Basic Thermodynamics BME304

Module - 5
IDEAL GASES
INTRODUCTION - IDEAL GAS:
Any equation that represents the relation among the three measurable properties pressure,
volume and temperature is called equation of state of the substance.
An ideal gas is one that follows equation of state,
pv = RT or pV = mRT
In this equation-
p – pressure in N/m2
V – Volume in m3
v – Specific volume in m3/kg
m – Mass in kg
T – Temperature in K
R – Particular gas constant in kJ/kg k

UNIVERSAL GAS CONSTANT:

Consider 1kmol [M – Molar mass or molecular weight] of any gas at one standard
atmospheric pressure, p0 = 1.01325bar and a standard temperature, T0 = 273.16K and according to
Avogadro’s principle, V0 = 22.416m3. Substituting in equation gives –
𝑝 𝑣
= 𝑀𝑅
𝑇
1.01325 × 10 × 22.416
= 𝑀𝑅
273.15
𝐽
𝑀𝑅 = 8314.3
𝑘𝑚𝑜𝑙 𝐾

IDEAL GAS MIXTURES:

Many times, the working substance encountered happens to be a mixture of gases.
– Example: Combustion products
To carry out a thermodynamic analysis of systems comprising gas mixtures, it is necessary to
know how the required thermodynamic properties of these mixtures could be obtained with
following assumption-
– The constituents gases are ideal gases
– The mixture behaves as an ideal gas itself
– The mixture is homogeneous and non-reactive

GRAVEMETREIC ANALYSIS:
The analysis of a gas mixture based on mass, that estimates the extent to which each
individual gas exists in the mixture is called Gravimetric analysis.
Consider m kg of a gas mixture. Let the individual constituents of the gas mixture be A, B, C
…. etc, and their masses in kg respectively be mA, mB, mC ….etc.
Therefore –
m = mA + mB + mC + ………... -1
Dividing above equation by m, we get;
m m m
1 = mA + mB + mC + ………... -2
Each term on the right hand side is called mass fraction.

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 Basic Thermodynamics BME304

m m m
Thus, mA , mB and mC are mass fractions of constituent gases A, B and C in the mixture.
Then, Mass fraction is denoted by ‘y’ with the name of the gas as its suffix.
Therefore –
mA mB mC
= yA , = yB and =y
m m m C
Hence Equation – 2 can be written as –
1 = 𝑦 +𝑦 +𝑦 + ………... or = Ʃ𝑦 -3
Where i = A, B, C ...etc.
“That is, the sum of the mass fractions of the individual constituents in a mixture is equal to one”

VOLUMETRIC or MOLAR ANALYSIS:

The analysis of a gas mixture based on volume, that estimates the extent to which each
individual gas exists in the mixture is called Volumetric or Molar analysis.
Let the number of molecules of the individual gas mixture be A, B, C …. etc, that make N
molecules of the mixture be NA, NB, NC ….etc.
Therefore –
N = NA + NB + NC + ………... -1
Dividing above equation by Avogadro number - 𝑁 , we get;
N NA NB NC
N
= N
+ N + N + ………... -2
0 0 0 0
In equation – 2, NA, NB, NC and N are proportional to corresponding masses, N0 is
proportional to the corresponding molar masses M, Therefore –
m m m m
M
= MA + MB + MC + ………... -3
0
Each term in equation – 3 is the number of moles ‘n’ of the corresponding gas. Therefore –
n = nA +nB +nC + ………... -4
Dividing above equation by n, we get;
n n n
1 = nA + nB + nC + ………... -5
Each term on the left hand side is called mole fraction ‘x’ of the constituent gases. Hence
Equation – 5 can be written as –
1 = 𝑥 +𝑥 +𝑥 + ………... or = Ʃ𝑥
Where i = A, B, C ...etc.
“That is, the sum of the mole fractions of the individual constituents in a gas mixture is equal to
one”

DALTON’S LAW OF ADDITIVE OR PARTIAL PRESSURE:

It states that, “ the pressure of a mixture of ideal gases is equal to the sum of the partial
pressures of constituent gases and the partial pressure of an individual constituent exist alone at the
mixture temperature and volume”.
As a mixture of ideal gases behaves like ideal gas,
nRT
p=
V
Here, n = nA +nB +nC + ………...
Hence,
(nA +nB +nC + …………)RT
p=
V
nA RT nB RT nC RT
p= + + + ……
V V V

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 Basic Thermodynamics BME304

Each term on the right hand side of the above equation can be termed pressure the individual gases
A, B, C ...etc. would exert. These pressures are called as partial pressures and are represented by
pA , pB , pC … …etc.
Therefore –
p = p + p + p + … … or = Ʃp
n RT
By definition – pi = iV , dividing and multiplying by ‘n’ number of moles of the mixture;
ni RT 𝑛 nRT 𝑛
pi = × = ×
V 𝑛 V 𝑛
We have = 𝑥 from molar fraction of ideal gas mixtures.
Therefore – pi =𝑝𝑥
That is, “The partial pressure of an individual constituent in a mixture of ideal gases is equal to the
product of the mole fraction of the constituent and the pressure of the mixture”.

AMAGAT’S LAW OF ADDITIVE OR PARTIAL VOLUMES:

It states that, “the volume of an ideal gas mixture is equal to the sum of the partial volumes
of constituent gases and the partial volume of an individual constituent is defined as the volume it
alone occupies at the mixture temperature and pressure”.
For an ideal gas mixture,
nRT
V=
p
Here, n = nA +nB +nC + ………...
Hence,
(nA +nB +nC + …………)RT
V=
p
nA RT nB RT nC RT
V= + + + ……
p p p
Each term on the right hand side of the above equation equals the volume of the individual gases A,
B, C ...etc. These volumes are called as partial volumes and are represented by VA , VB , VC … …etc.
Therefore – V = V + V + V + … … or = ƩV
ni RT
By definition – Vi = p
, dividing and multiplying by ‘n’ number of moles of the mixture;
ni RT n nRT ni
Vi = × = ×
p n p n
n
We have ni =𝑥i from molar fraction of ideal gas mixtures.
Therefore – Vi =V𝑥i
That is, “the partial volume of an individual constituent in a mixture of ideal gases is equal to the
product of the mole fraction of the constituent and the volume of the mixture”.

RELATION BETWEEN MOLE-FRACTIONs & VOLUME-FRACTIONs:

The analysis of gas mixture is based on volume.
For example – when the analysis of exhaust gas from an engine is carried out using a simple Orsat’s
apparatus the percentage of various constituents gases are obtained on volume basis.
Suppose ai is the volume fraction, then ai is the ratio of volume of individual gas Vi to sample
volume V of the mixture taken for analysis. The experiment is conducted such that both Vi and V
are measured at the same pressure and temperature.
Thus;
Vi
V
= ai -1
3 Sri. Ramesh B R, Dept. of Studies in Mechanical Engineering, UBDTCE, Davangere
 Basic Thermodynamics BME304

And also according to Amagat’s law of additive or partial volumes mole fraction –
V
xi = Vi -2
Comparing equation 1 and 2, we have – ai = xi
Therefore it can be generalized that “mole fractions are also equal to volume fractions”.

RELATION BETWEEN MASS-FRACTION & MOLE-FRACTION:

By definition, the mass fraction and mole fraction of any constituent are given by –
m n
𝑦i = mi and 𝑥i = ni -1
m m
Also; ni = Mi and n= M ,
i
Where Mi and M are the relative molar masses of the ith constituent and the mixture respectively.
Therefore –
mi = niMi and m = nM -2
Substituting for 1 from 2
ni Mi ni Mi Mi
𝑦i = = × =𝑥i
nM n M M
Thus, the relation between mass fraction and y and mole fraction x of any individual constituent is
given by –
Mi
𝑦i =𝑥i
M

PROPERTIES OF GASEOUS MIXTURE:

• In terms of properties of individual constituents
– Apparent Molar mass [M] and Gas constant [R]
– Specific properties
• Derived by mixing ideal gases at different temperatures and pressures
– Adiabatic mixing
– Non adiabatic mixing
– Mixing of gases in steady flow

Apparent Molar Mass [M] and Gas Constant [R]

1. Molar Mass [M]
As, mA + mB + mC + …… = m,
By definition mi = niMi and m = nM
nA MA +nB MB +nC MC + ……=nM
n M n M n M
+ + + ……=M
n n n
n n n
M= M + M + M + ……
n n n
M = 𝑥 M +𝑥 M +𝑥 M + ……
M = Ʃ𝑥 M
The apparent molar mass of a mixture is equal to the sum of the products of the mole fractions and
corresponding molar masses of the constituents.
2. Gas Constant [R]
For the mixture gas constant R is given by –
R
R=
M
Where for a mixture M=Ʃ𝑥i Mi

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 Basic Thermodynamics BME304

R
Therefore, R= Ʃ
i Mi
The gas constant of a mixture is equal to universal gas constant divided by the sum of the products
of the mole fractions and corresponding molar masses of the constituents.
3. Both R and M
R and M can also be evaluated using the mass fractions as below –
pV = nRT = n RT + n RT + n RT + … …
Since,
R=MR
nMRT = n M R T + n M R T +
n M R T+ ……
As, ni Mi =mi and pV = mRT
mR = m R T + m R T + m R T + … …
Dividing above equation by [mT] –
m m m
R= R + R + R + ……
m m m
Since by mass fraction we can write above equation as –
R = 𝑦 R + 𝑦 R + 𝑦 R + ……
or R = Ʃ 𝑦 R
R
4. R= M
R
R= = 𝑦 R + 𝑦 R + 𝑦 R + ……
M
R R
M
= + + + … … as Ri = M
i
Dividing above equation by R –
1 𝑦 𝑦 𝑦 𝑦
= + + + …… = Ʃ
M M M M M
1
M= 𝑦
ƩM
Apparent molar mass of a gas mixture is equal to the reciprocal of the sum of the ratios of mass
fractions and corresponding molar masses of the constituents.

Specific Properties
Suppose ‘Z’ is an extensive property of a mixture i.e. it could be volume (V) or internal
energy (U) or enthalpy (H) or entropy (S). For the mixture Z is equal to the sum of ‘Zi’ for the
individual constituents.
Therefore –
𝑍 = 𝑍 + 𝑍 + 𝑍 + …… -1
If ‘z’ were to denote the corresponding specific property, then –
𝑚𝑧 = 𝑚 𝑧 + 𝑚 𝑧 + 𝑚 𝑧 + … …
Dividing above equation by m –
𝑚 𝑧 𝑚 𝑧 𝑚 𝑧
𝑧= + + + ……
𝑚 𝑚 𝑚
𝑧 = 𝑦 𝑧 +𝑦 𝑧 + 𝑦 𝑧 + ……
or 𝑧 = Ʃ𝑦 𝑧 -2
Therefore –
Sp. Volume - 𝑣 = Ʃ𝑦 𝑣
Sp. Internal energy - 𝑢 = Ʃ𝑦 𝑢
Sp. enthalpy - ℎ = Ʃ𝑦 ℎ
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 Basic Thermodynamics BME304

Sp. entropy - 𝑠 = Ʃ𝑦 𝑠
Similarly it can also be shown that,
Sp. Heat - 𝑐 = Ʃ𝑦 𝑐 and 𝑐 = Ʃ𝑦 𝑐
Therefore – “the specific properties of a mixture are equal to the sum of the products of the mass
fractions and the corresponding specific properties of the constituent gases”.
M
Form molar fractions and mass fractions the relationship, i.e. 𝑦i =𝑥i Mi and substituting for
yi in equation-2 –
Mi
z = Ʃ𝑥i z
M
Mz = Ʃ𝑥i Mi z
Mz is the molar specific property and is usually denoted by z. Hence,
z=Ʃxi zi
Therefore – “Molar specific properties of a gas mixture are equal to the sum of the products of the
mole fractions and the corresponding molar specific properties of the constituent gases”.

Adiabatic Mixing of Gases

Applying first law of thermodynamics to mixing process-
Q – ΔU = W
During the process of mixing, Q = 0, W = 0 and ΔU = 0
That is, U – (UA + UB + UC) = 0
Where; U is the internal energy of the mixture and UA , UB , UC are the internal energies of
constituent gases of the mixture.
Therefore – U = (UA + UB + UC)
In general final temperature of the mixture is different from the temperatures of A, B, C.
Thus, the internal energy of each gas in the mixture has to be different from its initial value before
mixing subjected to their sum is still equal to U. Hence –
ΔUA + ΔUB + ΔUC = 0
Assuming the specific heats are constant and that the mixture temperature is T,
mA cvA (T - TA )+mB cvB (T - TB )+mC cvC (T - TC )=0
mA cvA TA +mB cvB TB +mC cvC TC
T= mA cvA +mB cvB +mC cvC
Ʃmi cvi Ti
T= Ʃmi cvi
The mixing process can be non-adiabatic, procedure adopted remains same and heat transfer is
given by –
Q=mcv [Tfinal - Tadiabatic ]
Mixing of gases in steady flow process and procedure adopted remains same as of adiabatic mixing
process –
Ʃṁi cpi Ti
T= Ʃṁi cpi

REAL GASES
REAL GASES:
A real gas is one which does not obey the ideal gas equation pv = RT at all temperatures and
pressures.
Real molecules do take up space and do interact with each other. Need to add correction
factors to the ideal gas law to account for these.

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 Basic Thermodynamics BME304

COMPRESSIBILITY FACTOR:
The deviation from ideal gas behavior at a given temperature and pressure can be accurately
predicted by introducing a correction factor called the compressibility factor.
Compressibility Factor The most useful way of displaying this new law for real molecules is to plot
the compressibility factor, Z –
For n = 1,
Z = pv / RT
Ideal Gases have, Z = 1

GENERALIZED COMPRESSIBILITY CHART:

In generalized compressibility chart, the compressibility factor Z is plotted as a function of
reduced pressure and temperature. According to these charts, one component substance which are
at same reduced pressure and temperature have the same compressibility factor.

The generalized compressibility chart provides one of the best means of expressing
deviation from ideal behavior and gives results with an accuracy of with 5%. A gas which has a
compressibility factor less than unity is more pressure than a perfect gas. The chart shows that both
temperature and pressure introduce deviation from ideal behavior.

LAW OF CORRESPONDING STATES [REDUCED PROPERTIES]:

The major disadvantage of any compressibility chart is that a separate chart is required for
each gas. It would be very advantageous and convenient for computations if it is possible to
construct a single compressible chart that could be used for all gases. Value of compressibility
factor of any can be determined experimentally. But it is also possible to determine values Z from
other properties of gas. This is accomplished by describing gases in terms of reduced properties.
p T v
pR = p , TR = T and vR = v
c c c
The compressibility factor of any one component substance is a function of only two
properties, usually temperature and pressure so that –
Z = f (TR , pR)
This equation is called the law of corresponding states.

VANDER WAAL’S EQUATION:

At high pressures the real gases are found to be less compressible. This is attributed to the
volume occupied by the molecules themselves. In contrary to ideal gas where the molecules do not
occupy any space, in real gases however the volume of molecules is significant. Thus the free

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 Basic Thermodynamics BME304

volume will actually be equal to the total volume minus the volume of the molecules themselves.
Hence the volume will be (v - b) where the constant b accounts for the reduction in volume due to
the finite size of the molecules of a real gas.
Volume Correction
 The actual volume free to move in is less because of particle size.
 More molecules will have more effect.
 “b” is a constant that differs for each gas.
i.e. v'=(v - b)
At low pressures the compressibility of real gases has a higher value than predicted by
perfect gas analysis. This is attributed to the attraction forces between the molecules and is more
noticeable at low pressures. When the molecule is not near the wall, it is surrounded by other
molecules and consequently it is equally attracted in all directions, resulting in a zero net force on
the molecule. On the other hand if the molecule is close to the wall, it is exposed to net attraction
force away from the wall towards the surrounding molecules. This prevents that particular
molecules form exerting its full pressure on the containing wall as in the ideal gas. This reduction in
pressure is known as the internal pressure, which is proportional to 1/V2. The pressures exerted by
the gas then equals a kinetic pressure ‘p’ as calculated by molecular change of momentum minus a
correction term to compensate for the attraction forces so that –
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.
 Since two molecules interact, the effect must be squared.
a
p = p - v2
a
p =p + v2
Gas equation for real gas is –
p' v'=R T
Hence the equation of state becomes –
a
p + 2 (v - b)=RT
v
This equation is called the Vander Waal’s equation where a and b are called Vander Waal’s
constant.

DETERMINATION OF VANDER WAAL’S CONSTANT:

Vander Waal’s equation is –
a
p + 2 (v − b) = RT
v
Therefore –
p= v − v -1
Differentiating equation – 1, we get

v
= − [v ]
+ v
dp
Since, constant at critical point is given by – dv c
=0
Therefore –
RT 2a
− [v -b]c 2 + vc 3
=0 -2
c
2a
RTc = v 3 [Vc – b]2 -3
c

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 Basic Thermodynamics BME304

Differentiating equation – 2, we get

d2 p 2RTc 6a
= −
dv c [vc − b]3 vc 4
d2 p
Since, constant at critical point is given by – dv c
=0
Therefore-
2RTc 6a
– =0
[vc − b]3 vc 4
3a
RTc = v 4 [vc − b]3 -4
c
From equation – 3 and 4,
2a 3a
[vc – b]2 = 4 [vc – b]3
vc 3 vc
After simplification, we get
vc = 3b -5
Substituting for v c in equation – 4, we get
RT = [ ] [3b − b] = × 8b
T = ×
-6
Substituting for v c and Tc in equation – 1, we get
8a × R a
p = −
27b × R[3b − b] [3b]
After simplification,
a
pc =
27b 2
Substituting for pc , v c and Tc in equation – 1 and simplifying, we get
a= and b =
And substituting for a and b in equation - 1 and simplifying, we get
v
R=

REDLICH & KWONG EQUATION OF STATE:

In 1949, Redlich and Kwong presented the following equation of state which has in it two
constants a and b. These constants are not same as the Vander Waal’s constants, but are different
functions of the critical state properties. This equation is more accurate than the Vander Waal’s
over a wide range.
p= v
− v v . -1
Where, V = Molar specific volume and constants a and b are given by –
.
a = 0.427 and b = 0.0866

BEATTIE – BRIDGEMAN EQUATION:

The Beattie – Bridgeman equation is the another widely used real gas equation of state.
There are five constants in this equation. This is used for formulating properties of vapour close to
the liquid phase at pressure less than critical pressure. The equation is more accurate when the
specific volumes involved are greater than twice the critical volume.
RT (1 – ∈) (v + B) A
p= v2
– v2

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 Basic Thermodynamics BME304

c
Where, ∈= VT and the constants are given by –
a b
A = A0 1 – v and B = B0 1 – v
In the above relations, v is in m3/kmol

***END***

10 Sri. Ramesh B R, Dept. of Studies in Mechanical Engineering, UBDTCE, Davanagere