1.

DISCUSS THE REAL GASES

Gases that deviate from ideality are known as Real Gases, which originate from two factors:
(1) First, the theory assumes that as pressure increases, the volume of a gas becomes very small
and approaches zero. While it does approach a small number, it will not be zero because
molecules do occupy space (i.e. have volume) and cannot be compressed. (2) Intermolecular
forces do exist in gases. These become increasingly important in low temperatures, when
translational molecular motion slows down, almost to a halt. However, at high temperatures, or
even normal, every day temperatures, the intermolecular forces are very small and tend to be
considered negligible.

Real gases are non-hypothetical gases whose molecules occupy space and have interactions;
consequently, they adhere to gas laws. To understand the behaviour of real gases, the following
must be taken into account:

 compressibility effects;
 variable specific heat capacity;
 van der Waals forces;
 non-equilibrium thermodynamic effects;
 issues with molecular dissociation and elementary reactions with variable composition

For most applications, such a detailed analysis is unnecessary, and the ideal gas approximation
can be used with reasonable accuracy. On the other hand, real-gas models have to be used near
the condensation point of gases, near critical points, at very high pressures, to explain the Joule–
Thomson effect and in other less usual cases. The deviation from ideality can be described by the
compressibility factor Z.

2. DIFFERENCE BETWEEN IDEAL AND REAL GAS

Ideal gas has no definite volume while real gas has definite volume.

2.Ideal gas has no mass whereas real gas has mass.

3.Collision of ideal gas particles is elastic while non-elastic for real gas.

4.No energy involved during collision of particles in ideal gas. Collision of particles in real gas
has attracting energy.

5.Pressure is high in ideal gas compared to real gas.

6.Ideal gas follows the equation PV=nRT. Real gas follows the equation (P + a/V2) (V – b) =
nRT.

3. SOLVED PROBLEMS
A.) VAN DER WAALS
1.

i) Using Van der Waals equation, calculate the temperature of 20.0 mole of helium in a
10.0 litre cylinder at 120 atmosphere pressure.

[Data - Van der Waals constants for helium: a = 0.0341 L2 at mol-2; b = 0.0237 L mol-1]

(ii) Compare this value with the temperature calculated from the ideal gas equation.

ANSWER:

(i) Using the Van der Waals equation:

Substituting in
(P + an2/V2)(V - nb) = nRT,
P = 120 atm
n = 20.0 mol
V = 10.0 L

(120 + 0.0341 x (20.0/10.0)2)(10.0 - 20.0 x 0.0237) = 20.0 x 0.0821 x T

[Note the value of R = 0.0821 because P is in atm and V in L]

(120 + 0.1364)(10.0 - 0.5) = 1.64 x T
T = 696 K
[Note that the correction to P is not significant as T is well above the temperature at
which helium gas will liquefy while the volume correction is significant due to the high
pressure.]

(ii) Using the Ideal Gas Equation:

Substituting in
PV = nRT,
120 x 10.0 = 20.0 x 0.0821 x T
T = 1200/1.642

= 731 K

2.

Carbon dioxide gas (1.00 mole) at 373 K occupies 536 mL at 50.0 atmosphere
pressure. What is the calculated value of the pressure using
(i) Ideal gas equation
(ii) Van der Waals equation?

[Data - Van der Waals constants for carbon dioxide:

a = 3.61 L2 atm mol-2; b = 0.0428 L mol-1]

Calculate the % deviation of each value from that observed.

At high pressures, it is convenient to quote pressure in atmospheres rather than kPa.

The value of the gas constant R depends on the units used for P and V.
If P is expressed as atmospheres and V as litres,
R = 0.0821 L atm K-1 mol-1.

(i) Using the Ideal Gas Equation

V = 0.536 L
n = 1.00 mol
T = 373 K
PV = nRT
P = nRT/V = 1.00 x 0.0821 x 373/0.536
= 57.1 atm

Actual pressure = 50.0 atm

% deviation = (7.1/50) x 100 = 14.2 %

(ii) Using Van der Waals equation.

(P + an2/V2)(V - nb) = nRT.
(P + 3.61 x (1.00/0.536)2)(0.536 - 1.00 x 0.0428) = 1.00 x 0.0821 x 373)
(P + 12.57)(0.493) = 30.62
P + 12.57 = 62.12
P = 49.6 atm

% deviation = (0.4/50) x 100 = 0.8%

B) VIRIAL
1.

C. BERTHELOT

The Berthelot equation of state is

 p= RT - a (3.1)

(Vm – b) TVm2

where Vm = V/n, and a and b are constants.

a) The internal pressure of a substance, T, is given by the expression

T = (U/V)T = T (p/T)V – p (3.2)

Find an expression for T for a gas obeying the Berthelot equation of state. Simplify your result as much
as possible.

b) Find a general expression for w (work) when 1.000 mol of a gas obeying the Berthelot
equation of state is expanded isothermally and reversibly from an initial volume Vi to a final volume Vf.

a) To find the internal pressure we need to evaluate the partial derivative (p/T)V

(p/T)V = /T)V RT - a = R + a

(Vm – b) TVm2 (Vm – b) T2Vm2

T = T (p/T)V – p = RT + a - p

(Vm – b) TVm2

RT + a - RT + a = 2a

(Vm – b) TVm2 (Vm – b) TVm2 TVm2

b) The process is isothermal and reversible, and so

w = - if pex dV = - if p dV

 = - if { [nRT/(V – nb)] - (an/TV2) } dV

Note we have used Vm = V/n to rewrite the expression for p in terms of n and V instead of in terms of Vm.

So w = - { RT ln[(Vf – nb)/(Vi – nb)] + (an/T) [ (1/Vf) – (1/Vi) ] }

D) DIETERICI
E)REEDLICH- KWONG