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Equations of State

Compiled by:
Gan Chin Heng / Shermon Ong
07S06G / 07S06H

How are states represented?

Diagrammatically (Phase diagrams)


Pressure

Solid

Liquid
Critical point

Triple point

Gas
Temp

How are states represented?

Mathematically
Using

equations of state
Relate state variables to describe property of
matter
Examples of state variables
Pressure
Volume
Temperature

Equations of state

Mainly used to describe fluids


Liquids
Gases

Particular emphasis today on gases

ABCs of gas equations


A
Avogadros

Law
B
Boyles Law
C
Charles Law

Avogadros Law

At constant temperature and pressure


Volume

of gas proportionate to amount of gas


i.e. V n

Independent of gas identity


Approximate molar volumes of gas

24.0

dm3 at 298K
22.4 dm3 at 273K

Boyles Law

At constant temperature
and amounts
Gas volume

inversely
proportionate to pressure,
i.e. V 1/p
The product of V & p, which
is constant, increases with
temperature

Charles Law

At constant pressure
and amounts
Volume

proportionate to
temperature, i.e. V T

is in Kelvins
Note the extrapolated
lines (to be explained
later)

Combining all 3 laws


V (1/p)(T)(n)
V nT/p
Rearranging, pV = (constant)nT
Thus we get the ideal gas equation:

pV = nRT

Assumptions

Ideal gas particles occupy


negligible volume

Ideal gas particles have


negligible intermolecular
interactions

But sadly assumptions fail


Nothing is ideal in this world
Its downright
squeezy here

Real gas particles DO occupy


finite volume

Real gas particles have


considerable intermolecular
interactions

Failures of ideal gas equation

Failure of Charles Law


At

very low
temperatures
Volume do not
decrease to zero
Gas liquefies instead
Remember the
extrapolated lines?

Failures of ideal gas equation

From pV = nRT, let Vm be molar volume


pVm

= RT

pVm

/ RT = 1

pVm / RT is also known as Z, the


compressibility factor
Z should be 1 at all conditions for an ideal
gas

Failures of ideal gas equation


Looking at Z plot
of real gases
Obvious deviation
from the line Z=1
Failure of ideal
gas equation to
account for these
deviations

So how?

A Dutch physicist named Johannes


Diderik van der Waals devised a way...

Johannes Diderik van der Waals


November 23, 1837
March 8, 1923
Dutch
1910 Nobel Prize in
Physics

So in 1873
I can approximate
the behaviour of
fluids with an
equation

Scientific
community

ORLY?
YARLY!

Van der Waals Equation


Modified from ideal gas equation
Accounts for:

Non-zero

volumes of gas particles (repulsive

effect)
Attractive forces between gas particles
(attractive effect)

Van der Waals Equation

Attractive effect
Pressure

= Force per unit area of container


exerted by gas molecules
Dependent on:
Frequency of collision
Force of each collision

Both

factors affected by attractive forces


Each factor dependent on concentration (n/V)

Van der Waals Equation


Hence

pressure changed proportional to

(n/V)2
Letting a be the constant relating p and
(n/V)2
Pressure term, p, in ideal gas equation
becomes [p+a(n/V)2]

Van der Waals Equation

Repulsive effect
Gas

molecules behave like small,


impenetrable spheres
Actual volume available for gas smaller than
volume of container, V
Reduction in volume proportional to amount of
gas, n

Van der Waals Equation


Let

another constant, b, relate amount of gas,


n, to reduction in volume
Volume term in ideal gas equation, V,
becomes (V-nb)

Van der Waals Equation


Combining both derivations
We get the Van der Waals Equation

n
p + a
V

[V-nb] = nRT

OR
a
p + 2
Vm

[Vm -b] = RT

Van der Waals Equation -> So


whats the big deal?

Real world significances


Constants

a and b depend on the gas identity


Relative values of a and b can give a rough
comparison of properties of both gases

Van der Waals Equation -> So


whats the big deal?

Value of constant a
Gives

a rough indication of magnitude of


intermolecular attraction
Usually, the stronger the attractive forces, the higher
is the value of a
Some values (L2 bar mol-2):

Water: 5.536
HCl: 3.716
Neon: 0.2135

Van der Waals Equation -> So


whats the big deal?

Value of constant b
Gives

a rough indication of size of gas molecules


Usually, the bigger the gas molecules, the higher is
the value of b
Some values (L mol-1):

Benzene: 0.1154
Ethane: 0.0638
Helium: 0.0237

Critical temperature and


associated constants

Critical temperature?
Given a p-V plot of a
real gas
At higher temperatures
T3 and T4, isotherm
resembles that of an
ideal gas

Critical temperature?

At T1 and V1, when gas volume


decreased, pressure increases
From V2 to V3, no change in
pressure even though volume
decreases
Condensation taking place and
pressure = vapor pressure at T1
Pressure rises steeply after V3
because liquid compression is
difficult

Critical temperature?

At higher temperature T2,


plateau region becomes shorter
At a temperature Tc, this
plateau becomes a point
Tc is the critical temperature
Volume at that point, Vc =
critical volume
Pressure at that point, Pc =
critical pressure

Critical temperature
At T > Tc, gas cant be compressed into
liquid
At Tc, isotherm in a p-V graph will have a
point of inflection

1st

and 2nd derivative of isotherm = 0

We shall look at a gas obeying the Van der


Waals equation

VDW equation and critical


constants

Using VDW equation,


we can derive the
following

a
p + 2 [Vm -b] = RT
Vm

RT
a
p=
- 2
Vm -b Vm

VDW equation and critical


constants

At Tc, Vc and Pc, its a


point of inflexion on pVm graph

dp

0
dVm T
d p
0

2
dVm T
2

VDW equation and critical


constants
dp
RT
2a
3


2
(Vm b) Vm
dVm T
d 2 p
2 RT
6a

2
3
dVm T (Vm b) Vm
Rearranging...
a
8a
Vm,c = 3b; p c =
; Tc =
2
27b
27Rb
pc Vm,c
3
Zc =
=
RTc
8

VDW equation and critical


constants

Qualitative trends
As

seen from formula, bigger molecules decrease


critical temperature
Stronger IMF increase critical temperature

Usually outweighs size factor as bigger molecules have


greater id-id interaction

Real

values:

Water: 647K
Oxygen: 154.6K
Neon: 44.4K
Helium: 5.19K

Compressibility Factor

Compressibility Factor
Recall Z plot?
Z = pVm / RT; also called
the compressibility
factor
Z should be 1 at all
conditions for an ideal
gas

Compressibility Factor
For real gases, Z not
equals to 1
Z = Vm / Vm,id
Implications:

At

high p, Vm > Vm,id, Z


>1
Repulsive forces
dominant

Compressibility Factor
At

intermediate p, Z <

1
Attractive forces
dominant
More significant for
gases with significant
IMF

Boyle Temperature
Z also varies with temperature
At a particular temperature

= 1 over a wide range of pressures

That means gas behaves ideally


Obeys Boyles Law (recall V 1/p)
This temperature is called Boyle Temperature

Boyle Temperature
Mathematical

implication

Initial gradient of Z-p plot = 0 at T


dZ/dp = 0

For

a gas obeying VDW equation

TB = a / Rb

Low Boyle Temperature favoured by weaker IMF


and bigger gas molecules

Virial Equations

Virial Equations

Recall compressibility factor Z?


Z

= pVm/RT

= 1 for ideal gases

What about real gases?


Obviously

Z1

So how do virial equations address this


problem?

Virial Equations

Form
pVm/RT

= 1 + B/Vm + C/Vm2 + D/Vm3 +

pVm/RT

= 1 + Bp + Cp2 + Dp3 +

B,B,C,C,D & D are virial coefficients


Temperature

dependent
Can be derived theoretically or experimentally

Virial Equations

Most flexible form of state equation


Terms

can be added when necessary


Accuracy can be increase by adding infinite
terms

For same gas at same temperature


Coefficients

B and B are proportionate but not


equal to each other

Summary

Summary

States can be represented using diagrams or equations

Ideal Gas Equation combines Avagadro's, Boyle's and


Charles' Laws

Assumptions of Ideal Gas Equation fail for real gases,


causing deviations

Van der Waals Gas Equation accounts for attractive and


repulsive effects ignored by Ideal Gas Equation

Summary

Constants a and b represent the properties of a real gas

A gas with higher a value usually has stronger IMF

A gas with higher b value is usually bigger

A gas cannot be condensed into liquid at temperatures


higher than its critical temperature

Summary

Critical temperature is represented as a point of inflexion


on a p-V graph

Compressibility factor measures the deviation of a real


gas' behaviour from that of an ideal gas

Boyle Temperature is the temperature where Z=1 over a


wide range of pressures

Boyle Temperature can be found from Z-p graph where


dZ/dp=0

Summary

Virial equations are highly flexible


equations of state where extra terms can
be added

Virial equations' coefficients are


temperature dependent and can be
derived experimentally or theoretically