3/14/2023

Thermal Physics Note

Thermal contact: two systems 2

ℏ π 2
2
En = 2
n
2mL
∂ Ω1 ∂ Ω2 L → L+δL
d Ωtot ( Etot )=d [ Ω1 ( E1 ) Ω2 ( E2 ) ]=Ω2 + Ω1
∂ E1 ∂ E2 i) work
1 ∂ Ω1 1 ∂ Ω2 energy changes induced by variations of
= external parameters (due to changes of
Ω 1 ∂ E1 Ω 2 ∂ E 2
energy levels)
1 ∂ ∂ 1
≔ ln Ω1= ln Ω2=: Δ E=W
kB T 1 ∂ E 1 ∂ E2 kB T 2
ii) heat
energy changes when external parameter
1.3 The First Law
remain fixed
- microstates
Δ E=Q
6N variables {⃗
p , q⃗ }
iii) combining
The first law of thermodynamics.
- macrostates
Δ E=W +Q
A few macroscopic observables (variables)
dE=δW +δQ
Such as E , N ,V , T , P

-exact vs. inexact

In equilibrium, the macroscopic property of
a system is characterized by a set of z=f (x , y )
functions of states. (state variables)
∂f ∂f
df =f ( x +dx , y+ dy )−f ( x , y )= dx + d y =Adx + Bdy
 Macroscopic observables (state ∂x ∂y
variables) function of states

( (
∂ ∂f
∂ y ∂x ) ) (∂x(∂ y) )
y x
=
∂ ∂f
x y
-quantum particle in a one-dimensional box

( ∂∂ Ay ) =( ∂∂ Bx )
x y
^
H ψ ( x )=Eψ ( x ) ⃗
F =( A , B )
2 2
−ℏ d Stoke’s theorem
ψ ( x )=Eψ (x)
2 m d x2 ❑

∮ ⃗F ∙ d ⃗x =∫ d ⃗s ∙(∇ × ⃗F )=0
ψ ( x )=
√ 2
L
sin (k n x ¿)¿, where k n=
nπ
L
∂s S

(∂x) (∂ y)
( ∇ × ⃗F )z = ∂ B − ∂ A =0
y x
 r⃗2 ⃗r2

∫ ⃗F ∙ d ⃗x =∫ ⃗F ∙ d ⃗x
r⃗1 ⃗r1

Path dependent!

-Inexact
2
δf =xydx + x dy
∂f x ∂fy
=x ≠ =2 x
∂y ∂x
1 ,1 1

∫ δf =0+( x−1 ) ∫ dy=1 2

0, 0 0

1 ,1 1
1
∫ δf =0+∫ xy d x y=1= 2
0, 0 0

1.4 Heat Capacity

δQ=dE−δW

( δQ
dT )
c=

dE ( T ,V )=(
∂T )
dT + (
∂V )
∂E ∂E
dV
V T

δW =PdV for quasi-statical process

δQ= ( ∂∂ ET ) dT +[( ∂∂ VE ) + p] dV
V T

At constant volume

cV = ( δQdT ) =( ∂∂ TE )
V V

At constant volume

dT ) ( ∂ T ) [( ∂ V )
( δQ ] ∂V∂T )
+P (
∂E ∂E
c P= = +
P V T P