Properties of Gases

• Kinetic Molecular Model

• Speed of gas
• Combining Kinetic Molecular Model and Ideal
gas Law
• Real gas
• Virial equation
• PV-plot for real gas
• Van der Waals equation
• Comparing ideal and real gas

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 Our first model of a many-particle system: the Ideal Gas
Models of matter: gas models (random motion of particles)
lattice models (positions of particles are fixed)
The ideal gas model -

works well at low densities (diluted gases)

• all the molecules are identical,
• the molecules are tiny compared to their average separation (point masses);
• the molecules do not interact with each other;
combination of Boyle’s, Charles’s Laws and
• the molecules obey
Avogadro’s principle)
• collisions between the molecules and the container walls are elastic.

•All gases at same T and P have the same properties

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 The Equation of State of Ideal Gases

an equilibrium
Geometrical P state
representation of the
equation of state: the equation-
of-state surface
f (P,V,T) = 0
V
P –
T
pressure [KPa or atm]
The ideal gas V – volume [L]
equation of state: n – number of moles of gas
T – the temperature in Kelvin's [K]

PV  nRT R – a universal constant

atm.L KPa.L
R  0.082 R  8.314
mol  K mol  K
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 The Ideal Gas Law

The equations of state cannot be derived within the

frame of thermodynamics: they can be either
Avogadro’s number considered as experimental observations, or
“borrowed” from statistical mechanics.
NA  6.0220451023

isotherms
Avogadro’s Law: equal volumes of different
gases at the same P and T contain the same
amount of molecules.

The P-V diagram – the projection of the surface

of the equation of state onto the P-V plane.

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• A vessel of volume 22.4 L contains 3 moles
(SO2) and 2 moles O2 at 290 K, all SO2 gas
reacts with a sufficient amount of O2.
• Calculate the following: before and after the reaction
– The mole fractions of each component
– The partial pressures
– The total pressure
• SO2 + 1/2 O2 SO3

5
• A vessel of volume 22.4 L contains 3 mol
H2 and 2 mol N2 at 273 K. Calculate the
partial pressures and the total pressure of
the mixture. If all the H2 reacted with
sufficient N2 to form NH3. Calculate the
partial pressures and the total pressure of
the final mixture.
N2 + 3H2 2NH3

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• A vessel of volume 22.4 L contains 3 mol
H2 and 2 mol N2 at 273 K. Calculate the
partial pressures and the total pressure of
the mixture. If 2 mole the H2 reacted with
sufficient N2 to form NH3. Calculate the
partial pressures and the total pressure of
the final mixture.
• N2 + 3H2 2NH3

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• Calculate the mole fractions and partial
pressure of O2 & N2 in air if the Pair = 740
mmHg at density 1.146 g/L at 27 oC.

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 Gas mixtures
• Dalton’s Law of partial pressures
The total pressure of a mixture of gases equals the sum of
the pressures that each would exert if it were present
alone (partial pressure)
PT=P1+P2+P3+….Pn
Mole fractions: xi = ni/n
Pi ni RT / V ni
 
PT nT RT / V nT
 ni 
Pi    PT  xi PT
 nT 
Q: If dry air is composed of N2, O2, Ar at sea level in
mass percent of 75.5: 23.2: 1.3. What is partial pressure
for each when total pressure is 1.0 bar (100 kPa)?
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 Diffusion
Thomas Graham proposed a Law
(1883) to summarize experimental
observations on diffusion

Rate of Diffusion  1/√M

Relative rates of
diffusion
r1 M2

r2 M1

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 Maxwell Distribution of Speeds
 Not all molecules travel at the same speed
 Distribution of speeds derived by James Clerk
Maxwell 3/ 2
 M 
f  4  
2  Ms 2 / 2 RT
se .s
 2RT 

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 Speed of gas
every gas does not travel at the same speed

The Maxwell distribution of speeds and its variation with the temperature.
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Real Gases – General Observations
• Deviations from ideal gas law are particularly important at high
pressures and low temperatures (rel. to condensation point of
gas)
• Real gases differ from ideal gases in that there can be
interactions between molecules in the gas state
– Repulsive forces important only when molecules are nearly
in contact, i.e. very high pressures
• Gases at high pressures (spn small), gases less
compressible
– Attractive forces operate at relatively long range (several
molecular diameters)
• Gases at moderate pressures (spn few molecular dia.)
are more compressible since attractive forces dominate
– At low pressures, neither repulsive or attractive forces
dominate - ideal behavior
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Real Gases - Other Equations of State
• Virial equation is phenomenolgical, i.e., constants depend
on the particular gas and must be determined
experimentally
• Other equations of state based on models for real gases as
well as cumulative data on gases
– Berthelot (1898)  na
2
 p
 (V  nB)  nRT
• Better than van der Waals at 2
• pressures not much above 1 atm
 TV 
2
• a is a constant nRT  n  RT a
p a    2
– Van der Waals (1873) V  nb  V  Vm  b Vm
RTe  a / RTVm

– Dieterici (1899) p
V b m
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 Virial equation
in search for equation of state for real gas, one looks at
P dependent of Z

Z  1  BP  C P 2  .......
or B C
Z  1    .......
Vm Vm 2
1
Since P
V
B, C , .......
and are 2nd, 3rd, …, virial coefficient respectively
B , C , .......

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 PVm
Replacing Z by
RT

PVm B C
 1   2
 .......
RT Vm Vm
nRT  B C 
P  1    ......
V  Vm 2
 Vm 
virial equation of state
virial coefficients vary with gas type
So does the virial equation of state

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 Compression Factor, Z
• Compression factor, Z, is ratio of the
actual molar volume of a gas to the
molar volume of an ideal gas at the
same T & P
– Z = Vm/ Vm°, where Vm = V/n
• Using ideal gas law, p Vm =
RTZ
• The compression factor of a gas is a
measure of its deviation from ideality
– Depends on pressure (influence
of repulsive or attractive forces)
– z = 1, ideal behavior
– z < 1 attractive forces dominate,
moderate pressures
– z > 1 repulsive forces dominate,
high pressures
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 The Van der Waals model of real gases
For real gases – both quantitative and qualitative deviations from the ideal
gas model

Electric interactions between

electro-neutral molecules :

Veff  V  nb  an 2 
 P  2 V  nb  nRT
repulsion  V 

an 2
Peff  P  2 The van der Waals equation of state
V for real gases
attraction (the only model with interactions
that we’ll consider)

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 Van der Waals equation
another attempt to find equation of state for real gas
To correct what’s wrong in kinetic molecular model, Van
der waals proposed
Pmeasured  P  Pideal
molecular attraction reduces impact force to wall
Vmeasured  Videal  V
volume of gas is the space where gas can travel in a container
•Ideal gas has no molecular volume, volume of gas is volume of container
•real gas has molecular volume , space that gas can travel is
less than volume of container
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P  (rate of collision) x (impact force)
n n
 X
V V
Attraction reduces rate of collision and impact force
Reduction in pressure (due to attraction)
2
n
 a 
V 
From ideal gas equation
nRT
P  (1)
V

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 real gas volume is less than ideal gas
Given b as molecular volume
Vreal  V  nb

Substitute V in (1) with V - nb

2
nRT n
P   a  (2)
V  nb V 
then
  
2

 P  a    V  nb   nRT
n
(3)
  V  
  “Van der waals ‘s equation”
a, b = van der waals parameter (obtained from experiment)

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 Van der Waal’s equation

For one mole n = 1

 2

 P  an v  nb   nRT
 2  For mole n = 1
 v 

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Van der waals parameters of gas.

23
Since Van der Waals equation comes from modification of
kinetic molecular model (theory) while a, b comes from
experiment
Van der waals equation is “semi-empirical”
virial equation is “empirical”

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 - Compression factor (Z)
Vm
Z 
Vmideal
Vm = molar volume or volume per mole
If Z < 1 molar volume of real gas is less than ideal gas
molecular attraction is dominant
Z > 1 molar volume of real gas is larger than ideal gas
molecular repulsion is dominant
RT
Substitute V ideal
m 
P
Vm PVm
Z  
RT P RT

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The variation of the compression factor, Z, with pressure for several gases
at 273 K
26
 PV plot for real gas
CO2

The experimental isotherms of CO2 at several temperatures.

27
•
Critical Constants
Consider what happens when you compress a real gas at constant T
(move to left from point A)
– Near A, P increases by Boyle’s Law
– From B to C deviate from Boyle’s Law, but p still increases
– At C, pressure stops increasing
• Liquid appears and two phases present (line CE)
• Gas present at any point is the vapor pressure of the liquid
– At E all gas has condensed and now you have liquid
• As you increase temperature for a real gas, the region where
condensation occurs gets smaller and smaller
• At some temperature, Tc, only one phase exists across the entire
range of compression
– This point corresponds to a certain temperature, Tc, pressure, Pc , and
molar volume, Vc , for the system
• Tc, Pc , Vc are critical constants unique to gas
– Above critical point one phase exists (super critical fluid), much denser
than typical gases
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• Solving these equations for p,Vm and T gives Pc, Vc
and Tc in terms of a and b
– Hint: you must use original eqn to do this
– Vc = 3b, Pc = a/27b2, Tc =8a/27Rb
– Critical compression factor, Zc, can be calculated using
definition for Z:
• PVm = RTZ

– This should be a constant for all gases and is

 RT a 
d   2 
dp  Vm  b Vm  RT 2a
   3 0 (1)
dVm dVm Vm  b  Vm
2

 RT 2a 
d   2 

3 
2
d p  Vm  b  Vm  2 RT 6a
   0 (2)
dVm dVm Vm  b  Vm
3 4

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 2a RT
from equation (1) 
Vm
3
Vm  b 2
6a 2 RT
from equation ( 2) 
Vm
4
Vm  b 3

6a 2a 2 RT RT
/ 3 /
4
Vm Vm Vm  b  Vm  b 
3 2

3 2

Vm Vm  b 
3Vm  b   2Vm
3Vm  3b  2Vm
3Vm  2Vm  3b
Vc = 3b
Vm  3b 30
 2a RT
from equation (1)  by sub Vm  3b
Vm
3
Vm  b 2
2a RT

(3b) 3
3b  b 2
8a
Tc  Tc =8a/27Rb
27bR
RT a
from Van der Waal ' s equation for 1 mole p  2
Vm  b Vm
8a
R[ ]
p 27bR  a  [ 8a ]x 1  a  [ 4a ]  a  4a  3a
3b  b (3b) 2 27b 2b 9b 2 27b 2 9b 2 27b 2
a
Pc  2
pc = a/27b
2
27b

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 Critical constants
pc Vc Tc Zc TB
atm cm3/mol K 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

Test van der Waal’s for reasonableness

pcVc 1  a   27 Rb  3
Zc    3b     0.375
RTc R  27b 
2
 8a  8

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 Comparing Different Gases
• Different gases have different values of p, V and T at
their critical point
• You can compare them at any value by creating a
reduced variable by dividing by the corresponding critical
value
– preduced = pr = p / pc; Vreduced = Vr = Vm / Vc; Treduced = Tr = T/ Tc
– This places all gases on the same scale and they behave in a
regular fashion; gases at the same reduced volume and
temperature exert the same reduced pressure.
• Law of Corresponding States
• Independent of equations of state having two variables

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Critical constants

34
- Reduced properties
P Vm T
Pr  , Vr  , Tr 
Pc Vc Tc

The compression factors of four gas.

35
- Van der waals loop

Isotherms calculated by using the van der waals equation of state.

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 Comparing ideal and real gas
V = 10 L , n = 1 mol
P (atm)
Ideal gas Vdw Virial*

N2 2.239 2.234 2.236

273 K CO2 2.239 2.212 2.205
O2 2.239 2.232
Air** 2.239 2.233
N2 4.920 4.926 4.931
600 K CO2 4.920 4.905 4.914
O2 4.920 4.922
Air 4.920 4.925

nRT  B
*P  1   ** AIR = 80%N2 + 20%O2
V  Vm 
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 Liquefaction-Irish Links!
• Refrigeration developed by Carl von Linde in 19th
Century, in response to a request from
Guinness in Dublin for a new cooling technique.
• Based upon the fact that gases cool as they
expand: Joule-Thomson effect (William
Thomson, later Lord Kelvin, born in Belfast),

The Linde refrigerator combines the JT process

with a counter-flow heat exchanger.

The gas is re-circulated and it cools on expansion

through the throttle. The cooled gas cools the
high-pressure gas, which cools still further as it
expands. Eventually liquefied gas drips from the
throttle.
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