Gas Mixtures

In this chapter, we deal with the problem of generating thermodynamic properties for
homogenous mixtures of gases and vapours that are not involved in chemical reactions.
We can define the composition of any mixture based on how we physically create the mixture.
For example, we can create a mixture by combining measured masses (or weights) of things or
by combining measured volumes of things. The items or things that make up the mixture are
called the components of the mixture, and knowing how much of each one is present defines
the composition of the mixture.

This all seems very simple, so why do we need to dwell on it here? First of all, there are two
ways to measure mass, the regular mass (lb or kg) and the molar mass (lbmole or kgmole), and
a composition based on the regular mass is not the same as a composition based on the
molar mass. Second, since the conservation of mass law tells us that the total mass of the
mixture is simply the sum of the masses of all the components in the mixture, is the total volume
of the mixture the same as the sum of the volumes of all the components in the mixture? Well,
that depends. If the components are immiscible, then the total volume is the sum of the
individual component volumes. But gases and vapours are not immiscible, so how do the
component volumes affect the total volume?

However, the mixture composition is not really our primary goal. Our primary goal is to be
able to determine the thermodynamic properties of a mixture so that we can apply the
first and second laws to an engineering system containing a mixture. Are mixture
thermodynamic properties just the sum of the thermodynamic properties of their components?
No! With the exception of mass, the extensive thermodynamic properties of a mixture are not
generally equal to the sum of the extensive thermodynamic properties of the components.

It turns out that the value of any thermodynamic property of a mixture is just the mass
weighted sum of the partial specific properties of the mixture’s components. Therefore, to
determine the numeric value of a thermodynamic property of a mixture we need to know (a)
The exact composition of the mixture and (b) The values of the partial specific properties
of all the components in the mixture. This is what the first half of this chapter is all about.

Dalton’s Law: -
Let us consider a closed vessel of volume V at temperature T, which contains a mixture of
perfect gases at a known pressure. If some of the mixture were removed, then the pressure
would be less than the initial value. If the gas removed were the full amount of one of the
constituents then the reduction in pressure would be equal to the contribution of that constituent
to the initial total pressure. Each constituent contributes to the total pressure by an amount
which is known as the partial pressure of the constituent.

The relationship between the partial pressures of the constituents is expressed by Dalton’s
law, as follows:

o The pressure of a mixture of gases is equal to the sum of the partial

pressures of the constituents.
o The partial pressure of each constituent is that pressure which the gas
would exert if it occupied alone that volume occupied by the mixtures at
the same temperature.
By mass consideration 𝑚 = 𝑚𝐴 + 𝑚𝐵

By Dalton’s law 𝑃 = 𝑃𝐴 + 𝑃𝐵
Dalton’s law is based on experiment and is found to be obeyed more accurately by gas mixtures
at low pressures. The above expression is referring to a mixture of two gases but it can be
extended to any number of gases.
𝑚 = 𝑚𝐴 + 𝑚𝐵 + 𝑚𝐶 + 𝑚𝐷 + 𝑚𝐸 = ∑ 𝑚𝑖 ……………………………..(1)

𝑃 = 𝑃𝐴 + 𝑃𝐵 + 𝑃𝐶 + 𝑃𝐷 + 𝑃𝐸 = ∑ 𝑃𝑖 ……………………………………(2)

Gibbs-Dalton Law: -
Dalton’s law was re-formulated by Gibbs to include a second statement on the properties of
mixtures. The combined statement is known as the Gibbs-Dalton law, and is as follows:

o The internal energy, enthalpy, and entropy of a gaseous mixture are respectively
equal to the sums of the internal energies, enthalpies, and entropies, of the
constituents.
o Each constituent has that internal energy, enthalpy and entropy, which it could
have if it occupied alone that volume occupied by the mixture at the temperature
of the mixture.

This statement leads to the following equations:

𝑚𝑢 = 𝑚𝐴 𝑢𝐴 + 𝑚𝐵 𝑢𝐵 + 𝑚𝐶 𝑢𝐶 + 𝑚𝐷 𝑢𝐷 + 𝑚𝐸 𝑢𝐸 + ⋯ ……………(3)

𝑚ℎ = 𝑚𝐴 ℎ𝐴 + 𝑚𝐵 ℎ𝐵 + 𝑚𝐶 ℎ𝐶 + 𝑚𝐷 ℎ𝐷 + 𝑚𝐸 ℎ𝐸 + ⋯ ……………(4)

𝑚𝑠 = 𝑚𝐴 𝑠𝐴 + 𝑚𝐵 𝑠𝐵 + 𝑚𝐶 𝑠𝐶 + 𝑚𝐷 𝑠𝐷 + 𝑚𝐸 𝑠𝐸 + ⋯ …………….(5)
Volumetric analysis of Gas Mixtures: -
Let us consider a volume V of a gaseous mixture at a
temperature T, consisting of three constituents A, B and C
having mass 𝑚𝐴 , 𝑚𝐵 , 𝑎𝑛𝑑 𝑚𝐶 respectively.

Fig 1
Now consider three separate containers, each containing
only one gas. By maintaining at temperature at T and
pressure at P, Gas A occupies volume 𝑉𝐴 , Gas B occupies
𝑉𝐵 and Gas C in 𝑉𝐶 . Three containers having mass
𝑚𝐴 , 𝑚𝐵 , 𝑎𝑛𝑑 𝑚𝐶 respectively.

Fig 2
Now using the equation 𝑃𝑉 = 𝑚𝑅𝑇 we get

𝑃 𝑉
𝑚𝐴 = 𝑅𝐴 𝑇 From fig 1
𝐴

𝑃𝑉𝐴
𝑚𝐴 = 𝑅 From fig 2
𝐴𝑇

Equating both

𝑃𝐴 𝑉 𝑃𝑉
= 𝑅 𝑇𝐴 ………….(6)
𝑅𝐴 𝑇 𝐴

i.e. 𝑃𝐴 𝑉 = 𝑃𝑉𝐴
𝑃𝐴 𝑉
𝑉𝐴 = 𝑃
In general

𝑃𝑖 𝑉
𝑉𝑖 = ……………(7)
𝑃
𝑃𝑖 𝑉 𝑉
∑ 𝑉𝑖 = ∑ = 𝑃 ∑ 𝑃𝑖 …………..(8)
𝑃
From equation (2) we know 𝑃 = ∑ 𝑃𝑖 , therefore

∑ 𝑉𝑖 = 𝑉…………………..(9)
Thus, the volume of a mixture of gases is equal to the sum of the volumes of the individual
constituents when each exists alone at the pressure and temperature of the mixture. This is the
statement of another empirical law, the law of partial volumes, sometimes called Amagat’s
law or Leduc’s law.
 Apparent Molecular Weight and Gas constant: -
In a gas mixture if a gas occupies a total volume of V at a temperature T, then from the
definition of partial pressure and equation 𝑃𝑉 = 𝑛𝑅0 𝑇, we have
𝑃𝑖 𝑉 = 𝑛𝑖 𝑅0 𝑇 𝑅0 = Universal gas constant

An apparent molecular weight is defined by the equation

𝑚
𝑀= (10) m = Mass of the mixture and n = Number of moles in mixture
𝑛
Gas Constant-
The apparent gas constant (similarly as above) is defined by the equation
𝑅0
𝑅= …….(11)
𝑀
It can be assumed that a mixture of perfect gases obeys all the perfect gas laws.
In order to determine the gas constant for the mixture in terms of the gas constants of the
constituents let us consider the equation pV = mRT both for the mixture and for a constituent
as follows

∑ 𝑚𝑖 𝑅𝑖 𝑚
𝑅 =()()() or ...(12) = Mass fraction of constituents
𝑚 𝑚𝑖
If we write Gas law in moles
𝑃𝑉 = 𝑛𝑅0 𝑇
𝑃𝑖 𝑉 = 𝑛𝑖 𝑅0 𝑇
Divide both equations
𝑃𝑉 𝑛𝑅0 𝑇
=
𝑃𝑖 𝑉 𝑛𝑖 𝑅0 𝑇
Or
𝑃𝑖 𝑛
= 𝑖 ………(13)
𝑃 𝑛
So from eq (7) and (13)
𝑷𝒊 𝒏𝒊 𝑽𝒊
= =
𝑷 𝒏 𝑽

Specific Heats: -
As per Gibbs-Dalton law, the internal energy of a mixture of gases is given by

Now characteristic gas constant is

Or from equation (12)

Questions: -
1. State Gibbs-Dalton law as applicable to gas mixtures.
2. Describe Dalton’s law of partial pressure.
3. Describe Amagat’s law of partial volume for a gas mixture.