Lecture 4

Gas Laws and Relations

Ideal Gases
 The most famous and widely used equation
which relates p,V,n and T for a gas is the
ideal gas law.

Where p is the absolute pressure of the gas

V is the total volume occupied by the gas
n is the number of moles of the gas
R is the ideal (universal) gas constant in
appropriate units
T is the absolute temperature of the gas
 Ideal gas law can also be written as
 In the above equation is the specific molar

volume which is the volume per mole V/n of

the gas.
 When gas volumes are involved in a problem

will be the volume per mole and not the

volume per mass. The inverse of is the molar
density which is the moles per volume.
Conditions for a gas to behave as
predicted by the ideal gas law
 The molecules do not occupy any space and are
infinitesimally small.
 No attractive forces exist between the molecules so the

molecules move completely independently of each other.

 The gas molecules move in random, straight line motion

and the collisions between the molecules and the walls

of the container are perfectly elastic.

 Ideal gas equation works in condition of low pressure

and moderate to high temperatures. If pressure is
increase or temperature is low ideal gas equation will not
be valid and some other gas relations will be used.
 Solids, liquids and gases at high density ( high
pressure and/ or low temperature) do not follow the
ideal gas law.
 Usually water vapour, nitrogen, oxygen, carbon

dioxide, hydrogen and methane follow the ideal gas

law under most ordinary conditions.
 There are equivalent standard states known as

standard conditions (S.C or S.T.P) known as standard

temperature and pressure.
 The two main standard conditions are in SI units and

the AE units where the conditions are exactly the

same but in different units.
System T p
SI 273.15 K 101325 Pa 22.415l/Kg mol

AE 491.67R 1 atm 359.05 ft3/lb mol

Using standard conditions to
calculate volume from mass
 Calculate the specific molar volume in cubic
meters occupied by 40kg of carbon dioxide at
standard conditions assuming carbon dioxide
acts as an ideal gas.
 Basis 40Kg of carbon dioxide
Standard Conditions: Pressure 101325Pa
Molar volume ?
Temperature 273.15 K
T
 In many processes going from an initial state
to a final state the ratio of the ideal gas laws
in respective states is used to eliminate R.
 Ten cubic feet of air at 70F and 1 atm is
heated to 610F and compressed to 2.50 atm.
What volume does the gas occupy in its final
state?
 In such a question divide the equation in 2
parts condition 1 and condition 2. 1 is the
initial state and 2 is the final state. Since
number of moles is not changing n1=n2.

Initial State: V=10ft, T=70F, P=1atm

Final State: V=?, T=610F, P=2.50 atm
 Remember F is not absolute scale so much be
changed in absolute value.
Ideal Gas mixtures
 Usually calculations are done for mixtures of
gases instead of individual gases.
 Ideal gas law can be used but a more useful

quantity called the partial pressure in many of

the calculations involving the gases is used.
Dalton’s Law of Partial Pressure
 Suppose na moles of a substance A, nb moles of a
substance B, nc moles of a substance C and so on are
contained in a volume V at a temperature T and a total
pressure P.
 The partial pressure and the pure component volume
of A in the mixture is defined as follows:
 : The pressure that would be exerted by moles of A
alone in the same total volume V at the same
temperature T.
 : The volume that would be occupied by moles of A
alone at the total pressure P and temperature T of the
mixture.
 Next we suppose that each of the individual
mixture components and the mixture as a
whole behave in an ideal manner. (Definition
of an ideal gas mixture).
 If there are n moles of all species in the

volume V at pressure P and temperature T

then the ideal gas equation can be applied
(Equation 1)
 From definition of partial pressure the
following equation can be formed
(Equation 2)
 By dividing the second equation by the first

equation the new equation that is yielded is

(the mole fraction of A in the gas)
 As a result the equation becomes
 The previous equation gives the partial pressure of
a component in an ideal gas mixture is the mole
fraction of that component times the total pressure.
 Moreover we know that
 Hence
 Hence Dalton’s Law of partial pressure of the
components of an ideal gas mixture add up to the
total pressure.
 Similarly calculations can be done for pure
component volumes to get the equation by
Amagat’s Law.
Calculation of Partial Pressures of the
Components in a Gas from Gas Analysis.
 In a certain process the off gas analyzes 14%
CO2, 6% O2 and 80% N2. It is at 300 F and
765mm Mercury pressure. Calculate the
partial pressure of each component.
 Basis 100 Kg mol of the off gas

Component Kg mol ni pi (mm Hg)

CO2 14 0.140 X

O2 6 0.060 Y

N2 80 0.800 Z

Total 100 1.00 765

 Pressure of each component can be found by
the equation of Dalton’s Law

X= 107.1 mm Hg
Y= 45.9 mm Hg
Z= 612.0 mm Hg

 It can clearly be observed that the sum of

each partial pressure is equal to the total
pressure and hence Dalton’s Law is proved.
Real Gases Equations of State
 Gases whose properties cannot be
represented by the ideal gas law are called
non ideal or real gases.
 Real gas properties are predicted by

equations called equation of state.

 Some common examples of equation of state

are Van der Waals, Peng Robinson, RK

equation, SRK equation.
Critical state and Compressibility

State

Phase
 The critical state or point for the gas liquid
transition is the set of physical conditions at
which the density and other properties of the
liquid and vapour become identical.
 The critical point occurs at the highest
temperature and pressure possible at which the
gas and the liquid can coexist.
 A supercritical fluid is a compound in a state
above its critical point.
 Other temperatures which are important to know
are termed as reduced variables.
 The reduced variables are conditions of
temperature, pressure ( absolute or given
values) divided by their respective critical
conditions.

 Reduced Temperature
 Reduced Pressure
 The ideal gas equation really comes from the
real gas equation PV=nZRT where Z is the
compressibility factor and has no units.
 Equation checks the non ideality of the gas
 The compressibility factor Z can be found

using the compressibility charts and has no

units.