Physical Chemistry

Ideal and Non Ideal

Gases
 Definition of Gas

Gas is a fluid (as air) that has neither

independent shape nor volume but tends
to expand indefinitely.

A gas is a substance that is normally in the gaseous state at

ordinary temperatures and pressures.
A vapor is the gaseous form of any substance that is a
liquid or a solid at normal temperatures and pressures
(25oC and 1 atm pressure, we speak of water vapor and
oxygen gas)
 Substances That Exist as Gases
Under normal atmospheric conditions (25°C and 1 atmosphere (atm) pressure)

• Hydrogen, nitrogen, oxygen, fluorine, and

chlorine exist as gaseous diatomic molecules:
H2 , N2 , O2 , F2 , and Cl2 . An allotrope of
oxygen, ozone (O3 ), is also a gas at room
temperature.
• All the elements in Group 8A, the noble
gases, are monatomic gases: He, Ne, Ar, Kr,
Xe, and Rn.

Molecular compounds such as example CO,CO2 , HCl, NH3 , and CH4 (methane) are
gases, but the majority of molecular compounds are liquids or solids at room
temperature
Intermolecular force dependence: the stronger these attractions, the less likely a
compound can exist as a gas at ordinary temperatures

Ionic compounds do not exist as gases at 25°C and 1 atm

 Substances That Exist as Gases
Of the gases listed in Table, only
O2 is essential for our survival
All gases have the following physical
characteristics:
• Gases assume the volume and shape of
their containers.
• Gases are the most compressible of the
states of matter.
• Gases will mix evenly and completely when
confi ned to the same container.
• Gases have much lower densities than
liquids and solids.

Hydrogen sulfide (H 2 S) and hydrogen cyanide (HCN) are deadly poisons

CO, NO2 , O3 , and SO2 , are somewhat less toxic.
He, Ne, and Ar are chemically inert; that is, they do not react with any other substance
Most gases are colorless. Exceptions are F2 , Cl2 , and NO2 . The dark-brown color of NO2 is
sometimes visible in polluted air.
Ideal and Non Ideal Gases

Characteristic and Properties of

Gases

Boyle’s Law

Ideal Gas Laws Charles’s Law

Gay-Lussac’s Law

Some Equations Related to Non

Ideal Gases or Real Gases
 Definition of Ideal Gas

An ideal gas is gas whose pressure (P),

volume (V), and temperature (T) are related
by the ideal gas law.

PV = nRT

where :
n = number of moles of the gas
R = the ideal gas constant
Ideal gases are defined as
having molecules with negligible size with an
average molar kinetic energy dependent only
on temperature.

At low temperature:
Most gases behave enough like ideal gases that
the ideal gas law can be applied to them.
 Characteristic and properties of gases

• The location of molecules very distant

• Constituent molecules move very freely

• Attractive forces between molecules is almost non

• Volume and shape easily changed

• Can fill the entire space available

Characteristic and Properties of Ideal Gases

• Gas consists of particles moving very much at

random, at a steady pace in the two collision.

• There was no attractive force or repulsive

force between gas particles.

• Gas particle collisions are resilient perfect.

• The volume of gas particles are
considered zero (negligible to the
volume of space).

• In the gas particles apply the laws of

mechanics.

• Average kinetic energy of gas particles is

directly proportional to the average
temperature of the room.
 Ideal Gas Laws

• Boyle’s Law
• Charles’s Law
• Gay-Lussac’s Law
 Boyle’s Law

Boyle investigated the relation between the

pressure and volume of gases in 1662 and
found that, for a fixed amount of gas kept at a
fixed temperature, P and V are inversely
proportional:
PV = k constant Θ, m
 Charles’ Law
Charles (1787) and Gay-Lussac (1802)
measured the thermal expansion of gases and
found a linear increase in volume with
temperature (measured on the mercury
centigrade scale) at constant pressure and
fixed amount of gas:
 The content of Charles’ law is simple

• The thermal expansions of gases and of liquid

mercury are quite similar
• The molecular explanation for Charles’ law lies in
the fact that an increase in temperature means the
molecules are moving faster and hitting the walls
harder and more often.
• Therefore, the volume must increase if the
pressure is to remain constant.
The Ideal-Gas Absolute Temperature
Scale
• Charles’ law is obeyed most accurately in the
limit of zero pressure; but even in this limit,
gases still show small deviations.
• These deviations are due to small differences
between the thermal-expansion behavior of
ideal gases and that of liquid mercury, which is
the basis for the u temperature scale.
• However, in the zero-pressure limit, the
deviations from Charles’ law are the same for
different gases.
• In the limit of zero pressure, all gases show the
same temperature-versus-volume behavior at
constant pressure.
Plots of volume versus centigrade temperature
for 1 mole of N2 gas at constant pressure

Temperature
 Gay-Lussac’s Law

“ At the same temperature and pressure ratio

of volume of gases that react and the reaction
proceeds directly as integers “

Where : P = Pressure of gas

T = Temperature in Kelvin
Some equations related to non ideal gases or real gases

•  Van Der Waals model

•  Redlich–Kwong model
•  Berthelot and modified Berthelot model
•  Dieterici model
•  Clausius model
•  Virial model
•  Peng–Robinson model
•  Wohl model
•  Beattie–Bridgman model
•  Benedict–Webb–Rubin model
 Van Der Waals Model

Where :
• P is the pressure
• T is the temperature
• R is the ideal gas constant
• Vm is the molar volume
a and b are parameters that are determined
empirically for each gas, but are sometimes
estimated from their critical temperature (Tc)
and critical pressure (Pc) using these relations:
 Redlich–Kwong model

• The Redlich–Kwong equation is another two-

parameter equation that is used to model
real gases.

• where a and b two empirical parameters that

are not the same parameters as in the van
der Waals equation.
• These parameters can be determined:
Berthelot and modified Berthelot model

 The modified version is somewhat more accurate :

Dieterici model
 Clausius model

Where

Vc is critical volume

 Virial model

The Virial equation derives from a perturbative

treatment of statistical mechanics.
 Peng–Robinson model
• Peng-Robinson equation of state has the
interesting property being useful in modeling
some liquids as well as real gases.
 Wohl model

• The Wohl equation is formulated in terms of

critical values, making it useful when real gas
constants are not available.
 Beattie–Bridgman model

• This equation is based on five experimentally

determined constants. It is expressed as
 Benedict–Webb–Rubin model

where :
• d is the molar density
• a, b, c, A, B, C, α, and γ are empirical
constants.
• Note that the γ constant is a derivative of
constant α and therefore almost identical to 1.
Ideal and Non Ideal Gases

Critical Phenomenon and

Compressibility factors

Non ideal gases, liquefaction of gases

Semi empirical equation of Van der Waal, theoretical

backgrounds and derivation
 Definition of Critical Phenomenon

Critical phenomena is the

collective name associated
with the physics of critical
points. The critical point is a
situation where the
boundary conditions
between the gas can be
liquefied and can not be
availed.
At temperatures above the critical point (Tc),
the kinetic energy of gas molecules equal to 3/2
kT and a kinetic energy which is quite large and
difficult to overcome if only by bringing
pressure from the outside. Therefore, the
kinetic energy of gas molecules is high enough,
then the force is not strong intermolecular
attraction molecules closer to each other or the
gas can not be liquefied.
If a gas at temperatures below the critical
temperature given enough pressure, the
volume of gas it will be smaller and then the
gas density to be very large, up to a price
where its density lies between the gas
density and the density of the liquid.
Gas can be availed by way of a sudden change the

gas density becomes larger or close to liquid

density. Phase transition from gas to liquid called

fluid. With this fluid one can distinguish between

liquid phase and gas phase.

When the fluid temperature is below the
critical temperature and molar volume
smaller than the molar volume of liquid, the
fluid is in the liquid phase. If both these
conditions are not met, then the fluid in the
gas phase.
real gas that value of Z < 1 indicates that the gas
is more easily compressed than the ideal gas, and
conversely when the value of Z > 1 the gas is
more difficult to compressed than an ideal gas.
Generalized compressibility factor graphs for pure gases
Liquefaction of gases is physical
conversion of a gas into a liquid state
(condensation).

The gas liquefied in

the condenser, where
the heat of vaporization is
released, and evaporated in
the evaporator, where the
heat of vaporization is
absorbed.
• Both a and b can be
obtained by using critical
properties (a = 0.4963
R2Tc2/pc, b =
0.18727RTc/pc ).
Sadus (1993) has demonstrated that Carnahan-
Starling equation can be used to predict the
Type III equilibria of non-polar mixtures with
considerable accuracy. The Guggenheim
equation (Guggenheim, 1965) is a simple
alternative to the Carnarhan-Starling. It also
incorporates an improved hard-sphere repulsion
term in conjunction with the simple van der
Waals description of attractive interactions.
 where b = b(T c / T) 3/m , m is
typically assigned a value of 10,
and V denotes molar volume.
The other equation of state
parameters can be derived from
the critical properties:
 QUESTIONS

1. Calculate the pressure that produced by 1

mole of CO2 at 0°C in a volume of 1 L, if the
gas is not ideal, a = 3.59 L2 atm mol-2 and b =
0.0427 L mol-1. Compare the price if gas is
ideal.
2. Calculate the average molecular mass in the
earth’s atmosphere at 500 km. At that altitude
the pressure is 1.6 x 10-11 bar, the temperature
is on the average 1580 K, and the density is
2.2 x10-12 gL-1.
3. What would be the volume of a helium-filled
balloon with a lifting power of 100 lb (45 kg)?
assume an air temperature of 20°C, a pressure of 1
bar, and a molar mass of air of 28.9 g.
4. Mass of neon gas is 255 mg, volume of 3L
and a temperature of 122 K. What is the gas
pressure when the gas is ideal?
5. What is the compressibility factor? Explain
with examples!

6. By using the Berthelot equation, determine

the volume of 3 mol Cl2 at 50°C and a
pressure of 2.5 atm!