熱力学』講義ノート

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mailto: tomita@phys.h.kyoto-u.ac.jp
2000 3 Ds[
2000 8 D.Y
2001 7 D.Y
2002 9 D~[
2003 9 D[

1 1
1.1 xat $sOqx . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 j q . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 8
2.1 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2 9S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3 6M . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.4 g>.q09S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3 12
3.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2 qHO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3 ji$a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.4 0| . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.5 g>.wO . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4 22
4.1 $qwMQ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.2 DoaqDoa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.3 wjg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.4 wjg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.5 Doq . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.6 $9S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.8 ws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.9 HO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.10 wjg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5 37
5.1 MMs: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
5.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.3 -fiL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.4 L>. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.5 $s% . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
ii

1 1
1.1 xat $sOqx . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 j q . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 8
2.1 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2 9S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3 6M . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.4 g>.q09S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3 12
3.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2 qHO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3 ji$a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.4 0| . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.5 g>.wO . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4 22
4.1 $qwMQ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.2 DoaqDoa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.3 wjg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.4 wjg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.5 Doq . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.6 $9S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.8 ws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.9 HO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.10 wjg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5 37
5.1 MMs: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
5.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.3 -fiL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.4 L>. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.5 $s% . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
ii
iii
5.6 g>.w~Q . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.7 flwMO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6 50
6.1 $!=wMqE . . . . . . . . . . . . . . . . . . . . . . . 50
6.2 Eq$Q . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
6.3 `tw> . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.4 ;q . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.5 w:O . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
7 61
7.1 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
7.2 -w . . . . . . . . . . . . . . . . . . . . . . . 62
7.3 O>.wM . . . . . . . . . . . . . . . . . . . . 64
7.4 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
7.5 H~O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
8 75
8.1 = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
8.2 R% . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
8.3 wo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
8.4 R% . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
8.5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
8.6 >.S ^;wO . . . . . . . . . . . . . . . . . . . . . . . . . 81
8.7 1,9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
9 89
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W (A B) = U(B) U(A) (3.3)
pK{\wqV|7tfg[^hpK%w)
[U(B) U(A)] W (A B) = Q(A B) (3.4)
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bsj
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s
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Qy|\w.u!=tPOwflb\qtb{
g>.U.u V T V pji$s9r`bqVt| t0ob {{

P dV = RT dV /V = RT d(log V ) | W = RT log(V /V ){\wOtfis9flsrwEUJ
dq| d W = P dV xts{w| d W = d(RT log V )
3.4
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hw0 qMM|{wQnZOAspK{z
x|rwOsEwqp9S[Ttlos{
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d Q = dU + P dV (3.8)
p\hOt|oms%wfi$SxfliT| Ux
mw6!:|Qy (T, V ) w:| U = U(T, V ) qsb\qUpV{bsj

U U
dU = dT + dV (3.9)
T V V T
\;MozU[^

U
dV = 0y CV = [d Q/dT ]dV =0 = [dU/dT ]dV =0 = (3.10)
T V
\\p / xzfloM{ \
U
d Q = dU + P dV = CV dT + + P dV (3.11)
V T
dP = 0y CP = [d Q/dT ]dP =0

U
V
= CV + +P yyyyyyy
V T T P

U
= CV + V +P (3.12)
V T
y y\\p|ht H = U + P V qMOby
dU = dH P dV V dP (3.13)
iT
dQ = dU + P dV = dH V dP (3.14)
3.5. g>.wO 17
qs|

H
y CP = [d Q/dT ]dP =0 = [dH/dT ]dP =0 = (3.15)
T P
U{m|
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yyy px d Q xqsy d Q = dH
pK{\wOt|uqTywEUJdy|ts\qUK{
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CP CV
d Q = CV dT + dV (3.16)
V
q{X\qUpV{\\p|a d Q = 0qMOCEZq|$
Sxnloqs| (T, V ) wt
CP CV
y CV dT + dV = 0 (3.17)
V
URqloM\qUT{
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yyyyyyyyy ad = V 1 [dV /dP ]
d Q=0
x|w mwz q ws9yVp ;Mo| ad = (CV /CP ) p)Q \q

d{ [ w T dT dV pfl|\ w 6M w dV =
V dT V dP tEo| dV q dP wz{yM{\xwpHOT
A;Mo|lqot{\qpV{ ]
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yy = P/V )
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U
y = 0 yyyyy (3.18)
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U U
dU = dT + dV = 0 (3.19)
T V V T
^t gALqo dT = 0 pK\qUTlhwpKT

U
=0 (3.20)
V T
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U + P V = U(T ) + RT 9SiZw:qsT| (1.15) tyz CP 9Si
Zw:pK|g>.px
y CP (T ) CV (T ) = R y: (3.21)
qs{ )xTt:pKU|fgxg>.qMQr:pxsX|tx9S
toM{wcpx| CV = 3R/2 srwAxsM{
y yE
d Q = dU + P dV = CV (T )dT + P dV = 0 (3.22)
t6Mw P = RT /V E|!:%tmby
dV CV (T )
= dT (3.23)
V RT
\6T6puo
T2
CV (T )
log V2 log V1 = dT (3.24)
T1 RT
2
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3.6. 19
qs{bsj|!=tSZ.u!=x!=ww9SiZp>|
T
CV (T )
(T ) = exp dT (3.25)
RT
qSZy|!=ww.uwzx!=ww9Sw:wz
V (T )
= (3.26)
V (T )
wp)Q\qUT{|z|hUlo
= CP /CV (3.27)
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dV 1 dT
= (3.28)
V 1 T
hUlo
( 1) log V + log T = constant T V 1 = (3.29)
\t P V = RT Eby|Xh<w!=wU
PV = (3.30)
3.6
y ytx!=Ulo|oM%fwwxti
w6rOs!= qMO{x|\T?SZoX;
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yyyyyyyyyyy = RT log(VC /VD )
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yyh|.u!=xy VD /VA = (T )/(T )
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pt0ohYflw = phu P dV
= |W1 | + |W2 | W3 W4
= Q |Q | (3.32)
h| VC /VB = (T )/(T ) = VD /VA VB /VA = VC /VD |ws;Mq

Q RT log(VB /VA ) T
= = (3.33)
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RT log(VC /VD ) T
hUlo|
Q |Q |
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T T

3
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3.6. 21
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yy
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b|xwqtxsM$sflqpK{
!=pxsMtx|oxw~u)lotfxt
-hoMwwZpx!=sM\qT| KMx qzy
hKpIVoM!=xji$!=qsb\qUpVT|
d Q
= dSext = Kw!= (4.23)
Text
pK{\;Mys (4.22) x
d(S + Sext ) 0 (4.24)
q|xGwtflqb\qUDpK{
y yGxwOttMQ\qpV{
yyy
y g>.wr`
tTloMlVtr`b|Mx9SU[pVTrOTTsM
qh6pKU|!=wpx9SUapKlh{f\p|!=ww
w)-bht|\q xtt!=bji$s9r` Qq
RT dV
T dS = d Q = dU (T ) + P dV = CV (T )dT + (4.25)
V
\\p dT = 0 qSZy
V
dV dV V
jis9!=p dS = R = Rd log V y S = R = R log (4.26)
V V V V
hUlor`hqV V > V tx|Tt)x S > 0 qs
|DopKqMO\qts{
\t0oji$s9apx|r`hqVxt0ohiZoTY
w!Zh S > 0|otyVhqVtxYwLZbh S < 0 yqs|Z
hwYt ao| {
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y ;
owhmw.w0xsX|T: C pKqO{xfg
w9SU T1 , T2 p|^dhKqtahqV9S Tf tslhqb{\wq
V|HO-
T1 + T2
C(Tf T1 ) = C(T2 Tf ) Tf = (4.27)
2
!=wMx|9Sx7pxsXqh6pK{f\p|!=ww
)-bh|tlo wj i$!= Q{Qy|fgw.
mot49S Tf pji$t!=^doSMoT^d{KMx|
t.w9SU7pxsMt-hOtocmoM{
\wqV| d Qi = CdT ;Mq|ji$!=px dSi = d Q/T = CdT /T pKT|
Tf
CdT Tf
Si = = C log (4.28)
Ti T Ti
Tf Tf Tf2
y S = S1 + S2 = C log + C log = C log >0 (4.29)
T1 T2 T1 T2
qs|MVsmw.^dhKqtIV;axDopKqMO

\qts{ s[ (T1 + T2 )/2 > 2? T1 T2 ;Mh{
4.10
(1)!:w yw: A(x, y), B(x, y) :qb|
d Q = A(x, y) dx + B(x, y) dy (4.30)
xcpxsMU|
d Q A(x, y) B(x, y)
= dx + dy (4.31)
T (x, y) T (x, y) T (x, y)
tbOs: T (x, y)u< 1.2,p.5UcOb{bsj| d Q = 0
hb (x, y) w.x|:p$t)Qfl
dy A(x, y)
= (4.32)
dx B(x, y)
t(MpMloRb{ZC:!Qo\w
S(x, y) = constant (4.33)
qflb\qtbq|\wx
S S
dS = dx + dy = 0 (4.34)
x y
4.10. wjg 33
\U d Q = 0 t0 oM\qT|Mpw dy/dx wflsMqSXq

S S
A(x, y) = B(x, y) (4.35)
x y
\w T (x, y) qSZy| A = T S/x| B = T S/y iT|<wOt{Z
d Q S S
= dx + dy = dS (4.36)
T x y
(2) !:w y!:wTpVOt

d Q = Ai (x1 , x2 , ...) dxi = 0 (4.37)
i
U
S(x1 , x2 , ...) = constant (4.38)
Rb\qU|u<UObAGEpK{\x
yyy

d Q = Ai (x , x , ...) dxi =0 (4.39)
i
qflq^{UR^y| dS = 0 pxapVwxaw:iZpK
|fww:xMXXoww:pKTpK{\wt
?;MoflqhwU| Carath eodorypK
yyy
\wqVu<UcO|\$9St|\p\qt
qst|0 ^d\qUpV{f\p|\wjgw
KMxwjgqss|\wpRqm,jgqO
qMOZpK{jgqwsQb\qx|{qmiZ[oS\O{
yyy
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34 4 HO
wfipw 0 = (T2 T1 )/T2 tSMo|kw9SU T1 = 0

pKyfip 100%qs|wjgxRqhsM{wjgtSMo|
0Stxab\qUDpKy|\&omww6Tw6
papVZ\qb\qUpV{\wflp| 0StxxapVsM\q
toSTsZyssM\qUÔ{fi 7.5 H~Ofl
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a n xtomwqbyTt
Q2 (T1 , T2 , nW ) = nQ2 (T1 , T2 , W )
Q1 (T1 , T2 , nW ) = nQ1 (T1 , T2 , W )
pK|%wzqy%tx n xqsM{\Uw n t0oRqmhtx|z
Q2 /Q1 x W pMoxsc| T2 , T1 iZp><wts
Q2
= F (T2 , T1 ) yyyyy
Q1
(3)F (T2 , T1 ) = f (T2 )/f (T1 ) wpK{

.....................................................................................................................................................................................
mwowtw9Swo T x^| T2 q T| T ...
....
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q T1 wtfg| C,C Td| C ...
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yyy C tSMoy Q/Q1 = F (T, T1 ) ..............................................................................................................
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yyy C+C+T tSMoyy Q2 /Q1 = F (T2 , T1 ) ...
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4.10. wjg 35
(4.5)
Do C x|o Ti T Qi !Zlhqb{\wqV|tOm9S T w
o;o|o T q Ti wt Ci Td|o T T Qi !Z|
o Ti t Qi o{\wqV| Ci tmMo
Qi Q
= iy
Ti T
hUlo
Qi 1
= Q () y
i
Ti T i i
o Ti xh Qi oMirT| C {Ti } {Ci } Kdhw$

pGVspixDopK|mwo TT i Qi !Z|t0

oYflw W = W + i Wi = i Qi +

i (Qi Qi ) =
i Qi loM{ W > 0 s
wjgtS| W < 0 sYwbot!Qh\qtsTDopK|

DopK\qtSb{hUlo W = 0 pK| () t i Qi /Ti = 0 qs{
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36 4 HO
(1) .ux`vcm!=|xpbT|jji$pb{
(2) spbT|!=pb{
(3) yxXt(pXHXwtxMsMT|wZxKd{
(4) hUlox!dT|9S!ps9!=pb{
\w>.w!= (P, V ) wpflohrOsbT
\x 10 rt\TjpRo| fiXgQhflqqj\h
qpK{Tt\w| (P, V ) tThs9 P V = RT
oMX{m|w6x6wpflqpV|ji$t_Q{T
|%pUQoM S = R log 2 > 0T|TtDopK
{M|~X)pitoMXqVtx|wXw~tTT
ytx`vpKU|XdoubqvsUAts{
>t.utbr`xji$pxsX|Myfiwlofl: (P, V )
T: (P/2, 2V ) pbpKO{wap|`vwx
wloMwi|qTtMOUsX| fiji$flpKUDopsMpK{
M|ji$afit6wpG\pV`v!=wuOvflqo
[bq|DowBqwAx|\wphflji$oD
Doqxots
ji$aDoa (4.40)
pK{wx|\wAwfl}wt wlTlhqs qtQO{
h|;wtSMo|mw.fgw9Sxt7tsOt-js
U|wcm^d\qt|cmbta\qUMQ
{xtt-hoM\qT|\wOsfiji$flqz\qU
M{ 6.3 `tw>TsU|\xTtDoaw/pKlh{
Mtji$a\wOt[o{ThJ{'b,
{3| 74 K|GJsrpxK>tdctfiji$
t?bq} }}flq{ToM\qMTAb{
wZXaOsUK{%wp=S srwDoqUI
VoMU| T px| fit%w9Sqs
M9SwotoMflqMOsQ|\t0os (4.22)
&;by
d Q T dS (4.41)
q{X\qUpVh|s (4.13) qoYtO\qUKTsM{
g=wJ{srp\wwstZqlhqVtx|\wMZoM{
wJ{w|t\OhqwMUqmOtO{Abtb
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5
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5.1
(0) y S(U, V )
yyyHOyyyy d Q = dU d W
yyy T, P U7sji!=y d W = P dV, dQ = T dS
yyy\wy T dS = dU +P dV yyyyyyyyyyyyyyyyyy (5.1)
\ww\qfiHOflq{MoKJ{KU|YtxfOpxsX|
\x6pKw[pK{HOx|KXpp
`hfiw-flflbwHw\qpK{xDo$
swqqMOTC_^hU|Mlh6qo[ôQy|
qx`tw7toM%w!:;Moflb\qUpV{bs
j|$SxpKlhT| (U, V ) q!:qbqV

1 P S 1 S P
dS = dU + dV = , = (5.2)
T T U V T V U T
(1) y U(S, V )
otq!:qQy| (5.1) x

U U
dU = T dS P dV =T , = P (5.3)
S V V S
(2) y H(S, P ) y
H = U + P V q| (S, P ) q!:qby| dH = dU + P dV + V dP

H H
dH = T dS + V dP =T , =V (5.4)
S P P S
(LeGendre) yq!: (x, y) w:| L(x, y) UKlo|fw
dL = X(x, y)dx + Y (x, y)dy (5.5)
U)QoMqb{\wqV|q!: x T:pK X |bsj

L
X(x, y) = , dX = Lxx dx + Lxy dy (5.6)
x y
37
38 5 :
tQq| x x\po (X, y) w ( ) :iT

x x 1 Lxy
dx = dX + dy (= dX dy) (5.7)
X y y X Lxx Lxx
hUlo
x
x

dL = Xdx + Y dy = X dX + dy + Y dy
X y y X
x

x
= X dX + X + Y dy
X y y X
X L
xy
= dX + X + Y dy (5.8)
Lxx Lxx
qs|\wp:x?q_wqMvsoMo|qOoMMwtxss
M{\wqV|H!:wMht
yy L = L xX yyyyyyyy (5.9)
qQoQy| dL = dL xdX Xdx ;Mo

L L
dL = xdX + Y (x(X, y), y)dy = x , =Y (5.10)
X y y X
q|tblVhtb\qUpV{
(3) (Helmholtz) y (S, V ) (T, V ) , F = U T S

F F
dF = SdT P dV = S , = P (5.11)
T V V T
(4) (Gibbs) y (S, V ) (T, P ) , G = U T S + P V

G G
dG = SdT + V dP = S , =V (5.12)
T P P T
y9S T UwqV dT = 0 | dF = P dV = d W p
K{bsj| U = F + T S q{MhqV| F x9SwE<pq
oZb\qUDs| s|\t0o T S x9Sbht
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yyy
A B
bsj|6U)Qy> F UKlo|6U AT B p!=bqV
s9%UT!Zqy W (A B) = F (B) F (A) (5.13)
!=t0o|\
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5.2. 39
qfl|
yyy
F
m|U}q%%tSZtbqo^hwq
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pK{ M\wx|tmMo{Mh
ppVo| fi}qflfis9flt| U F toThiZpK{
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$txp^cttnZ\qUDpK

F (F/T )
U = F + TS = F T = T 2 (5.15)
T V T V

G (G/T )
H = G + TS = G T = T 2
(5.16)
T P T P
tmMox p.83{\xw-pb;^w-B {
5.2
1 2 p~hOt|!:w
dL = A(x, y, ...)dx + B(x, y, ...)dy + ..... (5.17)
UpKhwAEx
A B 2L
= = etc. (5.18)
y x xy
pK{ ow0tmMoAebyAGE\p[^hmw
: TloM6T[^hOb: wt&;b

T P
(1) dU = T dS P dV = yyyyyyyyyy (5.19)
V S S V

T V
(2) dH = T dS + V dP = (5.20)
P S S P

S P
(3) dF = SdT P dV = (5.21)
V T T V

S V
(4) dG = SdT + V dP = (5.22)
P T T P
\ (Maxwell) qMO{t<wmx|%UXh
6M V = V (T, P ) UTy-pVtsloS|;pK{
MU)Qhh|$SUnloOqQoxssM{
wmmx|X_qH!:wwpKlo|>ofgww
40 5 :
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mr`pp)QqMO\qxtQTsM{j&dy|
xfwwpf<wwpsX|ctcqMO\qi{
g>.wwO dU = T dS P dV

U S
= T P
V T V T

P 2 (P/T )
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T V T V
hUlo|6MU|wOUfOpKOt V = f (P/T ) w
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U
yyywOy = 0 yyyyy
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zw)|ht CP > CV pK\q{
U
V
CP CV = +P
V T T P

S V
= T
V T T P

P V
= T
T V T P

P V 2 T V 2
= T = (> 0) (5.24)
V T T P
y{..w|uzwx|>.wqs.ut-mV
0+wr`SpKlo`pVsMh|pK{\\ph
Qy|jg$txyz|r`p|s9yVpqMOz$w0stl
o)Q\qts{ > 0 tmMox 6.2 w| p.54
zwflq

S
CV = [d Q/dT ]dV =0 = [T dS/dT ]dV =0 = T (5.25)
T V

S
CP = [d Q/dT ]dP =0 = [T dS/dT ]dP =0 = T (5.26)
T P
Qy
CV S S P 2P
=T =T =T =T
VT V T T V T T T 2
g>.xjpKU|y P U9S T ww| P = f1 (V )T + f2 (V ) w
pKy|z CV x9SiZp>\qts{
5.3. -fiL 41
5.3 -
fi -wg 3.5x| fito.u!=
^dhq\|9SU!sTlhflbsj|$tx

T
=0 (5.27)
V U
OqhwqtQ{\x 1.2 w (5) p.6ph (ii) &;o

T V U
= 1 (5.28)
V U U T T V
S|| (i) (V /U)T = 1/(U/V )T |h (U/T )V = CV

T U P P T
= CV = P T CV = (5.29)
V U V T T V CV
qs|wtg>.pxpK{ = (P/T )V xy:Ts
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1 w>.UMTM!lhqVt>.U!Zhx| y P1 p.u V1
iZ!|y P2 p.u V2 iZ!lhwpKT
P1 V1 P2 V2 ( = U2 U1 (5.30)
pK|!=iT\Uw!= U2 U1 tsM{hUlo
U1 + P1 V1 = U2 + P2 V2 H1 = H2 (5.31)
qs|\w!=x pK{hUlo|hwx
wEpy!QhqVw9S!=

T
= (5.32)
P H
42 5 :
pK{\ -qMO{wq7to

T P H
= 1 (5.33)
P H H T T P
V

T H
= CP = T V CP (5.34)
P H P T T P
hUlo
V (T 1)
:yy = yyyyy (5.35)
CP
wU{ = V 1 (V /T )P xr`pg>.px = 0 pKU|O

>.tmMoxwAL|t9px > 0|9p < 0 qs\qUTlh{
wU!9S qMM|Qy+p 200K SpK{ > 0w
| P < 0 wqV T < 0 iT
\ -qMM|o89SUz$M||
E8sr;Moflsrwktb;ôM{
y yg>.ws!=tSZ!={{
dH = T dS +V dP = 0 | dS = (V /T )dP = R(dP/P )|hUlo S = R log(P2 /P1 )
-axfiji$fl!=tTTcUQoM\q
t{ p.36
5.4
srppVh.w9S[q|9SUUtmz|zTz|
|+| }}}qCbOts{\ qMO{Rbw
U?vqslo?UL^wpK{oww?u)hUl
oLpV 1
g$s. qMM|\tL qMO{ 19 HD
w|qZtSMo.w\U$t|9wCw
A{tPlo]tZU| 20 HDst\ZbtqMO|qE
JOAsxhhqpK{
y tK@wXqxlpK {\x|TlhU@wpZS
ô6|ZoR\qUpVc|owUu)ôOTpK{KMxMl
1
Squ)xXjwpK{Tw?ou)pV.xSppK{S
pxwp;Mo|TqVqTZqVqpx|tap{
Z{hUloSpw.x|TZoM\Oqbow?flpoSb\qsX
TlotLb\qUpV{
5.4. L>. 43
YswTyqapUU_QfOi { wty
hwU|KZp._doOqMoaw+h^h{
+tZh^s@TMohU?_QsM fO|?_QsM{fU.
i{ Fxtw^wr\TtGpwyloMqMO\UZoX{
waDiqloMhU_mTsXslolh{ rO|v^
ilhOi{ pws8txfOMOqEgwgUloMhwi{
\wwK+oMXq|Sxoww?LpVOts{
f\p|ta\h?KMxw>.Q|f\tZh
^s@TZoX>..LwEgq| qMO{
ô|9S T w+ppVhtfia\hfl?w$Qoo
O{x|?xa\\qxpVc|+wfljwKT
TloL^{mw>.qxs|+www:xtx-h
c|.uUpKlofwSo.uKhww:x9Stlos
{TsU\wfi>.flqMOQx|tslo (Planck) w
>|Mp (Einstein) wUZôsogrÔtsl
hwpK{ 19 HDtxKXpw.pK?w$Qqo
y (a) Sx9SiZp> U/V = u(T )

y (b) yLy9SiZp>y P = u/3 y>.px P = 2u/3
wmwUoMh{ ?x?~wpKlo||tu)
KMxTL^MtxfwSqoLySb{

U S P T du u
=T P =T P = (5.36)
V T V T T V 3 dT 3
M

U U
= =u (5.37)
V T V
du dT
=4 (5.38)
u T
%wuo
log u = constant + 4 log T u = T 4 , CV = 4T 3(o.uph ) (5.39)
xz:qs{0+w^s@KMx9S T w.wflTo
~ouKhtL^vxS u tzz:
xS c qbq c/4 pKU|\wxxApxsM 9.3|
c
K = u = T 4 (5.40)
4
44 5 :
\ - (Stefan-Boltzmann) qMO{z: x
-:qzy|gty
= 5.67 108 [W/m2 K4 ] (5.41)
pK{ W xpw\xtwt
2 5 kB 4
= (5.42)
15c2 h3
pK\qUg$tTh{hi| kB = R/NA x:| h x

:pK{
|
T 4
4 3 4T 4
T dS = dU + P dV = d(T V ) + dV = 4T V dT + dV (5.43)
3 3
hUlo
4T 3 4T 3 V
dS = 4T 2 V dT + dV = d (5.44)
3 3
S .u V tzbT|\
4T 3 V T 4 V
S= , 7to F = U TS = (5.45)
3 3
qs{
y 1 yw*U 10mm|Û 1m w?t?vvZotahqV|?

U 2.5kW p?w9SU 1450K pKlh{\T -:{o
{?xlbYtyoSV|L^h?U6|?tu)^\qxsMq
QyM{qOMoM?wOt|?fl|KMxOflt
oSZy|?U!iOT
y 2 y Ewfl9Sx|Sf 5800K pK{ E -wm D x EwR R wS

f 200 pKqby|flp Et(tThu 1m2 w E?U 1 t!Z
Lx?XMtsT
y yxup EL!Z|xt0oflupLlo
)UloMqby|wSfwfl9SAb\qUpV{
wR 6400km qo-o{ Mtx>tAoMoSf 30%x
SôfltTsM|hTwzxatXM swEwq
o9SU>loM{MctdGw H2 O U.pOb 10 qs{
5.5. $s% 45
5.5
\\pxji$sqo|yt.u!=POiZQoVhU|
w0qs%x|jfiZpxsM{MXmT[oS\O{
(1)Q.
wjU>wtloS|Tw
tloTb\qt=o|wtqswUK{TTloM
wMt=\aQ.qMO{u A|^ l|.u V = Al wQ.
toKhwV: n wV|?vvb\qp=bqVw
{oO{oKhV: n wt?v J vhqVtw
tpVw^x| H = nJ p)Q{S B| = AB q
o|?voMXqVt\a I?x
d dB

= nl = nV (5.46)
dt dt
\woI?wq?Y dq(= Jdt) !wtAbx
dB
(
)Jdt = n(Jdt)V = V HdB (5.47)
dt
qs{pxo.uKhQ\qt| V = 1 qb{\wwtx|
wUpKloQwSwC
2
0H
d = 0 HdH (5.48)
2
UoMT|o.uwQ.U!Zx\o
d W = HdB 0 HdH = Hd(B 0 H) = HdM (5.49)
qs{\\p M = B 0 H x=SpK{hUlo
yyy dU = T dS + HdM
yyy dF = SdT + HdM
yyy dG = SdT MdH yyy\w F q G UotoM\qK
qs{xaG H lolhhth{wt0 b
x

S H S M
= , = (5.50)
M T T M H T T H
pK{\;Mq

U S H (H/T )
=T + H = T + H = T 2 (5.51)
M T M T T M T M
46 5 :
fi6MflU M = f (H/T ) wpKy| fix9SiZp>fl

\qts{M|Q.px9p (Curie)
C
M = 0 (T )H , =p 0 = (5.52)
T
C x':URqm\qUoM{MygQ.pK{h
S S

M

T dS = T dT + dH = CH dT + T dH (5.53)
T H H T T H
T|!= dS = 0px

T M
yy = CH (5.54)
H S T H
\b;by| (M/T )H < 0w'OpxfOpKw
\ qMM|Q.fwww9S<[ofw9Q$p|
g=pXb;ôM{
(2)Q
wÛ x wqVXÙ f pKqb{\wqV dx iZVybwt
Abx f dx pKT
dU = T dS + f dx , dF = SdT + f dx (5.55)
x
f S
= (5.56)
T x x T
pK{` f xcfiw|fltzsMU|9SS|^wKcp<w
QloM\qUoM{
yy (a) `x^ x qqtGby (f /x)T > 0
yy (b) `x9Stzbyyyyy f /T = (l) > 0
\wqV|g>.wq7to|

U S f (f /T )
=T + f = T + f = T 2
=0 (5.57)
x T x T T x T x
bsj| {ôpK{xws
Mg>.waswpKU|9St-loMtx|Ts^
hxwnhbiZp|w!=txssM{bs
j| T = wqV| dS = d W/T {otUGbqVxtTloY
wb{\wflpfiQx$sflqtO\qUK{^t

T x f
= 1 (5.58)
x f f T T x
5.5. $s% 47

T f f
= <0 (5.59)
x f x T T x
bsj| 7to

T S S f S T
= = = >0 (5.60)
x S x T T x T x T x Cx
bsj| zxtYpK{
wwtfiwtXQ|pqyoSMombq|U
hXswUTflq{MoKlh{^lfXgohU|xvhUw*M
oMiZp|9S!=xTsTlh{qwqTtxhwi{Vlq
(3)fl`
sKMxawswtx|upViZ^X
OqbUX{+#>PUtsOqbjpK{tTh>
$swwUVOo^Khw (:qMO{fl`
xwOsQqjUlo|w!wSMtxc|9SiZp>
\qUoM{
y\x|fl`w\at{Qya
wUb| 7 p{OOt ...
... F (, T )
wSw:qoZy$wOts| ...
... ..
wSxmw:Ytxw:p)
... ..
.
... ..
... .. .. . ..
Q{Xw]X,MciZxSU7px ... .... .... .
... ...... ....... ..
.
sX|Us\qqSwflU .......................... ... ..
.. ................
................. ..
................... ..
Kh|UObq\wiZU ..
..
..
.
.......
.
.....
..
.
.. ..
Xs{\Ufl`w\ajpK{\wa ..
..
.
..
..
.
..............................................................................................................................................
.
xiZthwutz 1 2
|ouKhpxwutxsM{
fl` (T ) qbq|uU dA QqVts^hx d W = dA pK{

F
dF = SdT + (T )dA , = (T ) (5.61)
A T
x.wutzbT F/A = (F/A)T = (T ) qs|
fl` (T ) = F/A = ouKhw (5.62)
pK{w6x| dF = SdT + dA| U = F + T S

F d S d
S= = A , = (5.63)
T A dT A dT
d
U d
U = F + TS = A T , = (T ) T (5.64)
dT A dT
qs{
48 5 :
5.6
(1) y P V = f (T )
(2) y (U/V )T = 0
y \wOhbwx f (T ) T wwqViZpK{
(3) (Dalton) yfg {ni } wg>.TR>.w|
Dp$s~pmôMhqVx|>.tmMo
P Vi = ni RT (5.65)
URqloMhqb{\wqV~Mo.w.u-lhbs

j V = i Vio9Sqyx!qMOgUoM{fObq

g>. y PV = P Vi = ni RT = nRT hi n= ni (5.66)
i i i
bsj|w>.w>.Qy>pK\qdc|:;
Mom.>.wOt{loMqMO\qts{>. Uop.u V h q
hqVwy| Pi = ni RT /V qMO{\wqV
ni RT Pi
V = Vi = = V , P = Pi (5.67)
i i P i P i
bsj| P Pi qMO(bs_MUDpK{
(4)
T
dU
CV (T ) = yy U(T ) = U0 + CV (T )dT (5.68)
dT T0
T
dH
CP (T ) = yy H(T ) = H0 + CP (T )dT (5.69)
dT T0
T
S CP (T )
CP (T ) = T yy S(T, P ) = S0 (P ) + dT (5.70)
T P T0 T

S V R P
yhy = = , loy S0 (P ) = S0 R log (5.71)
P T T P P P0
T
P CP (T )
S(T, P ) = S0 R log + dT (5.72)
P0 T0 T
7to T
V CV (T )
S(T, V ) = S0 + R log + dT (5.73)
V0 T0 T
G(T, P ) = H T S
T T
P CP (T )
= H 0 T S0 + CP (T )dT + RT log T dT (5.74)
T0 P0 T0 T
5.7. flwMO 49
5.7
tZoXlTMs -tqlo(bsMOUK{ n !:w: nx
w
ui(x1 , x2 , ...., xn ) (i = 1, 2, ..., n) (5.75)
t0o| (Jacobian) qzy<p[b{ det x
(u1 , u2 , ..., un ) u
i
= det (5.76)
(x1 , x2 , ..., xn ) xj
{ui /uj } x| ui /uj ij-Rqbflb{\wqV<wU;pK{
[p!: {ui} U {yi } po {xi } w:pKqV

(u1 , u2 , ..., un ) (u1 , u2, ..., un ) (y1 , y2, ..., yn )
= (5.77)
(x1 , x2 , ..., xn ) (y1 , y2, ..., yn ) (x1 , x2 , ..., xn )
yyyybsj|wqVqaOt UDqMO\qpK{
ui n
ui yk
= yywuqa
xj k=1 yk xj
h|wmwYM A, B t0o
det(AB) = (detA)(detB) yyyyyyyyyy
qwy: u = u(x, y, z, ...) U)QhqV

u (u, y, z, ...)
w y = yyyy (5.78)
x y,z,... (x, y, z, ...)
u1 = u, u2 = y, u3 = z, ..., x1 = x, x2 = y, x3 = z, ... qbyflx

u/x u/y u/z ........ ........ ........

0 1 0 0 0 .....

0 0 1 0 0 ..... u
=

0 0 0 1 0 ..... x

0 0 0 0 1 .....

..... ..... ..... ..... ..... .....
yyVpqs9yVpwz 3 4 wtZoVhw p.17

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

(V, S) (P, S) S S CV
= = =
(V, T ) (P, T ) T V T P CP
6
$%|E!Qsrt`g6TVmdy|%xM
6tTlo!=b{ 5 phOtHOtM6!:U^|!
:wwMXmTwOAsC_b\qUpVhU|HOxqq!=wMQ)
QwpK{\Fbs;Mo|7sE<pw6wE{
\qUpV{bptpt;MoVhU|QyzxcYpsZyssMqb
wx\wEtMvpK{
6.1
4.8 pHOw$sflqqo|ws
d Q
dS (6.1)
Text
h{ Text x d Q lhwow9SpK{\!b\qt|^
_sE<pwflqU{
(1) yrS d Q = 0 pKT
dS 0 (6.2)
ô| 6xH 2 phOt%p f!=sM 4`w6p

Klh{hUlo|%w6x|U7Gfw*w6tz
oGw6psZyssM{fOpsZy|iMt!=UIV\qU
DpKTpK{bsj
S = (6.3)
t|HO d Q = dU d W ;Mo (6.1) {VQy

dU d W
dS (6.4)
Text
(2) pxsMy dS = 0 px dU dW qs
y (2-1)s Qyu!= d W = P dV = 0px
MtIV!=y dU 0 (6.5)
yyyhUlo
U = (6.6)
50
6.2. Eq$Q 51
(3) y Text = T wowts (6.4) &;o
dU d W T dS hx d(U T S) = dF d W (6.7)
d W < 0 wqV\ |d W | |dF | q{Mo

yyy
qflqb\qK{KMx|\wtwU[
^hqQoM{
y (3-1)s9 px dF = 0 iT
d W 0 (6.8)
yji$ d W = P dV tvqVtx|s (6.7) x
dF + P dV = dG V dP 0 (6.9)
y (3-2)s9u!= dT = 0, dV = 0
MtIV!=y dF 0 (6.10)
yyyhUlo
F = (6.11)
y (3-3)s9y!= dT = 0, dP = 0
MtIV!=y dG 0 (6.12)
yyyhUlo
G = (6.13)
6.2
yEUK6w qoFôM|>t?T
wj 1pfw6T6U!=htx|fw6TloMw!=UIVo
i\qUDsh|\w6xpK{\wt|otGtslo
Mhqby|?Twjpf\Tmq|MtIV!=p\w6x
nbh|fw6TrrmoM|\w6xpK{
1
$3W|hxot3WqMO{$t_y|xtloS|6
tSMo%wpw$~xcoMsM{
52 6 EqQ
y y RqxOc\O{MoOMUM{
!:w: f (x1 , x2 , ...) U|: x0 = (x1 0 , x2 0 , ...) pqsEx| x wU x0 T
>t x = (x1 , x2 , ...) iZ!=hqo|\tmMo f 2
f 0 1 2f
0
f = xi + xi xj + ........
i xi 2 i,j xi xj
= (1) f + (2) f + ....... (6.14)
qSMhqV^w 0 x| x0 pwflb
() f =0 , () f >0 (6.15)
pK{j|Gs (2) f < 0 pK{Mtx!:wtxtx?Tw

EUJdoM\qUX|fwwExOvpK{
\\p x x|MtIV!= dx qlo| MtxDpKTsMtT
Tc >t!=hqhqMOMw!=flbwt;MoM{rs
tZoX>wjg $MwE{wt| loMs!=
bxcxsMwt>tfwT!hqh| }}}qwqapK{l
oSysx>UTsMiOt|sqs\qi y dx qxlo|c
`vqxQsMT|ApKyw|w| }}}{X{
y owiZbmw.TR}q%
\w|%wx|fgw ww p)Qq
b{ bsj
S = S1 (U1 , V1 ) + S2 (U2 , V2 ) hi V1 , V2 x: (6.16)
\wqV|Ex

(1)S1 S2 U1 U2
S= U1 + U2 = + =0 (6.17)
U1 V1 U2 V2 T1 T2
hi|.U}q%iT
Ey U1 + U2 = U1 + U2 = 0 (6.18)
UKh|!: U1 , U2 xqpxsX| U1 , U2 x|hqQMw!=qMQr

Utx!=pVsM{hUlo
1 1
(1) S = U1 = 0 (6.19)
T1 T2
w U1 ^MUxpxsX|MXpMtmMo\wsURqmh
tx|:psZyssMT
EEw y T1 = T2 y = T qX (6.20)
6.2. Eq$Q 53
qs|bpt9Sw[qofiHOflqotoVhU
{ \qlsMOsw.%UR^h\qhiZpKlo|\
tHOUThZpxsM\qt{
tGEEx| (6.17) w7wfl;Mo 2

(2) T1 1 2 T2 1
S = (U1 ) + (U2 )2
U1 V1 U2 V2

1 T1 1 T2
= 2 (U1 )2 2 (U2 )2
T1 U1 V1 T2 U2 V2
1 1 1
= 2 + (U1 )2 < 0 (6.21)

T CV 1 CV 2
\\p|7wp T1 = T2 S| U2 = U1 ;Mh{.wdx
pKT|\wsURqmhtxywwUYpsZysc|
()
qMOOAsAUT{M| 5.2 w phs CP CV = T V 2 /q|

w wRpA > 0Kdq|yzo
CP > CV >0
y lXqXDp~.uiZbmw%TR
yyy .usws%
yxji$!=|pxrUC\b{ q7to
U = U1 (S1 , V1 ) + U2 (S2 , V2 ) , V1 + V2 = , S1 , S2 x: (6.22)

U1 U2
(1)
U= V1 + V2 = P1 V1 P2 V2 = (P1 P2 )V1 = 0 (6.23)
V1 S1 V2 S2
Ey P1 = P2

P1 P2
U =
(2)
(V1 )2 (V2 )2
V1 S1 V2 S2
1 1
= ad
+ ad
(V1 )2 > 0 (6.24)
V1 1 V2 2
aiT|flb adiabatic w ad x^t{Mh{ hUlo

2
(6.17) T (6.21) -bMt| Ti 1 (Ui ) wUtsTsM{\x
1 1 1 1
(U1 ) + (U2 ) = (U1 + U2 ) = [(U1 + U2 )] = 0
T1 T2 T T
qs|sXoM{
54 6 EqQ
()
y7to|9Sp.uiZqbmw%wE F Ts9yV
p > 0 b\qUpV{\q| 3.4 w hx 5.7 w phs ad / = CV /CP |
S|wphA CP > CV Kdy|<wU^{ 3.4| p.17
> ad >0
yVpUpKOsAtZqlhtx|fxqDs|\`$s
6iqtsZyssMwpK{Mt|g$tTh6Mtx|f
wOsU\qUK{ 7.3 6M
y 2 E ym.sw 2 |Qyq>Uah0+wpb
QO{0+wErO)QTtlo|MXmTwQMURqm{
(3-1) .qo.uw0+
~u
yw: n1 , n2 |Kh w!:| .....................................................................................................................................................
...
... ............................................................................................................................... ....
..
... ... . . . . . . . . . . . . . . . . ... ...
(U1 , V1 , S1 ), (U2 , V2 , S2 ) qbq ... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ....
... .... . . . . . . . . . . . . . . . ..... ...
... ... . . . . . . . . . . . . . . . . .. ...
... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ....
... .... . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . ... ...
... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... ....
... .... . . . . . . . . . . . . . . . ... ...
S = n1 S1 (U1 , V1 ) + n2 S2 (U2 , V2 ) (6.25) ... ... . . . . . . . . . . . . . . . . ... ...
... .... . . . . . . . . . . . . . . . ..... ...
... ... . . . . . . . . . . . . . . . . .. ...
n2
... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ....
n1 n1 P1 ... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ....

(1) S = S1 n1 + U1 + V1 ... .... . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . ... ...
.... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... ....
T1 T1 .. ........................................................................................................................................................ ...
... .......................................................................................................................................................................................................... ...
... .......................................................................................................................................................................................................... ....
n2 n2 P2 .... ........................................................................................................................................................................................................................................................ ...
.. ............................................................................................................................................................ ...
+ S2 n2 + U2 + V2 (6.26) ... .......................................................................................................................................................................................................... ....
n1
... ........................................................................................................................................................................................................................................................ ...
T2 T2 ... ........................................................................................................................................................................................................... ....
... ........................................................................................................................................................................................................... ...
... ......................................................................................................................................................................................................... ...
... ............................................................................................................................................................................................................................................... ....
... ..
.......................................................................................................................................................
Gw 6 xwq!: (n1 , U1 , V1 ), (n2 , U2 , V2 ) t0o|
3 mwE
y 1) n1 + n2 = yyyy n2 = n1
y 2) n1 U1 + n2 U2 = yy n2 U2 = n1 U1 (U1 U2 )n1
y 3) n1 V1 + n2 V2 = yy n2 V2 = n1 V1 (V1 V2 )n1
UKhSx 3 pK{M|\sEo
1 1 P P2
1
(1) S = n1 U1 + n1 V1
T1 T2 T1 T2
U1 + P1 V1 U2 + P2 V2
+ S1 S2 n1 = 0 (6.27)
T1 T2
U1 , V1 , n1 w 3 mxqpiT
y 2 Ey T1 = T2 , P1 = P2 , G1 = G2Kh
7wEx| G = U + P V T S w[;Mo{VQh{EtMoxt
b{ EUvs\wtmMox| 5.5 wwMOpOS{O{f\p
6.2. Eq$Q 55
xlqotGwAX\qUpV{
(3-2) .qo.uws90+ T =
s9~u
.....................................................................................................................................................
...
yw: n1 , n2 |Kh w!:|
..
... .................................................................................................................................... ....
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dx
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VoMsMqVtx|-t|K dx t
udx w!=x| dx wzpwvwZw)iZp>T
d du djq d2 T
(udx) = jq (x) jq (x + dx) yy = = 2 (6.36)
dt dt dx dx
p)Q{hUlo|$t6tsloMtx jq = qs
d2 T
=0 T = c1 x + c2 (6.37)
dx2
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58 6 EqQ
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jx jy jz
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S1 (T, P ) = S2 (T, P ) , V1 (T, P ) = V2 (T, P ) (7.17)
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M = f (T, H + M) (7.19)
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1 0
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T
CH
f (T, H) = tanh (7.23)
T
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T 1+M
H= log M (7.24)
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M C(1 M 2 ) C
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\;My
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TC 2TC 1M
T 1+M
C= (H = 0)y = 2M log yyyyyy (7.26)
TC 1M
7.4. 8 71

M C
=p y = y (T TC ) yyyyyy (7.27)
H H=0 2(TC T )

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v: y M = 1 yyyyyyyy (7.28)
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T P P T T

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dT 1 2
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3R 9R[4T V 3 TC VC (3V VC )2 ]
dP = dT dV (7.36)
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72 7 q8

1 V 4V 2 (3V VC )
= = (7.37)
V T P 3[4T V 3 TC VC (3V VC )2 ]

1 V 4V 2 (3V VC )
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t TC
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2 2
t < 0 px
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S = S0 (T ) + R log 2VC + log(1 9|t|) (7.47)
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4
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7.5
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yy
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lim S1 (T, P1 ) = lim S2 (T, P2 ) (7.51)
T 0 T 0
pK{ (Nernst) \wUvpKy|\w,

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0 T 0 T
74 7 q8
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(3) y:x 0 tnX limT 0 = 0

T
P S
=
T V V T
h T
S
S(T, V ) = dT
0 T V
\T
(T ) T T 2S T T 2
P S S P
= dT = dT = dT = dT
T V V 0 T V 0 V T 0 T V 0 T 2

P T P (T ) P (T =0)
= =
T 0 T V T V
sr{
8
\\px|%Rbw:xqoVh{\ qMO{m.
%pxw\qUTyGp|:xOAsflmpxsM{TsU
tx|MtqwtwqUK |sw=S w
Ot%wpwqUK|^t%wsrpx|:{
:wzUfllhOAs!:ts{
8.1
\ptZoVh6!:x
yyy!: T, P
yyy!:ObO @!: V, U, H, S, F,: n hx{: N
pK{m.%wg=$Qx (T, P ) )Qy>|.wtxsM{\
wqV|!:wwqS
V (T, P, n) = nV (T, P, 1) , U(T, P, n) = nU(T, P, 1) etc. (8.1)
URqm{\%w 1 qMO{\t0o|!:Qy (S, P ) tqlh
V (S, P, n) = nV (S, P, 1) yy\w| = nV (S/n, P, 1) pK (8.2)

qsOt|COQ^btx!: (T, P ) q!:qo;MwUj(
bpK{ (T, P ) q!:tbt7?s{VMUpVwx|
G(T, P ) pKlh{bsj
COQy G(T, P, n) = nG(T, P, 1) (8.3)
n htq!:qo
dG = SdT + V dP + dn (8.4)
bsj|: n tmMow :

G
(T, P ) = ( = G(T, P, 1) ) (8.5)
n T,P
qMO{COQwE (8.3) | dG = nd + dn iT| (8.4) qz

o
SdT + V dP nd = 0 (8.6)
1
\x:xw%px>oRqhsM\qpKlo|cs\qpxsM{x
$%t0b&gqMOV\qUwmpK{
75
76 8 Mh%q%
psZyssM{\ - (Duhem) qMO{Abt|m.%

px :!:qoCQoSxQsM qMO\qfloM{
w!:tmMox|Qy F (T, V, n) = nF (T, V, 1) pKU

F U
= , 7to =
n T,V n S,V
xRqm{
8.2
RU {n1 , n2 , ..., n } w| -R%
G(T, P, n1 , n2 , ..., n ) y (8.7)
QO{\wqVfiH k Rw=fl

G
k = (8.8)
nk T,P, nk
qb{ 4Qw nk x| k Rw:xt-m\qflb{ \ww

COQx|w t0o 2
G(T, P, n1 , n2 , ..., n ) = G(T, P, n1 , n2 , ..., n ) (8.9)
qflbwU(bpK{\wqV|% poT = 1 qSX\qt

G
nk = G yyy G= nk k (8.10)
k=1 nk T,P, nk k=1
qs{\wpsZyssM\qx|RwqVw=U
KhwpKlhOt|KhTRUfg nk
cm|w=j/lhoMU|Rw k x>o
moMhqVwfpxsX|KXpwRwRttxoM
\qpK{Rwq7t

dG = SdT + V dP + k dnk = k dnk + nk dk (8.11)
k=1 k=1 k=1
2
fi p flww|
f
f (x1 , x2 , ...) = p f (x1 , x2 , ...) yy xk =pf
xk
k
URqm{ (Euler)
8.3. wo 77

y y SdT + V dP nk dk = 0 (8.12)
k=1
U{q7t\x|COQqMOg$Et0 b\wUmK
\qt|q!:U ( + 2) nqMO\qfloM{\w\qx
tx| Rz
nk
xk = (8.13)
j nj
;My| wg=$QxSp> k = k (T, P, {xj })|\wSw

txEqomw

xk = 1 (8.14)
k
URqloMh|SxnqMOtMMbMUTbMT
sM{
8.3
-R%tSMo| -wUoMQO{x

G= G(b) (T, P, n1 (b) , n2 (b) , ..., n (b) ) (8.15)
b=1
pK|!:w:x 2 + pK{\t0oEx
yy (1) EyoMw R t0o
k (1) = k (2) = ..... = k () (k = 1, 2, ....., ) (8.16)
yyyyp| ( 1) xwUK{
yy (2) COQEy tSMo -wURqmT

SdT + V dP nk (b) dk (b) = 0 (b = 1, 2, ....., ) (8.17)
k
yyyyw xwUK{
|q!:w:x (2 + ) ( 1) = 2 + |hUlo
f =2 + y 0 (8.18)
{\U w7ospK{
7osm.% = 1w| 3 qs|
yyyyy
y = 1 f = 2 (T, P ) x|Kcpqt)Q\qUpV{
y = 2 f = 1 T = T (P ) hx P = Ps (T ) fiflU>{
y = 3 f = 0:tsloO{bsjfiO:flU>{
78 8 Mh%q%
8.4
R% = 2px| 4 pKU|wmwiZQO{
(1) = 1w f =3
yy\x| (T, P ) tSKc ..
...
.. T
..
...
...
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... ...... ...
yypt!Q\qUDpK\q ...
...
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...
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.
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.
..
.
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n2 n2
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, x = (8.19) ... ..
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x ..
0 x 1
x = x (T, P ) , x = x (T, P ) (8.20) x x

G = (n1 + n2 )G (T, P, x ) + (n1 + n2 )G (T, P, x ) (8.21)
ET|Rw=xpp
1 = 1 (= 1 qSX{ ) , 2 = 2 (= 2 qSX{ ) (8.22)

pwKhwx
G = (1 x )1 (T, P ) + x 2 (T, P ) (8.23)

G = (1 x )1 (T, P ) + x 2 (T, P ) (8.24)
\T ...
...
...
...
...
...
...
...
...
. ...
G G ... ...

...
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...
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= 2 (T, P ) 1 (T, P ) (8.25) ...
...
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x x ...
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.
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... .. .
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G G ..... ... ........... ... ... ....... .... ... ... ....... .... ... ... ....... ... ... ...................... . .
G .... .
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(8.26) ...
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bw:x<wOt ... .. ... ...
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x ..
p> 0 x x x 1
8.5. 79
Rz x qo
n x + n x = (n + n )xyyy n (x x ) = n (x x) (8.27)
\wqV|w:wpx|:pKwwM
U|c|McwowwfXs{bsj
G = n G (T, P, x ) + n G (T, P, x ) (n + n ) min{G (x), G (x)} (8.28)
8.5
0+wpwg>. A,B t^dhqV|c_MpKl

oowqx>oI\sM{hUlo\wapx|wZxj
sMtTTc| xQoMxc pK{\w{o
O{
7sxw>.x~oMo|9Sqyxp (T, P )|:q.uUf
g (n1 , V1 ) q (n2 , V2 ) pKlhqb{wO 5.6t|
a9Sqyts{f\ptlo|!=-bht|a4
6tXwsji$!=b{
i) ct.u V1 + V2 p|ji$s9r`^dy\wqV|!=
x
P dV ni RdV
T dS = P dV yyyy dS = = (i = 1, 2) (8.29)
T V
hUlo
V1 + V2 n1 + n2
Si = ni R log = ni R log = ni R log xi (8.30)
Vi ni
MKdo
S = R(n1 log x1 + n2 log x2 ) (8.31)
ii) t<wOsfifl^|ji$a dS = 0p!
yMtx>. A( ) iZb\qwpVR|Mtx B iZbRU

òM{\w|RwQtwMUqoMh|lX
q!wtAqsM{hUlo| d Q = d W = 0 iT dU = 0 qs|
!i9Sx!loSc|yx P pK|a46qpV{
80 8 Mh%q%
..........................................................................................................................................................................................................................................................................................................................................................................................................................................
.... .. ........ . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .......................................................................... .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . ....
................................................... .A . . . . . . . . . . . ................................................... . . . . . . . . . . . . . . . . . . .
.... . . . . . . . . . . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..........................................................................A ...................... . . . . . . . . . . . . . . . . . . ..
.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................ .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..... ....................... xA

.. .... .... . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . .
.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....................................................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . ...
.... .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .. . .........................................................................B ........................... . . . . . . . . . . . . . . . ............................................. .
... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .....................................................................................................................................................................................................................................................................B . . . . . . ..
......................................
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A iZbR ......
...
.
... B iZbR
......
.
t|aowCx i) tSZ S iZpK| S > 0

pK{t:w>.TR>.wx|R {ni }|S xi =

ni / j nj qo 3

S = R ni log xi (8.32)
i
\ qMO{w$~x<p)Q

S= nk [ Sk0 R log xk ] , U = nk Uk0 , H = nk Hk0 (8.33)
k k k

G = H TS = nk [ Hk0 T Sk0 + RT log xk ]
k

= nk [G0k + RT log xk ] (8.34)
k
fg^t 0 Zhx|opObqVwKhw6pK{\
T 4
G
y k = = 0k + RT log xk yyy (8.35)
nk
{\\p| G0k q 0k xawpK{\wflU<pOAsLhb{
yw (8.32) X_q|RwRz
pMiZp|fgw>.b srx?oMsM{hUlo|dl
TXo-hwtfix~p~oMhwxa>.ilhi{]^fl
3
S > 0bwxM\qpxsM{otfi xi < 1 iTflp4{
4
\x|COQwAetpw<ApKlhtTTc| G wflw [...] ww xj = nj / l nl w
w nk <toMtmMoww\qU>tsUM{\x<wOto
QTsM{ log xj = log nj log( l nl )

log xj /nk = jk /nk 1/ nl (jk = 1 if j = k , jk = 0 otherwise)
l

y nj ( log xj /nk ) = 1 nj / nl = 1 1 = 0
j j l
8.6. >.S ^;wO 81
qMOp&;DsoS|\wp S > 0 )Q{M|9S T qy

P Usw>.xeKdo?I\c|$Qx!sM\gCO
Q T| S = 0 wxcpK{wZwapfiRfl;MoK|w>.w
x\wwUHoOU|fwOsMTUMw;MctaALX
\qUpVsMwTrOTxTpxsM{h|w)U$pKlo`vw)Ts
Mw>.wvpx|rjwAUYMwiOT KUhM\qtw0
tsj~wHpx|{w)xiqMQrxlVq'xhx:x
wqMOvs)loS|>otxOoMsM{ \wOt
x|tUCqA|mMoMXQoMqtQ{
8.6
\\pRq|xot4$sqt!oSXAxsM{
;MMUÛtots{
=S t)bR|S tlopV\Rbo>.pKOs=
S QO{QyXh
yyyyyyyS y 2H2 O2
2H2 O
pK{\w|%x+||+'w>.pKU|Rw:US
tlo!=b{hi|Rw:wtx|S tlo>EU
K{QywS px| +~~+w:!=x pK{
w=S

i Xi
j Xj
i j
q{\O{Rwt{T: {i } xosT:ts\qUoS|\
wstslhpK{\\px %tZoX: qo{O
\qtb{\wqV|Rw: {nk } w!=wtx| fi%pxflqMO
wpo
n1 : n2 : ...... = 1 : 2 : ....... (8.36)
wEUK{\\p|S wiSM flbM!: b{My

S wVYwMq_Oswfi2flpK{\;MyS t
Ex
nk = k (8.37)
qflb\qUpV{bsj|S mt0o2 wSUm)Qi

ZpK{
y)Qh (T, P ) wqpS U|RzUwtao!=
UIVsXslh6 qMO{\wwEx|S t{:
82 8 Mh%q%
:w!=t0ofiUflpKT| (8.34)| (8.35) S|

E (8.37) ;Mo

G = 0k (T, P ) + RT log xk nk
k

= k 0k (T, P ) + RT log xk = 0 (8.38)

k
pK{ xpKT| [.....] = 0 qs|S mt0o\wOsE

Um)Q\qts{ 5
E (8.38) {Vdy
1
k log xk = k 0k (T, P ) (8.39)
k RT k
KMx

xk k = K(T, P ) (8.40)
k
qs{\ qMO{\\p
1
K(T, P ) = exp k 0k (T, P ) (8.41)

RT k
qMM|S tlo> (T, P ) w:pK{=px|QywfiS
flw|R Xk wRz xk Xk wOtflqo
[H2 ]2 [O2 ]
= K(T, P ) (8.42)
[H2 O]2
q{X\qUK{S q\RwRzx|\whbOtspS U
ptabqMO\qts{\pTOt|S Vtb
tx| S rr|\RdldqbqMOKhQw\q
yM{
-y: K(T, P ) w (T, P ) Q\qt|
$Ew!=t6hUloRzUrwOt!T\qU
pV{\w$tx0:fl
1
log K(T, P ) = k 0k (T, P ) (8.43)
RT k
5
\\p [.....]

k 0k (T, P ) + RT log xk = A
k
qSMo qz\qUK{S UMXmbtxfb4QZ

\qtbq|=S UKwwx

dG = SdT + V dP Aa da
a
qs{bsj|=US 2 t0bfiflpK{
8.7. 1,9 83
;MwU(bpK{
1)yQ

log K 1 0k
= k (8.44)
P T RT k P T
0k xKhwiT (0k /P )T = V = RT /P |hUlo

log K
= ( k )/P (8.45)
P T k

qs{\\p ( k k ) xS Ufi = 1fliqVw:wCpK{
QyS pxfi 2+1=3 T 2 U\R^flwp|hUlo Kx Pw
n:pK{\wqV P GVXbq K x^XsT|S \Rw
RznbM|bsjS UpMtab\qts{\x
:nbM|bsjynbMpK{hUlo
yy
qtQ{
2)9SQ

log K 1 (0k /T ) 1
= k = k Hk0 (8.46)
T P R k T P RT 2 k
\\p| 5.1 w -w;M|RwKhw

h{

k Hk0 = Q (8.47)
k
x|syEwqpS Ufi = 1fliqVwwn|

hUloC\b pK{ Q > 0 wqVxCS | Q < 0 wqVxuS pK
{ Q > 0 wqVx| K x T wC:pK|9S[q: K UGVXs
|S U(p|bsjuwMphstab{hUlo
yy
qtQ{
\wOt
yy
\qts{\ (le Chatrier)- (Braun) qMO{
8.7
>.w%|Qy1,9wt|^s\qt>.w
wfl ;b\qUDpK{
84 8 Mh%q%
1,9w|yW$tMM9|M9qMO{fgw: n1 , n2
qo|\wxS
n2
c= ( 1) (8.48)
n1
q[bwU(bpK{\\ploVhRzx
n2 c
x= = = c(1 c + c2 .....) ( 1) (8.49)
n1 + n2 1+c
pK{
\wqV|Khw.ux
V (T, P, n1 , n2 ) = n1 V (T, P, 1, c)

V c=0
= n1 [V (T, P, 1, 0) + c + .....]
c T,P
= n1 V1 (T, P ) + n2 V2 (T, P ) ( +....) (8.50)
qs| (.....) `bq_TZfiRwflwt{Z{ qMO{

T\wwRwfi.uflx
y V1 (T, P ) = V (T, P, 1, 0)m.s9wKhw.u
y V2 (T, P ) = (V /c)c=0 9ehqVw.uCp
pKlo|xm.s9w.uqxXswglh 1m3
w6wt-{ 1 eo |tloxts\q^QDpK{7t
otmMo
c=0
U
U(T, P, n1 , n2 ) = n1 U1 (T, P ) + n2 U2 (T, P ) + ..., U2 (T, P ) = (8.51)
c T,P
q{Z{\t0ox| c = 0 pQUKh 6
|\wOs2x
pVsM{ U, V t0b2;Mo
dU + P dV n1 (dU1 + P dV1) n2 (dU2 + P dV2 )
dS = = + (8.52)
T T T
q{MhqV\\px=S xQoMsMT n1 , n2 x:pK|H
xTtm.s9wp
n1 (dU1 + P dV1 )
= n1 dS1
T
pK{hUlo|H
dU2 + P dV2 S n1 S1
=d (8.53)
T n2 n2
6
g>.tSMo
S = R(n1 log x1 + n2 log x2 ) = Rn1 [(1 + c) log(1 + c) c log c]
qs| c = 0 px0::wh2pVsM{
8.7. 1,9 85
q{X\qUpVT|?TwwpK{?wTTsMU|qTX
\w S2 q{Xq
dS = n1 dS1 + n2 dS2 (8.54)
q{X\qUpV|uo
S(T, P, n1, n2 ) = n1 S1 (T, P ) + n2 S2 (T, P ) + C(n1 , n2 ) (8.55)

qs{u:x (T, P ) tsMT|MrXq7tfis8Efl
)Q\qt>\qUpV{Qy|y P 0 qby|owx
CoM|g>.tnXT|u:x
C(n1 , n2 ) = R(n1 log x1 + n2 log x2 ) (8.56)

q>{\Oo1,9t>.wUpXwpK{\w
u:xwmtKOt c = 0 p$pK| c tmMo2pVsM{
\;Mqx
G(T, P, n1 , n2 ) = n1 G1 (T, P ) + n2 G2 (T, P ) + RT (n1 log x1 + n2 log x2 ) + ... (8.57)

hUlo
1 = G1 (T, P ) + RT log(1 x) (8.58)
2 = G2 (T, P ) + RT log x (8.59)
q{X\qUpV{\\p G1 (T, P ) xm.s9w= pKU| G2
xfOpxsX|
G2 V2 U2 + P V2
d dP
= dT (8.60)
T T T2
p)Qfi.wsMflpK{ 1 wflqtx|wqVq
7t 9U?pKT flbUloMsM\qoS\O{
(1):
9U4CQw|~>tSMo>x9wwm.>.qs
b\qUpV{\wqVEx|9t0oiZAe^
Gg (T, P ) = Gl (T, P ) + RT log(1 x) (8.61)

pK{\\p| G(T, P, 1, 0) xm.s9w.6wpK
T| Gl (T, P ) lh{)Qhy P wqp Gg (T, P ) = Gl (T, P ) hb9
SU: Tb pKlh{ x 1 wqVx|wshb T x Tb Tfrmox
MsMT| T = T Tb tmMo2o
Gg (T, P ) Gl (T, P )
R log(1 x) =
T T
G Gl
g
T
T T T T
H0 H0
= g 2 l T (8.62)
Tb
86 8 Mh%q%
log(1 x) x iT
RTb 2
T = x ( Lb = Hg0 Hl0 x9w>= ) (8.63)
Lb
qs|9wStzo:Ub{\ qMO{_o
TOt|z:x4CQpK\q9U?pKTtxsM{
(2):<
9q{U|{Um.s9wTRqQoMtx| (1) q
X7to
RTm 2
yy T = x (8.64)
Lm
U{t-vTZq%Zibq|k8wfiwUZAsM
Otbht;ôM=srU\pK{
(3) (Vant Ho) wO
(1) qa%p|9S T U)QoM|7to
P Gg Gl
P
Rx = (Vg Vl ) (8.65)
T P P T
\T
RT
P = x (8.66)
Vg Vl
\ KMx qMO{
(4)y
9q9U|9iZbRpooMqV|9,
Oqb$ $s UV|6px\!&o
mKOhwy)UApK{\ qMO{ 9tTlo
OqbypxsM{
yEx9t0o
G (T, P ) = G (T, P , 1, 0) + RT log(1 x) (8.67) ...........

... ...
..... ....
.
.... ....
.......
... ..................................................................................... ....
...
...........
. .
... .................................. ... ...
.... ...
... ...
... ...
........ P... ................................. ... ...
... ................................. .... ...
.. ................................. .. ..
m.s9w= G |9wm.s ... ... . . . . . . . . . . ... ................................. ... ...
.
... .............................................................................................................................................. .... ....
... ... . . . . . . . . . . . . . . . . . . . . ... ................................. .... ...
... ... . . . . . . . . . . ... ................................ ... ...
G q{MhU|rj
... ... . . . . . . . . . . ... ................................. ... ...
qVw= .... ... . . . . . . . . . . . . . . . . . . . . ... .................................. .... ...
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . . . . . . . . . . . ... ................................. ... ...
.6w9iTXa:pK{\T 9y
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . ... ................................. ... ... 9y
... ... . . . . . . . . . . . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . . . . . . . . . . . ... ................................. ... ...
RT x = G(T, P ) G(T, P + P ) P
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . . . . . . . . . . . ... ................................. ... ...
P
... ... . . . . . . . . . . ... ................................. ... ...
... ... . . . . . . . . . . ... ................................. ... ...
G ..
... ... . . . . . . . . . . . . . . . . . . . . ......................................... ... ...
= P = V1 P (8.68) ... ... . . . . . . . . . . ................................ ... ...
.
............................ R
... ... . . . . . . . . . . . ................................ ... ...
... ... . . . . . . . . . . . . . . . . . . . . . ................................ ... ...
P T ... ... . . . . . . . . . . ................................ .. ...
..
... ... . . . . . . . . . . . ................................ ... ...
... ... . . . . . . . . . . . . . . . . . . . . . ................................ .... ...
...
.
... .......................................................................................................................................................................................... ...
..
..................................................................................................................................................................................
V1 x9w.upK{\T
RT
yy (= P ) = x (8.69)
V1
8.7. 1,9 87
qs{9.w.u V = n1 V1 q9w: n2 = (n1 + n2 )x ;My

V = n2 RT (8.70)
qg>.w6MqatsfiQbM{1,9wp9xMt
^;b\qsX|KhTg>.wOtOmVsloMqQyM{
(5) (Henry) wO
wx|9w=;Mct^pV|9U?pKTts
MqpKlh{9wQtbqmiZ{loSX{
x+t9ThwOt|>x 9w qQoMUK{\w
txEx|9t0o
Gg (T, P ) = G2 (T, P ) + RT log x (8.71)
% P p o
log x
Vg = V2 + RT (8.72)
P T
V2 x>.U9Zh\qt9w.uCppKT| V2 Vg qoX

log x Vg 1
= = yyy x = c(T )P (8.73)
P T RT P
bsj| T P \ww
z: c(T ) x9iZpsX9wt{
( ) ^+>
\x1,9wJpxsMU|;MoaOs{MUpV
wpCoSX{
7.2 p[hOt|:qx)Qhywqpmww>qU
b9SpK|fw9S<pxotsxcpKlh{tTTc|9
p+xC|>txw+>Uwx?pKOT\x|
Gw:w[xfi+qm.s+>wfltloS|>w+>Qq
Vtx|>xfi>q+>w>.flqQsZyssMTpK{
y>x> n1 q+> n2 w
>.|xm.s+qoM| ............
... ..
...........
... ...
.......................................... ............
... ..
..... ....
. P .
. ... ... ...
Ex+t0o ... ... . .
.. ............................................................................................................................................................................................ ....
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. ..
. ..
. ..
. .. ... ... ......... ..
.
.... ............ .... .... .... ...
. ...
. ..
. ..
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.
... ....................................................................................................................................................................................................................... ....
... ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . ... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . .... ...
Gg (T, P ) + RT log x = Gl (T, P ) (8.74) y>
... ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . ... ... n1
... ... . . . . . . . . . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . ... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . .... ...
+
ywOT ... ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . .... ...
... ... . . . . . . . . . . . . . . . . . . . . . . . ... ... +> n2
... .. . . . . . . . . . . . . . . . . . . . . . . . ... ..
.... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... ....
... ................................................................................................................................................................................................................................................................................................ ...
... ......................................................................................................................................................................................................................... ...
n2 P2 ... ....................................................................................................................................................................................................................................................................................................................................................................... ...
x= = (8.75) +
... ................................................................................................................................................................................................................................................................................................. ...
... ................................................................................................................................................................................................................................. ...
... ............................................................................................................................................................................................................................................................................................................................................................... ...
n1 + n2 P ... ......................................................................................................................................................................................................................................................................... ...
... ........................................................................................................................................................................... ...
...................................................................................................................................................................................................
\;Mq|g>.w
wyQ| Gg (T, P ) = Gg (T, P0 )+
RT log(P/P0 ) o
88 8 Mh%q%
P2
Gg (T, P ) + RT log x = Gg (T, P ) + RT log = Gg (T, P2 ) (8.76)
P
pKT|Ex
Gg (T, P2 ) = Gl (T, P ) (8.77)

qs{bsj|y P w.w+q y P2 w+> qwEQyM\
qts{\wh|j>yp:Sf 100 <w9w>t+>U
OpVwpK{
...
...
...
G T given
y9S T wqVw^>y Ps qb{ P > Ps ...
...
...
...
...
wqV|$wOtos (8.77) hby ... Gg
....
...
...
...
... .
P2 {y|ywOt>t ...
...
......
...
...
...
... ..
..
O+>z x = P2 /P U>{\ ...
...
...... .......................................... Gl
...
...
...
...
. . ........................................................
...
.. ...... .........
.......................
...
qMM|\wtahqVU ... ...
... ...
...........................................
... ... ... ...
... .
. . ...
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S 100%w6pK{ot| P < Ps wqVx| ...
...
... .
.
.
.
... ...
...
............
... . ...
... .
.
. .
... ...
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. ... ...
....
P2 > P qsT|+U`XspCo ... ... ..
................................................................................................................................................................................................
P
O{ Ps P2 P
.px.u Vl xqso Gl (T, P ) Gl (T, Ps ) + Vl (P Ps )|>.xg

>.qb\qt|+>wyS|^S{o{
t P2 = Ps exp[Vl (P Ps )/RT ], x2 = (Ps /P ) exp[Vl (P Ps )/RT ]
9
(1) p.6y (1.15) wx7sph|h|ZoXwp|\\pYtg

roSMoIM{Qy U x9S T q.u V U)Qh>
|: U(T, V ) wOtfl^{M|q!:9S T qy P qo
MT|\wqVtx.u V U T q P w:qs|xw:
;My| U(T, V (T, P )) wOt T q P w:qofl^{\wqV Ux
tH!:w T iZpsX|H!:w V po T tbT

U U U V
= +
T P
T V
V T
T P
qs{
(2) p.16y\\xMlhM?loMwTflUTsMqMOUXZ{
qMOx|sXqwqtqoy[xpK{
TsU\Mtp>qth|tlhswpK{ {
:qMOfOpKO{ \\wAL;My| (3.10)

U
= CV
T V
(3.12)
U CP CV
= P
V T
V
hUlo| CV , CP , by|w9S T |.u V QU)
Q|: U(T, V ) UT\qts{
(3) p.17ywqtqoy|%w$tbwx
U pK| U U,$sqMO!ZTsMU|w
\q>tsMtSMox| U q H x6qowx0spK\
qtO{fg.u~yqMOEwqpwwZfl
qb6pK{xEwqpwwZflbp
KlhU|tfi9SflqMOEwqpwwZflbqo|
F qMO^{
(4) p.21ywp_Ot|mwooqk+wpX;wp
x|Ufip7GpK{mMtxqDsg$
;qofipwv)QoM{\\pfipqMOwx|ptQy
fifl|m)Qho;MoriZwUpVTqMO
89
90 9 4
pKlo|fww^xsM{xji$iT
`vtlXqhswpK{KMx;w;wQ
qox|qxtotriZwUpVTsZd
flbfipflOAsApKU|px\JtsM{ fiMM
obvflqfiUMflxqMO\q{
(5) p.27yfig>.psMqxMlhM? iflqMOUKU

\qUK{g>.pxsXObw>.;Mo7p\hwq
Xaji$dhwU|wmpK{\w (4.1) wA
x|g>.wwO;Mo[^h09S;oSZy|O>
.wp (3.34) qas
Q2 T2
=
Q1 T1
URqm\qfloMqgroMiO{wg
;qowQx|>o^qog>.;Mh\qtwpx
sM{
(6) p.32ytSMo| fimw%cm^dox~m|fgp9

SU7tsp4loTa\q&bflqo-xap|QM
opK{TsU|\jx$tqs^fi[wji$a
flpKlo|DopK{
(7) p.40yq7t|\w4w (1) w ;qo V = V (P, T (P, S)) tmMo

V V V T
= +
P S
P T
T P
P S
;My|s9yVp = (1/V )(V /P )T qyVp ad = (1/V )(V /P )S

ww ad = T V /CP X\qpV{KMx
2
CP /CV = /ad
(5.24) t&;o{s > ad xrOMOflmiOT
(8) p.44y S tmMox|x.utzbqQoM\qT

S = s(T )V |hUlo

S P 1 du
s(T ) = = =
V T
T V
3 dT
T{\qpV{ jwsx F tb
(9) p.48 (4):y!:w:wp|ubqV S(T, P )

G(T, P ) pfOoMOt fi!:w:wqX
aOto|c9S T puoTty P tmMouflpMMwTq
91
MOYUIVTsM{ fipKflKMxuUObqx|f
OMO\qswpK{m|K6TwK6p|rwOs&
hrloatVX\qU|pKqMO\qpK{i?>
pZoX-wqwqXxapK{
(10) p.53 yy (6.21) wwpfi.wdxpKTflq

oMU| fi.UapZRoMQyflpM{
(11) p.53 y filXqXDflqMOwx|Qywqwt

GsrUKh`vtlXqTZsMOtoK|qQoI
M{\wfifgw>.xywMUqoMsM|t
toS|K.uiZ!=hwiTh\qtspxsMTfl
qMOYU\aiO{TsU|\\px%pKwqT
_y|wMxôSc|hiUC\hiZswpK{
m\xfi >.w!=stAVZbZflqgrb
yMiO{%pKpxYw!ZlhhUQ
oS|Tt\wM dU < 0tT!=xIVsM{mUQ
\qtUotMo>.t| dU > 0 wMt!=UIV
\qxKsM{\t0ot^hnTQsUTb
tx|qwqU|rjVtp!=xDpK{
(12) p.53 y\qYS0wJKy.u 2V wwt$p

rsttZUp{ôS|tfg.u V p
9S T1 , T2 wg>.U 1 cm loM{hUloyx loMs
M{{xchKqtahqVww{{
J
(13) p.80y (8.35) tSMo|opObqVw=bsj~

x (5.74) t
G0 (T, P ) = G0 (T, P0 ) + RT log P/P0 (P0 x&ps,jy )
q{Z{M| Rz xi xy;My| xi = Pi /P pK\qT|

(8.35) x
k (T, P ) = 0k (T, Pk )
mfiy<pwm.>.w=flqrb\qpV{ p.88
fi^+>fl fifs>.wx|Rwy<pw=
j /lhiZp|KhQwAasMTflqtsMp
M{m.>.px|>ywx|KXp>y
wwpK|>o 0.5 >yww
pxsM

K o89S 42
y: 10 oD 15
58 ' (Curie) wO 46
8 61 ' - (Weiss) wg 69
: 6 66, 78
(Ehrenfest) w 71 `t 56
- 13 E 52
16, 37 $O 1
28 L 43
\R 58 Clausiuswjg 23
G 31 ws 29
$s 46, 86 -w 63
(Euler) wg 76 &g9S 9
Ostwaldwjg 24 fi -wg 18
9fiL 44 11
9S 8 Kelvinwjg 23
9S- 8 >. 42
9Sfl 57 fl 3, 58
. 42
T .L 42
= 82 Q 46
= 81 }q% 12
= 55, 75 79
Do 22 g>. 48
Doa 22
'R 68 ^
>!= 52 6< 2
COQ 75 19
a^ 68 O: 11, 64
wjg 32 = 45
Carnot 20 =p 71
26 !: 11, 75
wjg 29 S 88
>.: 11 ^;wO 81
>.w 22 C= 69
>.wr` 22 38
1,9 83 H!: 6
(Gibbs) w 38 r` 18
- (Duhem) w 76 14
wo 77 -: 42
w 80 -fiL 41, 42
-w 39 -wg 41
, 61 (Joule) wg 14
95
96 g
wO 17, 40, 48 s9u!= 51

- (Stefan-Boltzmann) s9!= 51
wO 44 w-g 2
-: 44 q!: 6
j6 67 ah% 75
ji$a 36 (Thomson) wjg 23
ji$ 15 (Dalton) wO 48
ji$s9r` 16
s
Q. 45
12, 37
6M 9
r 15
6 5, 13
58
!: 11
8 62
y 86
2E 54
uD 5
13
u< 5, 29
p 58
fl9S 9
o 15
09S 10
fip 21, 30
0S 11, 73
fiL 46
61, 63
58
5
(caloric) 12
61
12
$ 64
; 22, 32, 56
8 61
;S 57
;M 58
h
wp 14
Hq; 19
8
0 6wjg 66
E 50
Hq; 24
6 8
E? 44
L 42
E 14
r`p 9
R% 76
0 16
yVp 17, 49
: 37
17
HO 13
r` 25, 31
H~O 34, 73
46
HO 8
v 71
HO 31
yz 16
$Q 51
T3 74
$9S 27
uz 16
$% 8
o\wF 78 $S 9
?z 74 v 57
s!= 41 (Nernst) wg 73
s!= 29, 50 -wg 73
s9yVp 9, 17, 49 S 77
s9 51
s9y!= 51 x
g 97
C 58 (le Chatrier)- (Braun)

S 2 82 wjg 83
30 (LeGendre) ! 37
Doa 22 k 42
z 16 k 21
zz 19 w 57
3
:< 86
fl` 47
Mh% 75
Van der Waals)
6M 64
(Vant Ho) wO 86
: 62
: 85
w 44
: 82
(Helmholtz)
38
3
(Henry) wO 87
BoylewO 10, 48
Ly 43
^>y 62
^+> 87
(Maxwell) 39
wsu 67
rtC\ 25
:O 59
`v 4
flwMO 49
w:O 59
59
(Laplace) M 58
8 71
a 26
g>. 10
g$sDo; 20
{:w 55
: 64
R 68

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[

UKqb{\wqV| y :qsb\qt f 1 !: x w:qo{M|

q{XwqaflqQoM{!=fi duflfi dxflh qzy|Kq

f (x + dx) = f (x) + f (x)dx (1.5)

(3) yt| Qygt!:wwUpTlhqO{

du = A(x, y, ...) dx + B(x, y, ...) dy + ... (1.11)

U)QhqV|Mmp\U|K: f (x, y, ...) U_mTlo| x| y, ... q u w

yyyw xdx + ydy = d(x2 /2 + y 2/2) , ydx + xdy = d(xy)

pK{ (u f UOby|%xqt 2 f /xy )Q{

y\\p|K: T (x, y, ...) UKlo|.\plhw

du A(x, y, ...) B(x, y, ...)

UtsqV|bsj|K: S(x, y, ...) w!=wp{Z

pK{ arctan x tan wo:

(4) y: u = f (x, y) U)QoM| x, y w\q | u w\q

wOt{X{xfi x q z Uq!:pKw x tmMowfl|xfi x

1 !:ww&gT| (i) wOtfi-x:-iflqXXloMq|

du = f (x + dx, y + dy) f (x, y)

= fx (x, y) + dy dx + fy (x, y)dy

fiy TA = TC , TB = TC wqV TA = TB yfl (2.1)

V = V (T, P ) yyhxyy F (T, V, P ) = 0 (2.2)

|\w (T, V, P ) wtRqmw\qqofi6MflqMO{\

wqtqoy| 1025 xwfgU|qSp 6 mw$SloS

wOy P V = 9Sp>:yyyyyy (2.9)

cts{\w9Sx qzy|Sf 273 pK{f\p|\w9S

) yy R = 8.31 [J/mol K] yyyy (2.12)

9SwwgtmMox|fi MKS ofl;MwUqOwgtSZ

}q%UT!Zqy W (A B) = U(B) U(A) (3.1)

W (A B) = U(B) U(A) (3.3)

[U(B) U(A)] W (A B) = Q(A B) (3.4)

W (A B) + Q(A B) = U(B) U(A) (3.5)

x4wX<mq+w9Sww ... ... .

yyy cal15 = 4.1855 J 0+

.... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................ . ..

g>.U.u V T V pji$s9r`bqVt| t0ob {{

dP = 0y CP = [d Q/dT ]dP =0

x|w mwz q ws9yVp ;Mo| ad = (CV /CP ) p)Q \q

\wAL|uz CV = (U/T )V 9S T iZw:qs{ H =

U:qsdsy| R/CV = (CP CV )/CV = 1 iT

W (A A) + Q(A A) = U(A) U(A) = 0 (3.31)

\T|pxsXq Q = 0 wqVfi (W ) > 0 xDflbsjt

3. pT!Z W3 = LZb |Q |

4. pT!Z W4 = U(T ) U(T ) (= |W2 |

h| VC /VB = (T )/(T ) = VD /VA VB /VA = VC /VD |ws;Mq

qs{\wOtg$s pKlofip 100%tb\qxDpK

\\px| fiLloSZyflU^oOflqMO$sqq| fifip 100%w

\\pJtswxfirwOsMOp} }}flpK{ fi?TwflpKy|?TOM\

y wjgtSb C UKlhqo|\U9wo T1 T!Zlh

tSb C UKlhq|\U9wo T1 T9wo T2 Y

#|NthwJp ... 0 ...... .

a-swM tsiZp|\wJob\ .........................................

wxw p.34 tK{ \;Mo| f (T ) T qsOtM9S

p)Q\qts{Kqw 4.8 p\U7GpK\qU^{

qs{\`o|DoU9S {Ti } woqto|oT

x|&tdc6 A iZp>|bsj6pK{\G S pfl

m9S T Uu< 1 | p.5pK{\t|sXqDo!=ji$

d Q = T dS yyyy (4.13) T....

pK{9 T2 300K |9S)x 10 20K pKT|fipwtzoZl

qs{ Text qhwx|\w9SxQoM%ww9SpxsXo|MoV

U{\ KMx qMM|

d(S + Sext ) 0 (4.24)

d Q = A(x, y) dx + B(x, y) dy (4.30)

S(x, y) = constant (4.33)

\U d Q = 0 t0 oM\qT|Mpw dy/dx wflsMqSXq

.... Q > 0 ............

W (A B) = U(B) U(A) (3.3)