THE PROPERTIES OF GAS

REAL
GASES
  Real gases do not obey the
perfect gas law exactly except in
the limit of 𝑝 → 0.

REAL GASES  Deviations from the law are

particularly important at high
pressures and low temperatures,
especially when a gas is on the
point of condensing to liquid.
Deviation from Perfect Behavior

 Real gases show deviations from the perfect gas law because
molecules interact with one another.

 Repulsive forces between molecules assist expansion and

attractive forces assist compression.
 REAL GASES

Repulsive Forces Attractive Forces

• Relatively long range and are

• Significant only when molecules
are almost in contact.
• Repulsions can be expected to be
important only when the average
separation of molecule is small.
effective over several molecular
diameters.
• They are important when the
molecules are fairly close
together but not necessary
touching

Intermolecular forces are also important when the temperature is so low that the
molecules travel with such low mean speeds that they can be captured by one
another.
THE
VARIATION
OF THE
POTENTIAL
ENERGY OF
TWO
MOLECULES
ON THEIR
SEPARATION.
The Compression Factor

 The compression factor, Z:

molar volume of a gas
𝑉𝑚
𝑍= ° molar volume of a perfect gas
𝑉𝑚

𝑉
 Because 𝑉𝑚 = = 𝑅𝑇ൗ𝑝, then 𝑍 = 𝑝𝑉𝑚ൗ𝑅𝑇, which we can write as
𝑛

𝑝𝑉𝑚 = 𝑅𝑇𝑍

 For a perfect gas Z = 1 under all conditions

 Deviation of Z from 1 is a measure of departure from perfect behavior.
The variation of the compression
factor, Z, with pressure for several
gases at 0°C.

for the ideal gas Z = 1

Z < 1 – attractive forces

predominates between molecules

Z > 1 – repulsive forces

predominates between molecules
Practice Exercise

 The molar volume of a perfect gas at 500 K and 100 bar is 𝑉𝑚° =
0.416 𝑑𝑚3 𝑚𝑜𝑙 −1 . The molar volume of carbon dioxide under the same
condition is 𝑉𝑚 = 0.366 𝑑𝑚3 𝑚𝑜𝑙 −1 . Calculate the compression factor,
Z. What type of intermolecular forces dominate?
Answer to Practice Exercise

 The molar volume of a perfect gas at 500 K and 100 bar is 𝑉𝑚° =
0.416 𝑑𝑚3 𝑚𝑜𝑙 −1 . The molar volume of carbon dioxide under the same
condition is 𝑉𝑚 = 0.366 𝑑𝑚3 𝑚𝑜𝑙 −1 . Calculate the compression factor, Z.
What type of intermolecular forces dominate?

Solution
𝑉𝑚 0.366 𝑑𝑚3 𝑚𝑜𝑙 −1
𝑍= ° = = 0.880
𝑉𝑚 0.416 𝑑𝑚3 𝑚𝑜𝑙 −1

The fact that Z<1 indicates that attractive forces dominate repulsive forces
under these conditions.
Virial Coefficients

 At large molar volumes and high temperatures the real gas isotherms do
not differ greatly from perfect gas isotherms.

 The small differences suggest that the perfect gas law 𝑝𝑉𝑚 = 𝑅𝑇 is in
fact the first term in an expression of the form

𝑝𝑉𝑚 = 𝑅𝑇(1 + 𝐵′ 𝑝 + 𝐶 ′ 𝑝2 + ⋯ )

…or a more convenient expansion for many application is

𝐵 𝐶
𝑝𝑉𝑚 = 𝑅𝑇 1 + + +⋯ Virial equation of state
𝑉𝑚 𝑉𝑚2
 𝑩 𝑪
𝒑𝑽𝒎 = 𝑹𝑻(𝟏 + 𝑩′ 𝒑 + 𝑪′ 𝒑𝟐 + ⋯) 𝒑𝑽𝒎 = 𝑹𝑻 𝟏 + + 𝟐 +⋯
𝑽𝒎 𝑽𝒎

𝑝𝑉𝑚 = 𝑅𝑇𝑍

The coefficients B, C, …, which depend on temperature are the second,

third… virial coefficients; the first virial coefficient is 1.

The third virial coefficient, C, is usually less important than the second
coefficient, B, in the sense that the typical molar volumes
𝐶 Τ𝑉𝑚2 ≪ 𝐵Τ𝑉𝑚 . The values of the virial coefficients of a gas are
determined from measurements of its compression factor.
Second virial coefficients, 𝐁/(𝐜𝐦𝟑 𝐦𝐨𝐥−𝟏 )
Temperature
100 K 273 K 373 K 600 K
Air -167.3 -13.5 3.4 19.0
Ar -187.0 -21.7 -4.2 11.9
CH4 -53.6 -21.2 8.1
CO2 -142 -72.2 -12.4
H2 -2.0 13.7 15.6
He 11.4 12.0 11.3 10.4
N2 -160.0 -10.5 6.2 21.7
Ne -6.0 10.4 12.3 13.8
O2 -197.5 -22.0 -3.7 12.9
Xe -153.7 -81.7 -19.6
Practice Exercise

1. Use virial equation of state (up to the B term) to calculate

the pressure exerted at 100 K by 0.104 mol O2 (g) in a
vessel of volume 0.225 dm3.

2. Calculate the pressure of O2 gas (in no. 1 above) using the

perfect gas equation of state.
ANSWER TO PRACTICE EXERCISE

1. Use virial equation of state (up to the B term) to calculate the pressure exerted
at 100 K by 0.104 mol O2 (g) in a vessel of volume 0.225 dm3.
Solution
𝑉 0.225 𝑑𝑚3
𝑉𝑚 = = = 2.16 𝑑𝑚3 𝑚𝑜𝑙 −1
𝑛𝑂2 0.104 𝑚𝑜𝑙
Then, by using the value of B found in the Resource section,
𝐵 = −197.5 𝑐𝑚3 𝑚𝑜𝑙 −1 = −1.975 × 10−4 𝑚3 𝑚𝑜𝑙 −1
𝑅𝑇 𝐵
𝑃= 1+
𝑉𝑚 𝑉𝑚
8.3145 𝐽𝑚𝑜𝑙 −1 𝐾 −1 × 100𝐾 1.975 × 10−4 𝑚3 𝑚𝑜𝑙 −1
= 1−
2.16 × 10−3 𝑚3 𝑚𝑜𝑙 −1 2.16 × 10−3 𝑚3 𝑚𝑜𝑙 −1
= 3.50 × 105 𝑃𝑎, or 350 kPa
2. Calculate the pressure of O2 gas (in no. 1 above) using the perfect gas equation of
state.

Answer

𝑛𝑅𝑇 𝑅𝑇 8.3145 𝐽𝑚𝑜𝑙 −1 𝐾 −1 × 100𝐾

𝑃= = = ≈ 385,000 𝑃𝑎 = 385 𝑘𝑃𝑎
𝑉 𝑉𝑚 2.16 × 10−3 𝑚3 𝑚𝑜𝑙 −1

The perfect gas equation of state would give the calculated pressure as 385 kPa, or 10
percent higher than the value calculated by using the virial equation of state
Boyle Temperature, TB

 The Boyle temperature, TB is the temperature at which the properties of

the real gas coincide with those of a perfect gas as 𝑝 → 0.

 The virial equation of state has zero slope as 𝑝 → 0 if 𝐵′ = 0, so at the

Boyle temperature 𝐵′ = 0.

 It then follows that 𝑝𝑉𝑚 = 𝑅𝑇𝐵 over a more extended range of

pressures than at other temperatures because the first term after 1 in
the virial equation is zero and 𝐶 ′ 𝑝2 and higher terms are negligibly small.
Critical Constants

 There is a temperature, called critical temperature, Tc, which

separates two regions of behavior and plays a special role in the
theory of the states of matter.
 Critical Temperature, Tc - the temperature at which the gaseous
state appears to transform continuously into condensed state, and
at no stage is there a visible surface between the two physical
states.
 Critical point – one phase is present
 Critical pressure – the pressure at the critical point
 Critical volume – the volume at the critical point
Experimental isotherms of carbon
dioxide at several temperatures. The
‘critical isotherm’, the isotherm at
the critical temperature, is at
31.04°C. The critical point is marked
with a star.
Critical Constants of Gases
𝑝𝑐 /𝑎𝑡𝑚 𝑉𝑐 /(𝑐𝑚3 𝑚𝑜𝑙 −1 ) 𝑇𝑐 /𝐾 𝑍𝑐 𝑇𝐵 /𝐾

Ar 48.0 75.3 150.7 0..292 411.5

CO2 72.9 94.0 304.2 0.274 714.8
He 2.26 57.8 5.2 0.305 22.64
O2 50.14 78.0 154.8 0.308 405.9
Kr 54.27 92.24 209.39 0.291 575.0
N2 33.54 90.10 126.3 0.292 327.2
Ne 26.86 41.74 44.44 0.307 122.1
Super Critical Fluid

 the dense fluid obtained at a temperature higher than the

critical temperature.

 it behaves like a liquid in many respects (it has similar density

for instance)

 despite its density, it is not strictly a liquid because it never

posses a surface that separate it from a vapor phase.

 nor is it a gas, because it is so dense.

The van der Waals Equation

 Individual molecules do have finite size and do occupy space.

 Repulsive interactions between molecules are present.

The actual volume in which the molecules can travel is reduced to an
extent that is proportional to the number of molecules present and the
volume they each exclude

𝑉𝑟𝑒𝑎𝑙 = 𝑉𝑐𝑜𝑛𝑡𝑎𝑖𝑛𝑒𝑟 − 𝑛𝑏

Where, n = no. of moles

b = proportionality constant between the reduction in volume
and the amount of molecules present in the container.
(an empirical constant)
• Attractive force also present between molecules
- This reduce the pressure that the gas exerts on the walls of the
container.

Reduction in pressure α:

(reduction in frequency of impacts) x (reduction in average strength of

impacts)

α (molecular attraction) x (molecular attraction)

α (molar concentration) x (molar concentration)
α n/V x n/V

Reduction in pressure α (n/V)2

Reduction in pressure = a(n/V)2
where, a = proportionality constant (an empirical constant)
The van der Waals Equation

𝑛𝑅𝑇 𝑛2 𝑎
𝑃= − 2
𝑉 − 𝑛𝑏 𝑉
Correction Correction
for volume of for molecular
molecules attraction

𝑎𝑛2
𝑃+ 2 𝑉 − 𝑛𝑏 = 𝑛𝑅𝑇
𝑉

𝑎
𝑃+ 2 𝑉𝑚 − 𝑏 = 𝑅𝑇
𝑉𝑚
van der Waals Coefficients
𝑎/(𝑎𝑡𝑚 𝑑𝑚6 𝑚𝑜𝑙 −2 ) 𝑏/(10−2 𝑑𝑚3 𝑚𝑜𝑙 −1 )
Ar 1.337 3.20
C2H4 4.552 5.82
CO 1.453 3.95
CO2 3.610 4.29
H2 0.2420 2.65
H2O 5.464 3.05
N2 1.352 3.87
Ne 0.205 1.67
NH3 4.169 3.71
O2 1.364 3.19
SO2 6.775 5.68
Xe 4.137 5.16
Key Points

o The van der Waals equation is a model equation of state for a real gas expressed
in terms of two parameters, one corresponding to molecular attractions and the
other to molecular repulsions.

o The van der Waals equation captures the general features of the behaviour of
real gases, including their critical behaviour.

o The properties of real gases are coordinated by expressing their equations of

state in terms of reduced variables.
Relationship Between Critical Constants (Tc, Pc, and Vc)

…equations linking the van der Waals constant a and b to the critical
constants

𝑉𝑚3 − 𝑏 + 𝑅𝑇ൗ𝑃 𝑉𝑚2 + 𝑎ൗ𝑃 𝑉𝑚 − 𝑎𝑏ൗ𝑃 = 0

van der Waals equation of state

@ Tc : (Vm - Vc)3 = 0
We may equate equation of like powers

From the coefficients of 𝑉𝑚2 we have

From terms in Vm From the constant terms

From these three equations we obtain:

If the expressions obtained for a, b, and R are inserted into the van der
Waals equation for 1 mol of gas we obtain:

It is convenient at this point to replace each of the ratios P/Pc, V/Vc, and T/Tc
by Pr , Vr , and Tr respectively; these represent the reduced pressure Pr ,
reduced volume Vr , and reduced temperature Tr , and are dimensionless
variables.
Practice Exercise

1. Compare the pressure predicted for 0.8 dm3 of Cl2 weighing 17.5 g at
273.15 K using (a) the ideal gas equation and (b) the van der Waals
equation.

2. At 300 K and 20 atm, the compression factor of a gas is 0.86. Calculate

(a) the volume occupied by 8.2 mmol of the gas under these
conditions and
(b) an approximate value of the second virial coefficient B at 300 K.
ANSWER TO PRACTICE EXERCISE

1. Compare the pressure predicted for 0.8 dm3 of Cl2 weighing 17.5 g at 273.15 K
using (a) the ideal gas equation and (b) the van der Waals equation.
2. At 300 K and 20 atm, the compression factor of a gas is 0.86. Calculate
(a) the volume occupied by 8.2 mmol of the gas under these conditions and
(b) an approximate value of the second virial coefficient B at 300 K.

Solution

b) The approximate value of B can be obtained from the equation 𝑝𝑉𝑚 = 𝑅𝑇 ቀ1 +

𝐵 𝐶
+ 2 + ⋯ ቁ by truncation of the series expansion up to the second term, B/Vm, in
𝑉𝑚 𝑉𝑚
the series.
Then,
Other Equation of State

Berthelot Equation

In reduced form:
Dieterici Equation

where, a and b = constants not necessarily equal to van der

Waals constants

In reduced form:
Redlich and Kwong Equation

Beattie-Bridgeman

where

a, b, A0, B0, and c = empirically determined constants.