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-

( )

. .


( )
241 247

2003
1

1 1.
1.1.
1.2. ,
,
2 1.3. . .
8
3 1.4. .
12
1.5. .
4 2.
18

2.1. .
5 2.2. .
24
2.3.
.
6 2.4. .
30
2.5. F G

7 2.6. G
37
.
2.7. --.
. .
8 3.
45

3.1. .
3.2. Q.
3.3. Q .
9 3.4. .
52
3.5. .
3.6. .
10 3.7. Z. 57
3.8. Z.
3.9. .
11 3.10. .
65
3.11. .
3.12. .
.
12 3.13. .
73
3.14.
13 3.15.
79
.
3.16. . .

1
4. 09. 2003 .
1.
1.1.

:
1) ?
2) ?
.
:
.
.


,
.
.

, .

,
, .


. ,
U, S, .,
,

.

.

.

,
. ,
.

i A
i

k1

k 1

B ,
j j

(1.1)

i , j , i ,Bj
, k1, k-1
.
( ) (
k) -:

k1
K=
.
k 1

(1.2)

- (1.2)
.

,
.
.

.
.
,
.
1.2. , ,


,

.
.
, , ,
.
.

,
.
.
,

.
4

. ,

,

.

.
,
,
. .

.
,
.
,

.

m.
,
, , . . = 0, m = 0.

,
, . 0, m 0.
,
, . . 0, m = 0.

, . . Q = 0, Q .

, ,
.
, , ,

R. R ,
r. ,
N ~ R3, n,
r, n ~ R2r.

,
, ,
.

.
,
5

.

, . .

t.


,
t +
t +
t
=
,
t +

<< t , , >> .

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

. ,
.
i, .
, ,
, , , .
,
, ,
.

. ,
,
( F), I- i,
.
: V (
6

l), I- ni, .
, . . i = ,
I , .

dA = PdX.

,
.
,

,
,
.

,
i = + ,


.
. ,

dA = PidV = PedV = PdV

, :
dA = (Pi Pe)dV,

.
,
,
, .
.
,
.

2
11.09.2003 .
1.3. . .

.
U
, ,
,

.

.
.
U
.
,
, , .

U
.
1
.
,
.


.

1 2,

U = U2 U1,
U2 U1
.
U2 U1 , U
. ,
U,
. ,

. U

8

U = U2 U1 = Q A k,
Q , ;
, ; k
.
k ,
.
,


dUi = Qe Ae + Aek,

(1.3)

I , ,

, k , .

, 1 2
.

(1.3) .
Q

.
U, Q (1.3)
, 1
. ,
, . (

.
. dU (
).

.
(1.3) ,
, .
1840 . ,
.

( 1) ( 2).

.

1 (1.3)
, Qe Aek
.
dUi,
. Qe
Aek , .
.
,
A = pdV,
p = F/ , , F.
,
. (V = const) = 0.
( = const)

A = pdV = pV .
( = const) (dQ = 0)
,
(p,V,T) = 0.
(1.3)
dUi = Qe (pdV)e dx ,

(1.4)

,
, . . ,
.
, (1.4)
. ,
,
dVi dV di de.
,
.
,
.
.
i = Pe ,
. i Pe
.

10


,
i = Pe + P.

(1.5)

P ,
;
P.
, (1.5),
(1.4)
dUi = Qe pidV id,
.
,
:
dU = Q pdV d,

(1.6)

(1.6)
:
1.
,
;
2.

3.
.

11

3
18. 09. 2003 .
1.4. .

( ) .
, ,
(1.6).
dU = dQ pdV d.

(1.6)

V = const,
, (
,
) (1.6)
rUv = Qv,

(1.7)

v .
Qv
(
). (1.7) Qv > 0 , Qv < 0
.
= const,
, ,
(1.6)

rUp = Qp prV
Qp = r (U + pV)p

.
V , V
. = U + pV
, ,
r = Qp

(1.8)

12


. (1.7) (1.8)
.
Qv Qp

Qp Qv = rnRT,
rn .
rn 0.
rnRT 298 /,
Qp Qv /.
,
.

.

( ),

. U ,
1 2 :
V = const.

Qv = U12 = U2 U1 = jUj iUi;

= const

Qp = H12 = H2 H1 = jHj iHi,

I j
.

, .
,
, ,
.
,
, ,
= 298 = 1 . ,
2(), 2(), () , r() . .

( = 1 , = 298 )
rU0298 = j fU0298,j I fU0298,i;
rH0298 = j fH0298,j I fH0298,i;

13

(1.9)

0 = 1 , fU0298 fH0298

.
. ,

.
r0298 /
. ,
.
rU0
rH0 .

dQ V U
CV =
=
,
dT T V
(1.10)
dQ P H
CP =
=
,
dT T P
(1.9) (1.10)
, rU0 rH0 :
T

0 + C dT ,
rUT0 = rU 298
r V
298
T

0 + C dT , ,
r HT0 = r H 298
r P

(1.11)

298

rCP = j C P, j C ,i
i
j
i

(1.1). (1.11)
0
rH 298
rCP( 298).

0,298 , ,
:

0,() = + + 2,
0,() = + + /2.

, ,
.
,
. ,
14


, (1.10)
V = CV, + + + + ,

.
,
.
1.5 .
() D0
,
()
0 .
0.
.

R-

D0

V=0

. 1.1.
.
.
. ,
315 525 /.
414 /.
DH0298
,
.
15

,

1. 25 .
.
1) 4
4 3 + ,

-3 = rH0298= fH0CH3 + fH0H fH0CH4.

H-CH3 = 142 + 218 ( 75,0) = 435 /.


2) 4
4 () + 4.

0
r H 298
=

C H =

f H C0

( )

0
+ 4 f H H0 f H CH

717 + 4218 (75,0)


= 416 .

rH0
. fH0
,
.


.
,
.

0
0
0
m H 0 ,

f H 298
= ni D H 298
+
s

H
,i
j s 298, j

i D 298,i

(1.12)

ni mi
, sj ,
sH0298 .
-

16

r H 0 =

ni D H i0 m j D H 0j ,

(1.13)


, (1.12) (1.13)
.

17

4
25.09.2003 .
2.

2.1. .
1- (1.6)
dU = Q pdV d,

( Q) :
1.
,
;
2.


3.
.

,
, .
(1.6)
, dQ = 0.
, (1.6)
Q, ,
.

.
v Cp.
Q.
= const
dQ = CydT,

(y = V, p, )

,
. 2.1:

18

1 2
1 3
1 4
1 5
1 6

p = const,
= const,
pVn = const,
pVk = const,
V = const,

dQp = CpdT
dQ > 0, dT = 0
dQ > 0, dT < 0
dQ = 0, dT < 0
dQv = CvdT

Cp > 0,
CT = + ,
Cn < 0,
C = 0
Cv > 0

,
.
P
1
2
3

4
5
6
V
2.1. V
1 2, 3, 4, 5 6.
v .
,
:

U
CV =
,
T V

H
Cp =
.
T p

= const
,

19


Cy =
.

Q
. .

.
,
, ,
.

.

dAk = Pkdxk.
k xk ,

. k xk.
dxk 0
k . xk
.
.

Pik = Pek
k .
, ,
.
(1.6)

dU = Q Pk dxk .

(2.1)


:

,
, . . dx,
Q
Q = TdS.

(2.2)
20

(2.2) S , .
(2.2),
dS = Q / T
1/ Q
S.
U, S
.
(2.2)
,

.
,
.
1)
,
S,
(2.2).
( , )
:
,
.
S

,
.
,
.
, ,
, . . ,
.
.
,
( = i) :
dS > 0 dQe = 0

(2.3)


.
.
(2.3) ,

(i e)dx

, :
21

TdS Qe,

(2.4)

, Qe
, .
(2.3)
.
. ,
.
, V

dV =


(2.2).
(2.1)
,

dU = TdS pdV Pkdxk.

(2.5)

(2.5)
.
(2.5)
V1 V2.
dU = 0 TdS = PdV.

2

PdV = nRTlnV2/V1.
1

nRT ln

V2
V1

2
V
(2.6)
S = dS =
= nR ln 2 .
T
V1
1

V = const:
T
(2.7)
S = CV dT ,
V = const ,
o T
T
(2.8)
S = C P dT ,
P = const .

T
o
22


S:
.

, , ,
,

.
... ,
.

Q
T = 0.

Q/T

, . . ,
S, Q/T
.
, Q
(2.2), S
.
: .
,
Q = dU + pdV
. ,

Q = dU + pdV dx
.
. :
Q ,

,
.
.
.

. ,
.

23

5
2. 10. 2003 .
2.2. .
2.3.
.

2.2. .

.
,
,
.
( ,
). (,
) Q = 0 (2.4)
:

S. 0.

,
. ,

. S. = 0
, ,
.. .
,
, .. =.
Q.

dS.=dS + Q/=dS + Q/.


, Q =

Q, ,

dS=dS Q/.
dS
.

24

dS Q/ 0.

(2.9)


. ,
, .

. QV dU. (2.9)

dS dU/T 0 TdS dU

(V = const)

(2.10)

(2.10) .
,
QP = dH.

dS dH/T 0 TdS dH

( = const)

(2.11)

(2.10) (2.11) ,
: G
F. :

G = H TS,
F = U TS.

(2.12)
(2.13)

.
, (2.12) (2.13) :

dG = dH TdS
dF = dU TdS

(T = const),
(T = const).


= const (dH TdS) V = const (dU TdS).

dG 0
dF 0

(P T ),
(V ).

(2.14)
(2.15)


.
G F.

.
25

, = const.
Q .

dH = Q + d(PV).
,

dG = Q + PdV TdS = + dV.


- ,
( dV). ,
= ( dV),

dG = A,
G = A.

(P = const, T = const)

(2.16)


,
.
F V = const T = const.
.
.

, .

, . F = U TS

(S < 0 S > 0),
. ,

II
,
, .. U = const.
2.3. .
(2.5)
,
,
dU = TdS PdV.
(2.17)
U, S, T, P, V. , ,
V . U
26

. S
, , .
, V

(,V,) = 0,

U = U(V,T).

:
U(V,T), U(P,T), U(S,V), S(U,V), V(P,T), V(S,U) ..
.

,

.
, U(S,V) . S V
,
(2.17):
U
U

,
P =
T
=

S
V S
V

V .
V
S

H = U

, , S(U,V) V(S,U)
.
,
:
U = U(S,V),
H = U + PV,
F = U TS,
G = H TS.

(2.18)

27

(2.17) (2.18)

:
.
dH = dU + PdV + VdP = TdS PdV + PdV + VdP = TdS + VdP,
(S,P).
F.
dF = dU TdS SdT = TdS PdV TdS SdT = SdT PdV.
F(T,V).
G.
dG = dH TdS SdT = TdS + VdP TdS SdT = SdT + VdP.
G(T,P).

U(S,V),
(S,P),
F(T,V),
G(T,P)

.

, ,
,
.

:
dU = TdS PdV,
dH = TdS + VdP,
dF = SdT PdV,
dG = SdT + VdP.

(2.19)

(2.19)
,
.
. ,

d = A(X,)dX + (,)d,
:

= ( , ),

= ( , ),

(2.20)
28


=
.

(2.20) (2.19)
.
.
,; ,V
,V. ,

.

29

6
9. 10. 2003 .
2.4. .
2.5. F G

2.4 .

- ,
, ,
, V,
. ,
, ,
.
.
1875 .
(1839 1908 ).
. . 1871.
,
.
"i".
,
, , .

n
i

S ,V , n

n
i

S ,V , n

dni ,

-
j

i j, dni
. , ,
,

30

dU = TdS PdV +


i ni

S ,V , n

dni ,

(2.21)

.
U


i ni

(2.21) ,

S ,V , n

dni


S V = const. (2.21),
, F G:
H

i ni

dH = TdS + VdP +

S , P, n

i ni

dni ,
j

T ,V , n
j

dni ,

i ni
T , P, n j

dni .

dF = - SdT PdV +

dG = - SdT + VdP +

(2.22)

(2.21) (2.22) .
(2.21) dH (2.22).
VdP (2.21)

dU = TdS PdV + VdP VdP +


i ni

S ,V , n

dni ,
j

dH = TdS + VdP +


i ni

S ,V , n

dni .
j

(2.22),
.
,
31


i ni

S ,V , n


i ni

dni =
j

i ni
T , P, n j

S , P, n

dni =
j


i ni

T ,V , n
j

dni =

dni .

, j ,
i,
U

n
i

S ,V , n

dni =
j

n
i T , P, n

n
i

S , P, n

dni =
j

n
i

T ,V , n

dni =
j

dni .

n
i

S ,V , n

H
=
n
i

S , P, n

F
=
n
i

T ,V , n
j

G
=
n
i

P, T , n

= ,
i

(2.23)

nj "j"
"i". i .


:
i
i

dU = TdS PdV +

dni ,

dH = TdS + VdP + i dni ,


i

dF = - SdT PdV + i dni ,


i

dG = - SdT + VdP + i dni .


i

32

(2.24)

(2.23) .

i =
ni

(2.25)

P, T ,n j

,
= const

G.
= const (2.24)

dGT,P = 1dn1 + 2dn2 + + idni.

(2.26)

, i = const
(2.26)

GT,P = 1n1 + 2n2 + + ini.

(2.27)

(2.27) , n1, n2, n3,


ni = 0 G, = 0. (2.27) , ini
,
. ,
i Gi,m, Gi,m
. i = Gi,m
( ,
). i
,
, .
,
.
2.5. F G
.
F G ,

.
F G .
(2.19) = const
33

= S .

(2.28)

V = const F
F

= S.

(2.29)

, (2.12)
(2.13)

G = H TS,
F = U TS,
S (2.28) (2.29).

G

G = H + T
F =U

F
+ T

(2.30)

(2.31)

, "1" <>
"2" <>, (2.30) (2.31)
:

rG = r H
r F = rU

G
+ T r ,

(2.32)

(2.33)

F
+ T r

(2.30) (2.33)
" ". G F
34

,
. (2.32) .
2
:
G

T P

rG
r H
=

,
2
2
T
T

r H
.
2
T


,
F
r

(2.34)

rU
.
2
T

(2.35)

,
. rG

0
fG 298 .

.
.
, (1.1)
0
0
0
r G 298
= j f G 298
, j i f G 298, i .
j

(2.36)

j, i
.

35

7
16. 10. 2003 .
2.6 G .
2.7 --.
. .
2.6. G .

G, ..
,
F. .
,

G
dG = VdP SdT, = V .

(2.37)


1 2
P2

G2, m G1, m = Vm dP .

(2.38)

P
1

1. .
.
.

G2,m G1,m = (P2 P1)Vm,


,
G2,m G1,m.
.
2. . Vm = RT/P

36

P2 dP
P
G2, m G1, m = RT
= RT ln 2 .
P
P1
P1
0

1 1, G1,m = Gm

Gm = Gm0 + RTlnP
= 0 + RTlnP

(2.39)

,
.
3. . Gm
, Vm
.
,
f,
. f

dGT = RTdln f

(2.40)

dGT = RTdln P, ..
f. .
G = G0 + RTln f,


G = G0 + RTln P.

G0 G0
f = 1 = 1.
0`
0
G G . ,
G0` = G0. G G,

G G = RTln f/P = RTln ,


= f / P ,
.
,
,
.

37

, (2.40) GT ,
f .
(2.40),

(G2 G1)T = RTln f2/f1.


f -
, .
, ..
f/P = 1.
0.
f/P 1 0.

P
2

(G2,m G1,m)T = RTln f2/f1 = Vm dP

(2.41)

P
1

(, V, ) = 0.
( --)
.
,

= RT/P V = V V.
V = RT/P
(2.41),

2
f2
P2
RT ln = RT ln dP .
f1
P1 P
1

"1" ,
f1 = P1,

P2
RT ln f 2 = RT ln P2 dP,
P1
38

(2.42)

f2.

[()].
G(P) (2.39).
G(P) :
[()]
(2.42), (2.41) Gm
1 2.
2.7. --.
. .
(,V,T) = 0

PV = RT[1 + B(T) / V + C(T) / V2 + ],

(2.43)

V ; (), (), , ..
. (2.43)

().

.
, .
(), (), , .
,
, .
--
" " (1873 .).
, ..
.

RT
a
2.
V b
V

(2.44)

(2.44) --.

"b" ,
.
. , .
39

"" "b" .
, V - (.2.3).

dP
= 0,
dV

d 2P
= 0.
2
dV

,
-- "" "b":

T=const
+

V=b

. 2.3. -- -V
.

40

VK = 3b; TK =

a
8a
; PK =
.
2
27Rb
27b

(2.45)

(2.45) , ()

PV
RT

--

K =

PKVK 3
= = 0,375.
RTK 8


2.1. 0,375
.
2.1

2
N2
Cl2
CO2
H2O
CH4

0,306
0,305
0,291
0,276
0,275
0,227
0,289

--
:

=/ ;
=/ ;
=V / VK .

,

. .
(2.44). , - ,
V - VK ,
(2.45)
41

8
3
2.
3 1

(2.46)

, "" "b",
, . ,
(2.46) ,
--.
, ,
.
.
.
.
(2.43) 0
P2
f2
RT ln = dP,
P2
0

= V V,
V = RT/P,
V = RTZ/P (Z
). ,

RTZ RT RT
(Z 1),

=
P
P P


P
f 2 2 RT (
RT ln =
Z 1)dP,
P2 0 P

, ,

f =

P Z 1

P exp
dP .
0 P

(2.47)


(. 2.4).
=f/P (. 2.5).
42

.

2.2.
2.2. 273 .

= 33,5 , = 126,2 , V = 89,610-63/


=/
0.03
1,49
3
8,96
17,9

()
1
50
100
300
600

f()
0,99955
49,06
97,03
301,7
743,4

43

f--()
0,999
49,25
96
297
726

=f--/P
0,999
0,985
0,96
0,99
1,21

Z
10
1,0
2,0

0,8
1,6
0,6

1,4
1,2

0,4

=1,0
0.2
1

2.4.

ZK = 0,275.

1,4
1,2
3,0
1,0
2,0

0,8
1,6
0,6
1,2
0,4

= 1,0
0.2
2

10

12

14

16

18

. 2.5.

.

44

8
23. 10. 2003 .

3.

3.1. .
3.2. Q.
3.3. Q .

3.

3.1.

:
1. , ,
;
2.
, ;
3.
.
U
.
4. .
, N
. V
.
. L ,
. , V .
L
N.
.

( )
.

45

,
. ,

.
.

U.



.
. ,
.
.
, .
.
, L .
.
.

, .
L.

E
L

,
.

. ,
,
. L
.
.
, li i ,

E = li i , li = L,
i

li i
i

.
46


L ,. .

U=

li i
i

(3.1)

li,
i. .

li = L

i
e kT

i
Q = e kT
i

i
e kT

(3.2)

i
. ,

N =N
i

i
e kT

i
= e kT .
i

i
e kT

(3.3)

(3.3)
i , N .
(U = const, V = const)
, ,

i
e kT (3.3)

kT .
=
i


47

,
.

i. 0.
0 ,

= qi e
i

i 0
kT ,

(3.4)

qi , .
(3.4) . (3.4)
i, .
,
. ( )
, , , .. ,
, ,
.
,
,
. .

Q, (3.2).
3.2. Q.
,
N .
,
Q i ,

N
Q=
i
i =1

(3.5)

(3.5) , N
N
. , Q = Z ,
(, ).
, N ,
, ,
48

.

,
. N!.
, ,
N , (3.5)
N!:
N

N
.
=
N!
N!

Q = i =1

(3.6)

N !

Q =

N
e

, ln Q = N ln

e
.
N

(3.7)

3.3. Q .

, NA .
, Ni
N

i , , ,

U = N i .,
i
i

Ni = NA
(3.5).
:

( )

N N 1
Q

=
V
T V N !

q E E1 q E E2
N N 1 1 1
e kT + 2 2 e kT
=

N
kT 2
kT 2
i

+ "

, i = i 0.
2
kT Q, :

49

E1
E

q1 E1 kT
q2 E2 kT2
ln Q
ln
2
.

kT
kT
N
N
e
e
"
=

V
V

q Ei N
i e kT = i

N
N = NA
ln Q

2
2 ln Z = N E + N E + " =
=
kT
RT

1 1
2 2

V
= N i Ei = N i i 0 = U U 0 .
i
i

ln Q
ln Z
U U 0 = kT 2
= RT 2
.

(3.8)

(3.8)
,
:

TC
ST S0 = V
0 T

dT , H =U + RT ..


,
:

S(0T ) = R ln

ln
+ RT
,

P=1
NA

ln
ln

,
+
2
RT

=1
P =1

P0 (T ) = RT 2

(3.9)

50

(3.10)

ln
.
(0 ) (00) = RT 2

P =1

(3.11)

(0) 0 ,
(0) = U(0) = G(0) = F(0) 0.
, (3.9) (3.10)
:
,
. , lnZ

ln
ln

=
P V

1
+ .
T

(3.12)

(3.12)
, ,
.

51

9
30. 10.2003 .

3.4. .
3.5. .
3.6. .
3.4. .
,

i 0 = + + + .
0 ,
, .
(3.4)

g i, j, k , l e

+
+

kT

= .

(3.13)

i, j , k , l

g i, j, k , l = g i g
j g k gl

Q=

( )
N A!
N

NA

= Q Q Q Q ,

A

NA
NA
NA
, Q =
, Q =
, Q =
.
Q =
N A!

52

NA!
.
lnQ, lnQ
,

.

S0(T) = S0 + S + S + S,
0() = 0, + + + ,
0() 0(0) = 0 + + + .

(3.14)


.
(3.9 3.11)
.
,
,
:

Z
ln Z
ln Q
S = k ln Q + kT
,
= R ln + RT
T
T
N
P
V

= k ln Q + kT

d ln Q

S = k ln Q + kT
S = k ln Q + kT

dT

= R ln Z + RT

d ln Z
dT

d ln Q
d ln Z
= R ln Z + RT
,
dT
dT

d ln Q
d ln Z
= R ln Z + RT
.
dT
dT

.
,

.

.

53

3.5 .
,
< 3000
0.
-
.
,
lx, ly, lz
.

h2 2 2 2
2 2 + 2 + 2 = (E ),

z
8 m x
(,,z) ,
, , = ,
= const, m . (,,z)2dxddz

dV = dxddz (,,z). ,
= 0,

2
h 2 i x2 i i z2
+ 2+ 2 ,
Ei = E x + E + E z =
i
i
i 8m 2

lx l lz

(3.15)

ix, i, iz - , 1 .

, , , z.
, qi
i 1, . . qx,i = q,i = qz,i = 1.
Z. ,

. ,
, . .

Ei + 1 Ei Ei
=
<< 1.
kT
kT

54

Z i


i x2 h 2

8mkTl x2
kT
Z , x = g x,i e
dix = e
di x .
1
i
E x,i

Z , =

i 2
x di
e
x
1

i 2
x di
e
x
0

h2
= ,
2
8mkTl x

l
1
= 2mkT x .
h
2

Z, Z,z.

i 2
x

Z = e

i 2

di x e

3 0
2
(2mkT )

di e

i z2

diz = Z , x Z , Z , z =

(3.16)

V ,
h3
V = lxllz ,
.
1 ,
, (3.8)
(3.16)
3/ 2
3
ln Z
2 ln T

= RT .
U U 0 = RT 2
RT
=

T 2
T
V

(3.17)

, 1 ,

U = 3/2 RT,
,

V, = 3/2R.

55

3.6. .
1
,
ln Z ,
Z
S = R ln + RT

T
NA

ln Z ,
Z e
+ RT

NA
V
T

S = R ln

2MkT

Z = 2

h N A

3/ 2

RT
.
P
5
ln Z


RT
2 5 .

= RT = R.

T
T 2


S, :

1 2 MkT
S = R ln

N A h 2 N A
2k

+[R ln 2
h N A

3/ 2

3/ 2

RT 5
3
5
+ R = R ln M + R ln T R ln P +
P
2
2
2

5
k + R].
2


,
(k = 1,381023/;
NA = 6,0210231/;
h = 6,631034;
() = ()1,013105)

3
5
S = R ln M + R ln T R ln P 9,69 [ /( )] .
2
2

(3.18)

(3.18) ,
: [/], [K], [].
9,69 /(). (3.18)
,
,
.

56

10

6. 11. 2003 .
3.7 Z.
3.8 Z.
3.9. .

3.7 Z.
.

2
=
2 J
J , = J
, .
, ,
,

M=

h
2

j( j +1) ,

j = 0,1,2,3 - .
j

Ej =

h2
8 J
2

j( j +1),

(3.19)

gj = (2j + 1).

57

h2
2
j( j +1)

JkT
8
= (2 j +1)e
.

(3.20)

j=0

h2
= ,
2
8 Jk

[.]

. (3.20) Z
= /. ,
>>1, Z
(3.20)
(3.21)
=1+ 3e 2

, << 1, (3.20)

= (2 j +1)e j ( j +1) dj.


0

j(j + 1) x,

Z = e x dx
0

8 2 JkT
= =
.
2

h
1

(3.22)

,
(,2) 180
,
,
, (3.22) 2.

(NO) 180
(NOON), .
,

8 2 JkT
,
Z =
2
h

(3.23)

58

,
()
.
. , 2
= 2 Z (3.23).
,
.

,
.
,
. ,
Z
1/ 2

8 2 J1kT 8 2 J 2 kT 8 2 J 3kT
Z =

h 2 h 2 h 2

(3.24)

J1, J2, J3
. Z (3.24)

(3.23) (3.24) ,
.


.
,
, ,
(3.8) (3.24) 1

U = RT 2

d ln Z 3 2 d ln T 3
= RT
= RT .
2
dT
dT 2

,
3/2R R
.

59

3.8. Z.
.
U(r), ,
.
r
U r = r0.
.
. 3.1.

U(r)

rmin

rmax
r0

D
V=2
V=1
V=0

. 3.1.
.

.

.

60

1
2

= h ( +V ) ,

(3.25)

- , V ,
0, 1, 2, 3, .
(3.25)
r = r0.
1012 1014 1.
h = V+1 V, ,
22
20
610
610
.
gk = 1.

h (1 / 2 + V )

kT
e
=

V =0

h
2kT

1e

h
kT

(3.26)

,
= 0 0 = h, (3.26)

1
h

1e kT

(3.27)

(3.27)
:

= kT

d ln Z

= kT 2 d ln(1e
dT
dT

h
kT

h
h
e kT

(3.28)

0
. >> = h/k

61

h
e kT

=1+

h
+",
kT

U = kT.
, ,
,

. ,

,
.
, ,

, . . .
(3.27) (3.28)
, .

,
.
f , .

Z =

i= f
i,
i =1

i= f

i =1

1
h

i
1e kT

(3.29)

i i .


.
3.9. .

S = R ln Z + RT

d ln Z ,
dT

62

Z (3.23)
(3.24), >> .

RT

d ln Z
dT

RT
= R,
T

S = R(ln Z +1) = R ln J + R ln T R ln + R(1+ ln

8 2 k
).
2
h

S = R ln J + R lnT R ln + 877,3 [ /( )].

(3.30)

(3.30) J [2].

RT

d ln Z
dT

3 RT 3
= R,
2 T 2

3 1
3
3
(8 2 k ) 3 / 2
).
S = R(ln Z + ) = R ln( J1J 2 J3) + R lnT R ln + R( + ln
2 2
2
2
h3
,

1
3
S = R ln J1 J 2 J 3 + R ln T R ln +1320,8 [ /( )].
2
2

(3.31)

(3.31) J1, J2, J3 [2].


I-
, i.
(3.26),

63

S i ,

h
i

e kT

d ln
h

h i

h
i

kT

e 2 kT
h i

1
e
2
kT
= R ln
+T
= R 2kT ln1 e
h
i
dT

1 e kT

h i
h

kT
kT

ln
1
R
e
R
=

+ h i

e kT 1

d 1 e kT

h i

=
+T

2
h

2kT
kT
1 e
dT

I-
i =

h i
, f
k

i / T
= R i
ln1 e T

i =1 e T 1

(3.32)

(3.32) ,
I / T. 0
0.

i

3R
e

3R ln1 e

.
f ,
1/3 .
I / T .
. .,
. ., . ., . . ,
( ) . / . . .; .
., 2000. 100. Si, i,
. I / T
.

64

11
13. 11. 2003 .
3.10.
3.11. .
3.12.
. .
3.10.
3

< 10

.

Z = g0,

(3.33)

g0
. (3.33)

0.

S = Rlng0

(3.34)


19
1,6(10
1018) . 103
kT = 1,41020 . , < 1000
.
. NO
1 = 2,41021, , ,
, kT 4,21021.
NO

Z = g0 + g1e1/ kT,
g0 = g1 = 2. .

,
65


.
,
( ),
. , 13 , 12
4 1S, 2S, 2P 3S.
Al 3
,
Al 4.

. g0
1.
3.11. .
,
.

,
, ,
. , n ,
3n.
(n = 3). ,
3n 3 .
n
. n = 2.
,
Z, .
, ,
Z, .
,
n = 3.
f = 3n 3 n.
f = 3n 5, f = 3n 6.
, 2 f = 33 5 = 4
(. . 3.2.):
S ,
=;
S ,
=;
1 2 ,
.

66

aS

. 3.2. 2.
, 1 2
. .

,
.
3.12. .
.

.
, ..
.
,
i
.

. , i 0, ,
i << kT,

Ei
<< T .
k

(3.35)

67

i << kT exp( Ei / kT)


"i" ,
"i".
.
, ,
,
.
i

i = f(i),
f(i) , ,
, .

. i

(3.35) ,
:

>>

(3.36)


,
.
(3.35) (3.36) ,
.

.
:

1) .

(3.15)

h2 N A
h2
(Ex )i = 2 (2i x +1) = 2
(2i x +1),
8l x m
8l
68

, lx ,
.

h 2 N A
= 2
=
.
8l x M k k

(3.37)

( = 1 /)
1 :

(6,6210
810

34

10

) 6,0210
2

23

/ 1,3810

23

1018 .

, , , >>
,
.. 1,5RT. ,
, 1,5R.
2) .

h2
h2 N A
,
= 2
= 2
2
8 J k 8 M r k

(3.38)

J = r 2 - , r
m1 m2
, =
- ,
m1 + m2

69

h2
,
= 2
8 J min k
Jmin
.


(3.38) ,
:

24
M [ / ]r

[ ]

Ao

.
.

11
= 0,5 / , r = 0,74 Ao ,
1+1

24
87 .
2
0,5(0,74)

NO :

1416
24
= 7,5 / , r = 1,15 Ao , =
2,5 .
14+16
7,51.3

.
273
,
.
3) .

.
(3n-6) (3n-5)
.
12
14 1
10 10 .
70

h = Ev+1 Ev = ,
22

, 610

61020 .

h 6 10 22 10 20

=
50 5000 .
23
1
k
1,3810

(3.39)

1500 4000 .
( = 293 )
, , ,
= 1 .

.
~RT, - ~R.
= 0,92R.
3.1.
.
,

1 1
=
.
10

310

ch
31010 6,6210 27
=
=
= 1,438 [].
16
k
1,3810

71

3.1.


( )

-1

3000

3700

2100

==

1700


( )

-1

1600

300

==

1650

700

1450
1450

4) .

19
18
= 1 10 = 1,610
1,610
.

1,6 1019 1018


4 105 .
=
=

10
k
1,3810 23 1

(3.40)

, 1000

g0 .
g0 = 1.
.

72

12
20. 11. 2003 .
3.13.
3.14.

3.13.

U
CV =
.
T V
(3.28)
NA ,
2
ln Z
2 ln Z
.
CV = 2kT
+ kT
2
T
T V

(3.41)

(3.13), (3.41)

V = CV, + + + .
<< , , , ,
, ,
,
Z = Z = Z = 1, Z = g0. (3.41)
V = 0.


. U V,
>> U = 3/2 kT V, = 3/2 k
, .
,
. , ,
18
l = 1 , 10
.

73



kT k
.
,
J1, J2,
J3 . >>
k,
3/2 k. = 10 .
=
.
, ,
h << h + kT
>> .
h i
,
(3.28) U i, = h i
e kT 1

i
( i ) 2 e T

dU
.
d i
Ci, = i, =
k
= k T

i
i
dT
dT

T
T
e 1
(e 1) 2

, ,
= 0 >> i = 0
= k. f
,

C = R

i =1

i 2 Ti
( ) e
T
.

(e

i
T

1) 2


(3n 5)k,
(3n 6)k.
V , n
>> :
74

V = 3/2k + k + (3n 5)k = (3n 2,5)k.


V = 3/2k + 3/2k + (3n 6)k = (3n 3)k.




V = (3n 2,5)R.
V = (3n 3)R.

(3.42)
(3.43)

,
50 5000 .
4
5
= (10 10 )
,
.
. , ,
.
(3.41) ,
V
, .

V

V = + + 2,

(3.44)

V = + + / 2.

(3.45)

, ,
.
.
V
. 3.3
. .
3.4
, .

75

7k
6k
5k
4k
3k
2k
k
0

10

100

1000

10000

TK

. 3.3. ,

(2) .

= const.

.
0

. 3.4.
.

76

3.14.
,
, ,
. 26 3.
24
2, 33 3
.
2 3
.
, 3
.

120 240, .3.5.

13

0
0

4/3

8/3

. 3.5. 3
.
,
,
,
.
.

, ,
10 /. 13,2 /, 2
50 / , . .
/.. 300 RT = 2,49 /,

.
.
77


.
.

Z

Z = Z Z. .

1/ 2

8 3kTJ .
,
Z . =
2

(3.46)

J. ,
* .
,
,

J . =

J A J B
,
J A+JB

JA JB , .


360. ,
3 360
. * = 3
.
(3.46)

,
.
.

, ,
.

78

13
27. 11. 2003 .
3.15.
.
3.16. . .
3.16.1. .

3.15. .
,
,

dS =

Q CV dT

dS =

Q C P dT

S CV
,

=
T
T

S C P
= .
T P T

,
T C dT
V

S=

T C P dT

S=

= CV d ln T ,

= CP d ln T ,

V =const.
P = const.

(3.47)
(3.48)

(3.47) (3.48) ,

.
. (3.47) (3.48)
,
.
(~100 0 )
,

= 3,
79

- ,
.
. , ,


=
0

C P(.)

dT

C P( )
T

dT +

()

dT +
i

i H
.
Ti

(3.49)

(3.49) I (iH/Ti)

,
.
3.6.
/

P
dT

0 T

dT

P
dT
T

3.6. /
.


, (3.49)
80

3.2.
/().
,
298,15
1000
2000

S
143,4
168,6
183,0

S
42,3
57,6
66,2

S
0,4
21,5
56,7

S
0
0
0

S
186,1
247,7
305,9

S
186,2
248,1
306,5

3.16. . .

, .
(1844 1906) ,
.
1866 . :
; ,

;
;
;
.

. ,
.
, :

S = k ln W
, , ,
. .

. .
,
.
, ,
, . ,
.


.

S = f(W),
81

W , f .
,
.
.
. ,
.
S = S1 + S2,
W = W1W2,
1 2 .

f(W1W2) = f(W1) + f(W2).


W1 W2.

W2f(W1W2) = f(W1),
f(W1W2) + W1W2 f(W1W2) = 0.

f(W) + Wf(W) = 0.

f(W) = aln W + C,
.
f(W) = S,

S = aln W.

(3.50)


.
. ,

.
,
.
82

.
,
,
.


.
.
:

, (3.50).
(3.50) ,
. ,
. ,
(3.50)
,
,
.
3.16.1. .
W. .
N ,
V.
.
,
.
N 6- :
,
.


.
6N .

. ,
, -

.

.
, ( )
, ,
. , ,
,
83

W
,
. W
.
,

(3.50)

,
. ,
, (3.50).
.
, 2 ,. . 2N ,
2V.
. . , ..
.
n ,
. 2N n.
, . ,
n ,

,
2N n

W =C2nN =

(2N )! .
(2N n)!n!

W N = n, ..
.
. , ,

W = C2NN =

(2N )!.
( N!) 2

, , n N
, n = N.
,
.
W1 = 1. , ,
,

W2 =

(2 N )!.
( N!) 2

84

(3.50),

(2 N )!

S2 S1 = a(lnW2 lnW1) = a ln
ln
1
.
2
( N!)


[ln(N!) = N(lnN 1)],

S2 S1 =a[ln(2N )!2 ln(N!)]=2aN ln 2.



V 2V

S 2 S1 = 2R ln 2.
, N = NA,

a=

R
= k,
NA

k = 1,381023 / .
(3.50)

S = klnW.

(3.51)

, ,

.
,
.
, .
(3.51).

85