH
dt S,P,ni

iS
= T ddt
0,


CP =

H
T

(1.100)


,

(1.101)

(dH)P = [q.

(1.102)

) (T, V, ni ). HELMHOLTZ.

A(T, V, ni ) = U T S

dA = SdT P dV +

r
X

(1.103)

i dni

(1.104)

i=1


= S,

V,ni


= P
T ,ni

A
ni


= i .
T ,V,nj

(1.105)
HELMHOLTZ
( - ) .

A
T 2


V,ni

(A)T ,V,ni = 0 (),

(1.106)
 2 
 2 
A
A
0,
0,
0. (1.107)
2
V
n2i T ,V,nj
T ,ni
dA
dt T ,V,ni

iS
= T ddt
0.

(1.108)

) (T, P, ni ). GIBBS.

G(T, P, ni ) = U T S (P )V = H T S = A + P V
(1.109)

22

1. ----
Euler Gibbs

r
X

G(T, P, ni ) =

i (T, P )ni =

i=1

r
X

i ni

(1.110)

i dni

(1.111)

i=1

dG = SdT + V dP +

r
X
i=1


= S,

P,ni


=V

G
ni

T ,ni

= i . (1.112)
T ,P,nj

GIBBS ( - )
.

2G

T 2

P,ni

(G)T ,P,ni = 0 (),

(1.113)
 2 
 2 
G
G
0. (1.114)
0,
0,
2
P
n2i T ,P,nj
T ,ni
dG
dt T ,P,ni

iS
= T ddt
0.

(1.115)

) (T, V, i ). .

(T, V, i ) = A

r
X

ni i = A G = P V

(1.116)

i=1

d = SdT P dV

r
X

ni di

(1.117)

i=1


= S,
V,i


= P,

T ,i


= ni .
T ,V,j

(1.118)

( - ) .

1.10. MAXWELL

T 2


V,i

23

()T ,V,i = 0 (),

(1.119)
 2 
 2 


0,
0,
0 (1.120)
2
V
2i T ,V,j
T ,i
d
dt T ,V,i

1.10

(1.121)

Maxwell


V S

T

P S

S

V T

S

1.11

iS
= T ddt
0.

=
=

S


V


=
=

(1.122)

(1.123)

,
T V


V

(1.124)

S P

P

,
V

(1.125)

(X1 , X2 , . . . , Xr , Ir+1 , Ir+2 , . . . , Is ),

(1.126)

r , (X1 , X2 , . . . , Xr ) s r
, (Ir+1 , Ir+2 , . . . , Is ) :
:

d =

r
X

Ii dXi

i=1

s
X

Xj dIj .

(1.127)

j=r+1

Maxwell

Ii
Ij

Xj
Xi

Xi
Ij
Ii
Xj

=
=

, (j > r i r).

Xj
Ii
Ij
Xi

(1.128)

, (i, j r).

(1.129)

, (i, j > r).

(1.130)

24

1. ----

,
-

= 0.

(1.131)

(convex)

Xi2

0,

(1.132)

X1 ,...,Xi1 ,Xi+1 ,...,Xr ,Ir+1 ,...,Is

(concave)

2
2
Ir+j+1

!
0.

(1.133)

X1 ,...,Xr ,Ir+1 ,...,Ir+j ,Ir+j+2 ,...,Is

(Xi , Ii ):

Ii
Xi


0, [(S, T ), (V, P ), (ni , i )] .
X1 ,...,Xi1 ,Xi+1 ,...,Xr ,Ir+1 ,...,Is

(1.134)

1.12

Gibbs-Duhem

SdT V dP +

r
X

ni di = 0.

(1.135)

i=1

1.13

) (V, T ),
P = f (V, T ) ,

1.13.


(i)
(ii)
(iii)

CV

V T


S
V T


U


(iv)

(v)

V T

H
V

CP CV


(vi)

H
T


V

 2 
P
= T
T 2 V


P
=
T V


P
= T
P
T V




P
P
= T
+V
T V
V T


P
1
= T

T V
T
 2 


P
P
/
= T
T V
V T
 2

P
= T T V
T V
= T V 2 /T


P
= CV + V
T V

25

(1.136)
(1.137)
(1.138)
(1.139)
(1.140)
(1.141)
(1.142)
(1.143)
(1.144)

) (P, T ),
V = f (P, T ) ,

26

1. ----


(i)
(ii)

CP

P T


S
P

=
=

=

(iii)


=

=

(iv)


=

=
(v)

CP CV

=
=


(vi)

U
T


=
P

2V

T
T 2 P


V

T P
V




V
V
T
P
T P
P T
T V + P V T


V
V T
T P
V TV

 2 

V
V
T
/
T P
P T
T V 2 /T


V
CP P
T P
CP P V

(1.145)
(1.146)
(1.147)
(1.148)
(1.149)
(1.150)
(1.151)
(1.152)
(1.153)
(1.154)
(1.155)

) (dS = 0)

1.14.

27

V S

T

(i)
(ii)

=
=

=

(iii)

=
=
CP

(iv)

CV


P
V

=
=

1.14

(1.156)

CV T


T
V

CP T
TV

(1.157)
P

(1.158)

CP


CV V
CP P T

 2


V
V
T
+
P T
CP
T P
2 2
V T
T V +
CP
T
S


P



V T
CV
2 T
1
2

T V
T CV

P
T

(1.159)
(1.160)
(1.161)
(1.162)

 2
(1.163)
V

(1.164)

(Gibbs)

C .
()

F =C+2
F
C

=
=
=

(1.165)

,
,
.

, , , ,
, (X/ni )T ,P,nj , (ri ) i r ,

ri =

nri

,
nr

nr =

C
X

nri , r = 1, . . . , .

(1.166)

i=1

R M ()
,

F =C+2RM

(1.167)

28

1. ----

1.15

Duhem

,
,
.

2.1

,
.
.

2.2

(
) .
Taylor . ,
( 2.1),


Hessian , .

(df (x1 , x2 ))

f
f
=
.
x1 x2
x2 x1

(2.1)

df ,
. ,
-.

I

df (x1 , x2 ) = 0,
29

(2.2)

30

2.

2.1: x0 .
,
x0 .

f(x)
f(x)

f(x 0 )

L(x)=f(x0 )+f(x 0 )(xx0 )

f(x) = (df/dx)
L(0)=f(x0 )f(x 0 )x

x0

I
[f (x1 , x2 ) 6= 0.

(2.3)

( -),
- . f
f .
Taylor.

2.3

,
, , .
[3, 4].

2.4

.
.

2.5.

31

, , , ,
.
.
-
.
, +
.

2.5

2.2: Ei , i =
1, 2, . . . , Vi , i = 1, 2, . . . Ni , i = 1, 2, . . . .
.

E2 , V 2 , N 2

E1 , V 1 , N 1
E3 , V 3 , N 3

Ei , V i , N i

E4 , V 4 , N 4

p
X

Ei = UT ()

i=1
p
X

Vi = VT ()

(2.5)

Ni = NT ().

(2.6)

i=1
p
X
i=1

(2.4)

32

2.

. 2.3
.
.
(), . ,
(constrained) -
(unconstrained). 2.4.
2.3: () () -.

11111
00000
00000
11111
00000
11111
00000
11111
00000
11111

11111
00000
00000
11111
00000
11111
00000
11111
00000
11111
00000
11111

()

2.6

()

. , N Ei
( )

U=

N
X

Ei .

(2.7)

i=1

Ei = Ti + Vi .
(2.8)

2.6.

33

2.4: () () .

111
000
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
()

()

: .
.

dU = 0.

(2.9)

U = 0, U = 0.

(2.10)

.
.

,
- . , F 2.9.
z
.
, , .
, +,

dU = [q + [w.

(2.11)

[q [w
.
[q [w
( [).

34

2.

U = U U = q + w.

(2.12)

, q, w ,

.
, . , .

U = 0 = q + w, w = q.

(2.13)

,
.
(q = 0),
w = 0.

2.7

(-) .
: .

, - . ST
+ ,

dST
0.
dt

(2.14)

,
, (U, V, N ).
.

S(U, V, N )

S(U2 , V, N )

S(U, V, N ),

(2.15)

( , )

(2.16)

S(U1 , V, N ) U2 U1 ,

(2.17)

( , )(2.18)

S(U1 + U2 , V1 + V2 , N1 + N2 )

S(U1 , V1 , N1 ) + S(U2 , V2 , N2 ).

(2.19)

( , ).
2.5 2.6.
(concave)

2.7.

35

S (cU1 + (1 c)U2 ) cS(U1 ) + (1 c)S(U2 ),

c [0, 1].

(2.20)

2.5: .

S(cU 1+(1c)U2 ) >= cS(U 1) + (1c)S(U2 )

S2
S1

U1

U2

( 2.7,2.8).

U (S, V, N )

= U (S, V, N ),

(2.21)

( , )

U (S2 , V, N ) U (S1 , V, N ) S2 S1 ,

(2.22)
(2.23)

( , ) (2.24)

U (S1 + S2 , V1 + V2 , N1 + N2 ) U (S1 , V1 , N1 ) + U (S2 , V2 , N2 ).

(2.25)

( , ).
(convex) , (
2.7 2.8).

U (cS1 + (1 c)S2 ) cU (S1 ) + (1 c)U (S2 ),

c [0, 1].

(2.26)

36

2.

2.6: .

S = S(U ),

S1

S(U1 ),

(2.27)

S2

S(U2 ),

(2.28)

S(U ) = cS1 + (1 c)S2 , c [0, 1],

(2.29)

. U , S1
S2 .

U = U (cS1 + (1 c)S2 ).
,

(2.30)

2.7.

37

2.7: .

U[cS 1+(1c)S 2] <= cU(S1 ) + (1c)U(S2 )

U2

U1
S1

S(U ) = S[U (cS1 + (1 c)S2 )]

= cS1 + (1 c)S2

(2.31)

cS[U1 (S1 )] + (1 c)S[U2 (S2 )] (2.32)

S[cU1 (S1 ) + (1 c)U2 (S2 )].

(2.33)

U (cS1 + (1 c)S2 )) cU1 (S1 ) + (1 c)U2 (S2 ).

(2.34)

...

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

( (1.52) ).

( (1.73) ).

( ),
() .
.

38

2.

2.8: .

, ( (1.52) ) . ,
U
, U
2
,
2U ,





U
U
S U+
+S U

2
2




U
U
S U+
+S U
2S(U )
2
2




S U + U
+ S U U
2S(U )
2S
2
2
lim
=

U 0
U
U 2

S(2U ) (2.35)
0

(2.36)

0.

(2.37)

.
() ,
.
, , , ,
, (de S), -

2.8. --

39

(di S) ,

dS = de S + di S,

(2.38)

di S
0.
dt

(2.39)

p
l

di Sl
0,
dt

di Sl 0,

l = 1, . . . p.

(2.40)

dU + P dV
dU dw
dq
=
=
de S =
T
T
T

Pr

i=1

i de ni

(2.41)

- di S/dt.

2.8

--

, .
EULER


U (S, V, N ) =

U
S


S+
V,N

U
V


V +
S,N

U
N


N.

(2.42)

S,V

(S, V, N ), U


dU (S, V, N ) =

U
S


dS +
V,N

U
V


dV +
S,N

U
N


dN.

(2.43)

S,V

. ,
,
.
-- :

40

2.


U
S V,N


U
P =
V S,N


U
.
=
N S,V


:
:
:

(2.44)
(2.45)
(2.46)

, (x, f /x) .

U (S, V, N ) = T S P V + N.

(2.47)

2.9: ( W. Craig Carter, MIT,

Dept. of Materials Science and Engineering, http://pruffle.mit.edu/3.00/

~
F
, A.
dz ,

2.8. --

F~
A

41

(2.48)

(U/z)S
 A
U
=
,
V S
=

(2.49)
(2.50)

dV = Adz. , P V
,
.

S=

U
+ V N.
T
T
T

(2.51)

dS =

1
P

dU + dV dN.
T
T
T

(2.52)





S
U

S
V

S
N

1
T

(2.53)

P
T

(2.54)

V,N

U,N

U,V

= .
T

(2.55)

ST = S 0 + S

( ), (2.56)

UT = U 0 + U

( ), (2.57)

(),

(2.58)

().

(2.59)

VT = V + V
NT = N + N

, , , , ,

42

2.

2.10: .

U, V, N, S, T, P, M

U, V, N, S, T, P, M

(U, V, N ). , (1/T, P/T, /T ).

,
(U 0 , V 0 , N 0 , T 0 , P 0 , S 0 , 0 ).
dST
dt


dS 0
dS
+
dt
dt
 0

dS dU 0
dS dU
=
+
dU 0 dt
dU dt


1
1 dU 0
=

0.
T0
T
dt


(2.60)
(2.61)
(2.62)

T
( dS
dt = 0) , (T 0 = T ).
dU 0 /dt .
.
, T 0 > T ,

2.8. --
,

dST
dt

43

> 0,
dU 0
< 0,
dt

(2.63)

. , .
0
T 0 < T , dU
dt > 0 .


, P 0 >
P , .

P
S
= ,
V
T

(2.64)

dST
dt


S 0 dV 0
S dV
+
V 0 dt
V dt
 0

S
S dV 0
=

0
V
V
dt
 0

0
P
P dV

0.
=
T0
T
dt


(2.65)
(2.66)
(2.67)

(T 0 = T ) P 0 > P dV 0 /dt > 0, . () ().

,
.

= ,
N
T
dST
dt


S 0 dN 0
S dN
+
,
N 0 dt
N dt
 0

S
S dN 0

,
N 0
N
dt


0
dN 0
0.
0+
T
T
dt

(2.68)


=
=
=

(2.69)
(2.70)
(2.71)

(T 0 = T ),
0 = . 0 > dN 0 /dt < 0

.
N , d(/T )
d(/T )
z , dz , dz dz ,

44

2.
d(/T )

. , dz
z ,
.
.
, , ( fluctuations)
.
, , ,
. ,
, .

.
, 1/T , P/T /T .
,
, .
S(U, V, N ) (. 2.53).
, , U (S, V, N ), ,
, (. 2.44),
. ,
.

2.9

, . (T = 0) (S = 0).

( = 1). .

2.10

p
.
(Sj , Vj , Nj ), .
U (S1 , . . . , Sp , V1 , . . . , Vp , N1 , . . . , Np ) (Sj , Vj , Nj )

2.10.

F1

F2

F3

p
X
j=1
p
X
j=1
p
X

45

Sj ST = 0

(2.72)

Vj VT = 0

(2.73)

Nj NT = 0.

(2.74)

j=1

2.11: .

Sj
Vj

2.11 ,
() .
, . 2.12
()
.

-.

46

2.

2.12: .

Lagrange ( ).

G(Sj , Vj , Nj , i ) = U (Sj , Vj , Nj )

3
X

i Fi .

(2.75)

i=1

G
U
=
1
Sj
Sj
G
U
=
2
Vj
Vj
G
U
=
3
Nj
Nj

0 (j = 1, . . . , p)

(2.76)

0 (j = 1, . . . , p)

(2.77)

0 (j = 1, . . . , p).

(2.78)

Tj

= 1 (j = 1, . . . , p)

(2.79)

Pj

= 2 (j = 1, . . . , p)

(2.80)

= 3 (j = 1, . . . , p),

(2.81)

2.10.

47

2.13: .
, ,
, .
.

S(U)

1/T2

S2

1/T1

S1
T1 = T 2
U2 U1
U

T1
P1
1

= ...
= ...
= ...

=
=
=

Tp
Pp
p

=
=
=

( )
( )
( ).

( 2.13.
+,
(U, S, T, V, P, , N )
(U 0 , S 0 , T 0 , V 0 , P 0 , 0 , N 0 ) ,

U + U0

= UT

(2.82)

V +V

= VT

(2.83)

N +N

= NT ,

(2.84)

U + U 0

(2.85)

(2.86)

N + N 0

0.

(2.87)

V + V

ST = S 0 + S 0,

(2.88)

48

2.

P 0 0 0
U 0
+
V 0 N 0 ) 0,
T0
T0
T
P0
0
U
S 0 0 V + 0 N 0,
T
T
T

S + (

(2.89)
(2.90)

T 0 S U P 0 V + 0 N 0,

(2.91)

U T 0 S P 0 V + 0 N.

(2.92)

dU = T dS P dV + dN.

(2.93)

dU = [w + [q.

(2.94)

[w = P dV + dN,

(2.95)

T dS = [q.

(2.96)

T S = q.

(2.97)

- +

S + S 0 0.
(2.98)
T = T 0
, dS 0 = [q 0 /T . , [q 0 = [q

T dS [q ( CLAUSIUS),

(2.99)

T S q.

(2.100)

2.99 , T dS = [q .
, , - ( unconstrained) , U (Sl , Vl , Nl ; ST , VT , NT ) ( l, T ).

2.10.

49

, U (S, V ),

(Gradient) (U )S,V,N = 0 (),
(2.101)

"

(Hessian) 2 U 0 (), .,
#

 2 2
2U 2U
U
2U
0 .
0,

S 2
S 2 V 2
SV

(2.102)
(2.103)

2U
S 2


=
V

T
S


=
V

T
0.
CV

(2.104)

2U 2U

S 2 V 2

2U
SV

2
0,

T (P )
T (P )

0,
S V
V S


 

 

T
T
P
P

+
0.
S V V S
V S S V

(2.105)

(2.106)
(2.107)

P
S V

T
S V

P
V

T
V

S

(2.108)

( )

(P, T )
(P, T )
=
0.
(S, V )
(V, S)

(2.109)

- (V, T )

(P, T )/(V, T )
0.
(V, S)/(V, T )

(2.110)

(P/V )T
0.
(S/T )V

(2.111)

50

2.

(kT ) :



V
P

V kT =

0.

(2.112)

T,N

, (T (S/T )V ),
.
...


0.

(2.113)

T,V


CP = T

S
T


,

(2.114)

P,N

CP CV > 0,

(2.115)

[q = T dS = CV dT.

(2.116)


CV =

U
T


.

(2.117)

V,N

[q = T dS = CP dT

(2.118)

1
V

V
T


(2.119)
P,N

1
T =
V

V
P


(2.120)
T,N

S =

1
V

V
P


(2.121)
S,N

2.11.

2.11

51

. ( 2.14
N , T0 ,
, V1 , V2 ,
, P1 P2 . ( 2.14
,
.
SA = S1 + S2
, SB .

SB SA .

. SA = SB
, q = T S = 0.

w = U =

3
kB (2N )(T T0 ).
2

T .
,

3
S = kB N ln T + N kB ln
2

V
N


+


V1 + V2

3kB N ln T + 2N kB ln
2N
 
 
3
V1
3
V2
kB N ln T0 N kB ln
kB N ln T0 N kB ln
= 0.
2
N
2
N


SB SA




 
 
2
V1 + V2
1
V1
1
V2
3kB N ln T + ln
ln T0 ln
ln
=0
3
2N
3
N
3
N
T
ln
= ln
T0

T = T0

1/3
4V1 V2
(V1 + V2 )2
1/3
4V1 V2
.
(V1 + V2 )2


52

2.

2.14:
P2 > P1 .
.

A
T0, P1, V1, n
S1

111
000
000
111
000
111
T0,P2,V2,n
000
111
000
111
000
111
S2
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111
000
111

()

2.12

B
T,V/2,P,n
S/2

11
00
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11
00
11

T,V/2,P,n
S/2

()

, ,
.
(fluctuations) ( )
( ).
, Legendre.
Legendre
(/) .

- , (di S/dt),
, , , ,

. (S, U, T, V, i , ni ) (S 0 , U 0 , T 0 , V 0 , 0i , n0i )

2.12.

S(Ueq + U, Veq + V, neqi + ni )

53

Seq (Ueq , Veq , neqi )

S(U, V, ni )
1 2
S(U, V, ni )
2
.

+
+

(2.122)


S(U, V, ni ) =

1
1

T
Teq


U +

P
Peq

T
Teq


V

r 
X
i
i=1

eqi
Teq


ni .
(2.123)

S = 0

= Peq

Teq ,

= eqi ,

i = 1, , r,
(2.124)

1 2
S(U, V, ni ) =
2


 
 
1
1

1
+
(U )2
0
2 U T
U
T0

 
 0 
1
P

P
+
(V )2
0
2 V T
V
T0

 0 
1 X  i 

i
+
(ni n0j ).
2 ij nj T
nj T 0

+
+

 
1

=
U T
 

P
=
V T



1
1
T
2
= 2
,
T
U V
T CV


1 P
1
=
,
T V T
T V T

1 2
S(U, V, ni ) =
2

1 (U )2
2
2 CV Teq


CV
1+ 0
CV


1 1 (V )2
V
1+ 0
2 Teq T Veq
V



 0 
1X
i

i
+
(ni n0j ).
2 ij nj Teq
nj Teq

54

2.

U = CV T

1 2
S(T, V, ni ) =
2

1 CV (T )2
2
2 Teq



CV
1+ 0
CV


2
1 1 (V )
V
1+ 0
2 Teq T Veq
V



 0 
X
1

i
+
(ni n0j ).
2 ij nj Teq
nj Teq

CV <<

CV0

nj

V << V ,

i
Teq

<<
nj

0i
Teq


,

1 2
S(T, V, ni ) =
2



1 CV
(T )2 (< 0),
2
2 Teq

(2.125)

(2.126)

1
1
(V )2 (< 0),
2 Teq Veq T

(2.127)

(2.128)




i
1X
(ni nj ) (< 0). (2.129)
2 ij nj Teq

(nk = k k ), ( )

1 2
1X 1
S(i ) =
2
2 ij Teq


Ai
(i j ) (< 0),
j

(2.130)

Ai ith , i
mole, k
k .
Duhem-Jougeut
,
.

1 2
2 S(T, V, ni )

X
1 2
1
S(T, V, ni ) =
(T S P V +
i ni ).
2
2Teq
i

(2.131)

S = q/T = CV T /T,

P = V /V T ,

i =

X
j

(i /nj )nj .

2.12.

55

.
S = 0

S Seq = 1/2 2 S < 0.

(2.132)

,
- di S = Seq
S = 1/2 2 S > 0, .
. 2 S 0,
.
(Seq )
:
Lyapunov

L(U, V, ni ) =

1 2
S(U, V, ni ) < 0,
2

(2.133)

dL(U, V, ni )
d
=
dt
dt

2 S(U, V, ni )
2


> 0.

(2.134)

1 d( 2 S)
2 dt

 
1
=

J~u dV
T
V
Z X
 
i

J~i dV
T
V i
Z X  
Ai
+

vi dV,
T
V i
Z

(2.135)
(2.136)

(2.137)

Ju , Ji , vi ,
. Ai ith
.

56

2.13

2.

Legendre

,
.

, ;
, .

Legendre [5, 6, 7] .
Legendre .
Legendre
2.15. y = f (x) Legendre

L(df /dx) = f (x(df /dx))

df
x(df /dx).
dx

(2.138)

f (x) . 2.15a

. ,
(x, f (x))
x
 y, L, .
(

df
dx

, L) ( 2.15b).


df
dx


=
x

f (x) L
,
x0

(2.139)

df
x.
dx

(2.140)

Legendre

L = f (x)

. f (x) .
x df /dx, x(df /dx).

Legendre ( 2.15c).

, . ()
() .

2.13. LEGENDRE

57

2.15: Legendre.

f=df/dx

f(x)

L=f(x)fx
L1

f(x)

L(f)

L1
f=df/dx

f=df/dx

0
1
1
0
1
0
11
0
0
0
1

f(x1)
Lm
0

Lm

x1 xm x2

0
1
1
0
1
0
0 0
1
1
0
1
x1 xm x2

L2
L2

2.16: () .

f(x)

f(x)

f(x1) + f(x1)(xx1)
f(x) <= f(x1) + f(xx1)
f(x) >= f(x1) + f(xx1)

f(x1) + f(x1)(xx1)
x1 x

x1 x

f (x) x, x1 x2 ,
y1 = f 0 (x1 ) y2 = f 0 (x2 ).

f (x) f (x1 ) + y1 (x x1 ) = f (x1 ) + y1 x y1 x1 ,

(2.141)

f (x) y1 x f (x1 ) y1 x1 = L(y1 ).

(2.142)

x2 .

f (x) y2 x f (x2 ) y2 x2 = L(y2 ).

(2.143)

58

2.

Legendre y . , x
cy1 + (1 c)y2 ,

L[cy1 + (1 c)y2 ]

f (x) x[cy1 + (1 c)y2 ]

f (x) + cf (x) cf (x)

(2.144)

x[cy1 + (1 c)y2 ]

(2.145)

c[f (x) xy1 ] + (1 c)[f (x) xy2 ]

(2.146)

c[f (x1 ) x1 y1 ] + (1 c)[f (x2 ) x2 y2 ] (2.147)

= cL(y1 ) + (1 c)L(y2 ).

(2.148)

f (x, z)
Legendre x z , L(y, z) z . ,

L(y, [cz1 + (1 c)z2 ])

= f (x, [cz1 + (1 c)z2 ]) yx

(2.149)

cf (x, z1 ) + (1 c)f (x, z2 )

cyx (1 c)yx

(2.150)

= c[f (x, z1 ) yx] +

(1 c)[f (x, z2 ) yx]
= cL(y, z1 ) + (1 c)L(y, z2 ).

(2.151)
(2.152)

...

f (x) = ln(x).
, f 0 = df /dx = 1/x Legendre

L(f 0 ) = f (x) xf 0 = ln(1/f 0 ) 1 = [1 + ln(f 0 )].

L(f 0 ) f 0 .

.

Legendre.
[6] [5], 5, 131. Legendre
Stephen Boyd and Lieven Vandenberghe [8],
Convex Optimization "http://www.stanford.edu/ boyd/cvxbook.html".
Legendre

2.13. LEGENDRE

59

1. (S, P, N ). .

H(S, P, N ) = U (P )V,

H
S


P,N

(2.153)

dH = T dS + V dP + dN,




H
H
= T,
= V,
= .
P S,N
N S,P

(2.154)
(2.155)

Maxwell

T
P

T
N

V
N

=
S,N


=

S,P


=
S,P

V
S

(2.156)

(2.157)

(2.158)

P,N

P,N

S,N

H(S, P, N ) = U + P V,

(2.159)

dH = dU +d(P V ) = dU +(P dV +V dP ) = (T dSP dV +dN )+(P dV +V dP ),

(2.160)
(2.161)

dH = T dS + V dP + dN.


dH =

H
S


dS +

P,N

H
P


dP +
S,N

H
N


dN.

(2.162)

S,P

H
S


= T,

P,N

H
P


= V,
S,N

H
N


= .
S,P

(2.163)

60

2.
dH

2H
2H
=
,
SP
P S

(2.164)

T
P


=
S,N

V
S


.

(2.165)

P,N

2H
2H
=
,
P N
N P

(2.166)

V
N


=

S,P


.

(2.167)

S,N

2H
2H
=
,
SN
N S

(2.168)

T
N


=

S,P


.

(2.169)

P,N

...

dU = [q , (P =)
dH = [q , P V .

dU = [q P dV = [q.

H
dH

(2.170)

= U + PV

(2.171)

= dU + d(P V )

(2.172)

= dU + P dV + V dP

(2.173)

= dU + P dV

(2.174)

= [q.

(2.175)

2.13. LEGENDRE

61

...

Joule-Thomson
Joule-Thomson .

2.17: Joule-Thomson .

P1 , V 1 , T 1 , U 1

111
000
000
111
000
111
000
111
000
111
P,V ,T ,U
000
111
000
111
000
111
2

(q = 0) (P1 , P2 )
. ,

U = U2 U1 = w = P2 (V2 0) P1 (0 V1 ) = P1 V1 P2 V2 , (2.176)
U2 + P2 V2 = U1 + P1 V1 ,

(2.177)

H2 = H1 .

(2.178)

Joule-Thomson


JT =

T
P


.
H

(2.179)

62

2.

T
P


=
H

=
=
=
=

(T, H)
(P, H)
(T, H)/(P, T )
(P, H)/(P, T )
(H/P )T

(H/T )P


T V
T P V
CP
V (T 1)
.
CP

(2.180)
(2.181)
(2.182)
(2.183)
(2.184)

S
P


=
H

(H/P )S
V
= < 0.
(H/S)P
T

(2.185)

...

2. (T, V, N ). Helmholtz.

A(T, V, N ) = U T S,

A
T


V,N

dA = SdT P dV + dN,




A
A
= S,
= P,
=
V T,N
N T,V

(2.186)
(2.187)
(2.188)

Maxwell

S
V


=
T,N

P
T


, etc.
V,N

(2.189)

2.13. LEGENDRE

63

(dV = 0) (T =)
Clausius A.
,

T dS [q = dU + P dV,

(2.190)

dU T dS 0,

(2.191)

d(U T S) = dA 0.

(2.192)

Helmholtz - .

dA
dt


= T
T,V,ni

di S
0.
dt

(2.193)

3. (T, P, N ). Gibbs.

G(T, P, N ) = (T, P )N = N

G
T


P,N

dG = SdT + V dP + dN,




G
G
= S,
= V,
= .
P T,N
N T,P

(2.194)
(2.195)
(2.196)

Gibbs .
Maxwell

S
P


=
T,N

V
T


, etc.
P,N

(2.197)

64

2.

(P =) (T =) Clausius Gibbs
G.
,

T dS [q = dU + P dV,

(2.198)

dU T dS + P dV 0,

(2.199)

d(U T S + P V ) = dG 0.

(2.200)

Gibbs - .

dG
dt


= T
T,P,ni

di S
0.
dt

(2.201)

P V , .. ,

[q = dU + P dV dwe .

(2.202)

d(U T S + P V ) = dG +dwe .

(2.203)

dwe0 = dwe .

dwe0 dG.
(2.204)
-P V
Gibbs.

4. (T, V, ). .

(T, V, ) = A N = A G = P V,


V,

d = SdT P dV N d,





= S,
= P,
= N.
V T,
T,V

(2.205)
(2.206)
(2.207)

2.14.

65

Legendre
.

2.14

,
.
.

:

U (S, V, N, z) = U0 (S, V, N ) + mgz,

(2.208)

m , g ,
z
. U0 .
,

66

2.
1.
f dl : () x ()

2.
d : ( ) x ()

3.
AdQ : ( ) x ()

4.
BdI : ( ) x ( )

5. ...
.

(X1 , X2 , . . . , Xr , Ir+1 , Ir+2 , . . . , Is ),

(2.209)

r , (X1 , X2 , . . . , Xr ) s r , (Ir+1 , Ir+2 , . . . , Is ) :

:

d =

r
X
i=1

Ii dXi

s
X

Xj dIj .

(2.210)

j=r+1

Maxwell

Xj
Ii
=
, (j > r i r).
Ij
Xi

(2.211)

Xi
Xj
=
, (i, j r).
Ij
Ii

(2.212)

Ii
Ij
=
, (i, j > r).
Xj
Xi

(2.213)

2.14.

67

,
-

= 0.

(2.214)

(convex)

2
Xi2


0,

(2.215)

X1 ,...,Xi1 ,Xi+1 ,...,Xr ,Ir+1 ,...,Is

(concave)

2
2
Ir+j+1

!
0.

(2.216)

X1 ,...,Xr ,Ir+1 ,...,Ir+j ,Ir+j+2 ,...,Is

(Xi , Ii ):

Ii
Xi


0, [(S, T ), (V, P ), (ni , i )] . (2.217)
X1 ,...,Xi1 ,Xi+1 ,...,Xr ,Ir+1 ,...,Is

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

( (1.52) ).

( (1.73) ).
( ),
()
. .

68

2.

2.15

Gibbs-Duhem

, , (S, V, Ni )
P
(T, P, i ) . ,
U = T S P V + i i Ni ,

(T, P, i ) 0 = U T S + P V

i Ni .

(2.218)

d(T, P, i ) = 0 = dU T dS SdT + P dV + V dP

i dNi

Ni di .

(2.219)

dU = T dS P dV +

i dNi .

SdT V dP +

Ni di = 0.

(2.220)

Gibbs-Duhem.
, .
2.220 .
, , ,
, , .
,

V (N1 , N2 , . . . , ) = V (N1 , N2 , . . . ).
Euler

V =


Ni

V
Ni


=
T,P,Nj 6=i

Ni v i ,

(2.221)

vi .
. 2.221
(Ni vi ).

dV =


dNi

V
Ni


=
T,P,Nj 6=i

dNi vi .

(2.222)

dV =

X
i

dNi vi +

X
i

Ni dvi .

(2.223)

2.16.

69

(2.222, 2.223),

Ni dvi = 0.

(2.224)

vi

X  vi 
dvi =
dNk .
Nk T,P

(2.225)

. 2.224

Ni

X  vi 
dNk
Nk T,P

!
=

X X
k


Ni

vk
Ni

dNk = 0. (2.226)
T,P

2V
2V
vk
vi
=
=
=
.
Nk
Nk Ni
Ni Nk
Ni

(2.227)

dNk



Ni

vk
Ni

= 0.

(2.228)

T,P

Gibbs ( ).
2.228

G=


Nk

G
Nk


=
T,P

Nk k ,


Ni

k
Ni


= 0.

(2.229)

T,P

Helmholtz (ak )
(hk )

A=


Nk

H=

X
k

2.16


Nk

A
Nk

H
Nk

=
T,P

=
T,P

Nk a k ,

Nk hk ,


Ni

Ni

ak
Ni

hk
Ni

= 0.

(2.230)

= 0.

(2.231)

T,P

T,P

(w, q, T, P, V, CV , CP , , T , S ) (S, U, A, G).

70

2.
1. (V, T ),
P = f (V, T ) ,

(i)
(ii)
(iii)
(iv)


CV
V T


S
V T


U
V T


H
V T


2P
T
T 2 V


P
T V


P
T
P
T V




P
P
T
+V
T V
V T


P
1

T
T V
T
 2 


P
P
/
T
T V
V T

 2
P
T T V
T V

=
=
=
=
=

(v)

CP CV

=
=


(vi)

H
T


V

= T V 2 /T


P
= CV + V
T V

(2.232)
(2.233)
(2.234)
(2.235)
(2.236)
(2.237)
(2.238)
(2.239)
(2.240)

(i)
dA = SdT P dV.

S=

A
T


, P =
V


CV

= T
= T

S
T

A
V

(2.241)


.

(2.242)

2A
.
T 2

(2.243)
V

(2.244)

2.16.

CV
V

71

3A
T 2 V


A
2
= T
T 2 V T
 2 
P
.
= T
T 2 V
= T

(2.245)
(2.246)
(2.247)

(ii)
dA = SdT P dV.

(2.248)

Maxwell

S
V


=
T

P
T


.

(2.249)

(iii)
dU = T dS P dV.

U
V


S
P
V T


P
T
P.
T V

(2.250)

= T

(2.251)

(2.252)

(iv)
dH = T dS + V dP.

H
V




S
P
+V
V T
V T




P
P
= T
+V
.
T V
V T

(2.253)

= T
T

(2.254)
(2.255)

72

2.

(v)

CV


S
T V
(S, V )
= T
(T, V )
(S, V )/(T, P )
= T
(T, V )/(T, P )

V

S
T P P T


= T
V
= T

(2.256)
(2.257)
(2.258)
S
P T

V
T

P

(2.259)

P T


= T

S
T




+T
P
2

V
T

 2 

V
/
P T
P

= CP + T V 2 /(V kT ).

(2.260)
(2.261)

CP CV =

2
T V.
kT

(2.262)

...

2. (P, T ),
V = f (P, T ) ,

2.16.

73


(i)
(ii)


CP
P T


S
P T

=
=
=

U
P

H
P


(iii)

=
T

=

(iv)

=
T

=
(v)

CP CV

=
=


(vi)

U
T


=
P

 2 
V
T
T 2 P


V

T P
V




V
V
T
P
T P
P T
T V + P V T


V
V T
T P
V TV
 2 


V
V
/
T
T P
P T
T V 2 /T


V
CP P
T P
CP P V

(2.263)
(2.264)
(2.265)
(2.266)
(2.267)
(2.268)
(2.269)
(2.270)
(2.271)
(2.272)
(2.273)

3. (dS = 0)

74

2.


T
V S


T
P S

(i)
(ii)

(2.274)

(2.275)

=

(iii)

V
P



T
P
CV T V


T
V
CP T P
TV
CP


CV V
CP P T



 2
V
T
V
+
P T CP
T P

=
S

= T V +


(iv)

P
V

CP
CV


2 V 2 T
CP

T
S


 2

P
T
P
=

V T CV
T V
=

2 T
1
2
T V
T CV

(2.276)
(2.277)
(2.278)
(2.279)
(2.280)
(2.281)
(2.282)

(i)


T
V

(S/V )T
(S/T )V


T
P
.
=
CV T V

=
S

(2.283)
(2.284)

(iii)


V
P


=
S

=
=
=

(V, S)
(P, S)
(V, S)/(V, T ) (V, T )
T
(P, S)/(P, T ) (P, T )



S
V
T V


S
P T
T P


CV V
CP P T

(2.285)
(2.286)
(2.287)
(2.288)

2.17.

75

...

2.17

(Gibbs)
F = C + 2.
F
C

(2.289)

= ,
= ,
= .

G = n,

(2.290)

( ).
, .. ,

Gm = (T, P ).

(2.291)

Gm . C ()

G=

C
X

i ni .

(2.292)

i=1

n=

C
X

ni ,

(2.293)

i=1
C

Gm

G X ni
=
=
i ,
n
n
i=1

(2.294)

76

2.

i =

ni
.
n

(2.295)

Gm =

C
X

i i

(2.296)

i=1
C
X

i = 1.

(2.297)

i=1

(C 1) + 2 , (C 1) ,
.

,
. ,
.
C

Gr ,

(2.298)

ri nri .

(2.299)

nri , r = 1, . . . , ,

(2.300)

G=

r=1

Gr =

C
X
i=1

n =

C
X
i=1

Grm =

X nr
Gr
i r
=
, r = 1, . . . , .
r i
nr
n
i=1

(2.301)

i r

ri =

nri
.
nr

(2.302)

r
C

Grm

X
Gr
= r =
ri ri , r = 1, . . . , ,
n
i=1

(2.303)

2.17.
C
X

77

ri = 1, r = 1, . . . , .

(2.304)

i=1

G ( ) (C 1)+2
. i

1i = 2i = =
(2.305)
i = i ,
( 1) . C C( 1) C( 1) .
. Gibbs
C

F = (C 1) + 2 C( 1) = C + 2,

(2.306)

. ,

. , ,
. , C
(R),
(M ).

F = C + 2 R M.

(2.307)

Gibbs
(T, P, 1 , 2 , . . . , C ),
(2 + C) . , . Gibbs-Duhem
().
F = (2 + C) = C + 2.

.
1) : F = 2 (
).

2) : F = 1 ( 2.18, 2.19).

78

2.

2.18:
.

chemical potential

14
12
10
8
6
4
2
0
-2
-4

8
7
6
1

5
2

3
5

2
7

8 1

. (T, P )
.
; ClausiusClapeyron (T, P ).
1 2

1 (T, P ) = 2 (T, P ),

(2.308)

1 dP
2
2 dP
1
+
=
+
.
T
P dT
T
P dT

(2.309)

d = Sm dT + Vm dP,

(2.310)

Sm Vm .
1
Sm
+ Vm1

dP
dP
2
= Sm
+ Vm2
dT
dT,

(2.311)

Clausius-Clapeyron.
1
Sm
dP
S 2 Sm
=
= m2
,
dT
Vm Vm1
Vm

(2.312)

2.17.

79

2.19:
.

Tc

Sm = q/T.

dP
q
=
.
dT
T Vm

(2.313)

(.. -)
,
(T, S) (T, V ), ( 2.20).

2.20: Tc .

Tc

Tc

80

2.

(T, P ) (T, V ) 2.21.

2.21: .
.

P = P1

2
2
1,2
1+2

1
1
T

V
P2

2+3

P1

3
2
1,3

2
1+2

1+3

2,3
1,2

1
T

3) ( = 3),
F = 0. , (Tc , Pc ) . (Tc , Pc )
.

4) x1 x2 , (x1 + x2 =
1) F = 3 .
, ,

2.17.

81

2.22: .



CV < 0, CV =

U
T V

S 2
U V

2S
U 2

dT
T2

. d

1
T

S
2

1+2

, .. x1 .

5) , F = 2 .
, x1A x1B .

8 9 Atkins [9]
.

82

2.

2.23: . ( Legendre LS (T, Vm ) = S(U, Vm ) U/T =

Am /T . , S(U, Vm ) U
, LS (T, Vm ) .
Helmholtz, Am (T, Vm ) = T LS , T Vm
.)

Am

1
2
1+2

Vm

2.24: . ( Legendre LS (T, P ) = S(U, Vm ) U/T

P Vm /T = Gm /T . S(U, Vm ) U
Vm , LS (T, P )
. Gibbs, Gm (T, P ) = T LS ,
T P .)

Gm

Gm
1

1+2
I
II

2
1
1+2

2
1+2
1

2.17.

83

2.25: . (
.)

Gm

Tcr1

Tcr1
Tcr Tc2

Tc1

Tcr
1

Tc2
1
Tc1

1
Vm
T

84

2.

2.26: . (
(bifurcations) (pitchfork) - (saddle-node).)

T < Tc
Tcr
P
Tc

T1

T2

1
T > Tc

T
Gm
Tc

T1 < Tc

T2 > Tc

1
1+2

1+2

1+2

Vm

Vm

Vm

T1 < Tc

T2 > Tc

Vm

Tcr

Tc

2.18. DUHEM

2.18

85

DUHEM

,
, (Ni0 )

.
Duhem Gibbs

Duhem .
, C Ni0 , i = 1, . . . , C , (2 ) C ,
nri , , r = 1, . . . , .
C

nri = Ni0 ,

i = 1, . . . , C

(2.314)

r=1

1i (T, P ) = 2i (T, P ) = =
i (T, P ),

i = 1, . . . , C

(2.315)

C( 1) .

F = C + 2 C( 1) C = 2.


(a ) ,
a.

86

2.19

2.

2.19.

87

2.1: .
(U ) - ,
(H ) - ,
Helmholtz (A) - ,
Gibbs (G) - ,

U (S, V, N )
dU (S, V, N )
dU (S, V, N )

=
=
=

T S + (P )V + N
T dS + (P )dV + dN
T dS P dV + dN

H(S, P, N )
dH(S, P, N )
dH(S, P, N )

=
=
=

U (P )V
d(U + P V )
T dS + V dP + dN

U
S
V,N
U
V
S,N
U
N S,V

T
P

H
S
P,N
H
P
S,N
H
N S,P

T
V

P
 S V,N

T
P S,N


T
N S,P

T
V S,N


T
N S,V

P
N S,V

=
=

=
=

V,N

V
N S,P

S,N

V
 S P,N

P,N
S,N

A(T, V, N )
dA(T, V, N )
dA(T, V, N )

=
=
=

U TS
d(U T S)
SdT P dV + dN

G(T, P, N )
dG(T, P, N )
dG(T, P, N )

=
=
=

U T S (P )V
d(U T S + P V )
SdT + V dP + dN

A
T
V,N
A
V
T ,N
A
N T ,V

S
P

G
T
P,N
G
P
T ,N
G
N T ,P

S
V

S
V T ,N


S
N T ,V

S
P T ,N


S
N T ,P

P
N T ,V

=
=

=
=

P
 T V,N

V,N
T ,N

V
N T ,P

=
=

=
=

V
 T P,N

P,N
T ,N

88

2.

3.1

P V = nRT,

3.1.1

( )

(3.1)

U (T, n) =

3
nRT.
2

(3.2)

3.1.2

w = nRT ln(Vf /Vi ).

89

(3.3)

90

3.1.3

3.


S = CV ln T + nR ln

V
n


+ .

(3.4)

S = CP ln T nR ln P + .

(3.5)

3.1.4

CV =

3
nR.
2

(3.6)

CP =

5
nR.
2

(3.7)

3.1.

91

CP CV = nR.

(3.8)

3.1.5

-
T = Pex. V /CV .

(3.9)

3.1.6

P V = .

(3.10)

= CP /CV .

(3.11)

92

3.

w = CV Ti [(Vi /Vf )1 1].

(3.12)

3.1.7

S = nR ln(Vf /Vi ).

(3.13)

3.1.8

,

G(P ) = G(P 0 ) + nRT ln(P/P 0 ).

(3.14)

3.1.

93

G(P )

=
=
=
=

3.1.9

V dP

G(P ) +

nRT
dP
P
P0
Z P
dP
G(P 0 ) + nRT
P0 P
G(P 0 ) + nRT ln(P/P 0 ).
G(P 0 ) +

(3.15)

P0
Z P

(3.16)
(3.17)
(3.18)

(P ) = (P 0 ) + RT ln(P/P 0 ).

(3.19)

.
G(P ) = G(P 0 ) + nRT ln(P/P 0 ).
(3.20)

G(P )
G(P 0 )
=
+ RT ln(P/P 0 ).
n
n

3.1.10

(3.21)

Clausius-Clapeyron
()-
d ln P/dT = Hm,. /RT 2 .

(3.22)

94

3.

dP
dT

= q/(T Vm )

dP
P dT
d ln P
dT

(3.23)

Hm,. P/RT 2

(3.24)

Hm,. /RT 2

(3.25)

Hm,. /RT 2 .

(3.26)

"

#
Hm,.  1
1
P = P exp

.
R
T
T

(3.27)

d ln P = Hm,. dT /RT 2 .

(3.28)

(T , P ) (T, P )

ln(P/P ) =


Hm,.  1
1
.
R
T
T

(3.29)

3.1.11

xi

Gmix = nRT [xA ln xA + xB ln xB ] .

(3.30)

3.1.

95

P ,

Gi

= nA A
+ nB B
i




i

P
P


+ nB B + RT ln
.
= nA A + RT ln
P
P

(3.31)
(3.32)

PA PB ,

Gf

B
= nA A
f + nB f






PA
PB


= nA A + RT ln
+ nB B + RT ln
.
P
P

(3.33)
(3.34)

Gmix = Gf Gi







PB
PA
+ nB RT ln
. (3.35)
= nA RT ln
P
P

PA = A P,
Gmix

PB = B P.

= nA RT ln A + nB RT ln B
nA
nB
= nRT [
ln A +
ln B ]
n
n
= nRT [A ln A + B ln B ],

(3.36)

(3.37)
(3.38)
(3.39)

n = nA + nB .

Smix = nR [xA ln xA + xB ln xB ] .

(3.40)

G
= S.
T

(3.41)

96

3.

G
= S.
T

(3.42)

Smix = nR [xA ln xA + xB ln xB ] .

(3.43)

Smix = Gmix /T.

(3.44)

Umix = Hmix = Vmix = 0.

(3.45)

Gmix = Hmix T Smix .

(3.46)

Hmix = 0.

(3.47)

G
= V.
P

(3.48)

G
= V.
P

(3.49)

Gmix
= 0 = Vmix .
P

(3.50)

G = U T S + P V.

(3.51)

Umix = 0.

(3.52)

1.
, .

Gmix = T Smix .

(3.53)

3.1.

97

2.

.
3. ;

3.1.12

: 0 =

J J.

(3.54)

r G m =

j j .

(3.55)

nB
nC
nA
=
=
= = ,
A
B
C

(3.56)

, J .
J
.

98

3.

r G =

nj j

(3.57)

j j

(3.58)

j j

(3.59)

r G =

r G/

r Gm

r G/
X
j j .

(3.60)
(3.61)

r Gm = 0.

(3.62)

aA + bB pP + qQ,

(3.63)

pP + qQ = aA + bB .

r G
m =

(3.64)

j
j .

(3.65)

j f G
m,j ,

(3.66)

r G
m =

X
j

f G
m,j j .

3.2.

r Gm = r G
m + RT ln Q.
Y  Pj j
Q=
.
P
j

99

(3.67)
(3.68)

r G
m = RT ln K.
Y  Pj j
K=
k .
P
j

(3.69)
(3.70)

3.2

3.2.1

van der Waals

P =

 n 2
nRT
a
.
V nb
V

(3.71)

100

3.2.2

3.

Hess

: 0 =

J J.

(3.72)

r H =

J f HJ .

(3.73)

3.2.3

Kirchhoff
Z

T2

r CP (T )dT.

r H(T2 ) = r H(T1 ) +

(3.74)

T1

r C P =

J CP,J .

(3.75)

3.2.

3.2.4

101

Gibbs

r G =

J f G
J.

(3.76)

r S =

J SJ .

(3.77)

3.2.5

Gibbs-Helmholtz


(G/T )
T


=
P

H
.
T2

(3.78)

G = H T S.

(3.79)

G
H
=
S.
T
T

(3.80)

102

3.

G
T


=
P

H
T

T H /T
P

CP
CP
H
2
T
T
T
H
= 2.
T
=

S
T


(3.81)
P

(3.82)
(3.83)

3.2.6

(G/T )
T


=
P

H
.
T2

(3.84)

Gibbs
G(P ) = G(P 0 ) +

V dP.

(3.85)

P0

G
P


= V.

(3.86)

dG(P ) = V dP,

(3.87)

T,n

G(P ) = G(P ) +

V dP.
P0

(3.88)

3.2.

3.2.7

103

Raoult
PA = xA PA .

(3.89)

.
xA A .
PA A .
PA .
A (l) = A (l) + RT ln(xA ).

(3.90)

3.2.8

: A = A xA .

(3.91)

A (l) = A (l) + RT ln(A ).

(3.92)

3.2.9


T =

RT 2
Hb,m


xB

(3.93)

104

3.

3.2.10

Hf,m
ln(xB ) =
R

1
1

T
T


(3.94)

3.2.11

: ,
vant Hoff
V = nB RT.

(3.95)

3.2.12

nl /ng = d0 /d.

(3.96)

3.2.

105

V = nv = nxl vl + nxg vg

(3.97)

v = xl vl + (1 xl )vg

(3.98)

xl = (vg v)/(vg vl )

(3.99)

xg = (v vl )/(vg vl )

(3.100)

xl /xg = (vg v)/(v vl )

(3.101)

d = vg v
d = v vl
nl /ng = d0 /d

3.2.13

(3.102)

vant Hoff:
d ln K
r H
=
.
dT
RT 2

(3.103)

106

3.

107

108

4.

LEGENDRE
G(q1 , . . . , qs ) s ,
, L,
qi , i = 1, . . . , r uj = G/qj , j =
r + 1, . . . , s. Legendre

L(q1 , . . . , qr , ur+1 , . . . , us ) = G(~q)

s
X

qi ui .

(.1)

i=r+1

dG =

s
X
G
i=1

qi

dqi =

s
X

ui dqi ,

(.2)

i=1

s
X

dL = dG

(qj duj + uj dqj )

(.3)

j=r+1

r
X

ui dqi

i=1

s
X

qj duj .

j=r+1

Maxwell

dG =

s
X

ui dqi .

(.4)

i=1

2G
2G
=
qi qj
qj qi
109

(.5)

110

. LEGENDRE

ui
uj
= uij = uji =
.
qj
qi
Maxwell.

(.6)

L(q1 , . . . , qs ) = p L(q1 , . . . , qs ).

(.1)

pp1 L(q1 , . . . , qs ) =

s
X
i=1

L
1 X L
qi =
qi .
(qi )
i=1 qi

(.2)

pp L(q1 , . . . , qs ) = pL(q1 , . . . , qs ).

(.3)

, = 1

pL(q1 , . . . , qs ) =

Euler.

111

s
X
L
qi .
q
i
i=1

(.4)

112

LAGRANGE
L(q1 , . . . , qs ) s , m (s > m)

Fi (q1 , . . . , qs ) = 0, i = 1, . . . , m,

(.1)

G(~q, ~) = L(q1 , . . . , qs )

m
X

i Fi (q1 , . . . , qs ),

(.2)

i=1

.,

G(~q, ~) = L

m
X

i Fi = 0.

(.3)

i=1

i m (.1)
(.3).

113

114

. LAGRANGE

f (x1 , x2 ) =

f ~
f ~
i+
j = 0.
x1
x2

f
= 0,
x1

f
= 0.
x2

(.1)

(.2)

,
Hessian. ,
/ /, (
) .





2
| f (x1 , x2 ) I| = 



f 2
x21

f 2
x2 x1

f 2
x1 x2
f 2
x22





 = 0,



(.3)

I .

2 + p + q = 0,
115

(.4)

116

p=

f 2
f 2
+
,
x21
x22

f 2 f 2

q=
x21 x22

f 2
x1 x2

(.5)

2
.

(.6)

1 + 2 = p,

(.7)

1 2 = q,

(.8)

() q > 0, p > 0
() q > 0, p < 0. q < 0.

(JACOBIANS)

u = u(x, y),

v = v(x, y).

(.1)

(u, v)
(x, y)

  

 u


u
 x y

 y x 
= 



v
v
 x y

y
x
   
   
u
v
v
u

=
x y y x
y x x y

(.2)

(.3)

dudv
(u, v)
(x, y)

(u, v)
dxdy
(x, y)
(u, v)
=
(y, x)
(v, u)
=
(x, y)
(v, u)
= +
(y, x)
=

117

(.4)
(.5)
(.6)
(.7)

118

u
x

(u, y)
(x, y)

=
y


u
y
 x
v
y
 x
v
x y

(u, x)
(u, x)
=
(y, x)
(x, y)
(v, x)
(v, x)
=
(y, x)
(x, y)
(v, y)
(x, y)

=
=
=

(.8)
(.9)
(.10)
(.11)

x(y, z)
1)

x
y

 
z

y
x


=
z

(x, z) (y, z)
= +1.
(y, z) (x, z)

(.12)

2)

x
y

 
z

y
z

 
x

z
x


=
y

(x, z) (y, x) (z, y)

.
.
(y, z) (z, x) (x, y)

(x, z) (x, y) (y, z)

.
.
(y, z) (x, z) (x, y)
= 1
=

(.13)
(.14)
(.15)

3)

x
y


=
z

(x, z) (w, z)
.
(w, z) (y, z)
(x/w)z
(y/w)z

(.16)
(.17)

, ..
, ,
, , ...
. , O ,

,
.

:
1. : (U, V, N ) ( )
2. : (T, V, N ) ( )
3. : (T, V, ) ( )
4. - ((T, P, N )
p , O

O < O >=

n
X

p O ,

(.1)

=1

n , p

n
X

p = 1.

=1

119

(.2)

120

(O)2 < (O)2 > =

=

< (O < O >)2 >

(.3)

< O2 > (< O >)2 .

(.4)

S = kB

p ln p .

(.5)

. p
Lagrange.

F = S (

n
X

p 1),

(.6)

=1

S .
.

F
p
kB (ln p + 1)

(.7)

(.8)

kB ln p

( + kB )

(.9)

exp[( + kB )/kB ]

(.10)

p =

1
,
(U, V, N )

(.11)

(U, V, N ) U , V N .
E ,
V N ;

, +

ptotal = penv p ,

(.12)

121
. ptotal penv
.
p = ptotal /penv .
(.13)
( )

p (E , V , N ) =

env [(Etotal E ), (Vtotal V ), (Ntotal N )]

.
total [Etotal , Vtotal , Ntotal ]

(.14)

exp

p (E , V , N ) =

i
E ), (Vtotal V ), (Ntotal N )]
h
i
.
exp k1B Stotal [Etotal , Vtotal , Ntotal ]

1
kB Senv [(Etotal

(.15)
(S )

Stotal (Etotal , Vtotal , Ntotal ) = Senv (Etotal U, Vtotal V, Ntotal N )+S(U, V, N ).

(.16)

U , V , N , .
Taylor
, Etotal U , , Vtotal V ,
, Ntotal N .

Senv [(Etotal E ), (Vtotal V ), (Ntotal N )]

Senv [(Etotal U + U E ), (Vtotal V + V V ), (Ntotal N + N N )]

Senv [(Etotal U ), (Vtotal V ), (Ntotal N )]

Senv
(Etotal E ) |Etotal U (U

Senv
(Vtotal V ) |Vtotal V

E )

(V V )

Senv
(Ntotal N ) |Ntotal N (N

N )

Senv [(Etotal U ), (Vtotal V ), (Ntotal N )] +

S
E |U (U

Senv [(Etotal U ), (Vtotal V ), (Ntotal N )] +

1
T

E ) +

(U E ) +

P
T

S
V |V

(V V ) +

(V V )

T (N

exp
p (E , V , N ) =

1
1
kB [( T

(U E ) + PT (V V )
h
i
exp k1B S(U, V, N )

T (N

i
N )]
(.17)

S
N |N (N

N )

N )

122


p (E , V , N ) = exp




1
1
(U T S + P V N ) exp
(E + P V N ) .
kB T
kB T
(.18)

1. Helmholtz, A(T, V, N )
.


p (E ) = exp




E
1
A(T, V, N ) exp
.
kB T
kB T

(.19)

Z=



E
,
exp
kB T

(.20)


p = exp


1
A(T, V, N ) Z = 1.
kB T

(.21)

= 1/kB T .

p = exp [A(T, V, N )] Z = 1,

(.22)

123

A =

kB T ln Z

(.23)

1 ln Z

(.24)

< E >=

E p

(.25)

E eE /Z

(.26)

(ln Z)/

(.27)

(A)/


ln Z
kB T 2
T
V,N
X
2 (AE )
(E U ) e

(.28)

=
< (E U )2 > =

(.29)
(.30)

(E U )

(AE )
e

X
U
(E U )e(AE )

kB T 2 CV

(.32)
(.33)
(.34)


S

(.31)

kB ln Z + kB T

ln Z
T


(.35)
V,N


ln Z
kB T
V
T,N


ln Z
kB T
N T,V

(.36)
(.37)

2.
, (T, V, )
.




1
1
p (E , N ) = exp
(U T S N ) exp
(E N )
kB T
kB T


p (E , N ) = exp [(T, V, )] exp [(E N )]

(.38)
(.39)

e(E N )

(.40)

124

U N

= kB T ln

(.41)

= 1 ln

(.42)

= (ln )/

(.43)

= ()/

(.44)


S

= kB ln + kB T


= kB T


= kB T

ln
V

ln

ln
T


(.45)
V,

(.46)
T,

(.47)
T,V

3. -

, G(T, P, N )
.




1
1
(U T S + P V ) exp
(E + P V )
p (E , V ) = exp
kB T
kB T


(.48)

p (E , V ) = exp [G(T, P, N )] exp [(E + P V )]

(.49)

e(E +P V )

(.50)

125

G =

kB T ln

(.51)

1 ln

(.52)

=
=

(ln )/
(G)/


U
kB
(1/T ) P/T,N

(.53)

U + PV

< (E )2 > =

(.54)
(.55)

kB T 2 CP 2kB T 2 P V + kB T P 2 V T (.56)


V
kB
(.57)
(1/T ) P/T,N

=
< (E )(V ) > =

kB T 2 V kB T P V T


V
kB
(P/T ) 1/T,N


V
kB T
P T,N

=
< (V )2 > =
=
=

kB T V T

(.58)
(.59)
(.60)
(.61)

4.
X0 , X1 , . . . , Xs

F0 , F1 , . . . , Fs , Xi , .. (U, 1/T ), (V, P/T ), (N, /T ), X0 , X1 , . . . , Xs





1
1
p = exp (S F0 X0 Fs Xs ) exp (F0 X0 + + Fs Xs )
kB
kB
(.62)

W =

k1 (F0 X0 ++Fs Xs )
B

(.63)

LS [F0 , . . . , Fs ] Legendre

LS [F0 , . . . , Fs ] = S F0 X0 Fs Xs
(.64)





1
1
p = exp LS [F0 , . . . , Fs ] exp (F0 X0 + + Fs Xs )
kB
kB
(.65)

126


W = exp

1
LS [F0 , . . . , Fs ]
kB


(.66)

LS [F0 , . . . , Fs ] = kB ln W.

(.67)


< Xj Xk >= kB

Xj
Fk


(.68)
F0 ...Fk1 Fk+1 ...Fs Xs+1 ...Xt

. ( ) (E )
H
Schrodinger

= E ,
H

(.69)

< | >= .

(.70)

( )

eH = eE

(.71)

eE =< |eH | >,

(.72)

A =

ln

eE

(.73)

ln

< |e H | >

(.74)

ln T r(e H ).

(.75)

T r < |e H | >.

127

. ,

. , ( Fermi-Dirac)
( Bose-Einstein).

(-)

H(xi , yi , zi , pxi , pyi , pzi ), i = 1, . . . N.

H

(.76)

xi , yi , zi , pxi , pyi , pzi

N .
)
, h Planck.

dxN dyN dzN dpx dpy dpzN

dx1 dy1 dz1 dpx1 dpy1 dpz1
. . . 1/2 1/2 1/2 1/2N 1/2N 1/2
1/2
1/2
1/2
1/2
1/2
1/2
h h h
h
h
h
h
h h
h
h
h

(.77)

1
h3N

N
i dxi dyi dzi dpxi dpyi dpzi

(.78)

1 N
dxi dyi dzi dpxi dpyi dpzi .
h3N i

(.79)

Z=

1
h3N

eH(xi ,yi ,zi ,pxi ,pyi ,pzi ) N

i dxi dyi dzi dpxi dpyi dpzi

(.80)

Z =

1
h3

Z Z Z

Z Z Z
dxdydz

dpx dpy dpz e(px +py +pz )/2m .

(.81)

128

Z =

V
3/2
[2mkB T ] .
h3

(.82)

Z =

VN
3N/2
[2mkB T ]
.
N !h3N

(.83)

(ln Z )

U =< E >=

()
P =

!
=
V

(ln Z )

3N
3
= N kB T,
2
2

N
,
V

(.84)

(.85)

P V = N kB T.

(.86)

, U (xi , yi , zi ), ,

H = T + U.
(.87)
Helmholtz

A = kB T ln Z = kB T ln Q + c(T, V, N ),

Z
Q(T, V, N ) =



1
exp
U (xi , yi , zi ) N
i dxi dyi dzi
kB T

(.88)

(.89)

c(T, V, N ) .
c , , ,
, .
. .
, .
. A B

U (xi , yi , zi )

(1 )UA (xi , yi , zi ) + UB (xi , yi , zi ),

(.90)

UA + (UB UA ),

(.91)

129
. = 0 A = 1 B .
.

A()
=


,

(.92)

( )

2 A()
1
=
2
kB T

"*

2 A()
1
=
2

kB T

"*

2 +



 2 #
(.93)

 2 +#
0.

(.94)

<>
.

A = A(b ) A(a ) =
a


d.

(.95)

ln Z( ) =
0

ln Z()
d,

(.96)

Z() =

exp[U ()/kB T ]dU,

(.97)

Z
=

1 U
kB T


exp[U ()/kB T ]dU,

ln Z
1 Z
=
.

(.98)
(.99)

ln Z
1
=

kB T

exp[U ()/kB T ]
Z


dU,

(.100)

130

ln Z
1
=

kB T

1
ln Z( ) ln Z(0) =
kB T
0

(.101)


d.

(.102)

A = kB T ln Z,

Z 0 
U
A = A(0 ) A(0) =
d.

0

(.103)
(.104)

...

.
(.94)
. BOGOLIUBOV
.
Helmholtz. Helmholtz
[10, 11, 12].
.92
.

A =

A =

(A+ A )

(.105)

min = 0
max = 1 .

A = kB T ln Z ,
Z
Z (T, V, N ) =

(.106)



1
exp
U (xi , yi , zi ) N
i dxi dyi dzi ,
kB T

U+

= U + (U+ U )


A = kB T (ln Z+ ln Z ) = kB T ln

Z+
Z

(.107)

(.108)


,

(.109)

131

"R

=
=

#
eU /kB T e(U+ U )/kB T N
kB T ln
i dxi dyi dzi
Z

Z  U /kB T 
e
e(U+ U )/kB T N
dx
dy
dz
kB T ln
i
i i .
i
Z
(.110)

e(U+ U )/kB T , U .
hD
E i
A = kB T ln e(U+ U )/kB T
,
(.111)

BOGOLIUBOV

(H0 ) (H1 )

H = H0 + H1 ,

(.112)

Helmholtz BOGOLIUBOV

A At = A0 + < H1 >0 .

(.113)

H1
H0 .

A T S0 + < H >0 .

(.114)

, BOGOLIUBOV ( .113)
.
.
BOGOLIUBOV (.94).
H0 H1

H = H0 + H1 ,

(.115)

132

Ht = H0 + < H1 >0 ,

(.116)

( ),

< Ht >0 =< H >0 ,

At () = A0 + < H1 >0 .

(.117)

= 1 BOGOLIUBOV, At A.
( .1)

.1: BOGOLIUBOV, At A,
.
.92 .95

A
< t= 0+ <1>

At
A

A0

: S = kB ln

.
S
S1 S2
1 2 ,

S = S1 + S2 ,

(.1)

= 1 2 .

(.2)

S , S = f (),
.

f () = f (1 ) + f (2 ).

(.3)

1 :

df () d
df (1 )
df ()
=
=
d1
d d1
d1

(.4)

f (2 ) 1 .

d
= 2 =
,
d1
1

(.5)

df ()
df (1 )
=
,
d 1
d1

(.6)

133

134

. BOLTZMANN

df ()
df (1 )
df (2 )
=
=
= = kB .
dln
dln1
dln2

(.7)

1
2.
.

df ()
= kB ,
dln

(.8)

Boltzmann

S = f () = kB ln() + .

(.9)

S 0 = 1, =
0, .
...

-


.
() ,
,
.
11 Introduction to Modern Thermodynamics Dilip Kondepudi [13].
-
Onsager 1931, -
De Donger, Prigogine . -
- ,
Ilya Progogine .
,
, -
, ,
, , ... . , ,
, , ,
135

136

. -

i
, ~
x, , t

T = T (~x, t),

i = i (~x, t), i = 1, , r.

P = P (~x, t),

s[T (~x, t), i (~x, t)] = s(~x, t),

u[T (~x, t), i (~x, t)] = u(~x, t),
i (~
x, t) i .
~
x

T (~x)ds(~x) = du(~x)

i (~x)di (~x).

(.1)

.

-

(~x, t) =

di s(~x, t)
0.
dt

(.2)

di S
=
dt

Z
(~x, t)dV 0.

(.3)

- Fi Ji

Fi Ji .

(.4)

, ,
, .

Ji =

Lij Fj .

(.5)

Lij Onsager. ,

X
ij

Lij Fi Fj 0.

(.6)

137
Lij
Onsager
, Lij = Lji .
.
.
1)


Fq =

1
T (~x)


,

Jq = (T (~x)) (Jm2 s1 ),

(.7)

( Fourier).
2)


FD =

k (~x)
T (~x)


,

JD = Dk (k (~x)) (mol m2 s1 ),

(.8)

Dk ( Fick).
3)

Fe =

E
()
= ,
T
T

Je =

V
E
=
(Cm2 s1 ),
R

(.9)

, E , I , V
, (R, ) ( Ohm).
3)

Fr =

Ar
,
T

Jr = vr =

1 dr
(mol m3 s1 ).
V dt

(.10)

Ar r, r
mole, vr
V.
-.
r
0 = a1 A1 a2 A2 an An + b1 B1 + b2 B2 + + bm Bm ,

(.11)

dnA1
dnA2
dnAn
dnB1
dnB2
dnBm
=
= =
=
=
= =
= dr .
a1
a2
an
b1
b2
bm

(.12)

(AFFINITY) .11

Ar =

n
X
i=1

ai Ai

m
X
i=1

bi Bi ,

(.13)

138

. -

Ai Ai Bi
Bi .
Gibbs

Ar = r Gm .

(.14)

:
1. Ar = 0 dr /dt = 0.
2. Ar > 0
3. Ar < 0 .
, Gibbs
. .
- , r ,

X Ar dr
di S
=
0.
dt
T dt
r

(.15)

Gibbs .
: -
, Gibbs
.
r

vr =

1 dr
= Rf (r ) Rr (r ),
V dt

(.16)

Rf Rr
. molL1 s1 .

aA + bB = cC + dD

Rf = kf [A]a [B]b ,

Rr = kr [C]c [D]d .

(.17)

i
, i ,
i =
(.18)
i + RT ln(i ),

Qn

Ar = RT ln(Kr (T )) + RT ln

i=1
Qm
i=1

ai
A
i
bi
B
i

!
.

(.19)

139

Kr (T )

Kr = kf /kr .

(.20)

( 3.65 3.69)

r G
m =

j
j = Ar ,

(.21)

r G
m = RT ln Kr .

(.22)


Ar = RT ln

Rf (r )
Rr (r )


.

(.23)

, -



X
1 di S
1 X Ar dr
Rf (r )
=
=R
[Rf (r ) Rr (r )] ln
.
V dt
V r T dt
Rr (r )
r

(.24)

X
d 2 S
1 2
S=
=
Fk Jk 0,
2
dt 2

(.25)

2 S Fk
Jk Fk
Jk .

, s(u, i ), i =
1, , r,



r 
X
s
s
u +
i
u i
i u
i=1
 
r 
X
1
i 
=
u +

i .
T
T
i=1


s(u, i )

(.26)

(.27)

140

. -

2 s(u, ) =

2s
u2

(u)2 + 2
i


r 
X
X  2s 
2s
ui +
i j .
ui
i j u
i=1
ij

(.28)
. ,

d[ 2 s(u, i )]
= 2 s(u,
i )
dt


2s
u u
= 2
u2 i

r 
X
2s
+ 2
( u
i + u i )
ui
i=1
X  2s 
i j ,
(.29)
+ 2
i j u
ij




r 
X
1
1
s(u,
i ) = 2
u u + 2
u
i
u T
i T
i=1

r 
X  j 
X
i
u i + 2
j i ,(.30)
+ 2
u T
i T
u
ij
i=1


  

X 1 
1
1
=
u +
i
T
u T
i T
i

 
i


=

i
u T


u +

X  i 
j ,
j T
j

(.31)

(.32)

s(u,
i )

"  
#
X  i 
1
2
u +

i .
T
T
i

(.33)

#
Z "  
X  i 
1
2 S = 2

u +

i dV.
T
T u
i

(.34)

u =
u =

J~u ,
J~u ,

(.35)
(.36)

141

J~i +

ij vj ,

(.37)

J~i +

ij vj .

(.38)

ij ith , vi . u,
i
.

~ = f J~ + Jf,
~
(f J)

(.39)

Gauss

(f~J)dV =

~ a,
f Jd~

(.40)

~
f JdV
+

~
Jf
dV =

~ a,
f Jd~

(.41)

1 2
S=
2
+
+

 
 
Z
1
1
J~u d~a +

J~u dV
T
T

V
Z X  
Z X
 
i
i

J~i d~a

J~i dV
T
T
i
V i
Z X  
Ai
vi dV.

T
V i
Z

(.42)

V d~a P
. j ij (j /T ) = (Ai /T ).

.

1 2
S
2

 
1
J~u dV
T
V
Z X
 
i
J~i dV

T
V i
Z X  
Ai

vi dV
T
V i
Z

1 2 X
S=
Fk J~k
2
k

...

0.

(.43)
(.44)

(.45)

(.46)

142

. -

.1

(X D ) (X L ) - (S, T). [S], [L] ,

k3r , k3r << 1.

S+T
S + T + XL
S+T
S + T + XD
XL + X D

*
) XL , (k1f , k1r ),
*
) 2XL , (k2f , k2r )
*
) XD , (k1f , k1r ),

(.47)

*
) 2XD , (k2f , k2r ),
*
) P, (k3f , k3r ).

(.50)

(.48)
(.49)
(.51)

L
R1f

= k1f [S][T]

(.52)

L
R1r
D
R1f
D
R1r
L
R2f
L
R2r
D
R2f
D
R2r

= k1r [XL ]

(.53)

= k1f [S][T]

(.54)

= k1r [XD ]

(.55)

= k2f [XL ][S][T]

(.56)

= k2r [XL ]2

(.57)

= k2f [XD ][S][T]

(.58)

= k2r [XD ]

(.59)

R3f

= k3f [XL ][XD ]

(.60)

R3r

= k3r [P ]

(.61)

XL XD

d[XL ]
L
L
L
L
= R1f
R1r
+ R2f
R2r
R3f + R3r
dt

(.62)

d[XD ]
D
D
D
D
= R1f
R1r
+ R2f
R2r
R3f + R3r
dt

(.63)

.24 [0, T ] , V = 1.



di S L(D)
L(D)
= R Rf
[r (t)] RrL(D) [r (t)] ln
dt

L(D)

[r (t)]

L(D)

[r (t)]

Rf
Rr

!
.

(.64)

= [S][T],

[XL ] [XD ]
2

[XL ] + [XD ]
2

(.65)

.1.

143

d
= k1r + k2f 2k2r
dt
d
= k1f k1r + k2f k2r ( 2 + 2 ) k3f ( 2 2 )
dt

(.66)

(.67)

, .62 - .64,
.

k1f

0.5

k1r

0.01

k2f

0.5

k2r

0.2

k3f

1.5

k3r

0.001

(.68)

[S]

0.5

[T]

[S]

[P]

[XD ]0

0.0

[XL ]0

[XD ]0 +

(.69)

144

. -

.1: [.47 - .51],

. [2-6]
[.47 - .51].


[1] L. D. Landau and E. M. Lifshitz, Statistical Physics, Chapter II, Pergamon
Press, 1970. 1
[2] David Chandler, Introduction to Modern Statistical Mechanics, Oxford Univ.
Press, 1987. 1
[3] N.M. Hugenholz, C -algebras and statistical mechanics Operator Algebras
and Applications, (Proc. Symp. Pure Math. 38) part2, ed. R.V. Kadison
(Providence, RI: American Mathematical Society) pp. 407-465, 1982. 30
[4] D. Ruelle, Statistical Mechanics, Rigorous Results, London: W.A. Benjamin, 1969. 30
[5] Herbert B. Callen, Thermodynamics and Introduction to Thermostatistics,
Second Edition, John Wiley and Sons, Inc., 1985. 56, 58
[6] L. Galgani and A. Scotti, On Subadditivity and Convexity Properties of
Thermodynamics Functions, Pure and Appl. Chem. 22, 229, 1970. 56, 58
[7] Robert A. Alberty, Legendre Transforms in Chemical Thermodynamics,
Pure and Appl. Chem. 69, 2221-2230, 1997. 56
[8] Stephen Boyd and Lieven Vandenberghe, Convex Optimization, Cambridge
University Press, 2004. 58
[9] P. W. Atkins, Physical Chemistry, Part I, Crete University Press, 2000. 81
[10] Thomas Simonson, Free Energy Calculations, in Computational Biochemistry and Biophysics, edited by Oren M. Becker, Alexander D. MacKerell,
Jr., Benoit Roux, and Masakatsu Watanabe Marcel Dekker, Inc., pp. 169
197, 2001. 130
[11] Daan Frenkel and Berend Smit, Understanding Molecular Simulations:
From Algorithms to Applications, Academic Press, San Diego, CA USA,
1996. 130
[12] Christophe Chipot and Adrew Pohorille (Eds), Free Enegy Calculations:
Theory and Applications in Chemistry and Biology, Springer - Verlag,
Berlin Heidelberg, 2007. 130
145

146

[13] Dilip Kondepudi, Introduction to Modern Thermodynamics, John Wiley

& Sons, Chichester, England, 2008. 135


, 4
, 126
, 15
, 1
, 13, 26, 34, 91
, 17, 21, 22, 115
, 103
, 13
, 17, 48, 130
, 11, 33, 119
, 4, 13, 26, 91
, 9
, 103
, 9
, 27
, 142
, 47
, 13, 39, 40, 93
, 14, 15,
34
, 18, 19, 139
, 104
, 3, 31
, 91, 92
, 2, 12
, 17, 21, 22, 48
, 21, 22, 62, 92
, 2, 12
, 6, 12, 34, 90
, 20, 58
, 14, 33, 89
, 3
, 11, 32

, 19, 55
, 104
, 23
, 12
, 27, 94
, 75, 93
, 126
, 102
, 7, 89
, 60
, 92
, 18
, 16, 47
, 16, 47
, 16, 47
, 104
, 1
, 126
, 127
, 11, 33, 119
, 67, 76
, 34, 67, 130
, 15
, 17
, 130
, 27
, 95
, 68
, 20, 56
, 4, 13, 91
, 4
-, 45

147

148
, 12
, 34
, 31, 33, 34
, 11, 31
, 27
, 9
, 128
, 11
, 2, 12, 111
, 11
, 75
, 13, 39, 40
, 51
, 9
, 11
, 45
, 14, 33
, 103
, 12
, 11
, 11
-, 124
, 122
, 123
, 119
, 122
, 3, 14
, 50
,
18
, 18
, 16
, 40
, 13, 109
, 4, 9, 109
, 16, 44
, 120
, 111
, 131
, 13
, 4, 14, 33
, 50, 90
,
18

,
18
, 24
, 13, 39, 40
Avogadro, 1
Bogoliubov, 130
Boltzmann, 12, 133
Bose-Einstein, 127
Clausius-Clapeyron, 78, 93
Clausius, 17, 48
Duhem-Jougeut, 54
Duhem, 28, 85
Euler, 2, 39, 111
Fermi-Dirac, 127
Gibbs-Duhem, 24, 68
Gibbs-Helmholtz, 101
Gibbs, 12, 21, 27, 63, 75, 82, 100, 102
Gradient, 9, 15, 17
Helmholtz, 21, 62, 82, 122, 128, 130
Hessian, 9, 15, 17, 29, 115
Hess, 99
Jacobians, 116
Joule-Thomson, 61
Kirchhoff, 100
Lagrange, 17, 46, 113, 120
Legendre, 20, 56, 109, 125
Lyapunov, 20, 55
Maxwell, 23, 66, 71, 109
Planck, 127
Raoult, 102
Schrodinger, 126
Taylor, 5, 9, 29, 121
concave, 24, 34, 67
convex, 24, 35, 67
fluctuations, 44
unconstrained, 15, 21, 22, 48
van der Waals, 99
vant Hoff, 104