Thermodynamics and Statistical

Mechanics

First Law of Thermodynamics

Review of van der Waals Critical
Values

vC  3b
8a
TC 
27 Rb
a
PC  2
27b
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 van der Waals Results
1 a 8 a
vc  3b Pc  2
Tc 
27 b 27 bR
1 a
3b
Pc vc 27 b 2 3
   0.375
RTc R 8 a 8
27 bR

Thermo & Stat Mech - Spring 2006 Cl 3

 van der Waals Results

Substance Pcvc/RTc
He 0.327
H2 0.306
O2 0.292
CO2 0.277
H2O 0.233
Hg 0.909

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 Configuration Work

đW = PdV
Gas, Liquid, Solid:

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 Kinds of Processes

Often, something is held constant. Examples:

dV = 0 isochoric or isovolumic process

dQ = 0 adiabatic process
dP = 0 isobaric process
dT = 0 isothermal process

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 Work done by a gas

đW = PdV
Vf
W   PdV
Vi

For isochoric process dV = 0,

so W = 0
For isobaric process dP = 0,
so W = PV
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Work done by a gas

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 Work done by an ideal gas
Vf
W   PdV
Vi

For isothermal process dT = 0,

so T = constant.
RT
P
V

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Isothermal Process

Vf dV
W  RT 
Vi V
W  RT lnV 
Vf
Vi

V f 
W  RT ln 
 Vi 

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 Heat Capacity

Heat capacity measures the amount of heat that

must be added to a system to increase its
temperature by a given amount. Its definition:
 dQ 
Cy   
 dT  y
where y is a property of the system that is kept
constant as heat is added.

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 Heat Capacity

Properties that are usually kept constant for a

hydrostatic system are volume or pressure.
Then,
 dQ   dQ 
CV    , or CP   
 dT V  dT  P

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 Heat Capacity

Clearly, the heat capacity depends on the size

of the system under consideration. To get rid of
that effect, and have a heat capacity that
depends only on the properties of the substance
being studied, two other quantities are defined:
specific heat capacity, and molar heat
capacity.

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 Specific Heat Capacity

Specific heat capacity is the heat capacity per

mass of the system. A lower case letter is used
to represent the specific heat capacity. Then, if
m is the mass of the system,
CV 1  dQ  CP 1  dQ 
cV     , or cP    
m m  dT V m m  dT  P

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 Molar Heat Capacity

Molar heat capacity is the heat capacity per

mole of the system. A lower case letter is used
to represent the molar heat capacity. Then, if
there are n moles in the system,
CV 1  dQ  C P 1  dQ 
cV     , or cP    
n n  dT V n n  dT  P

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 Shorter Version

Use heat per mass.

 dq   dq 
cV    , or cP   
 dT V  dT  P

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 cP – c V

đq = du + Pdv where u(T,v)

 u   u 
du    dT    dv
 T v  v T
 u   u  
dq    dT     P  dv
 T v  v T 

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 Constant Volume

 dq   u  du
cv       , often
 dT v  T v dT

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 Constant Pressure

 dq    u    u   P  dv 
        
 dT  p  T v  v T  dT  P
 u  
c p  cv     P  v
 v T 
 u  
c p  cv     P  v
 v T 
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 Ideal Gas

u is not a function of v.

cP  cv  R

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 Adiabatic Process

For an ideal gas, and most real gasses,

đQ = dU + PdV
đQ = CVdT + PdV,.
PdV
Then, when đQ = 0, dT  
CV

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 Adiabatic Process

For an ideal gas, PV=nRT, so

PV PdV  VdP
T , and dT 
nR nR
Then,
PdV PdV  VdP
 
CV nR

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 Adiabatic Process

pV PdV  VdP
T , and dT 
nR nR
Then,
PdV PdV  VdP 1 1  VdP
0   PdV    
CV nR CV nR  nR
 nR  CV  VdP
0  PdV   
 CV nR  nR
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 Adiabatic Process

 nR  CV 
0  PdV    VdP
 CV 
nR  CV  CP
CP 
0  PdV    VdP   PdV  VdP
CV 
Cp
where,  
CV
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 Adiabatic Process

 PdV  VdP  0
dV dP
   0, which can be integrated,
V P
 ln V  ln P  constant
ln V  ln P  ln  PV
 
  constant

PV  constant
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 Adiabatic Process

PV  constant
With the help of PV  nRT
this can also be expressed as,
 1
TV  constant

T
 1
 constant
P
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 for “Ideal Gasses”
2
  1

2
monatomic :   1   1.67
3
2
diatomic :   1   1.40
5
2
polyatomic :   1   1.33
6
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