Equations of state

Active study of gases is

done by changing pressure,
volume, temperature, or
quantity of material and
observing the result.
pV/nT (J/mol K)

8.60
H2
8.40
N2
8.20
CO
8.00

7.80
O2

10 20 30 P (atm)

Ideal-gas

      

    
                   
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In reality, there are no gases that fit this definition perfectly.
We assume that gases are ideal to simplify our calculations

Ideal gas regime: low pressure/high temperatures/low densities

 Ideal-gas equation

     


  

pV = nRT 
      
 

        


  
                

"     #       $
mtotal = nM !


     

mtotal
pV =
%     
RT
M
ρ = mtotal / V
"     #       $
ρ
    $

%      pM
ρ=
RT
&        
'      
      (         
 )      *      

Ideal-gas equation

     


  

pV = nRT 
      
 

        


  
                

N = nN A
"     #       $
-          
+ ,

R
%     
pV = N T = NkT
NA
The constant term R/NA is referred to as Boltzmann's constant, in honor
of the Austrian physicist Ludwig Boltzmann (1844–1906), and is
represented by the symbol k:
 Ideal-gas equation (contd.)
         
'     
p1V1 p2V2
=
T1 T2
              
'     
pV = const. Boyle’s law

      

CPS question
A quantity of an ideal gas is contained in a balloon. Initially
the gas temperature is 27°C.
You double the pressure on the balloon and change the
temperature so that the balloon shrinks to one-quarter of its
original volume. What is the new temperature of the gas?

A. 54°C
B. 27°C
C. 13.5°C
D. –123°C
E. –198°C
CPS question
p
This pV–diagram shows three
possible states of a certain amount
of an ideal gas. 3
Which state is at the highest 2
temperature?
1
A. state #1
B. state #2 V
O
C. state #3
D. Two of these are tied for highest temperature.
E. All three of these are at the same temperature.

Summary:Equations of state

pV = nRT

     


  


      
 

        


  
                

pV = NkT
k: Boltzmann’s constant ; k=R/NA=1.38x10-23 J/K
 Kinetic theory of an ideal gas

Pressure of a gas
The pressure that a gas exerts is
caused by the impact of its
molecules on the walls of the
container.
Consider a cubic container of
volume V containing N molecules
with a speed v
Consider a gas molecule colliding elastically with the right wall of
the container and rebounding from it.

The force on the wall is obtained using Newton’s second law as

follows, ∆P
F= , ∆P: change in momentum
∆t
And the pressure:
1 1 ∆P
P= F= ,
A A ∆t

Total change in momentum ∆P of all the molecules during a time interval ∆t =

Change in momentum of one molecule, times the number of molecules that
hit the wall during the interval ∆t:
Change in momentum of one molecule:

∆p = mv x − ( −mv x ) = 2mv x
Change in momentum of all the molecules:

∆P = (2mv x ) × N hit
N 1 N
N hit = v x ∆tA ∆P = mv x2 ∆tA
V 2 V
Finally, the pressure is given by:

1 ∆P N
P= = mv x
2

A ∆t V
Particles move in random directions, so we replace vx2 by (vx2 )av

N
P= m(v x2 ) av
V
or, equivalently

1
PV = 2 N ( mv x2 )av
2

Molecular interpretation of temperature

1
PV = NkT = 2 N ( mv x2 )av
2
or
1 1
( mv x2 )av = kT
2 2
There is nothing special about the x direction, in general:
(v ) = (v ) = (v )
2
x av
2
y av
2
z av
and
( v ) av = ( v x ) av + ( v y ) av + ( v z )av = 3(v x2 )av
2 2 2 2

Therefore: The average kinetic energy of a molecule is:

1 3
E Kin = ( mv 2 )av = kT
2 2
The absolute temperature is a measure of the average
translational kinetic energy of the molecules
CPS question

An ideal gas is trapped in a chamber, inside a thermally

insulated container (see figure). When the partition is broken or
removed, the gas expands and fills the entire volume of the
container. As a result, the final temperature of the gas after the
expansion is:
A. Lower than the initial
temperature
B. Higher than the initial
temperature
C. The temperature remains
constant

Equipartition theorem
1 3
E Kin = ( mv 2 )av = kT
2 2
When a substance is in equilibrium, there is an average
energy of 1/2kT per molecule, or 1/2RT per mole, associated
with each degree of freedom
z
y

x
 Molar heat capacity
Kinetic energy per mole:

3
EKin = RT
2
dQ = dE Kin
3
CV dT = RdT
2

C = 3R
V
2
 C = 3 (8.314J/mol.K) = 12.47J/mol.K
V
2

Molar heat capacity

Kinetic energy per mole:

3
EKin = RT
2
dQ = dE Kin
3
CV dT = RdT
2

C = 3R
V
2
 C = 3 (8.314J/mol.K) = 12.47J/mol.K
V
2
Works well for monoatomic gases… what’s wrong with the others…?
 Heat absorption into degrees of freedom
A molecule can absorb energy in translation, and
also in rotation and vibrations in its structure

CPS question
The molar heat capacity at constant volume of diatomic
hydrogen gas (H2) is 5R/2 at 500 K but only 3R/2 at 50 K.
Why is this?

A. At 500 K the molecules can vibrate, while at 50 K they cannot.

B. At 500 K the molecules cannot vibrate, while at 50 K they can.
C. At 500 K the molecules can rotate, while at 50 K they cannot.
D. At 500 K the molecules can rotate, while at 50 K they cannot.
 Heat capacity of solids
Solids can absorb energy in the vibrational
modes. A 3-dimensional solid has 3
vibrational degrees of freedom+3
translational…
CV = 3R

CV = 3(8.314J/mol.K ) = 24.9J/mol.K

Dulong and Petit’s law

(Valid at high temperature due to

quantum nature of the vibrations)

     
            

   
   

2kT 2 RT
vmp = =
m M
The fraction of molecules dN with speeds
between v and v+dv is given by
dn = f ( v )dv

vave = ∫ vf (v )dv =
The average speeds are given by:
∞ 8kT
πm
= ∫ v 2 f (v )dv =
0

∞ 3kT
v 2 ave
0 m