Real Gases: Sections 1.4-1.6 (Atkins 6th Ed.), 1.3-1.5 (Atkins 7th, 8th Eds.)

Real Gases
Sections 1.4-1.6 (Atkins 6th Ed.), 1.3-1.5 (Atkins 7th, 8th Eds.)
Molecular Interactions
Compression factor
Virial coefficients
Condensation
Critical Constants
Van der Waals Equation
Corresponding States
Real gases have very different behaviour from ideal gases,

notably in cases of high pressure or near the condensation
point - a number of additional interactions must be considered
Last updated: Sept. 18, 2006, Slides 1, 16 slight modifications; Added slide 7
Molecular Interactions
Repulsive forces:
assist expansion of gas
- significant when molecules are
close to one another
- operative at high pressures, when
intermolecular distances are near a
single molecular diameter
Attractive forces:
assist compression of gas
- can have influence over a long
distance (close but not touching)
-operative at moderate pressures
Compression Factor
The compression factor of a gas can be
defined as
pVm
Z '
RT
where Vm is the molar volume, V/n
Ideal gas: Z = 1
Departure from Z = 1 means that a gas is
not behaving as an ideal gas
Intermediate Pressure: Z < 1

Compression is favoured, due to
dominance of attractive forces
High Pressure: Z > 1

Expansion is favoured, as repulsive forces
come into play
Virial Coefficients
For a real gas with large molar volumes and higher temperatures, the
isotherms are almost identical to those of an ideal gas. However, there
are some small differences which suggest that the perfect gas law is
only the first term in a power series:
B C
pVm ' RT (1 %B )p% C )p 2 %...) ' RT (1 % % % ...)
Vm V 2
m
These are the virial equations of state, where coefficients B and C

have to be evaluated at each temperature!
p = 0: Close to ideal gas law, but not exact

p increases: B contributes, linear relation between Z and P
p higher: C and higher order terms contribute, deviation from linearity
Virial: comes from that Latin word vis, viris, meaning force - the
coefficients in the virial equation depend on the forces of interaction
between molecules of the gas
Boyle Temperature
Perfect gas: dZ/dp = 0 (since Z = 1), but
in a real gas
dZ
' B ) % 2pC ) % ... 6 B ) as p 6 0
dp
dZ
6 B as Vm 6 4 , or p 6 0
d(1 /Vm)
At low T: initial dZ/dp < 0, B is negative
At high T: initial dZ/dp > 0, B is positive
(Correspond to the first order B coefficients
at these temperatures)
The temperature at which the initial slope is

zero is the Boyle Temperature, TB, where
B = 0 (real gas corresponds to an ideal
gas)
Virial Coefficients for Methane
Virial coefficients for methane up to about 400 Bar, 350oC
pVm ' RT (1% B )p% C )p 2 % D )p 3)
T (oC) B& (x 10-3 bar-1) C& (x 10-6 bar-2) D& (x 10-9 bar-3)
0 -2.349 -0.877 29
25 -1.727 +0.438 17
50 -1.274 +1.353 7.9
100 -0.677 +1.447 4.1
150 -0.324 +1.219 2.0
200 -0.106 +0.967 0.99
250 +0.0345 +0.749 0.56
300 +0.125 +0.583 0.31
350 +0.186 +0.461 0.16
Virial Coefficients for Methane, 2
Here are the coefficients B, C and D plotted as functions of
temperature:
4
1
B (x10-3)
C (x10-6)
D (x10-10)
0
25 50 100 150 200 250 300 350
-1
-2
-3
T (oC)
Condensation
CO2 gas compressed by a piston at 20oC:
A: p rises, in accordance with Boyle’s law
B: deviations from ideal gas behaviour
CDE: piston moves without any pressure
increase at all - non-ideal behaviour
This line: vapour pressure (liq-gas eqb)
A liquid appears, just to the left of C, amount

of liquid increases moving from C to D to E
Pressure does not increase, since the gas is
beginning to condense
E: sample is almost entirely liquid

Even a small volume reduction (E to F)
requires an immense increase in applied
pressure from the piston
Critical Constants
The 31.04oC isotherm for CO2:
If compression takes place at the so-called

critical temperature, Tc, the surface
separating the gas and liquid phases does not
appear, and horizontal parts of the isotherm
merge at the critical point - liquid phase does
not form above the critical temperature
The critical temperature, molar volume and

pressure, Tc, Vc and pc, are called the critical
constants, which are unique to each
substance
Certain substances have a very dense phase
which can fill an entire volume at T > Tc, and
these are referred to as supercritical fluids
van der Waals Equation
Johannes Diderik van der Waals (1837-1923), a Dutch
physicist, won the 1910 Nobel Prize in Physics for his
work on the equation of state for gases and liquids.
This is an semiempirical theory, which means it is based
upon experimental observations, combined with a
rigourous thermodynamic treatment.
The van der Waals equation is written as
2
nRT n RT a
p ' & a ' &
V & nb V Vm & b 2
Vm
where a and b are van der Waals coefficients, specific to each gas
Term a is adjusted to represent the attractive forces of the molecules,

without giving any specific physical origin to these forces; V - nb, not V,
now represents the volume in which molecules can move
Justifying the van der Waals Equation*
The coefficients a and b are adjusted to model certain features of the
gas behaviour, and are dependent upon the attractive and repulsive
forces between molecules in the gas.
V - nb: nb is the very small approximate volume occupied by

the molecules themselves
Frequency and forces of the collisions are reduced by attractive forces,

by a strength proportional to n/V (molar concentration); thus, pressure is
reduced as the square of this concentration, and is written as:
-a(n/V)2: a is a positive proportionality constant
a and b should not be assigned specific molecular properties, but rather,

serve as coefficients which help to accurately model gas behaviour, and
can be assigned specifically to each type of gas
Reliability of the van der Waals Equation
It is unrealistic to expect that such a simple equation
will be a perfect equation of state for all gaseous
substances.
- van der Waals equation:
analytical expression, allows for some general
observations on real gases (see table, next page)
- virial equation:
many accurate measurements at many temperatures,
and numerical analysis
Compare these calculated isotherms with the
experimental isotherms of CO2: the most
notable anomaly are the so-called van der
Waal’s loops, where the isotherms drop
suddenly below Tc (they suggest increase p
results in increased V) - they can be fixed by
a Maxwell construction (loops replaced by
horizontal lines). The vdW coefficients are
found by comparison of experimental and
theoretical curves
Selected Equations of State
A variety of equations of state similar to van der Waals equation have been
developed and applied to differeny types of gases.
Note the different critical constants that can be calculated “exactly” from the
coefficients a and b
Summary of the vdW Equation
(1) Perfect gas isotherms are obtained at high temperatures and large molar
volumes:
# at high T, the first term may be much greater than the second
# if Vm is high, then Vm - b . Vm, p = RT/Vm
(2) Liquids and gases exist when cohesive and dispersive forces are balanced:
# first term from KE and repulsion, second term from attraction
(3) Critical constants are related to the van der Waals coefficients:
# for T < Tc calculated isotherms oscillate, passing through a
minimum followed by a maximum, converging as T 6 Tc
# at the flat inflection, the 1st and 2nd derivatives are zero:
dp RT 2a Solve the two equations in two unknowns:
'& % ' 0
dVm 2
(Vm & b) Vm 3 Vm and T, then find p with the equation of
state! This gives:
d 2p 2RT 6a
' & ' 0 a 8a
2
dVm (Vm & b) 3 4
Vm
Vc ' 3b , pc ' , Tc '
27b 2 27Rb
At this point, the critical compression factor, Zc = pcVc/RTc = 3/8

Principle of Corresponding States
In many areas of science it is useful to compare a fundamental property of
different objects on a relative scale for purposes of comparison. For different
gases, we use reduced variables:
p Vm T
pr ' , Vr ' , Tr '
pc Vc Tc
Van der Waal “hoped” that gases in the same reduced volume at the same
reduced temperature would exert the same pressure: he was correct - these
gases behave the same - principle of corresponding states.
Rewrite vdW with reduced constants
RT rTc a
prpc ' &
VrVc & b Vr2Vc2
Replace constants with critical point values
apr 8aTr a
' &
27b 27b(3bVr& b) 9b 2Vr
2
Rearrange for pr: a and b are gone!

8Tr 3
pr ' &
3Vr & 1 2
Vr

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Real Gases

Van der Waals Equation

Real gases have very different behaviour from ideal gases,

Intermediate Pressure: Z < 1

High Pressure: Z > 1

These are the virial equations of state, where coefficients B and C

p = 0: Close to ideal gas law, but not exact

The temperature at which the initial slope is

pVm ' RT (1% B )p% C )p 2 % D )p 3)

A liquid appears, just to the left of C, amount

E: sample is almost entirely liquid

If compression takes place at the so-called

The critical temperature, molar volume and

Term a is adjusted to represent the attractive forces of the molecules,

V - nb: nb is the very small approximate volume occupied by

Frequency and forces of the collisions are reduced by attractive forces,

-a(n/V)2: a is a positive proportionality constant

a and b should not be assigned specific molecular properties, but rather,

At this point, the critical compression factor, Zc = pcVc/RTc = 3/8

Rearrange for pr: a and b are gone!

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