Está en la página 1de 50

# Equations of State

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

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

Liquids
Gases

A

Law
B
Boyles Law
C
Charles Law

Volume

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

finite volume

## Real gas particles have

considerable intermolecular
interactions

## Failure of Charles Law

At

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

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)

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]

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

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?

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

Waals equation

constants

## Using VDW equation,

we can derive the
following

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

RT
a
p=
- 2
Vm -b Vm

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

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

## That means gas behaves ideally

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

Boyle Temperature
Mathematical

implication

dZ/dp = 0

For

TB = a / Rb

## Low Boyle Temperature favoured by weaker IMF

and bigger gas molecules

Virial Equations

Virial Equations

Z

= pVm/RT

Obviously

Z1

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

Terms

## can be added when necessary

Accuracy can be increase by adding infinite
terms

Coefficients

## B and B are proportionate but not

equal to each other

Summary

Summary

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

## A gas cannot be condensed into liquid at temperatures

higher than its critical temperature

Summary

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

dZ/dp=0

Summary

## Virial equations are highly flexible

equations of state where extra terms can