/ , / - . , , .
, , . (W).
/ . , . :
S = k ln W
k (k = R/Na = 1,38۰10-23 /)
:
0, , .
W = 1, S = k ln 1 = 0 S = 0
, (, , .) , . , 0 .
9.
.
, . . , , .. , , . , . , .
I. - ( ).
δQ = dU + δA
δA = δQ dU => δA ≤ TdS - dU
dS ≥
TdS≥δQ
δA = TdS dU
δA < TdS dU => δA > δA
δA =const
Amax = T(S2-S1) (U2-U1) = TS2 TS1 U2 + U1 = (U1 TS1) (U2 TS2)
U TS = F => Amax = F1 F2 = -ΔF
F , - .
.. Amax , =const V=const - .
U = F + TS : (F) (TS)
( F) , . , ..
|
|
TdS = δQ
(≠ const) .
F = U TS:
dF ≤ -PdV SdT
: dF = -PdV SdT
: dF < -PdV SdT
=const dF = -PdV
=> F .
V=const => dF = SdT; = - S => F , .
V=const =const
(dF)V,T ≤ 0 => F V=const =const; .. dF < 0; dF = 0 => F=const. () F , .
.. :
, - . , .
II. - .
, .
δA = PdV + δA
δA .
=> δA ≤ TdS dU - PdV
: δA = TdS dU PdV
= const = const:
G= U-TS+PV * - ( ).
- = const = const
G=U-TS=PV
F=U-TS => G = F + PV
H=U=PV G = H TS
(*) :
dG ≤ -SdT + VdP (**)
(**) :
) = const => dG = VdP
) = const => dG = -SdT
.
= const = const
. .
III. - .
δQ = δA + dU
dU = δQ δA
dS ≥ => δQ ≤ TdS dU ≤ TdS PdV
(dU)S,V ≤ 0
S V (dU<0) (dU=0).
, .
:
IV. - .
H = U + PV; U ≤ TdS - δA; A = PdV; dH = dU + PdV + VdP
: dH ≤ TdS + VdP
S P: (dH)S,P ≤ 0
, = const S = const .
|
|
.. .
:
, .. . . , .
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