Properties of Gases

Objectives of this chapter:

Knowledge of variations of properties of
real gas from ideal gas
Understanding properties of ideal gas
Understanding properties of real gas
Competency in assembling equations of
state, their use and interpretations
Major concepts
•Ideal gas/perfect gas
•Equations of State
•Real Gases
•Virial Series
•Vdw
 The perfect gas
• A simplest state of matter (fills any container it occupies)
• A gas as a collection of molecules (or atoms) in continuous
random motion, with average speeds that increase as the
temperature is raised.
• A gas differs from a liquid in that, except during collisions,
the molecules of a gas are widely separated from one another
and move in paths that are largely unaffected by
intermolecular forces
• perfect gas can be pictured as a collection of molecules in
continuous random motion, with speeds that increase with
Temp
 States of gases
• The physical state (physical condition) of a sample of a
substance, is defined by its physical properties.
• Two samples of a substance that have the same physical
properties are in the same state.
• Physical properties are its volume, V, amount of substance
(number of moles), n, pressure, p, and temperature, T
• It is sufficient to specify only three of these variables, for
then the fourth variable is fixed.
• i.e. that each substance is described by an equation of
state, an equation that interrelates these four variable
 Variables of states; specify the state
of the a system
The state of a pure gas is specified by giving values of V, n, P, & T.
p = f (T,V,n) general form of equation of state

Physical Characteristics Typical Units

Volume, V liters (L)
Pressure, P atmosphere
(1 atm = 1.015x105 N/m2)
Temperature, T Kelvin (K)
Number of atoms or mole (1 mol = 6.022x1023
molecules, n atoms or molecules)
 Equations of state
• Mainly used to describe fluids
– Liquids
– Gases
• Particular emphasis for this chapter is on gases
• The general form of an equation of state is
p = f(T,V,n)
This equation tells us that, if we know the values of T, V, and n for a
particular substance, then the pressure has a fixed value.
Equation of state: mathematical relationship between variables that
characterize a system
 Pressure
• Pressure is defined as force divided by the area to which the force is
applied. The greater the force acting on a given area, the greater the
𝑁
pressure 𝑃 = 𝐴𝐹 = 2 units are N m-2 (SI unit is pascal).
𝑚
1 atm = 1.01325 x 105 Pa.
• Example: same weight applied on different volume, heel has less
volume whereas a sneaker has larger volume
• Which shoe will exert more pressure when stepped on?
Measurement of Pressure
• The principle of manometer is based on
the displacement of a fluid inside a
column by a gas sample
• The gas sample exerts force on the
fluid forcing it move up
• The pressure of the gas is balanced out
by the fluid column
• Fluid that is used for this is mercury
• The pressure exerted by the atmosphere
is measured with a barometer invented
by Torricelli. Gas sample is an entire
atmosphere
• It follows that the height of the
mercury column is proportional to the
external pressure
 Derive an equation for the pressure at the base of a
column of liquid of mass density ρ (rho) and height h at
the surface of the Earth.
𝐹
• 𝑃= where F is force applied to area A
𝐴
• 𝐹 = 𝑚𝑔 m =
mass of a column and g accelaration due to gravity
• 𝑚 = 𝜌𝑉 (𝜌 = 𝑚𝑎𝑠𝑠 𝑑𝑒𝑛𝑠𝑖𝑡𝑦, 𝑉 = 𝑣𝑜𝑙𝑢𝑚𝑒)
• 𝑉 =𝐴 ×ℎ
𝑚𝑔 𝜌𝑉𝑔 𝜌𝐴ℎ𝑔
• ∴𝑃= = = =𝜌ℎ𝑔
𝐴 𝐴 𝐴
 Temperature
• A change in physical state (for example, a change of volume)
can occur when two objects are in contact with one another.
• The temperature, T, is the property that indicates the direction
of the flow of energy through a thermally conducting
(diathermic), rigid wall.
• A boundary is adiabatic (thermally insulating) if no change
occurs even though the two objects have different
temperatures
 ABCs of gas equations/laws

Avogadro’s Law
•A
Boyle’s Law
•B

Charles’ Law
•C

 Boyle’s Law
 Pressure and volume
are inversely related at
constant temperature.
 PV = K
 As one goes up, the other
goes down.
 P1V1 = P2V2
“Father of Modern Chemistry”
Robert Boyle
Chemist & Natural Philosopher
Listmore, Ireland
January 25, 1627 – December 30, 1690
 Molecular interpretation of Boyle’s Law:
• As a sample is compressed to half its volume, twice as many
molecules strike the walls in a given period of time than before
compression.
• Results in doubling average force on the walls.
• Hence, when the volume is halved the pressure of the gas is doubled
• Valid only at low pressures (limiting law).
Boyle’s Law: P1V1 = P2V2

Each of the curves in

the graph corresponds
to a single
temperature and hence
is called an isotherm
Charles’ Law
 Volume of a gas varies
directly with the absolute
temperature at constant
pressure.
 V = KT
 V1 / T1 = V2 / T2
Jacques-Alexandre Charles
Mathematician, Physicist, Inventor
Beaugency, France
November 12, 1746 – April 7, 1823
Charles’ Law: V1/T1 = V2/T2
Charles’ Law: V1/T1 = V2/T2
 Charles’s Law:
• The lines in this illustration are examples of isobars, or lines showing
the variation of properties at constant pressure.
• Raising temperature of a gas increases the average speed of its
molecules. The molecules collide with the wall more frequently and
with greater impact, thus exerting greater pressure.

• Boyle’s and Charles’s laws are examples of a limiting law, a law that
is strictly true only in a certain limit, in this case p → 0.
 Avogadro’s Law

At constant temperature

and pressure, the volume of
a gas is directly related to
the number of moles.
V = K n
V1 / n1 = V2 / n2
Amedeo Avogadro
Physicist
Turin, Italy
August 9, 1776 – July 9, 1856
Avogadro’s Law: V1/n1=V2/n2
• V = constant x n (at constant T & P), the constant of
proportionality is independent of the identity of the gas and
only depends upon the number of molecules.
Fig 1.7. illustrates the linear
variation of pressure with
temperature. The lines in this
diagram are isochores, or lines
showing the variation of
properties at constant volume
• The empirical observations summarized above can be
combined into a single expression: pV = constant × nT
• This expression is consistent with Boyle’s law (pV = constant)
when n and T are constant, with Charles’s law ( V ∝ T) when
and with Avogadro’s principle (V ∝ n)
• The constant of proportionality, which is found experimentally
to be the same for all gases, is denoted R and called the gas
constant. The resulting expression pV = nRT perfect gas
equation.
• This is the approximate equation of state of any gas, and
becomes increasingly exact as the pressure of the gas
approaches zero.
• A gas that obeys this equation exactly under all conditions is
called a perfect gas (or ideal gas)
 Assumptions
• Gas molecules are infinitely small
• They exert force on the walls of the
container but not on each other
• However, real gases have volume, this
reduces volume in which they can move.
• They exert attractive forces on each other
and container’s walls, which reduces the
pressure
 Failures of ideal gas equation
• Failure of Charles’ Law
– At very low temperatures
– Volume do not decrease
to zero
– Gas liquefies instead
 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
Differences Between Ideal and Real Gases

Ideal Gas Real Gas

Obey PV=nRT Always Only at very low

P and high T
Molecular volume Zero Small but
nonzero
Molecular attractions Zero Small

Molecular repulsions Zero Small

 Intermolecular Forces
Intermolecular forces are the attractive forces that
exist between molecules.

In order of increasing strength, these are:

• London dispersion forces
• Dipole–dipole interactions
• Hydrogen bonding

The strength of the intermolecular forces determines

whether a compound has a high or low melting point
and boiling point, and thus whether it is a solid,
liquid, or gas at a given temperature. 31
 Real Gases
Real molecules do take up space and do interact with
each other (especially polar molecules).
•Real gases have molecular interactions, both attractive and
repulsive.
Short range – strongly repulsive •Long range – weakly
attractive
Need to add correction factors to the ideal gas law to
account for these.
At this point, we have a small
enough space between
molecules
Gives rise to attractive
interaction
Partial positive charge is close
enough to interact with the
partial negative charge of the
other molecule forms dipole-
dipole interaction
If they are forced too close to
one another (High P) they
repel each other.
High P means small V, so
molecules are forced to close
together and eventually repel
 Compressibility Factor
• Z: ratio of Vm(real) to Vm(ideal) at the same
conditions
• Z= Vm(real)/ Vm(ideal)
• If Z<1: Vm(real) < Vm(ideal) attractive forces
dominate (compressible)
• If Z>1: Vm(real) > Vm(ideal) repulsive forces
dominate (less compressible)
• If Z=1: Vm(real) = Vm(ideal)
• Ideal (perfect) gas has Z=1 and any
deviation proves non ideality of a
gas.
• The lower the T, the curve has
chances of condensation.
• KE of the molecules is lower that
the intermolecular force hence
condensation Vm real <<Vm ideal
(Vliquid) at lower T.
• At P approaches zero Z=1 ( all
gases are ideal)
• At moderate T and low P we
have a close behaviour of real
gas and ideal gas
• This T is therefore known as
Boyle Temperature:
temperature at which a gas
follows ideal gas law at an
appreciable P range.
• For high T and low T there is
an immediate deviation as soon
as P increases
 Variation of Z of different gases
with P (at constant T)
• The behaviour of all gases at
P=0, Z=1 and infinite Vm will
be that of ideal gas
• Experimental deviation of Z
from the ideal can be used to
construct an equation of state
from curve fitting
• General equation for curve
fitting: Z=1+B’P+C’P2+…..
• B’ and C’ are called virial
coefficients can vary with T
and type of gas
 Virial Coefficients
• At low P and high V the ideal gas law does a good job at
modelling reality
• Therefore ideal gas law is a good first approximation to
modelling gases and then do an expansion of the compression
factor into terms that depend on the increasing powers of
variable that break down the model
• To determine how real gases deviate from ideality, we use
𝑃𝑉
compression factor 𝑍 = 𝑚 = 1
𝑅𝑇
• 𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3
• If the gas does not behave ideally, then these constants provide
an idea of how far away from ideality the gas is
𝑅𝑇
• 𝑃= (1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3+……) ideal gas virial
𝑉𝑚
equation of state
• Virial equation of state can also be expressed as a function of the
inverse of molar volume
𝑅𝑇 𝐵 𝐶 𝐷
• 𝑃= (1 + + + +……)
𝑉𝑚 𝑉𝑚 𝑉𝑚2 𝑉𝑚3
• These virial equation of states are used to discuss real gases with
moderate deviations from ideality
• B, C, and D are called virial coefficients and are used to calculate
intermolecular interactions and are functions of temperature
• First term (1) represents non interacting particles (ideal gases)
• 2nd term (B) represents pairs of molecules
(±), tells the behavious of Z curve at moderate P
• If B is positive then repulsion forces dominate and if negative
attractive forces dominate
• The third term (C) is usually less important than B, in a sense that
at typical molar volumes C/V2 m << B/Vm
Condensation and critical points
• At E, the sample is entirely liquid and the piston rests on
its surface.
• Any further reduction of volume requires the exertion of
considerable pressure, as is indicated by the sharply
rising line to the left of E.
• Even a small reduction of volume from E to F requires a
great increase in pressure
•
Critical constants
The isotherm at the temperature Tc (304.19 K, or 31.04°C for
CO2 ) plays a special role in the theory of the states of matter.

• An isotherm slightly below Tc behaves as we have already

described: at a certain pressure, a liquid condenses from the gas
and is distinguishable from it by the presence of a visible
surface.

• If, however, the compression takes place at Tc itself, then a

surface separating two phases does not appear and the volumes
at each end of the horizontal part of the isotherm have merged
to a single point, the critical point of the gas.
• The temperature, pressure, and molar volume at the critical
point are called the critical temperature, Tc, critical
pressure, pc, and critical molar volume, Vc, of the
substance.

• Collectively, pc, Vc, and Tc are the critical constants of a

substance .

• At and above Tc, the sample has a single phase that occupies
the entire volume of the container.

• Such a phase is, by definition, a gas.

• Hence, the liquid phase of a substance does not form above the
critical temperature.
• The critical temperature of a substance is
the temperature at and above which vapor
of the substance cannot be liquefied, no
matter how much pressure is applied.
• The critical pressure of a substance is the
pressure required to liquefy a gas at its
critical temperature
 The van der Waals equation
• The van der Waals equation is
• P = (RT / Vm – b) - (a / V2 m)
• Justification is very important as it describes the origin of
parameters a and b.
• Correction factors are added to the ideal gas law to account
for the variations. Go through it to familiarize yourself
with how the van der Waals is originated, i.e how the
repulsive and attractive forces are explained to generate the
van der Waals equation.
The van der Waals equation of
state
 Volume Correction

 Ideal gas as point particles, gas molecules do not occupy

space. Real gas molecules do occupy significant amount of
space. Vreal>Videal
 The blue part represent ideal gas volume and real gas volume
gas in a small box.

 Volume Correction
 Vreal is given by Videal and nb
 nb is the excluded volume, where b
is the volume of the gas molecules
per mol (L/mol) (VDW volume
correction)
 Corrected volume Videal = Vreal-
nb
 “b” is a constant that differs for
each gas, unique for each gas and
related to the size of gas of a
molecule
 Pideal (Vreal – nb)=nRT
• The repulsive interactions between molecules are taken
into account by supposing that they cause the molecules to
behave as small but impenetrable spheres.
• The nonzero volume of the molecules implies that instead
of moving in a volume V they are restricted to a smaller
volume V - nb, where nb is approximately the total volume
taken up by the molecules themselves.
• This argument suggests that the perfect gas law p =
nRT/V should be replaced by p = nRT/ V-nb when
repulsions are significant
 Pressure
• The pressure depends on both the frequency of collisions with
the walls and the force of each collision.
• Both the frequency of the collisions and their force are reduced
by the attractive forces, which act with a strength proportional
to the molar concentration, n/V, of molecules in the sample.
• Therefore, because both the frequency and the force of the
collisions are reduced by the attractive forces, the pressure is
reduced in proportion to the square of this concentration.
• If the reduction of pressure is written as −a(n/V)2, where a is a
positive constant characteristic of each gas, the combined effect
of the repulsive and attractive forces is the van der Waals
equation of state as expressed in the above equation.
 Pressure Correction
Because the molecules are
attracted to each other, the
pressure on the container will be
less than ideal.
Pressure depends on the
number of molecules per liter.
Since two molecules interact,
the effect must be squared.
n 2
Pobserved  Pa ( )
V
 Pressure correction

The VDW equation of state, accounts for these interactions to be

attractive in nature.
Velocity of A will be reduced to the extend of the intermolecular
forces of interaction between A and B
This lowers the pressure exerted by real gases
P <P
Pressure Correction
 Van der Waal’s equation
n 2
[Pobs  a ( ) ] (V  nb)  nRT
V

Corrected Pressure Corrected Volume

 “a” and “b” are determined by
experiment
a relates to the IMFA and b relates to the
volume of the gas
 “a” and “b” are different for each gas
 bigger molecules have larger “b”
 “a” depends on both Johannes Diderik van der Waals
size and polarity Mathematician & Physicist
Leyden, The Netherlands
November 23, 1837 – March 8, 1923
VDW equation of state
VDW equation in terms of molar
volume
 VDW cubic equation
• VDW is cubic in volume, so has
3 roots. For every P there will
be 3 possible molar volume
• Curve T1 and T2 show 3 Vm
roots and the curves have both +
and – slope????
• Positive slope suggest that
increase in P also increase V,
circled region is physically
unrealizable
• T4>T3>T2>T1
Correction of VDW equation
• Critical point occurs at high P and T
• Supercritical fluid-no distinction
between liquid and gas phase
• Name properties of critical point and
supercritical fluid