The Virial expansion and Real gas

 Virial equation of states for gas

 Virial expansion is a power series of variables and
has a form of:

 B(T) = 2nd virial coefficient

Function of Temperature
 C(T) = 3rd
virial coefficient
 Z = compression factor –use to measure deviation from
ideal gas (Z = 1)
 In chemical thermodynamic – 3rd virial coefficient rarely
used
 A real gas obeys ideal gas as P 0, but not all
properties of real gas
 For an ideal gas:

B’ = BR and C’’ = CR2

 For real gas

3rd virial coefficient are rarely used

A real gas does not behave like an ideal gas in all

respect as P→0
Example 1
 Show how the second virial coefficient of a gas and its
molar mass can be obtained by plottting P/ρ versus P,
where ρ is a density of the gas. Apply this method to the
following data on ethane at 300 K.

P/bar 1 10 20
ρ/10-3 g cm-3 1.2145 13.006 28.235

Example 2:
 Calculate a second and third virial coefficient of hydrogen
at 0 C from the fact that the molar volume at 50.7, 101.3,
202.6 and 303.9 bar are 0.4634, 0.2386, 0.1271 and
0.09004 L mol-1 respectively.
Langmuir isotherm
 The extent of adsorption expressed as fractional
coverage, 

  depends on pressure overlying gas

 Free gas and adsorbed gas = in dynamic equilibrium

ka
A (g) + M (surface) AM
kd
 Due to adsorption:
ka = rate constant of adsorption
N = total number of sites
N(1-) = number of vacant sites

 Due to desorption:
kd = rate constant of desorption

N = number of adsorbed sites

 Solve the equations:

Langmuir isotherm
Example 3
 The following data is for the adsorption of CO gas on charcoal at 273
K. Confirm that the data fitted with Langmuir isotherm and find a
constant K and the volume corresponding to complete coverage.

P/torr 100 200 300 400 500 600 700

V/cm3 10.2 18.6 25.5 31.5 36.9 41.6 46.1

Effect of temperature in rate of reaction
 Expressed by Arrhenius law:

k = rate constant
A = Arrhenius constant/pre-exponential factor
Ea = Activation energy
T = Absolute temperature
R = gas constant, 8.314 J K-1 mol-1

 In logarithmic form:

y = mx + C
 A plot of ln k vs give a straight line:

ln k C = ln A

m=
Example 4
 The rate of second order decomposition of acetaldehyde was
measured over the temperature range of 700 – 1000 K, and the rate
constant are reported below. Find the activation energy and pre-
exponential factor.
T/K 700 730 760 790 810 840 910 1000

k/M-1s-1 0.011 0.035 0.105 0.343 0.789 2.17 20.0 145

 Deduce the linear equation from the following Wayne- Eyring-Jones.

Use the above data to obtain S‡
 S# 
   Ea 
k T  R   
k  e2  B  e  
e  RT 

 h 