最近在看林宗涵的《热力学与统计物理》
浅浅地在这里记一下笔记吧
p-V-T系统的一些偏微分关系
原题目来自教材98页
对于任何p-V-T系统,可以普遍证明(请读者自行完成)
( ∂ c v ∂ V ) T = T ( ∂ 2 p ∂ T 2 ) V \left(\frac{\partial c_v}{\partial V}\right)_T = T\left(\frac{\partial^2 p}{\partial T^2}\right)_V (∂V∂cv)T=T(∂T2∂2p)V
首先明确对于定压情形,设微元过程中没有能量耗散,可认为是可逆过程:
δ
Q
=
T
d
S
⇒
c
v
=
δ
Q
v
d
T
=
T
(
∂
S
∂
T
)
V
\delta Q = T\mathrm{d}S \Rightarrow c_v = \frac{\delta Q_v}{\mathrm{d}T} = T \left(\frac{\partial S}{\partial T}\right)_V
δQ=TdS⇒cv=dTδQv=T(∂T∂S)V
另外我们有自由能以
V
V
V和
T
T
T为基本变量的微分关系:
d
F
=
−
S
d
T
−
p
d
V
\mathrm{d}F = -S\mathrm{d}T - p \mathrm{d}V
dF=−SdT−pdV
我们有:
∂
F
∂
V
=
−
p
∂
F
∂
T
=
−
S
\frac{\partial F}{\partial V} = - p \qquad \frac{\partial F}{\partial T} = - S
∂V∂F=−p∂T∂F=−S
因此我们有:
∂
2
F
∂
V
∂
T
=
−
(
∂
p
∂
T
)
V
∂
3
F
∂
V
∂
T
2
=
−
(
∂
2
p
∂
T
2
)
V
\frac{\partial^2 F}{\partial V \partial T} = - \left(\frac{\partial p}{\partial T}\right)_V \qquad \frac{\partial^3 F}{\partial V \partial T^2} = - \left(\frac{\partial^2 p}{\partial T^2}\right)_V
∂V∂T∂2F=−(∂T∂p)V∂V∂T2∂3F=−(∂T2∂2p)V
以及
∂
2
F
∂
T
2
=
−
(
∂
S
∂
T
)
V
=
−
c
v
T
∂
3
F
∂
T
2
∂
V
=
−
1
T
(
∂
c
v
∂
V
)
T
\frac{\partial^2 F}{\partial T^2} = - \left(\frac{\partial S}{\partial T}\right)_V = -\frac{c_v}{T} \qquad \frac{\partial^3 F}{\partial T^2\partial V} = - \frac{1}{T}\left(\frac{\partial c_v}{\partial V}\right)_T
∂T2∂2F=−(∂T∂S)V=−Tcv∂T2∂V∂3F=−T1(∂V∂cv)T
由于
F
F
F和
∂
F
/
∂
T
\partial F/ \partial T
∂F/∂T都是
(
T
,
V
)
(T,V)
(T,V)的连续可微函数,交换偏导数的次序不应改变其函数值,即有:
−
(
∂
2
p
∂
T
2
)
V
=
∂
3
F
∂
V
∂
T
2
=
∂
3
F
∂
T
2
∂
V
=
−
1
T
(
∂
c
v
∂
V
)
T
-\left(\frac{\partial^2 p}{\partial T^2}\right)_V =\frac{\partial^3 F}{\partial V \partial T^2} = \frac{\partial^3 F}{\partial T^2\partial V} = - \frac{1}{T}\left(\frac{\partial c_v}{\partial V}\right)_T
−(∂T2∂2p)V=∂V∂T2∂3F=∂T2∂V∂3F=−T1(∂V∂cv)T
化简后有:
(
∂
c
v
∂
V
)
T
=
T
(
∂
2
p
∂
T
2
)
V
\left(\frac{\partial c_v}{\partial V}\right)_T = T\left(\frac{\partial^2 p}{\partial T^2}\right)_V
(∂V∂cv)T=T(∂T2∂2p)V