CHP 242 ENGINEERING THERMODYNAMICS

COURSE CONTENT

- Basic definitions and concepts, work and energy

- Enthalpy, heat capacity and phase rule.
- Steady state flow process
- PVT behaviour of pure substances, virial, ideal and cubic equations of state,
generalised correlations.
- Second law and Entropy
- Entropy changes for an ideal gas.

i
REFERENCES

1. Van Ness et al (2005) ‘Introduction to Chemical Engineering Thermodynamics,’ 7th

Ed. McGraw-Hill Education, Singapore.
2. Van Ness et al (1959) ‘Introduction to Chemical Engineering Thermodynamics,’ 2th
Ed. McGraw-Hill Book Co., New York.
3. Kyle B.G. (...........) “Chemical and Process Thermodynamics”2nd ed.

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 CONVERSION FACTORS

1. Force
1 newton = kg-m/sec2 = 0.012 kgf
1 kgf = 9.81 N
2. Pressure
1 bar = 750.06 mm Hg = 0.9869 atm = 105 N/m2 = 103 kg/m-sec2
1 N/m2 = 1 pascal = 10–5 bar = 10–2 kg/m-sec2
1 atm = 760 mm Hg = 1.03 kgf/cm2 = 1.01325 bar
= 1.01325 × 105 N/m2
3. Work, Energy or Heat
1 joule = 1 newton metre = 1 watt-sec
= 2.7778 × 10–7 kWh = 0.239 cal
= 0.239 × 10–3 kcal
1 cal = 4.184 joule = 1.1622 × 10–6 kWh
1 kcal = 4.184 × 103 joule = 427 kgf-m
= 1.1622 × 10–3 kWh
1 kWh = 8.6042 × 105 cal = 860 kcal = 3.6 × 106 joule

kgf −m= ( 4271 ) kcal=9.81 joules

4. Power
1 watt = 1 joule/sec = 0.860 kcal/h
1 h.p. = 75 m kgf/sec = 0.1757 kcal/sec = 735.3 watt
1 kW = 1000 watts = 860 kcal/h
5. Specific heat
1 kcal/kg-°K = 0.4184 joules/kg-K
6. Thermal conductivity
1 watt/m-K = 0.8598 kcal/h-m-°C
1 kcal/h-m-°C = 1.16123 watt/m-K = 1.16123 joules/s-m-K.
7. Heat transfer co-efficient
1 watt/m2-K = 0.86 kcal/m2-h-°C
1 kcal/m2-h-°C = 1.163 watt/m2-K.

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COURSE CONTENT.................................................................................................................i

REFERENCES..........................................................................................................................ii

CONVERSION FACTORS......................................................................................................iii

1. INTRODUCTION AND FIRST LAW OF THERMODYNAMICS.................................1

1.1 JOULE’S EXPERIMENT (1818-1889)........................................................................................1

1.2 INTERNAL ENERGY.................................................................................................................1
1.3 FIRST LAW OF THERMODYNAMICS........................................................................................1
1.4 WORK AND HEAT...................................................................................................................3
1.4.1 Work..............................................................................................................................3
1.4.2 Heat...............................................................................................................................3
1.4.3 Comparison of Work and Heat.......................................................................................4
1.5 THE REVERSIBLE PROCESS......................................................................................................5
1.6 IRREVERSIBLE PROCESS..........................................................................................................5
1.6.1 External irreversibility....................................................................................................6
1.6.2 Internal irreversibility.....................................................................................................6
1.7 BASIC DEFINITIONS AND CONCEPTS......................................................................................8
1.7.1 Measures of amount of size...........................................................................................8
1.7.2 Force..............................................................................................................................8
1.7.3 Pressure.........................................................................................................................9
1.7.4 Energy..........................................................................................................................10
1.8 PHASE RULE.........................................................................................................................14
1.9 CONSTANT –V & CONSTANT-P PROCESSES..........................................................................16
1.9.1 For a constant volume process....................................................................................16
1.9.2 For a constant pressure process..................................................................................16
1.10 ENTHALPY............................................................................................................................17
1.11 HEAT CAPACITY....................................................................................................................17
1.11.1 Heat capacity at constant volume................................................................................18
1.11.2 Heat capacity at constant Pressure..............................................................................18
2 THE IDEAL GAS.............................................................................................................21

2.1 RELATIONSHIP BETWEEN HEAT CAPACITIES........................................................................21

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 2.1.1 Ratio of specific heat capacities...................................................................................22
2.2 CONSTANT TEMPERATURE (ISOTHERMAL) PROCESS...........................................................23
2.3 REVERSIBLE ADIABATIC PROCES (CONSTANT ENTROPY).....................................................24
2.4 POLYTROPIC PROCESES........................................................................................................29
2.5 STEADY STATE FLOW PROCESS............................................................................................35
3 PVT BEHAVIOUR OF PURE SUBSTANCES..............................................................38

3.1 The Single phase region.......................................................................................................40

3.2 Cubic Equations of State......................................................................................................42
3.2.1 The Van der Waals Equation of State...........................................................................42
3.2.2 The Redlich/Kwong Equation of State..........................................................................44
3.2.3 Theorem of corresponding states; Acentric Factor......................................................46
3.3 Virial equation of state........................................................................................................48
3.3.1 Generalised compressibility factor Correlations for gases...........................................51
3.3.2 Generalised Second Virial coefficient Correlation for gases.........................................55
4 THE SECOND LAW OF THERMODYNAMICS..........................................................61

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1. INTRODUCTION AND FIRST LAW OF THERMODYNAMICS

1.1 JOULE’S EXPERIMENT (1818-1889)

- He placed a known amount of water, oil and mercury in an insulated container and
agitated the fluid with a rotating stirrer.
- Amounts of work done on the fluid were accurately measured and temperature change
carefully noted.
- He found that a fixed amount of work is required for a unit temperature rise per unit
mass of substance.
- Original temperature could be restored by cooking.
- He deduced that a quantitative relationship exists btn heat and work and therefore,
heat is form of energy since work is.

1.2 INTERNAL ENERGY

From Joule’s experiment, energy (work) applied must be existing in a form between its time
of addition and the time of its transfer. It is contained in a fluid in a form called internal
energy.

This is the energy in the form of vibrational and molecular activity in a molecular scale. It
cannot be measured but can be quantified from calculations.

1.3 FIRST LAW OF THERMODYNAMICS

“Although energy assumes many forms, the total energy is constant and when it disappears
in one form, it appears simultaneously in other forms”.

Definition of terms:

System:

It’s the region in which the process occurs.

Surroundings:

Its everything closer to the process which the system interacts with.

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Closed system:

Its system with a boundary that does not permit the transfer of matter between the system and
the surroundings (constant mass).

Open system:

Its a system with a boundary which matter crosses the system boundary as streams that enter
and leave the process equipment.

Extensive properties:

These are principle thermodynamic coordinates that depend on the quantity of the material in
the system e.g. volume, internal energy, enthalpy e.t.c.

Intensive properties:

These are principle thermodynamic coordinates that are independent on the quantity of the
material in the system e.g. temperature, pressure e.t.c.

Equilibrium

This implies the absence of tendency to change in macroscopic scale. It occurs when the
driving forces are at balance.

Adiabatic System
An adiabatic system is one which is thermally insulated from its surroundings.
It can, however, exchange work with its surroundings.
If it does not, it becomes an isolated system.
Phase
A phase is a quantity of matter which is homogeneous throughout in chemical composition
and physical structure.
Homogeneous System
A system which consists of a single phase is termed as homogeneous system. Examples:
Mixture of air and water vapour, water plus nitric acid and octane plus heptane.
Heterogeneous System
A system which consists of two or more phases is called a heterogeneous system. Examples:
water plus steam, ice plus water and water plus oil.

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1.4 WORK AND HEAT

1.4.1 Work
Work is said to be done when a force moves through a distance.
If a part of the boundary of a system undergoes a displacement under the action of a pressure,
the work done
W is the product of the force (pressure × area), and the distance it moves in the direction of
the force.
Consider:

Work is a transient quantity which only appears at the boundary while a change of state is
taking place within a system.
Sign convention:
If the work is done by the system on the surroundings, e.g., when a fluid expands pushing a
piston outwards, the work is said to be positive (+ W)

If the work is done on the system by the surroundings, e.g., to a piston to compress a fluid,
the work is said to be negative. i.e., Work input to system = – W

1.4.2 Heat
Heat (denoted by the symbol Q), may be, defined in an analogous way to work as follows:

“Heat is ‘something’ which appears at the boundary when a system changes its state
due to a difference in temperature between the system and its surroundings”.

Heat, like work, is a transient quantity which only appears at the boundary while a change is
taking place within the system.

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It is apparent that neither δW or δQ are exact differentials and therefore any integration of the
elemental quantities of work or heat which appear during a change from state 1 to state 2
must be written as:
2
W =∫ δ W =W 1−2∨W
1

2
W =∫ δ Q=Q 1−2 ∨Q
1

Sign convention
If the heat flows into a system from the surroundings, the quantity is said to be positive and,
conversely, if heat flows from the system to the surroundings it is said to be negative.
In other words:
Heat received by the system = + Q
Heat rejected or given up by the system = – Q.

1.4.3 Comparison of Work and Heat

Similarities :
i. Both are path functions and inexact differentials.
ii. Both are boundary phenomenon i.e., both are recognized at the boundaries of the
system as they cross them.
iii. Both are associated with a process, not a state. Unlike properties, work or heat has
no meaning at a state.
iv. Systems possess energy, but not work or heat.
Dissimilarities :
i. In heat transfer temperature difference is required.
ii. In a stable system there cannot be work transfer, however, there is no restriction
for the transfer of heat.
iii. The sole effect external to the system could be reduced to rise of a weight but in
the case of a heat transfer other effects are also observed.

1.5 THE REVERSIBLE PROCESS

A process is reversible when its direction can be reversed at any point by an infinitesimal
change in external conditions.

Characteristics of a reversible process:

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 a. It is frictionless
b. Is never more than differentially removed from equilibrium
c. Is driven by forces whose imbalance is differential in magnitude
d. Can be reversed at any point by differential change in external conditions
e. When reversed, it retraces its forward path, and restores the initial state of system and
surroundings

No real process is truely reversible but some processes may approach reversibility, to close
approximation.
Examples
Some examples of nearly reversible processes are:
i. Frictionless relative motion.
ii. Expansion and compression of spring.
iii. Frictionless adiabatic expansion or compression of fluid.
iv. Polytropic expansion or compression of fluid.
v. Isothermal expansion or compression.
vi. Electrolysis.

1.6 IRREVERSIBLE PROCESS

An irreversible process is one in which heat is transferred through

a finite temperature.
Examples
i. Relative motion with friction
ii. Combustion
iii. Diffusion
iv. Free expansion
v. Throttling
vi. Electricity flow through a resistance
vii. Heat transfer
viii. Plastic deformation.
An irreversible process is usually represented by a dotted (or discontinuous) line joining the
end states to indicate that the intermediate states are indeterminate
Irreversibilities are of two types :

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1.6.1 External irreversibility
These are associated with dissipating effects outside the working fluid.
Example
Mechanical friction occurring during a process due to some external source.

1.6.2 Internal irreversibility

These are associated with dissipating effects within the working fluid.
Example
Unrestricted expansion of gas, viscosity and inertia of the gas.
Consider a reversible process of compression of a piston and cylinder below:

Let us consider an ideal frictionless fluid contained in a cylinder above a piston as shown in
the above figure.
Assume that:
i. the pressure and temperature of the fluid are uniform and
ii. that there is no friction between the piston and the cylinder walls.
Let A = Cross-sectional area of the piston,
p = Pressure of the fluid at any instant,
(p – dp) A = Restraining force exerted by the surroundings on the piston, and
dl = The distance moved by the piston under the action of the force exerted.
Then work done by the fluid on the piston is given by force times
the distance moved,
i.e., Work done by the fluid
= (pA) × dl = pdV
(where dV = a small increase in volume)
Or considering unit mass

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Work done = pdv (where v = specific volume)
This is only true when
(a) the process is frictionless and
(b) the difference in pressure between the fluid and its surroundings during the
process is infinitely small.
Hence when a reversible process takes place between state 1 and state 2, we have
Work done by the unit mass of fluid
2
W =∫ Pd V
1

When a fluid undergoes a reversible process a series of state points can be joined up to form a
line on a diagram of properties. The work done by the fluid during any reversible process is
therefore given by the area under the line of process plotted on a p-v diagram below.
i.e., Work done = Shaded area on the figure below
2
W =∫ Pd V
1

When p can be expressed in terms of v then the integral∫ Pd V can be evaluated.

1

1.7 BASIC DEFINITIONS AND CONCEPTS

1.7.1 Measures of amount of size

The common measures are:

- Mass, m

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 - Number of moles, n
- Total volume, V t
m
n=
M
Where M, is the Molecular weight

t t
V V
Specific volume V = Molar volume=V =
m n

m
Specific density=ρ=
Vt

n
Molar density=ρ=
Vt

ρ∧V are intensive properties

1.7.2 Force
It is the product of mass m, and acceleration a.
F=ma
SI unit = newton, N
i) Temperature

It measures the degree of hotness or coldness of a body or fluid.

Its symbol is t for degree celcius and K for kelvin.

t ° C=T ( K )−273.15

° C is equal in quantity to Kelvin

Other scales are Fahrenheit and Rankine. Rankine scale is absolute, thats directly related to
the Kelvin scale by:-

T ( R ) =1.8 T ( K )

Relation between Fahrenheit and Rankine

t ° F=T ( R )−459.67

Relation between Fahrenheit and ° C

8
t ° F=1.8 t °C +32

1.7.3 Pressure
It is the normal force exerted by the fluid per unit area of the surface.

F mg A h ρg
P= = = = ρgh
A A A

ii) Work
It refers to the force acting through a distance. Quantity of work is given as:-
dW =Fdl

Upon integration, it gives the work of a finite process.

Its value is positive in the direction of the force and negative to the opposite.

It can also involve changes in volume e.g. expansion of a fluid in a cylinder.

( )
t
V
dW =−PAd
A

Since A is constant

( )
t
V
dW =−PAd
A

Upon integration,
t
V2

W =∫ PdV t
V t1

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1.7.4 Energy

1.7.4.1 Kinetic Energy

When a body of mass m, acted upon by force F, is displaced distance dl during differential
interval of time dt, the work done is given by

dW = m.a.dl

dU
but a= where U is the velocity
dt

dU dl
Thus dW =m dl=m .dU
dt dt

dl
But U = by definition, so
dt

dW =mUdU

Upon integration we get:-

( )
U2
U 22 U 21
W =m ∫ UdU =m −
U1 2 2

( )
2 22
mU 2 mU 1 mU
W= − =Δ
2 2 2

Each of the quantities above is a kinetic energy.

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Therefore, work done on a body by accelerating it from velocity U1 to U2 is equal to the
change in kinetic energy.

1.7.4.2 Potential energy

Upon lifting a body of mass m from z1 to z2, the minimum force required to lift it should at
least be equivalent to the weight of the body.

F=ma=mg

The minimum work done on this body to rise it is equal to the product of the minimum force
and the height of the elevation.

W =F ( z 2−z 1 )=mg ( z 2−z 1 )= Δ ( mgz )

Example

A horizontal piston and cylinder place in a constant temperature bath and held with a pressure
of 14 bar. The initial volume is 0.03 m3. Force is gradually reduced so that the system
expands to double the volume frictionlessly. If volume and pressure have the relation:
t
P V =k . Whats the work done by the gas during expansion. How much work would be done
if the external force is suddenly reduced to half its initial value instead of being gradually
reduced?

Solution

From literature, the process is reversible:

V2

Therefore: W =−∫ Pd V applies.

t

V1

V2
K V t2
¿−∫ t d V =Kln t
t

V V1
V1

V t2=0.06 m3 V t1=0.03 m3

t t 5
K=P 1 V 1=P2 V 2=14 × 10 × 0.03=42000 J

W =42000 × ln ( 0.03
0.06 )
=−29,112.2 J

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Sudden expansion doesn’t follow a reversible process.

K 42,000 J
P2= = =700,000 Pa
t
V2 0.06

We know P = F/A

So F 1=P1 A=14 A

F2 F 1 14 A
P2= = = =7 bars
A 2A 2A

Eventually heat transfer returns the system to the final equilibrium state as in the reversible
process. Work therefore equals the equivalent external pressure times the volume change.

W =−( 7 ×1 05 ) ( 0.06−0.03 )=−21,000 J

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1.8 PHASE RULE

The number of intensive properties (independent variables) needed to be specified in a certain

system to determine the state of the system is given by J. Willard Gibbs law for non-reacting
species.

F=2−π + N … … … … … P h ase rule

Where π are the number of phases, N is the number of chemical species, F is the degrees of
freedom of chemical species.

The intensive state of a system at equilibrium is established when its temperature, pressure
and composition of all the phases are fixed. These are the phase rule variables bur they are
not all independent.

Phase rule therefore gives the number of variables from the above set which must be
arbitrarily set to fix all the remaining variables.

Phase:- It’s an homogeneous region of matter e.g. a gas or mixture of gases, a liquid or a
liquid solution, a crystalline solid. It may or may not be continuous e.g. a gas dispersed as
bubbles in a liquid, liquid dispersed as droplets in a gas, a liquid dispersed as droplets in
another liquid with which it is immiscible e.t.c. are examples of discontinuous phases
whereby the dispersed phase need to be distributed throughout the continuous phase.

Many phases can co-exist in equilibrium, so long as they are in equilibrium e.g. saturated
aqueous salt solution at its boiling point with excess salt crystals present (three phase
equilibrium)

The phases are:- crystalline, aqueous solution and the vapour generated. The chemical species
are :- salt and water. Therefore the degree of freedom is:-

F=2−π + N thus F=2−3+2=1

NOTE

i. Phase rule variables are intensive properties, independent of the extent of the
system and other individual phases.
ii. Only individual phase compositions are phase rule variables.

13
 iii. Total or overall compositions are not phase rule variables if more than one phase
is involved.
iv. The minimum number of phases for any system is zero and implies that the
system is invariant e.g. the triple point of water (0.0061 bar, 0.01 ºC)

Examples

How many degrees of freedom has each of the following:

a. Liquid water in equilibrium with its vapour

b. Liquid water in equilibrium with a mixture of water vapour and nitrogen
c. A liquid solution of alcohol in water in equilibrium with its vapour

Solution

a. Chemical species =1
Phases =2

F=2−π + N

F=2−2+1

F=1

b. Chemical species =2
Phases =2

F=2−π + N

F=2−2+2

F=2

c. Chemical species =2
Phases =2

F=2−π + N

F=2−2+2

F=2

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1.9 CONSTANT –V & CONSTANT-P PROCESSES

For n moles of a homogeneous fluid in a closed system, the energy balance is:

d ( nU )=dQ+dW

The work for a mechanically reversible, closed system process is given by:

dW =−Pd (nV )

Combining the two equations:

d ( nU )=dQ−Pd (nV )

This is general energy balance for n moles of homogeneous fluid in a closed system
undergoing a mechanically reversible process.

1.9.1 For a constant volume process

The work term is zero, thus:

d ( nU )=dQ

Upon integration:

Q=nΔU

Thus, the heat transferred in a mechanically reversible, closed system at constant volume
process is equal to the change in internal energy of the system

1.9.2 For a constant pressure process

From 1st law:

d ( nU )=dQ−Pd (nV )

dQ =d ( nU ) + Pd( nV )

For constant pressure phenomenon:

dQ =d ( nU ) + Pd ( nV )=d [ n (U + PV ) ]

But U + PV is enthalpy H. So:

dQ=d ( nH )

15
Q=nΔH

Thus, the heat transferred in a mechanically reversible, closed system at constant pressure
process is equal to the change in enthalpy of the system

1.10 ENTHALPY

It is given by:

H=U + PV

Where U, V and P are state functions. H therefore is a state function. The differential form is:

dH =dU + d( PV )

The above equation applies whenever a differential change occurs in the system. The integral
form of it is:

ΔH =ΔU + Δ ( PV )

The above equations apply to unit masses.

Example

Calculate ΔU and ΔH for 1 kg of water when it is vapourised at the constant temperature of

100 ºC and the constant pressure of 101.33 kPa. The specific volumes of liquid and vapour
water at these conditions are 0.00104 and 1.673 m3kg-1 For this change, heat in the amount of
2,256.9 kJ is added to the water.

Solution

Xxxxxxxxxxxxxxxxxx

1.11 HEAT CAPACITY

The smaller the temperature change in a body caused by the transfer of a given quantity of
heat, the greater its heat capacity.

dQ
It’s defined as: C=
dT

It is a state function.

16
1.11.1 Heat capacity at constant volume
It’s defined as:

CV= ( ∂U
∂T )v

This definition applies to both molar heat capacity and specific heat capacity depending on
whether U is in molar or mass basis.

It relates to constant volume non flow process and can be written as:

dU =CV dT

Upon integration yields:

T2

ΔU =∫ C V dT
T1

The result for mechanically reversible, non flow system undergoing thermodynamic process
at constant volume is:

T2

Q=nΔU =∫ CV dT
T1

If the volume varies in the process but in the end returns to its initial process, the process
cannot be rightfully said to be a constant volume process. However, changes in state
functions are independent of the path and may therefore be calculated by equations for a truly
constant volume process with the same initial and final values. In a constant volume process,
W equals zero.

1.11.2 Heat capacity at constant Pressure

It’s defined as:

CP= ( ∂∂TH )
P

This definition applies to both molar heat capacity and specific heat capacity depending on
whether H is in molar or mass basis.

It relates to constant pressure non flow process and can be written as:

17
dH =C P dT

Upon integration yields:

T2

ΔH =∫ C P dT
T1

The result for mechanically reversible, non flow system undergoing thermodynamic process
at constant pressure is:

T2

Q=nΔH=∫ C P dT
T1

Since H, T & Cp are state functions, then the above equation applies to any process for which
the initial and final pressures are the same whether or not hte process is actually carred out in
constant pressure or not.

NOTE:

Only for the non flow mechanically reversible processes can the following equations be
used:

Q=nΔH

T2

Q=n∫ C P dT
T1

W =−Pn ∆V

Example

Air at 1 bar and 298.15 K is compressed to 5 bar and 298.15 K by two different mechanically
reversible processes:

a. Cooling at constant pressure followed by heating at constant volume

b. Heating at constant volume followed by cooling at constant pressure

Calculate the heat and work requirements and U and H of the air for each path. The following
−1 −1
data was given: C V =20.78 C P =29.10 J mol K

PV/T = constant regardless of the changes

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Molar volume = 0.02479 m3mol-1 at 298.15 K and 1 bar

Heat capacities for air may be assumed independent of temperature.

Solution

Xxxxxxxxxxxxxxxx

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2 THE IDEAL GAS

At temperatures that are considerably in excess of the critical temperatures of a fluid, and also
very low pressures, the vapour of the fluid tends to obey:

PV
=R=constant … … … … … … … … … … … ..2. 1
T

In reality, no gas obeys this formulation but most gases tend towards it. A hypothetical gas
that obey this law is called an ideal gas/perfect gas. The above equation is called the
characteristic equation of state of a perfect gas. It can be written as:

PV =mRT OR

PV =nRT … … … … … … … … … … … … … … … 2.2

m
Where n= (moles)
RMM

For a perfect gas, the values of C P ∧CV are constant for any one gas over all temperature and
pressure ranges.

For real gases, the values of C P ∧CV vary over different temperature ranges but for practical
purposes, an average value is usually taken to simplify calculations.

Joules law states that the internal energy of a perfect gas is a function of the absolute
temperature only ie U =f ( T ) alone .

2.1 RELATIONSHIP BETWEEN HEAT CAPACITIES

Consider a perfect gas being heated between two temperature levels at constant pressure:

From first law: Q−W =∆U

But ∆ U =mC v ( T 2 −T 1 ) … … … … … … … … … ..2. 3

Q−W =m C v (T 2−T 1)

For a constant pressure process, W =P ∆ V =P ( V 2−V 1 ) … … … 2.4

20
We also know: P V 2=mR T 2∧P V 1=mR T 1 ¿

Upon manipulation, we get:

Q−P(V 2−V 1 )=mC v (T 2−T 1)

Q−(mR T 2−mR T 1)=mC v (T 2−T 1 )

Q=mC v ( T 2−T 1 ) +mR (T 2−T 1)

Q=m(C ¿¿ v + R) ( T 2−T 1 ) … … … … … … … … … … .2 .5 ¿

But for constant pressure processes:

Q=mC P ( T 2−T 1 ) … … … … … … … … … … … … ….2 .6

Thus

Q=mC P ( T 2−T 1 ) =m(C¿¿ v+ R) ( T 2−T 1 ) … …..2. 7 ¿

Therefore

C P =C v + R … … … … … … … … … … … … … … … …2.8

C P −C v =R … … … … … … … … … … … … … … … … .2.9

2.1.1 Ratio of specific heat capacities

The ratio of the specific heat capacity at conctstant pressure to the specific heat capacity at
constant volume is given by the quantity, gamma (γ )

CP
=γ … … … … … … … … … … … … … … … … … … 2.10
Cv

Since R is +ve and C P −C v =R then C P >C v always in an ideal gas. Therefore it follows that
γ >1 always as far as ideal gas is concerned.

Since C P −C v =R then

CP R
−1=
Cv Cv

R
γ−1= … … … … … … … … … … … … … … … … ..2.11
Cv

21
 R
C v= … … … … … … … … … … … … … … … … … .2.12
γ −1

γR
C P =γ C v = … … … … … … … … … … … … … … 2.13
γ −1

2.2 CONSTANT TEMPERATURE (ISOTHERMAL) PROCESS

This is a process that is occurring at constant temperature.

For an isothermal process, ΔU = ΔH=0 since ΔU ( T )∧ ΔH ( T ) too .

This only holds for ideal gases.

In an isothermal expansion, heat must be added continuously in order to maintain the

temperature at a constant value. Likewise, in an isothermal compression, heat must be
continuously removed so that the temperature can be kept constant.

For isothermal process of an ideal gas: PV =RT =constant and:

PV =P1 V 1=P2 V 2 =constant

From the NFEE

dU =dQ −dW

For a mechanically reversible process, constant temperature, NFEE becomes

dQ=PdV and thus

2
Q=W =∫ PdV equal¿ the area of the shaded region below
1

22
 C
PV =C so , P= … … … … … … … … … … … … … .2.14
V

( ) ( )
2
C V2 V2
Q=W =∫
V
dV =C [ lnV ]V =P 1 V 1 ln
2
=P2 V 2 ln … … … … … 2.15
1 V 1
V1 V1

Also:

P1 V 1=P2 V 2 so

V 1 P2
= so … … … … … … … … … … … … … … … … .2 .16
V 2 P1 ❑

Q=W =P1 V 1 ln
( )
P1
P2
=P2 V 2 ln
( )
P1
P2
… … … … ..2.17

Also, P1 V 1=RT so ,

Q=W =RTln
( )
P1
P2
P
( )
=RTln 1 … … … … … .2 .18
P2

2.3 REVERSIBLE ADIABATIC PROCES (CONSTANT ENTROPY)

An adiabatic process in the one in which no heat is transferred to or out of the process. Such a
process can be reversible or irreversible. A reversible process shall be considered in this
section. For an adiabatic process to take place, perfect thermal insulation is necessary.

From NFEE

∆ U =Q−W but Q=0 , so :

23
∆ U =−W … … … … … … … … … … … … … … … .2 .19

For a perfect gas, consider differential form of the NFEE:

dU =dQ −dW

For a reversible process, dW = pdV so,

dQ =dU + pdV =0 … … … … … … … … … … a 2.20

From the definition of enthalpy:

H=U + PV

In the differential form we have:

dH =dU + PdV +VdP

From manipulation of equation 2.20

dU + PdV =dH−VdP=0 … … … … … … … … … b 2.21So,

dH −VdP=0

dH =VdP … … … … … … … … ….. … … … … … … … c 2.22

Combining equation a2.20 with the general ideal gas law:

dV
dU + RT =0 … … … … … … … … … … .… ….. d 2.23
V

We know dU =CV dT

Combining with equation d2.23

dV
C V dT + RT =0 … … … … … .. … … … … … .. e 2.24
V

Dividing through by T

dT dV
CV +R =0 … … … … … … … … .… … .. f 2.25
T V

Integrating:

24
C V lnT + R lnV =constant … … … … … ….. g 2.26

Using ideal gas equation to replace T and dividing through by C V :

ln ( PVR )+ CR lnV =constant … … … … … . h 2.27

V

We know that:

R R
C v= ∧so , =γ −1
γ −1 Cv

Therefore,

ln ( PVR )+( γ −1) lnV =constant … … .. i2.28

ln ( PVR )+ ln (V γ −1
) =constant … … … … .. j2.29

ln ( PV V γ −1
R )
=constant … … … … … … … .. k 2.30

( )
γ
PV
ln =constant … … … … … … … … … ..l 2.31
R

( )
γ
PV constant
=e =constant … … … … ..m 2.32
R

P V γ =constant … … … … … … … … … .. … .. n2.33

Equation n2.33 is a simple relationship relating to P and V for any reversible adiabatic
process involving a perfect gas. Each perfect gas has its own value of γ

RT
From ideal gas law, P= , combining with equation n2.33:
V

RT γ
V =constant … … … … … … … … … ....o 2.34
V

γ−1
TV =constant … … … … … … … … … .... p 2.35

25
 RT
Also, V = , combining with equation n2.33
P

P ( )
RT γ
P
=constant … … … … … … … … … .. q 2.36

γ ❑
T T
γ −1
= (γ −1) /γ =constant … … … … ... r 2.37
P P

Therefore the general equation can be written also as:

γ P1 V 2 γ
γ
P1 V =P2 V =constant∨ =
1 2
P2 V 1 ( )
… … … … … … … … . s 2.38

From equation p2.35:

( )
γ −1
γ −1 γ−1 T V
T 1V 1 ¿ T 2V 2 =constant∨ 1 = 2 … … … … … .. t 2.39
T2 V1

From equation r2.37:

( )
( γ−1 ) / γ
T1 T2 T 1 P1
= =constant ∨ = … … ...u 2.40
P1 ( γ −1) / γ
P2 ( γ−1) / γ T 2 P2

From first law equation, the work done by a perfect gas on an adiabatic process is given by:

∆ U =−W … … … … … … … … … … … … … … 2.41

So,
−W =CV (T 2 −T 1 )

R
But C v = so,
γ −1

R (T 2−T 1 ) P2 V 2−P1 V 1
−W = =
γ −1 γ −1

P1 V 1−P2 V 2
W= … … … … … … … … … ... v 2.42
γ −1

A reversible adiabatic process involving a perfect gas can be sketched as shown in the P-V
diagram below:

26
The area under the curve can be represented by the function:

V2

W =−∫ PdV … … … … … … … … … … … …2.43

V1

Example;

Air at 1.02 bar 22 ºC, initially occupying a cylinder volume of 0.015 m3, is compressed
reversibly and adiabatically by a piston to a pressure of 6.8 bars. Calculate the final
temperature, the final volume and the work done on the cylinder mass of air in the cylinder.
Take γ for air to be 1.4

27
28
2.4 POLYTROPIC PROCESES

It is found that in many processes in practice approximate to a reversible law of the form:

P V n=c (constant) where n is a constant. Both vapours and perfect gases obey this type of
law closely in many non-flow processes.

These processes are internally reversible.

From equation 2.43

V2

W =−∫ PdV … … … … … … … … … … … … …..2.4 3

V1

Where P V n=c relation apply, then:

( ) ( )
V2 −n+1 −n+1 −n+1 −n+1 n 1−n n 1−n
dV V 2 −V 1 V2 −V 1 P2 V 2 V 2 −P1 V 1 V 1
W =−c ∫ n =−c =c =
V V 1
−n+1 n−1 n−1

P2 V 2−P1 V 1
W= … … … … … … … … … … … … … … . i2.44
n−1

It follows that for any polytropic process the relation:

P1 V n1=P2 V n2=c∨ =
( )
P1 V 2 n
P2 V 1
… … … … … … ii 2.45 holds

29
 RT
From ideal gas law, P= , combining with equation ii2.45:
V

RT n
V =constant … … … … … … … … … … … … . iii2.46
V

n −1
TV =constant … … … … … … … … … … … ....iv 2.47

RT
Also, V = , combining with equation ii2.45
P

( )
n
RT
P =constant and so,
P

Tn ❑ T
n−1
= (n−1 )/ n =constant … … … … … … … . v 2.48
P P

Therefore the general equation can be written also as:

P1 V n1=P2 V n2=constant ∨ =
( )
P1 V 2 n
P2 V 1
… … vi2.49

From equation iv2.47:

( )
n−1
n−1 n−1 T1 V2
T 1 V 1 ¿T 2 V 2 =constant ∨ = … … … … … … . … … … .. vii 2.50
T2 V1

From equation v2.48:

( )
( n −1 ) / n
T1 T2 T 1 P1
= ( n−1) /n =constant ∨ = … … … … … ….. viii 2.51
P1
( n−1) /n
P2 T 2 P2

It can be seen that the equations for the polytropic processes resemble those of the adiabatic
process. This because and adiabatic process is a special case of polytropic process.

Note that the equations vi, vii and viii, cannot be used to evaluate vapours undergoing
polytropic processes. This is because the equation that was used to derive them was the ideal
gas law. Ideal gas law doesn’t apply to vapours.

For a perfect gas expanding polytropically, its sometimes convenient to express input in
terms of temperatures at the end states i.e. from equation i2.44

30
 P2 V 2−P1 V 1
W= … … … … … … … … … … … … … … i2.44
n−1

From ideal gas equation:

P1 V 1=R T 1∧P2 V 2=R T 2

Combining with equation i2.44, gives:

R(T ¿ ¿ 2−T 1 )
W= … … … … … … … … … … … … … … ix 2.52 ¿
n−1

From NFEE,

∆ U =Q+W

R (T ¿ ¿2−T 1 )
Q+ =CV (T ¿ ¿ 2−T 1 ) … … … … … …... x 2.53 ¿ ¿
n−1

R
But C v = so,
γ −1

R(T ¿ ¿ 2−T 1) R(T ¿ ¿ 2−T 1)

Q= − ¿¿
γ −1 n−1

( n−1−γ +1 )
Q=R (T ¿ ¿ 2−T 1 ) =¿ ¿
( n−1 ) ( γ −1 )

Q= ( w ) ( n−γ
γ−1 )
… … … … … … … … … .. ….... xi2.54

Equation xi2.54 is a convenient and concise expression relating the heat supplied and the
work input in the polytropic process.

In a compression process, work is done on the gas and hence the term W is positive.

From Equation xi2.54, it can be deduced that when the polytropic index n is greater than γ in
a compression process, then the right hand side of the eequation is positive (i.e. heat is
supplied during the process). Conversely, when n is less than γ , in a compression process
then heat is rejected by the gas. It is the converse with regards to an expansion process.

Example

31
1 kg of a perfect gas is compressed from 1.1 bars

32
33
34
2.5 STEADY STATE FLOW PROCESS

The laws of mass and energy conservation apply to all processes ie both open and closed
systems.

Open systems include closed systems as special cases.

Measures of flow:

- Mass flowrate, m
- Molar flowrate, n
- Volumetric flowrate, q
- Velocity, u

Key items on measures of flow:

m (kg/s) = Mn where M is the relative molecular mass

q =uA (where A is the cross-sectional area of the conduit)

n = uA ρ

m= uA ρ

The region of space identified for analysis of an open system is called the control volume
and is separated from its surroundings by a control surface.

Streams in: m1, m2

35
Streams out: m3

Control volume mass balance:

d mcv
+m1+ m2−m3=0 … … … … … … … … … … 2.55
dt

General energy balance of a system

The rate of change of energy within the control volume equals the net rate of energy transfer
into the control volume.

Streams flowing into and out of the control volume carry with them energy in the form of
internal, potential and kinetic energies.

Consider the control volume below:

Energy balance for the control volume system

d (mU ¿¿ cv )
dt {[ (
1 2
=− m U + u + zg
2 )] −[( m (U + 12 u + zg))]
¿
2

out }
+Q+W … .2 .56 ¿

Work rate, W, includes:

i. Flow work that is associated with the movement of the fluid from the entrance
through to the exit i.e. PV work
This type of work is associated with the contraction and expansion of the fluid inside
the system.

36
 ii. Shaft work, Ws. This is the stirring work , which could be rotational or
reciprocating

d (mU ¿¿ cv )
dt [ ( 1
)]
=− m ∆ U + u2 + zg + ∆ m [ PV ] + Q+ Ws … … .2 .57 ¿
2

Combining equation 2.57 with the enthalpy term i.e. H=U+PV, we get:

d (mU ¿¿ cv )
dt [ ( 1 2
)]
=− m ∆ H + u + zg +Q +Ws … … … … … . … … ..2.5 8 ¿
2

d (mU ¿¿ cv )
For steady state operation, Accumulation, =0 ¿, thus:
dt

[ ( 1 2
)]
m ∆ H + u + zg =Q+ Ws … … … … … … .. … … . … . … … …...2.5 9
2

Equation 2.59 is the mathematical expression of the first law of thermodynamics to steady
state flow systems.

QUESTIONS

XXXXXXXXXXXXXXXXXX

37
3 PVT BEHAVIOUR OF PURE SUBSTANCES
The quantities of heat and work needed are calculated from knowledge of such
thermodynamic properties of internal energy and enthalpy. Internal energies and enthalpies
are evaluated from measurements of molar volumes as functions of pressure and temperature.
This yields the PVT relation.

PVT relation can be expressed mathematically using equations of state.

The simplest equation of state is the perfect gas law.

Equations of state serve the purpose of metering of fluids and sizing of vessels and pipelines.

Consider the PT diagram below:

The lines 1-2, 2-C & 2-3 display conditions of pressure and temperature at which two phases
may coexist and divide the diagram into single phase regions.

- Line 1-2: Sublimation line that shows solid vapour equilibrium

- Line 2-3:Fusion curve that separates solid and liquid regions
- Line 2-C: vaporisation curve that separates the liquid and vapour phases

Point C is the critical point and is the highest point in terms of temperature and pressure at
which pure chemical species are observed to exist in vapour/liquid equilibrium.

38
Point 2 is the triple point and it is invariant as the degree of freedom is zero.

Consider the PV diagram below:

PT diagram doesn’t give any information about volumes but instead it merely displays the
phase boundaries just as lines.

The PV diagram display the phases as regions where two phases-Solid/liquid, solid/vapour
and liquid/vapour coexist in equilibrium.

Temperatures above Tc do not cross a phase boundary.

The lines labelled T1 and T2 are subcritical temperatures with three regions. The horizontal
region is a liquid/vapour phase and give all the possible mixtures ranging from 100 % liquid
at the left to 100 % vapour at the right.

Along line BC, it represents saturated liquid line while line CD represents saturated vapour
line.

The two phase region (vapour/liquid phase) lies under dome BCD

To the left of BC is the sub-cooled liquid region

To the right of line CD is the superheated vapour region.

39
Sub-cooled liquid exists at temperatures below, and superheated vapour, at temperatures
above the boiling point at a given pressure.

3.1 The Single phase region

In the single phase region on the PT diagrams a PVT equation of state can be analytically
expressed as f(PVT) = 0. It relates Pressure, molar or specific Volume and Temperature for a
pure homogeneous fluid in equilibrium state.

The ideal gas equation ie PV =RT has approximate validity for the low pressure region.

An equation of state can be solved for any of the three quantities as a function of the other
two e.g. if V is considered a function of T and P then: V= V(T,P), and

dV = ( ∂∂ VT ) dT +( ∂V
P ∂P)T
dP … … … … … … … … .. … … ..3.1

The partial derivatives in this equation have definite physical meanings, and are related to
two properties, commonly tabulated for liquids, and defined as:

Volume expansivity:

β= ( ) … … … … … … … … … … … … … … … … .. … ..3.2
1 ∂V
V ∂T P

Isothermal compressibility:

κ=− ( ) … … … … … … … … … … … … … … … … … 3.3
1 ∂V
V ∂P T

In combination equation 3.1, 3.2 &3.3 yield:

dV
=βdT −κdP … … … … … … … … … … … … … … … … .3 .4
V

The isotherms to the left side of the PV diagram are very steep and closely packed.

This is due to the low compressibility of liquids. Therefore ( ∂∂TV ) and ( ∂∂VP ) and hence both
P T

β & κ are small.

In fluid mechanics, this phenomenon is regarded as incompressibility of fluids and thus β &
κ are taken as zero.

40
In reality, no true fluid is incompressible, but this idealisation is useful as it simplifies
complex phenomena and approximates the real case meaningfully.

For liquids, β is always +ve (except liquid water between 0 ºC and 4 ºC) and κ is necessarily
+ve. At this conditions not close to the critical point, β & κ are weak functions of
temperature and pressure. Thus, for small changes of P and T little error is introduced if they
are assumed constant.

Integration of equation 3.4 yields:

V2
ln =β ( T 2−T 1 )−κ ( P2−P1 ) … … … … … … … … … … … … … … … … .3 .5
V1

This is less restrictive approximation than the assumption of an incompressible fluid.

Example

For fluid acetone at 20 ᵒC and 1 bar,

β=1.487 ×1 0−3 ᵒ C−1 κ=62 ×1 0−6 ¿¯−1 V =1.287 cm3 g−1 ¿

For acetone, find:

a. The value of ( ∂ P/∂ T )V at 20 ᵒC and 1 bar

b. The pressure generated by heating at constant volume from 20 ᵒC and 1 bar to 30 ᵒC
c. The change in volume for a change from 20 ᵒC and 1 bar to 0 ᵒC and 10 bar.

Solution:

a. Since volume was regarded as constant, the derivative ( ∂ P/∂ T )V was obtained by use
of equation 3.4
βdT −κdP=0

( ) ∂P β 1.487× 10−3
= =
∂T V κ 62× 10 −6
=24 ᵒ̄ C
−1

b. If β &κ are assumed constant over the 10 ᵒC temperature interval, then the equation
derived in (a) may be written (V=const):
β
∆ P= ∆ T =( 24 ) ( 10 )=240 ¯¿
κ
¿

41
 P2=P1 + ∆ P=1+240=241 ¯¿
c. Using equation 3.5:
V2
ln =β ( T 2−T 1 )−κ ( P2−P1 )
V1
V2
ln =( 1.487 ×1 0−3 ) (−20 ) −( 62× 10−6 ) ( 9 )=−0.0303
V1
V2
=0.9702
V1
¿
3 −1
V 2=( 0.9702) ( 1.287 ) =1.249 cm g
Then:
∆ V =V 2−V 1=1.249−1.287=−0.038 cm3 g−1

3.2 Cubic Equations of State

An equation that is represented by a PVT behaviour of both liquids and vapours must
encompass a wide range of temperature and pressure.

It must also not be so complex as to present excessive difficulties in application.

Polynomial equations that are cubic with respect to molar volume offer a compromise
between generality and simplicity that is suitable to many applications.

3.2.1 The Van der Waals Equation of State

It was the first practical cubic equation of state (by J.D. Van der Waals in 1873)

RT a
P= − 2 … … … … … … … … … … … … … … 3.6
V −b V

a & a are +ve constants. When they are zero, the equation turns to be ideal gas law.

a=3 PC V 2C … … … … … … … … … … … … … … … ….3 .7

1
b= V C … … … … … … … … … … … … … … … … … … 3.8
3

3 R TC
V C= … … … … … … … … … … … … … . … … … 3.9
8 PC

42
 2 2
27 R T C
a= … … … … … … … … … … … … … … … … 3.10
64 PC

1 R TC
b= … … … … … … … … … … … … … … … … … … 3.11
8 PC

For the isotherm T 1>T C , pressure is a monotonically decreasing function with increasing
molar volume.

The critical isotherm T C , has an a horizontal point of inflection at C characteristic to the

critical point.

For the isotherm T 2<T C , pressure decreases rapidly in the sub-cooled liquid region with
increasing volume. After the saturated liquid line, it experiences a minima and then a
maxima. Upon crossing the saturated vapour line, it continues to decrease as it enters the
superheated region.

Experimental isotherms do not experience minima and maxima in the two phase region but
instead it exhibits a constant pressure line.

This is where the equations of state fail in the approximation of molar volumes.

This phenomenon exhibited by the cubic equations of state in the two phase region is realistic
if pressure is decreased on a saturated liquid devoid of vapour nucleation sites in a carefully
controlled environment where vapourisation does not occur and liquid persist alone to
pressures well below its vapour pressure.

Similarly, where raising pressures of saturated vapour in a suitable experiment does not cause
condensation, and vapour persists alone to pressures well above the vapour pressure.

43
Cubic equations of state have three volume roots of which two may be complex. Roots that
have physical meaning are real, positive and are greater than the value of the constant b.

a. For T > T C only one such root exist

b. For T =T C there are three roots which are equal and identical.
c. For T < T C the equation can have one or three real roots, depending on the pressure.
Although these roots are positive and real, they are not physically stable states for the
portion of an isotherm between saturated liquid and saturated vapour.
The smallest root are liquid like volumes and the largest roor is a vapour like volume.
The third root lies between the two and is of no physical significance.

3.2.2 The Redlich/Kwong Equation of State

It was by Redlich and Kwong in 1949.

It is of the form:

RT a
P= − … … … … … … … … … … … … … …3.12
V −b V T ( V + b )
1/ 2

44
 2 2.5
0.42748 R T C
a= … … … .. … … … … … … … … … … … … … … .3 .13
PC

0.08664 RT c
b= … … … … … … … … … … … … … … … … … … … 3.14
Pc

The three roots of the equation are mostly solved by iteration. However, iteration bring about
convergence problems. This can be avoided by by re-arranging the equation to a form suited
to the solution for a particular root.

Vapour volume iteration equation

RT a(V i−b)
V i+ 1= +b− … … … … … … … … … … … 3.15
P ( 2)
1

PVi T V +b ( i )

and,

RT
V o= … … … … … … … … … … … … … … … … … … … … … … ...3.1 6
P

The equation for Z is obtained by substituting Z=PV /RT

Liquid volume iteration equation

Equation 3.12 is re-arranged to the form:

[ ]
2
1 RT V i ab
V i+ 1= V 3i − − … … … … … … … … … … … … .3 .17
C P
PT
( 2)
1

Where:

bRT a
C=b 2+ − … … … … … … … … … … … … … … … ..3.1 8
P ( 12 )
PT

This equation with a starting iteration value of V = b converges upon iteration at the liquid
volume or liquid like root.

Example:

Given that the vapour pressure of n-butane at 350 K is 9.4573 bar, find the molar volumes of:

45
 a. Saturated vapour and
b. Saturated liquid

of n-butane at this conditions as given by Van der Waals and Redlich/Kwong equations.

Solutions:

Xxxxxxxxxxxxxxxxxxxxx

3.2.3 Theorem of corresponding states; Acentric Factor

From experiment, it is noted that Z for different fluids exhibit similar behaviour when
correlated as a function of reduced temperatureT r, and reduced pressure Pr .

These provide the basis for the simplest form of the theorem of corresponding states which is
formulated as:

“All fluids, when compared at the same reduced temperature and reduced pressure, have
approximately the same compressibility factor, and all deviate from the ideal-gas behaviour
to about the same degree”

Corresponding –state correlations of Z based on this theorem are called two parameter
correlations, because they require the use of the two reducing parametersT C, & PC .

This correlation is near exact for simple fluids (argon, krypton and xenon), deviations are
realised for more complex liquids.

To improve this, Pitzer K.S. and co-workers introduced a third parameter (in addition to T C,
& PC ) that takes care of the molecular structure of the substances, the Acentric Factor, ω .

The Acentric Factor for pure chemical substances is defined with reference to its vapour
pressure. Because the logarithm of the vapour pressure of a pure fluid is approximately linear
in reciprocal of absolute temperature:

dlog Prsat
=s … … … … … … … … … … … … … … … … … … 3.19
d ( 1/T r )

Where Psat
r is the reduced vapour pressure,
T r is the reduced temperature, s is the slope of the

plot of logP sat

r vs
1/ T r

46
If the two parameter corresponding state were valid, then the slope s, would be same for all
the substances. This is not true as each fluid has its own characteristic of s.

This s value is identified as the third corresponding state parameter.

It is noted that all the corresponding state parameter s, for simple fluids Ar, Kr, Xe lie on the
same line when logP sat
r vs
1/ T r is plotted.

The same line passes throughlogP sat

r =−1 at T r =0.7 . This is illustrated in the diagram below:

Other types of fluids define different lines and their locations can be fixed by measuring the
deviation from simple fluids (SF) i.e.

sat sat
logP r ( SF )−logP r … … … … … … … … … … … … … … ..3.20

The Acentric Factor is defined as:

ω=−1−log ⁡( P ¿ ¿ r )T =0.7 … … … … … … … … … … … … ….3 .21 ¿

sat
r

Therefore ω can be determined for any fluid from T r , P r and a single vapour pressure
measurement made at T r=0.7.Values of ω , T r ,∧Pr are obtainable from thermodynamic
tables.

Therefore, ω for neon, krypton and xenon have a value of zero and experimental data yields
compressibility factors for all three fluids that are correlated by the same curves when Z is

47
represented as a function of T r ,∧Pr . This is the basis of the three parameter theorem of
corresponding states which is outlined as:

All fluids having the sameω, when compared at the sameT r ,∧Pr , have about the same
value of Z, and all deviate from ideal gas behaviour to about the same degree.

3.3 Virial equation of state

Isotherms for liquids and gases above the critical point and to the right of the PV diagram are
simple curves in which V decreases with increase in P. Here, the product PV for a given T is
fairly constant and analytical representation can be made e.g. the power series law with
respect to P below:

PV =a+ bP+c P 2+ dP3 +… … … … … … … … … … … .3 .22

If b=a B' , c=a C' e . t . c . then:

PV =a ( 1+ B P+ C P + D P + … ) … … … … … … … … 3.23
' ' 2 ' 3

Where a , B' C ' e .t . c are constants for a given temperature and a given chemical species.

In principle equation 3.23 is an infinite series, but in practice, finite number of terms is used.

' '
B C e .t . c are parameters that depend on both species and temperature, but a is found
experimentally to be a function of temperature alone. Consider the plot below. The limiting
values of PV asl P tends to zero is the same for all gases and is equal to a

lim ( PV ) =a=f ( T )=RT … … … … … … … … … … … … 3.24

P ❑0
⇒

PV =a=RT … … … … … … … … … … … … … … … … … ….3 .35

48
Another useful thermodynamic property is defined by the equation having the compressibility
factor as:

PV
Z= … … … … … … … … … … … … … … … … … … . … .3.26
RT

Combining equation 3.24, 3.25 and 3.26, we get:

' ' 2 ' 3

Z=1+B P+C P + D P +… … … … … … … … … 3.27

Another way of expressing Z was proposed by Kamerlingh and is given equation 3.28

B C D
Z=1+ + + + … … … … … … … … … … … … 3.28
V V2 V3

Both of these equations are known as Virial expansions and the parameters B, C, D ......and
B’, C’, D’ .......are called virial coefficients. Virial coefficients are functions of temperature
alone.

Considering equations 3.27 and 3.28 the following relations can be obtained:

' B
B= … … … … .. … … … … … … … … … … … … … .3 .29
RT

2
'C−B
C= 2
… … … … .. … … … … … … … … … … … .3 .30
( RT )

' D−3 BC +2 B3
D= … … … … .. … … … … … … ….3 .30
( RT )3

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 PV
To obtain the above relations, we set Z= in equation 3.28 and solve for P. This allows for
RT
elimination of P and the resulting equation is in power series of (1/V) which then is compared
term by term to yield the required relation.

Virial equations are fairly acceptable and are form purely on statistical mechanics. The
contribution of terms as the order of the power series increases keep on decreasing and a
reasonable truncation of the virial equation is acceptable and practical.

Application of the Virial Equations

The two Virial expansion forms are only useful for practical purposes where convergence is
very rapid (i.e. where two or three terms suffice for reasonably close approximations).

When truncated to two terms, we get:

'
Z=1+B P … … … … … … … … … … … … 3.31

Replacing for B' with equation 3.29:

PV BP
Z= =1+ … … … … … … … … ….3 .32
RT RT

Equation 3.32 is often used for vapours between sub-critical temperatures to their saturation
pressures.

Volume explicit virial equation can also be truncated to two terms ie

PV B
Z= =1+ … … … … … … … … … .3 .33
RT V

For more accurate results, virial equation can be truncated to three terms as:

PV B C
Z= =1+ + 2 … … … … … … … … ….3 .34
RT V V

Equation 3.34 can be solved directly for P but is cubic with respect to volume and therefore
iterative approach is used to solve for V.

Example:

Reported values for the virial coefficients of isopropanol vapour at 200 C are:

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B = -388 cm3mol-1 C = -26000 cm6mol-2

Calculate V and Z for isopropanol vapour at 200 C and 10 bar by:

a) Ideal gas equation

b) Pressure explicit virial equation truncated to two terms
c) Volume explicit virial equation truncated to three terms

Solution (page 89)

3.3.1 Generalised compressibility factor Correlations for gases

Most of the correlations of the kind developed by Pitzer et al are of the compressibility factor
Z and for the second virial coefficient B.

The correlation for Z is:

0 1
Z=Z +ω Z … … … … … … … … … … … … … … ..3.35

Where Z 0∧Z 1 are functions ofT r ,∧Pr . When ω=0 which is a case of simple fluid, the second
term disappears and Z 0 becomes identical with Z.

Z can be obtained from Lee Kesler tables which are analytical data of the modified
Benedict/Webb/Rubin equation. The tables present Z 0∧Z 1 as functions ofT r ,∧Pr .

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Lee Kesler correction provides reliable results for gases which are non-polar or only slightly
polar (these have errors of between 2-3%). It doesn’t apply to highly polar or gases that
associate.

3.3.2 Generalised Second Virial coefficient Correlation for gases

For low to moderate pressures, truncated virial equation to the second term is regarded as
sufficiently valid.

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Consider equation 3.32:

PV BP
Z= =1+ … … … … … … … … ….3 .32
RT RT

Thus

PV ^P
B r
Z= =1+ … … … … … … … … … .3 .36
RT Tr

Where

^B= B PC … … … … … … … … … … … … … ..3.3 7
R TC

Pitzer and co-workers proposed a second correlation which yields the values of ^Bas:

^B=B0 +ω B1 … … … … … … … … … … … ..3.3 8

Combining equation 3.36 and 3.38 we get:

PV 1 Pr 0 Pr 1 Pr
=1+ [ B +ω B ] =1+ B
0
Z= +ω B … … … … … … … … … .3 .39
RT Tr Tr Tr

Comparing equation 3.39 with equation 3.35

0 0 Pr
Z =1+B … … … … … … … … … .3.40
Tr

1 1 Pr
Z =B … .. … … … … … … … … … .3 .41
Tr

The second virial coefficients are functions of temperature alone and similarly, B0∧B1are
functions of reduced temperature only. Their values can be obtained from the following
equations:

0 0.422
B =0.083− 1.6
… .. … … … … … … … … … .3.42
Tr

1 0.172
B =0.139− 4.2
… ..… … … … … … … … ….3 .43
Tr

Example:

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Determine the molar volume of n-butane at 510 K and 25 bar by each of the following
methods:

a. The ideal gas equation

b. The generalised compressibility factor correlation
c. The generalised second virial coefficient correlation

Solution

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4 THE SECOND LAW OF THERMODYNAMICS

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