ASSOC. PROF.

DR RUBIYAH BAINI
DEPARTMENT OF CHEMICAL ENGINEERING & ENERGY SUSTAINABILITY
Email: ruby@unimas.my
Tel: 082-583457
The study of the underlying principles that
govern the properties and behavior of
chemical systems either based on
microscopic (quantum chemistry-atomic
structure, spectroscopy) or macroscopic
(thermodynamics-heat work, energy)
viewpoint.
Also include the study of kinetics- rate of
processes – chemical reaction, diffusion.
Perfect gas can be illustrated as a collection of
molecules (or atoms) in continuous random
motion, with average speeds that increases as
the temperature increases. The molecules of
a gas are widely separated from one another
and move in paths that are largely unaffected
by intermolecular forces.
According to the ideal gas law, when a gas is compressed
into a smaller volume, the number and velocity of
molecular collisions increase, raising the gas's
temperature and pressure.
Assumptions:
 The gas consists of molecules of mass, m, in

ceaseless random motion.

 The size of the molecules is negligible, in the

sense that their diameters are much smaller

than the average distance travelled between
collisions.
 The molecules interact only through brief,

infrequent, and elastic collisions.

An elastic collision is a collision in which the total
translational kinetic energy of the molecules is conserved.
The pressure and volume of the gas is related by,
1/ 2
1  3RT 
pV  nMc 2  nRT ; c   
3  M 
Where,

M  mN A , the molar mass of the molecules

c  v 2 , this depends only on the temperatur e.
At constant temperature, pV=constant
(Boyle’s law)
 Deviations from ideal gas law are particularly important at
high pressures and low temperature.
 Real gases differ from ideal gases in that there can be
interactions between molecules in the gas state
◦ At high pressure, the repulsive forces dominates when
molecules are nearly in contact (molecules occupy a small
volume).The gas is expected to be less compressible.
◦ At moderate pressures, the attractive forces dominates
when the average separation of the molecules is only a few
molecular diameters. The gas is expected to be more
compressible than a perfect gas because the forces help to
draw the molecules together.
◦ At low pressures, neither repulsive or attractive forces
dominate. The gas is expected to behave ideally.
The physical state of the gas can be described
based on its volume (V), pressure(P),
temperature(T) and its mole number(n), and
using the equation of state.

Equation of state, P=f(T, V,n)

For ideal/perfect gas, PV=nRT

For real gas, Van der Waals equation
Extensive properties are additive: if an amount
of a subtance is divided into 2 parts with V1
and V2, total, V = V1+V2

Intensive properties are independent of the

amount of matter/size of system and are not
additive, such as pressure, temperature and
density.
 Equation of state for perfect gas

PV = nRT;
Increasingly true as P  0 a limiting law

For a fixed amount of gas (n, constant)

plot of properties of gas give surface
◦ Isobar - pressure constant - line, V  T
◦ Isotherm - temperature constant, hyperbola, PV
= constant
◦ Isochor - volume constant – line, P  T
 R: gas constant
 0.082 L atm K-1 mol-1
 0.08314 L bar K-1 mol-1
 8.314 L kPa K-1 mol-1
 8.314 J K-1 mol-1
 62.36 L Torr K-1 mol-1
Name Symbol
pascal 1 Pa = 1 Nm-2=1 kgm-1s-2
Bar 1 bar = 105 Pa
atmosphere 1 atm = 1.01325 x 105 Pa
Torr 1 Torr
Millimetres of mercury 1 mmHg
Pound per square inch 1 psi

A pressure of 1 bar is the standard pressure, denoted as

pƟ
The equation of state of a low-pressure gas was
established by combining a series of experimental results.

Boyle’s law: pV = constant, at constant n, T

Charles’s law:
V = constant × T, at constant n, p
p = constant × T, at constant n, V

Avogadro’s principle:
V = constant × n at constant p, T
The law states that the volume of a given mass of a gas at
constant temperature is inversely proportional to its pressure.
The isotherm of gases are hyperbolas
p α (1/V) ; pV = constant

Increasing T

isochores line-
constant volume
Isobars line-constant pressure
Charles law
The law states that the volume of a
given mass of a gas at constant
pressure is directly proportional to
the absolute temperature.

V α T ; V = constant x T, at constant n,p

p = constant x T, at constant n, V
 Avogadro's principle
This states that equal volumes of gases, under
similar conditions of temperature and
pressure, contain equal number (N) of
molecules.
Vαn
 Combined gas law gives,
 pV= nRT (perfect gas equation)

P1V1 P2V2

T1 T2
Dalton's Law of partial pressure
The total pressure exerted by a mixture of two or
more non-reacting gases in a definite volume, at
any given temperature is equal to the sum of the
partial pressures.

pJ=xJp, x is the mole fraction of the component J

xJ=nJ/N, N = nA+ NB ;  xJ =1
 For a mixture of gases, A, B, C, D, the total pressure is the
sum of partial pressure of the gases

ptotal = pA + pB + pC + pD + ……. ;
p =  pJ =  xJ p, this is true of all gases, not just ideal
gases

pJ V = nJRT
 
  nJ  RT
ptotal  J 
V
 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
 Consider the experimental
isotherms for carbon dioxide CO2
◦ At high temperatures (>50°C)
and high molar volumes (Vm >
0.3 L/mol), isotherm looks close
to ideal
◦ Suggests that behavior of real
gases can be approximated
using a power series
pVm  RT (1  B' p  C ' p 2  ...)

 B C 

pVm  RT 1    ....... 
 Vm V 2 
 m 
Virial coefficients, B(cm3mol-1)
Temperature
273K 600K
Ar -21.7 11.9
CO2 -149.7 -12.4
N2 -10.5 21.7
Xe -153.7 -19.6
  Consider what happens when you compress a
real gas at constant T (move to left from
CO2 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
2 phases  Tc, Pc , Vc are critical constants unique to gas
◦ Above critical point one phase exists (super
critical fluid), much denser than typical gases
 2
nRT n
p  a 
V  nb V 

Temperature
a/(atmdm6mol-2) b/(10-2dm3mol-
1
)
Ar 1.337 3.20
CO2 3.610 4.29
N2 0.0341 2.38
Xe 4.137 5.16
 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
the corresponding
critical value
◦ preduced = pr = p / pc;
Vreduced = Vr = Vm / Vc;
Treduced = Tr = T/ Tc

pr
In an industrial process, nitrogen is heated to
500 K in a vessel of constant volume. If it
enters the vessel at 100 atm and 300 K,
what pressure would it exert at the working
temperature if it behaved as a perfect gas?
[Ans: 167 atm]
P1V1 P2V2

Use this equation,
T1 T2
The mass percentage composition of dry air at
sea level is approximately N2: 75.5; O2:23.2;
Ar:1:3. What is the partial pressure of each
component when th etotal pressure is 1.00
atm?
[Ans: 0.703, 0.189, 0.0084, 0.00027 atm]

Hint: Find the mol fraction of each component.

 Physical Chemistry by Atkins, P.W
 Physical Chemistry by Levine, I. N.
 Physical Chemistry by Ball, D.W.
 Physical Chemistry by Robert J.S.
Final exam : 50%
Test : 30%
Assignment : 20%