ME5301

ENGINEERING THERMODYNAMICS
UNIT 5
GAS MIXTURES AND
THERMODYNAMIC RELATIONS
Dr. K. Arshad Ahmed
Teaching Fellow
Institute for Energy Studies
Department of Mechanical Engineering
CEGC, Anna University,
Chennai – 600 025 1
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 Gas Pressure
• Just as a ball exerts a force when it
bounces against a wall, a gaseous
atom or molecule exerts a force
when it collides with a surface.

• The result of many of these

molecular collisions is pressure.

• Pressure is the force exerted per

unit area by gas molecules as they
strike the surfaces around them.

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 Gas Pressure

• Gas pressure is a result of the constant movement of the gas

molecules and their collisions with the surfaces around them.

• The pressure of a gas depends on several factors:

✓Number of gas particles in a given volume
✓Volume of the container
✓Average speed of the gas particles

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 Cont..
• Ideal gas has zero cohesive force
• Has no controlling force/molecular force of attraction, it
migrates freely
• Has more disorderness, SIG > SRG
• It does not undergo phase change
• However,

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Characteristics of IG:
• Zero controlling force, hence viscosity is zero

• Volume occupied by IG > RG

• Pressure developed by IG > RG

• Entropy maintained by IG > RG

• IG can maintain constant specific heats

• It does not undergo phase change

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 Cont..
• Atmospheric air is a best example for IG mixture.

Water
Dry air
vapour
0.95 kg
0.05 kg
m1 n1 m2 n2

Let m1 = mass of dry air

Atm. m2 = mass of water vapour

air n1 = No. of moles of dry air
1 kg
m = m1 + m 2 n= n1 + n2 n2= No. of moles of water vap.

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 Cont..
• Mass fraction of dry air, y1 = m1/m

• Mass fraction of water vapour, y2 = m2/m

• Mole fraction of dry air, x1 = n1/n

• Mole fraction of water vapour, x2 = n2/n

Note:

i. Sum of mass fractions = 1 (y1 + y2 + ….yn)

ii. Sum of mole fractions = 1 (x1 + x2 + ….xn)

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 Cont..
iii. IG equation:
p V = mRT (or) RT (or) p = ρRT
p V = nµRT (as m = nµ)
p V = nRuT (as Ru= µR)
R = Characteristic gas constant (0.287 kJ/kg K)
Ru = Universal gas constant (8.314 kJ/kmol K)
n = No. of moles
µ = Molecular mass

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Gas Mixture
➔Mixture of gases

➔ Air, LPG, Producer gas, Biogas. Syngas

➔ Laws for Gas Mixtures

➔ Properties of Gas Mixtures

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 DALTON’S LAW
OF
PARTIAL PRESSURES

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DALTON’S LAW OF PARTIAL PRESSURES

It states that the total pressure of a mixture of ideal

gases is equal to the sum of the partial pressures of all
of its component gases.

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DALTON’S LAW OF PARTIAL PRESSURES

It states that the total pressure of a mixture of ideal

gases is equal to the sum of the partial pressures of
all of its component gases.

p = p1+p2+……+pc

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DALTON’S LAW OF PARTIAL PRESSURES

It states that the total pressure of a mixture of ideal

gases is equal to the sum of the partial pressures of all
of its component gases.

p = p1+p2+……+pc
− − −
n1 R T n2 R T nc R T
p1 = , p2 = , ..., pc =
V V V
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NOTE
−
pV = n R T

−
pV = (n1 + n2 + ... + nc ). R T
−
pV =  nk . R T
−
pkV = nk . R T

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Mole Fraction
pk nk
=
p  nk
nk Number moles of kth component gas
=
 nk Total Number moles of gas mixture
nk
= Mole Fraction of kth gas ( x k )
 nk

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Mass Fraction
mk mk
yk = =
m  mk
Mass of kth component gas
yk =
Mass of gas mixture

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Composition of Atm Air
Vol% Wt%
O2 21 23
N2 79 77
Total 100 100

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Mole Fraction of Atm Air
nk nk
x o2 = = = x1
 nk n
21
x o2 = = 0.21 = x1
100
nk nk
x N2 = = = x2
 nk n
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x o2 = = 0.79 = x 2
100

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Mass Faction of Atm Air
mk mk
y O2 = =
m  mk
23
y O 2 = y1 = = 0.23
100
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y N2 = y 2 = = 0.77
100
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Relationship between
x and y

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Mass(g) = No of moles x Molecular Mass (g/mol)
(or)
Mass(kg) = No of kmoles x Molecular Mass (kg/kmol)
(or )
m = nM
mk = nkMk

mk nkMk
=
m nM M =  = Molecular Mass
Mk
yk = xk
M

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Amagat Law
It states that the total volume of a mixture of ideal gases is equal to the
sum of the partial volumes of the constituent gases.

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Partial Volume
Partial volume of a components gas in the gaseous
mixture is the volume of that gas component when it
is maintained at the same temperature and pressure
as that of the mixture

Vi = volume at pi = p, Ti = T

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Mole and Mass Fraction
pV = mRT for the gaseous mixture

For kth gas

pVk = mk Rk T

Vk mk Rk
=
V mR
Vk Rk
= yk
V R
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Vk Rk
= yk
V R
Vk R / Mk
= yk
V R /M
Vk M
= yk
V Mk
M
xk = y k
Mk
Mk
y k = xk
M
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Molecular Mass of Gas Mixtures
m=m1+m2+m3+…+mk
n= n11 +n22+ ….. +nckc
 = x11+x22 + ……+xcc
 = (xkk)

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Molar mass of a gas mixture:

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Gas constant of a gas mixture:

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Specific Internal energy, enthalpy and specific heats:

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 Problems:
1. 0.45 kg of CO and 1 kg of air is contained in a vessel of volume 0.4 m3 at

150oC. Air has 23.3 % of O2 and 76.7% of N2 by mass. Calculate the partial

pressure of each constituent and total pressure in the vessel. Molar masses

of CO, O2 and N2 are 28, 32 and 28 kg/kmol.

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2. A closed vessel has a capacity of 0.5 m3. It contains 20% nitrogen and 20% oxygen &

60% carbon di-oxide by volume at 200oC and 1MPa. Calculate the molecular mass, gas

constant, mass percentages and the mass of mixture.

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3.

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4. A rigid tank of 5 m3 contains gas mixture comprising 3 kg of O2, 4 kg of N2 and 5

kg of CO 2 at 290 K. Calculate the molar specific volume, initial pressure of the gas. If

it is heated to 350 K, calculate the heat transfer and change in enthalpy. Also verify

the Gibbs theorem for entropy. (Universal Gas Constant, Ru = 8.314 kJ/kmol.K)

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 Equation of state:

• Equation of state also known as ideal gas equation

• At low pressure and high temperature, density of gas decreases & the
gas behaves like an ideal gas

• But, in practice there is no ideal gas. All the gases that we come
across are real gas

• Gases tend towards ideal gas behaviour to simplify the calculation

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The Simple Gas Laws
• Boyle’s Law
• Charles’s Law
• Gay Lussac Law
• There are three basic properties of a gas: pressure (P),
volume (V) and temperature (T).
✓These properties are interrelated—when one changes, it
affects the others.
✓The simple gas laws describe the relationships between
pairs of these properties.

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 An IG obeys the following laws,
• Boyle’s law, Charle’s law, Gay Lussac law, Joule’s law, Regnault’s law & Avagadro’s law

Boyle’s Law: Robert Boyle (1627–1691)

Temperature = constant
• Robert Boyle and Robert Hooke
used a J-tube to measure the volume
of a sample of gas at different
pressures.

• They trapped a sample of air in the

J-tube and added mercury to
increase the pressure on the gas.
✓ They observed an inverse relationship
between volume and pressure.
✓ Hence, an increase in one causes a
decrease in the other. 66
 Boyle’s Law
• Pressure of a gas is inversely proportional to its
volume.
✓Constant T and amount of gas
• As P increases, V decreases by the same factor.
• P × V = constant
P1 × V 1 = P2 × V 2

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 Charles’s Law: Volume and Temperature
Pressure = constant

• The volume of a fixed amount of gas at a constant pressure increases

linearly with increasing temperature in kelvins.
✓The volume of a gas increases with increasing temperature.
• Kelvin T = Celsius T + 273
V = constant × T
(if T measured in Kelvin)

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 Charles’s Law
V1 / T1= V2 / T2

If we move a balloon from an ice water bath to a boiling water bath,

its volume expands as the gas particles within the balloon move
faster (due to the increased temperature) and collectively occupy
more space.
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 Gay Lussac Law: Pressure and Temperature
Volume = constant

• The pressure of a given amount of gas at a constant volume is

directly proportional to the absolute temperature temperature in
kelvins.
✓The pressureof a gas increases with increasing temperature and vice versa.
• P1 / T1= P2 / T2

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Joule’s Law
• IE of a given gas depends only upon temperature. It is
independent of pressure & volume.
ΔU = CvΔT

Regnault’s Law

• Two specific heats, Cp & Cv of a gas do not

change with the change in temperature and
pressure. Cp & Cv always remains constant.

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Avagadro’s Law
• Equal volumes of different perfect gases at the same
temperature and pressure contain equal number of
molecules.
• The vol. of one gram mole of all gases at the pressure
of 760 mm of Hg and temperature of 0 ᵒC is same &
equal to 22.4 litres.
one gram mole of gas = 22.4 litres = 22.4 x 10-3 m3
one kilo gram mole of gas = 22.4 m3

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Vanderwal’s equation of state:

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Contd..

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Contd..

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Contd..

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Other equation of state:

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Compressibility chart:
• Since pv=RT for an IG, Z = 1
for any IG

• Z takes non zero positive

values, less than or greater
than one for any real gas

• Z is not a constant & it’s a

function of temperature and
pressure

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 Contd..
• At high pressures, the gas starts to deviate from the
IG behaviour.
• This deviation has to be accounted. To account this
deviation, a factor called compressibility (Z) is
introduced.
• Hence, the equation of state for real gas for unit mass
is given by,
pv = ZRT
• this compressibility factor is written as, Z = pv/ RT
• In terms of molar quantities, Z = pv̅ / RuT
This is real gas equation in terms of compressibility
factor.

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 Contd..
• The physical meaning of compressibility factor can be
studied as,
For actual gas (RG), pva = ZRT
For ideal gas (IG), pv = RT
• Taking ratio of these two, we get
Z = (va / v) = act. Gas specific vol./ IG specific vol.
• Z at a given pressure and temperature accounts for
deviation of RG from its corresponding IG
• If Z is close to 1, then the behaviour of RG is close to
IG behaviour

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Principle of corresponding states:

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 Contd…

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Generalized EOS:
• An equation of state (EOS) is a model for the P-V-T behavior of a fluid.

• The simplest, and the least accurate, is the ideal gas model, PV = RT,

where V is the molar volume and R is a universal constant.

• For real gases, the ratio, PV/RT, is not in general one, but varies with

the temperature and pressure. This ratio is called the compressibility

factor, z.

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Problems:
1. The specific heat ratio of acetylene (C2H2) was measured experimentally
to be 1.25. Find cp and cv.

Ans: cp = 1.5988 kJ.kg K, cv = 1.28 kJ.kg K

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2. Calculate the specific volume of NH3 at 500°C and 2 kbar using the
reduced Z chart and compare to the ideal gas law prediction. Take Tr = 405
K & pr = 111 atm.

Sol:

From Corresponding states:

Tr = (773 K)/(405.5 K) = 1.91;

Pr = (2000 atm)/(111 atm) = 18.02

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 Contd…

Tr = 1.91
Z = 1.62

Pr = 18.02

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 Contd…

Z = 1.62 = pv/RT
(2000 atm)V
Z = 1.62 =
(0.080256 atm L mol−1 K −1 )(773 K )
as R = 0.080256 atm L mol-1 K-1
V = 0.050 L mol−1

Ideal gas law: pv = RT

RT (0.080256 atm L mol−1 K −1 )(773 K )
V = = = 0.0310 L mol−1
P (2000 atm)
V = 0.0310 L mol−1

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3. N2 gas is stored at 175 K and 9500 kPa in a container. Calculate the specific
volume of the gas if it is considered as, (i) IG, (ii) Van der waals gas and (iii)
also cal. The compressibility factor. Use the constants: 0.175 kPa.m6/kg2 &
0.00138 m3/kg.

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4.

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T dS RELATIONS

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Thank
You
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