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3 Laws of Thermodynamics
O) If two systems are in equilibrium with a third, they are in equilibrium with each other.
1) Conservation of energy Eth = ! "
#) $he entro%y of an isolated system never decreases. $he entro%y either increases until it reaches
equilibrium, or if it&s in equilibrium, it stays the same.
given two system w'1 ( #, heat will be s%ontaneously transferred from system 1 to #.
heat cannot be com%letely converted into wor).
$hermodynamic basics
*artition function+
s '
s
, e

*robability of being in a state w'energy

'
e
+ *- )
.



s
'
s
s
e
.

$he fundamental assum%tion+ a closed system is equally li)ely to be any of the quantum states
accessible to it.
g-/, 0) $he multi%licity of a system with / %articles and energy
1 = )2 = )2logg-/, u)
1%ecific case+ 3ermonic oscillator+ g-/, n) =
-/ n 1)4
n4 -/ 1)4
+

where / = 5oscillators, n = quantum 5

1%ecific case+ / magnets with 1% in e6cess ,s = /
7 /

+

g-/, s) =
/4
/ 4/

where
/
/

=
182
182 182
e
e e

+
where 2 is the magnetic field and 8 is the magnetic moment
9inds of energy+
d = du ! %d: 7 /
.
log.
=
_

,
3elmholt. ;ree Energy
-isothermal) ; = u 7 = 7 log. d; = du 7 d ! d/
= 7d 7 *d: ! d/
-isobaric) Enthal%y
3 = ! %: d3 = d ! :d% 7 d/
-isobaric, isothermal) <ibbs ;ree Energy
< = ;!%: = u!%: 7 d< = 7d ! :d% ! d/
v
v v
u
C
_ _



, ,
, %
* % %
u v
C %
_ _ _
+


, , ,
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>istributions
;ermi 7 >irac + =verage occu%ancy of an orbital w'energy , for fermions
- ) '
1
f- )
e 1


+
2ose 7 Einstein+ =verage occu%ancy of an orbital w'energy , bosons
- ) '
1
f- )
e 71


*lan) distribution+ $hermal average number of %hotons in a single mode a
'
1
s
e 71

< >
h
Ideal gas
*: = n?$ = /)2$
1 1 # #
1 #
* : * :
if the container is scaled
$ $
_

,
= 9Eavg =
2
@
9 $
#
-
1
2
#
) $ for each degree of freedom, note that f %otential energy, each of those
degrees of freedom gets
1
2
#
) $
as well by the Equi%artition $heorem)
3eat ca%acity, constant volume +
v 2
v
u @
C / )
#
_

,
- = )2$)
% 2
% % %
u u A
C * /)
#
_ _ _
+


, , ,
*artition function of an atom in a bo6. ,1 = " "
n 'n n :
na =
( )
@
#
.
8 ' . h
*artition function of / atoms in a bo6 +
/
/ 1
1
, ,
/4

Entro%y 1 = )2 = )2/
( )
A
nq
log
n
#
1
+
1
]
Chemical %otential +
( )
n
log
n"

=verage occu%ancy of an orbital of energy
'
f- ) e

where = e
'
;ree energy+
( )
n
; / log 1
n"
1

1
]
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*er atom in a
monatomic gas
Gate Forum Correspondence Course
u# 7 u1 # 7 1 "
O
#
1
:
/log
:
#
1
:
7/log
:
#
1
:
/ log
:

#
@
1
1
#
: @
/ 1
# :
1
_
1


1
,
]
O
#
@
1
1
#
: @
/ 1
# :
1
_
1


1
,
]
O
O
#
1
:
/log
:
O O
>iatomic <as+
@ translation, # rotation
2
A
u ) $,
#

@ )inetic ' translation

@ vibration
B
2
1olid + u @) $
#C> ideal gas
u = )2$, Cv = /)2 C% = #/)2
:an >eralls 7 attem%s to modify the ideal gas law to ta)e into account interactions between atoms
or molecules
( )
#
b
#
/ a
* : / /
:
_
+

,
where a is a measure of the longCrange attractive %art -adds to internal %ressure) of the interaction
and b is a measure of the shortCrange re%ulsion -volume of molecules themselves)
Critical %oints + *c = #
a
#Db ,
:c = @/b,
c
Ea
#Db

at this %oint, there is no se%aration between the va%or
and liquid %hases -a hori.ontal %oint of inflection)
- 9 91 %
#FG
;ig. 1G.1G)
-;or a given
c
*
*
, H c, : H :1 liquid : ( :# gas,
:1 H : H :# both show that sum of volume of
liquid < gas = :)
*hase >iagram
$ri%le %oint + $he one value of $ and * for which all three %hases
can ha%%ily coe6ist. 3a%%ily.
Critical %oint+ below this %oint a %hase change between liquid I
gas. =bove this %oint %hase change -fluid continuously
between high I low density)
>iffusion
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?eversible isothermal
?eversible isentro%ic
Irreversible e6tension into
vacuum
v
1
v
#
#
v
v
c
*
*
H
c
=
c
(
c
1
o
l
i
d
Jiquid
Critical %oint
$ri%le %oint
$
Gate Forum Correspondence Course
#
8v
#t
1
#
# #
rms
@
: : e
8

_

,
, ( )
#
? CltK
8ain free%ath
8ain s%eed
1
#
#
%article diameter of %articles
density
1
C K l
8
n d

,
8a6well velocity distribution
#
8v
#
@
#
#
8
*-:) L : e
#

_

,
;ic)&s Jaw
n
%article flu6 density
M > n

uur
cl
>
@
-diffusion constant)
;ourier&s Jaw
n
thermal flu6 density
M 9

uur
:
heat ca%city %er unit volume
1
N
9 C cl -$hermal conductivity)
@

Carnot cycle and or) in general

or) done on a system =
#
1
%d:

= 7-area under %: curve)

Energy in+ heat from resevoir ?3 -O 3)
Energy out+ heat to resevoir ?J -O J H 3)
;or a reversible engine, 3 = J -if 3 J, only wor) may be transferred)
efficiency+
J
3 3
, 17
"
-heat engine)
_

,
1) com%ress isothermally -" )
#) com%ress isentro%ically - )
@) e6%and isothermally -" )
L) e6%and isentro%ically -)
-for a heat %um%, reverse order)
for the carnot cycle, efficiency is at a ma6imum
J
c
3
1

or
J J
c
3 L
C


-engine) -%um%'refrigerator)
;or an ideal gas, isothermal %rocess "3 = = /3 log
#
1
:
:
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:
*

:
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isentro%ic %rocess = = ( )
3 J
@
/
#


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