V S. V =f(V, S). ,
(89)
(88) (89),
(90)
(91)
. . U ( V S) (90) (91).
V (S, V) :
( ,
(92)
(90) (91) ,
(93)
(93) .
S,
= f (p, S).
(94)
(88). Vdp,
dU + Vdp = TdS pdV + Vdp
dU + Vdp + pdV = TdS + Vdp.
d (U + pV) = T dS + Vdp.
U + pV = H,
dH = TdS + Vdp. (95)
(94) (95),
(96)
(97)
(S, )
( dS = δQpfT = μcpdTfT)
(98)
(96) (97) ,
,
(99)
(100)
, (S, ) S, μcp.
(- )
V , dU TdS = pdV. SdT:
SdT + dU TdS = pdV SdT,
d(U TS) = pdV SdT.
(UTS) U S , , . - . V F:
F = U TS. (101) (101)
F ,
dF = pdV SdT. (102)
, V :
(103)
(102) (103), , F V
(104)
(105)
μcv, . .
|
|
(106)
(102) pdV ( ) ,
dF = δ SdT.
( = const)
dF = δ, (107)
- (V = const const)
dF == δ = δA, (108)
δA =δA' + pdV.
, (F) (F = U Ts), -- , .
TS = U F . = const , .
(-ר )
.
dU + pdV TdS =0
Vdp S dT.
dU + pdV TdS + Vdp SdT = Vdp S dT.
d (U TS + pV) = Vdp SdT.
TS,
d (H TS) = Vdp SdT.
͗TS ; . G - :
G = H TS. (109)
(H TS) G,
dG = Vdp SdT. (110)
dG . :
(111)
(110) (111)
, (112)
(113)
, G V S.