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ng
Federal University of Agriculture, Abeokuta

COURSE CODE: MCE 204

COURSE TITLE: Engineering Thermodynamics
NUMBER OF UNITS: 3 Units
COURSE DURATION: Three hours per week

COURSE DETAILS:
COURSE DETAILS:

Course Coordinator: Dr Salami Olasunkanmi ISMAILA, ND, BSc, MSc, PhD

Email: [email protected]
Office Location: Room 1 PG School
Other Lecturers: None

COURSE CONTENT:

Definition of terms and general concept of systems, surrounding, process, temperature,

heat work and energy. First law of thermodynamics and application to open systems.
Second law of thermodynamics and application to heat engines. Entropy. First and
second laws combined. Perfect gases. Joule-Thompson coefficient. Equilibrium
processes. Maxwell’s relations. Two phase system. Thermodynamic functions of
solution. P.V.T – relationship. Work from heat energy. Refrigeration.

COURSE REQUIREMENTS:
This a compulsory course for all students in the College of Engineering. Students are expected to
participate in all course activities and have minimum of 75% attendance to be able to write the
final examination.

READING LIST:

1. Cengel Y. A. & Boles M. A. (2006). Thermodymanics: An Engineering Approach. Tata

McGraw-Hill, 7 West Patel Nagar, New Delhi 110008.
2. Jones J. B. & Dugan R. E. (2006). Engineering Thermodynamics. Prentice-Hall of India
Private Limited, New Delhi-110001.
3. Moran M. J. & Shapiro H.N. (1998). Fundamentals of Engineering Thermodynamics.
John Wiley & Sons Ltd., Baffins Lane, Chichester, West Sussex PO19 IUD, England.
4. Osore O.A. (1999). Essentials of Classical Thermodynamics. IPS Educational Press,
P.M.B 173, Ilaro, Ogun state, Nigeria.

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LECTURE NOTES
LECTURE

1.0 INTRODUCTION

Thermodynamics was obtained from two Greek words namely thermos meaning heat and dynamis
meaning power. Engineering thermodynamics deal with the laws that govern the processes involving the
conversion of heat into work and vice-versa. It gives the interrelationship between thermal, mechanical
and chemical processes in heat engines and refrigerating engines; studies these processes and properties
of these bodies under various physical conditions.
Thermodynamics is the science that deals with heat and work and those properties of substance that bear
a relation to heat and work. Thermodynamics is the study of the patterns of energy change. More
specifically, thermodynamics deals with (a) energy conversion and (b) the direction of change.
Thermodynamics is an empirical science and is thus based on experimental observation. The principles
of thermodynamics are summarized in the form of four laws known as zeroth, first, second, and the third
laws of thermodynamics.
The zeroth law of thermodynamics deals with thermal equilibrium and provides a means of measuring
temperature.
The first law of thermodynamics deals with the conservation of energy and introduces the concept of
internal energy.
The second law of thermodynamics dictates the limits on the conversion of heat into work and provides
the yard stick to measure the performance of various processes. It also tells whether a particular process
is feasible or not and specifies the direction in which a process will proceed. As a consequence it also
introduces the concept of entropy.
The third law defines the absolute zero of entropy.

1.1 Thermodynamic System:

An important concept in thermodynamics is the “system”. A system is the region of the universe under
study. A system is separated from the remainder of the universe by a boundary which may be imaginary
or not, but which by convention delimits a finite volume. The possible exchanges of work, heat, or
matter between the system and the surroundings take place across this boundary. Two types of exchange
can occur between system and surroundings: (1) energy exchange (heat, work, friction, radiation, etc.)
and (2) matter exchange (movement of molecules across the boundary of the system and surroundings).

Defining the system and surroundings is arbitrary, but it becomes important when we consider the
exchange of energy between the system and surroundings.

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Based on the types of exchange which take place or don't take place, five dominant classes of systems
may be defined:

There are:

Isolated Systems – matter and energy may not cross the boundary.
Adiabatic Systems – heat may not cross the boundary.
Diathermic Systems - heat may cross boundary.
Closed Systems – matter may not cross the boundary.
Open Systems – heat, work, and matter may cross the boundary.

For isolated systems, as time goes by, internal differences in the system tend to even out;
pressures and temperatures tend to equalize, as do density differences. A system in which
all equalizing processes have gone practically to completion, is considered to be in a state of
thermodynamic equilibrium.

1.2 Control Volume

• Control volume is defined as a volume which encloses the matter and the device inside a control surface.
• Every thing external to the control volume is the surroundings with the separation given by the control
surface.
• The surface may be open or closed to mass flows and it may have flows from energy in terms of heat
transfer and work across it.
• The boundaries may be moveable or stationary.
• In the case of a control surface that is closed to the mass flow, so that no mass can enter or escape the
control volume, it is called a control mass containing same amount of matter at all times.

1.3 Property

In thermodynamics a property is any characteristic of a system that is associated with the energy and can
be quantitatively evaluated. The property of a system should have a definite value when the system is in
a particular state. Thermodynamic property is a point function. Properties like volume of a system that
depend on the mass of a system are called extensive properties.
Properties like pressure or temperature which do not depend on the system mass are called intensive
properties.
The ratio of extensive property to the mass of the system are called specific properties and therefore
become intensive properties.
Substance can be found in three states of physical aggregation namely, solid, liquid and vapor which are
called its phases.
If the system consists of mixture of different phases, the phases are separated from each other by phase
boundary.
The thermodynamic properties change abruptly at the phase boundary, even though the intensive
properties like temperature and pressure are identical.

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1.4 Thermal Equilibrium

A system is said to be in thermal equilibrium if the state of all bodies composing a thermodynamic state
does not change for a long period of time. If there is no external spontaneous factor a system cannot be
out of the state of equilibrium
When the property of a system is defined, it is understood that the system is in equilibrium.
If a system is in thermal equilibrium, the temperature will be same throughout the system.
If a system is in mechanical equilibrium, there is no tendency for the pressure to change. In a single
phase system, if the concentration is uniform and there is no tendency for mass transfer or diffusion, the
system is said to be in chemical equilibrium.
A system which is simultaneously in thermal, mechanical, and chemical equilibrium is said to be in
thermal equilibrium.

1.5 Process

A process is path followed by a system in reaching a given final state of equilibrium state starting from a
specified initial state.

An actual process occurs only when the equilibrium state does not exist.

An ideal process can be defined in which the deviation from thermodynamic equilibrium is
infinitesimal.

All the states the system passes through during a quasi-equilibrium process may be considered
equilibrium states.

For non-equilibrium processes, we are limited to a description of the system before the process occurs
and after the equilibrium is restored.

Several processes are described by the fact that one property remains constant.

The prefix iso- is used to describe such processes.

A process is said to be reversible if both the system and its surroundings can be restored to their
respective initial states by reversing the direction of the process.

Reversible: if the process happens slow enough to be reversed.

Irreversible: if the process cannot be reversed (like most processes).
Isobaric: process done at constant pressure
Isochoric: process done at constant volume
Isothermal: process done at constant temperature
Adiabatic: process where q=0
Cyclic: process where initial state = final state

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1.6 Internal Energy

The internal energy is associated with the molecular structure and molecular activity of a system.

The molecule as a whole can move in x, y and z directions with respective components of velocities and
hence possesses kinetic energy.
There can be rotation of molecule about its center of mass and than the kinetic energy associated with
rotation is called rotational energy.
In addition the bond length undergoes change and the energy associated with it is called vibrational
energy.
The electron move around the nucleus and they possess a certain energy that is called electron energy.
The microscopic modes of energy are due to the internal structure of the matter and hence sum of all
microscopic modes of energy is called the internal energy.
Bulk kinetic energy (KE) and potential energy (PE) are considered separately and the other energy of
control mass as a single property (U).
The total energy possessed by the body is given by:
E = KE + PE + U

1.7 Work

Whenever a system interacts with its surroundings, it can exchange energy in two ways- work and heat.
In mechanics, work is defined as the product of the force and the displacement in the direction of the
force.

Work done when a spring is compressed or extended: According to Hooke's law

Spring force = - k (x – x0)

Where k is the spring constant, x0 is the equilibrium position, and x is the final position. The negative
sign shows that the direction of the spring force is opposite the direction of the displacement from x0.
The external force is equal in magnitude but opposite in sign to the spring force, so

External force (force of your hands) = k (x –x0).

Now, we want to calculate the work done when we stretch the spring from position 1 to position 2.

W = F dx = k (x – x0) d(x-x0) = 1/2 k [(x2-x0)2 - (x1-x0)2]

Work done when a volume is increased or decreased

Consider a gas in a container with a movable piston on top. If the gas expands, the piston moves out
and work is done by the system on the surroundings. However, if the gas inside contracts, the piston
moves in and work is done by the surroundings on the system. Why would the gas inside contract or
expand?

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It would if the external pressure, Pex, and the internal pressure, Pin, were different. To calculate the work
done in moving the piston, we know that the force = pressure times area and then work equals pressure
times area times distance or work equals pressure times the change in volume. So, W = the integral of
(Pex) dV

The differential work done (dW) associated with a differential displacement (ds) is given by

dW = F ds

For a piston cylinder assembly,

dW = F ds = PA (ds) = P dV

If the gas is allowed to expand reversibly from the initial pressure P to final pressure P, then the work
done is given by
W = ∫ p dV

The integral represents the area under the curve on a pressure versus volume diagram. Therefore the
work depends on the path followed and work is a path function and hence not a property of the system.

The above expression does not represent work in the case of an irreversible process.

The thermodynamic definition of work is “ Work is said to be done by a system on the surrounding if
the sole effect external to the system could be reduced to the raising of a mass through a distance”.

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1.8 Heat

Heat like work, is a form of energy.

The energy transfer between a system and its surroundings is called heat if it occurs by virtue of the
temperature difference across the boundary.
The two modes of energy transfer – work and heat- depend on the choice of the system.
Heat energy moves from a hotter body to a colder body upon contact of the two bodies.

If two bodies at different temperatures are allowed to remain in contact, the system of two bodies will
eventually reach a thermal equilibrium (they will have the same temperature).

A body never contains heat. Rather heat is a transient phenomenon and can be identified as it crosses the
boundary.

1.9 The Parameters of State

The physical state of a system is completely described certain quantities that determines the given state.
These quantities are called the parameters of state.

Once a sufficient number of properties are specified, the rest of the properties assume some values
automatically. A number of quantities can serve as parameters of state and examples are specific
volume, enthalpy, entropy, pressure, temperature etc.
The state of a simple compressible system is completely specified by two independent, intensive
properties.
The system is called a simple compressible system in the absence of electrical, magnetic, gravitational,
motion, and surface tension effects.
The state of a body requires that the two properties specified be independent to fix the state.
Two properties are independent if one property can be varied while the other one is held constant.
Temperature and specific volume, for example, are always independent properties, and together they can
fix the state of a simple compressible system.
Thus, temperature and pressure are not sufficient to fix the state of a two-phase system.
Otherwise an additional property needs to be specified for each effect that is significant.
An additional property needs to be specified for each other effect that is significant.

1.10 Reversible and Irreversible Processes

A reversible process occurs when a system changes its state and passes through a continuous series of
thermodynamic states such that both the system and its surroundings can be restored to their original
state. For a system to undergo a reversible process, it must have passed through series of thermodynamic
equilibrium state points that can be joined up to form a continuous line on a diagram of properties.

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2.0 ZEROTH LAW OF THERMODYNAMICS

We cannot assign numerical values to temperatures based on our sensations alone. Furthermore, our
senses may be misleading.
Several properties of material changes with temperature in a repeatable and predictable way, and this
form the basis of accurate temperature measurement.
The commonly used mercury-in-glass thermometer for example, is based on the expansion of mercury
with temperature.
Temperature is also measured by using several other temperature dependant properties.
Two bodies (eg. Two copper blocks) in contact attain thermal equilibrium when the heat transfer
between them stops.
The equality of temperature is the only requirement for thermal equilibrium.
The Zeroth Law of Thermodynamics states that: If two bodies are in thermal equilibrium with a third
body, they are also in thermal equilibrium with each other. This obvious fact cannot be concluded from
the other laws of thermodynamics, and it serves as a basis of temperature measurement.

By replacing the third body with a thermometer, the zeroth law can be restated two bodies are in thermal
equilibrium if both have the same temperature reading even if they are not in contact

The zeroth law was first formulated and labeled by R.H. Fowler in 1931.

2.1 Ideal and Real Gases

Pure Substance: A pure substance is one that has a homogeneous and invariable chemical composition.
It may exist in more than one phase but chemical composition is the same in all phases.

Some times the mixture of gases, such as air is considered a pure substance as long as there is no change
of phase. Further our emphasis will be on simple compressible substances

Early experiments on the variables of state (such as T, P, V, and n) showed that only two of these
variables of state need to be known to know the state of a sample of matter.

Extensive variables: depend on the amount of substance present. Examples include the volume, energy,
enthalpy, and heat capacity.

Intensive variables: do not depend on the amount of substance present. Examples include the temperature
and pressure.

Equations of State
An equation of state is an equation which relates the variables of state (T, P, V, and n). It's particularly
useful when you want to know the effect of a change in one of the variables of state

Solids and Liquids: If the pressure on a solid or liquid is increased, the volume does not change much. If
the temperature is increased, the volume doesn't change much either. Therefore, an appropriate equation of
state describing such systems would be: V(T,P) = constant.

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Gases: In contrast, changing the pressure or temperature of a gas will have an easily observable effect on
the volume of that gas. For an ideal gas (no intermolecular interactions and no molecular volume) n
appropriate equation of state would be: V(T,P,n) = (nRT)/P.

There are many equations of state describing real gases. These equations take in consideration molecular
volume and interactions. The most well-known such equations is probably the Van der Waals equation.

Ideal and real gases

An ideal gas is one which follows the ideal gas equation of state, namely
PV = (m/M) (MR) T = n Ru T

The universal gas constant has a value of 8.314 J/mol K or kJ/kmol K and is related to the specific gas
constant by the relation Ru = (R /M)

The ideal gas equation of state can be derived from the kinetic theory of gases where the following
assumptions are made:

1. The molecules are independent of each other. In other words, there are no attractive forces between the
molecules.
2. The molecules do not occupy any volume. That is the volume occupied by the molecules is
quite negligible compared to the volume available for motion of the molecules.

The internal energy of an ideal gas is a function of temperature only and is independent of pressure and
volume. That is,
u= u(T)
(∂u/∂P)T =0, (∂u /∂v)T = 0

2.2 Enthalpy and specific heat

h = u+ Pv
For an ideal gas u = u(T) only and PV = mRT and hence h = h(T) only.

The specific heat at constant volume is defined as the amount of energy transferred as heat at constant
volume, per unit mass of a system to raise its temperature by one degree. That is,

Cv = (dq/dT)v

The specific heat at constant pressure is defined as the energy transferred as heat at constant pressure, per
unit mass of a substance to raise its temperature by one degree. That is Cp = (dq/dT)P

For a constant pressure process dq = du + dw = du + Pdv = du+ Pdv +vdP (since dP=0 for a constant
pressure process)
Or dq= du+d(Pv) = d(U+ Pv) = dh
or dq=dh
CP = (∂h/∂T)P

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The ratio of specific heat (γ) is given by

γ= C P/Cv

For mono-atomic ideal gases γ = 1.67 and for diatomic gases γ= 1.4.

Relation between two specific heats:

The two specific heats are related to each other.
h= u + Pv or dh = du + d(Pv)
For an ideal gas, the above equation reduces to
dh = du + d(RT) = du + RdT or
dh/dT = du/dT+R or CP = Cv+ R
or CP –Cv =R for an ideal gas.

γ= CP /Cv or CP = R/(γ-1) and Cv = Rγ/(γ-1)

Real gases:

The ideal gas law is only an approximation to the actual behavior of gases.

At high densities, that is at high pressures and low temperatures, the behavior of actual or real gases
deviate from that predicted by the ideal gas law. In general, at sufficiently low pressures or at low
densities all gases behave like ideal gases.

Tables of Thermodynamic Properties

Tables of thermodynamic properties of many substances are available, and in general, all these have same
form.

Steam tables are selected because steam is used extensively in power plants and industrial processes.
The steam tables provide the data of useful thermodynamic properties like T, P, v, u, h and s for saturated
liquid, saturated vapor and superheated vapor.

Since the properties like internal energy, enthalpy and entropy of a system cannot be directly measured;
they are related to change in the energy of the system.
Hence one can determine Δu, Δh, Δs, but not the absolute values of these properties. Therefore it is
necessary to choose a reference state to which these properties are arbitrarily assigned some numerical
values.

For water, the triple point (T = 0.01o C and P = 0.6113 kPa) is selected as the reference state, where the
internal energy and entropy of saturated liquid are assigned a zero value.
In the saturated steam tables, the properties of saturated liquid that is in equilibrium with saturated vapor
are presented.

During phase transition, the pressure and temperature are not independent of each other. If the
temperature is specified, the pressure at which both phases coexist in equilibrium is equal to the saturation
pressure.

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Hence, it is possible to choose either temperature or pressure as the independent variable, to specify the
state of two-phase system.
Depending on whether the temperature or pressure is used as the independent variable, the tables are
called temperature or pressure tables.
The two phases- liquid and vapor can coexist in a state of equilibrium only up to the critical point.
Therefore the listing of the thermodynamic properties of steam in the saturated steam tables ends at the
critical point (374.15o C and 212.2 bar).
If the steam exists in only one phase (superheated steam), it is necessary to specify two independent
variables, pressure and temperature, for the complete specification of the state. In the superheated steam
tables, the properties- v, u, h, and s- are tabulated from the saturation temperature to some temperature for
a given pressure.
The thermodynamic properties of a liquid and vapor mixture can be evaluated in terms of its quality. In
particular, the specific volume, specific internal energy, specific enthalpy and specific entropy of a
mixture of quality X are given by

v = (1-X)vf + Xvg, u = (1-X)uf + Xug, h = (1-X)hf + Xhg = hf + Xhfg, s = (1-X)sf + Xhg

where hfg = hg - hf = latent hat of vaporization.

3.0 FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics is the thermodynamic expression of the law of conservation of energy.
This law simply stated by saying that “energy can not be created or destroyed” or that “the energy of the
universe is constant”. This law can be stated for a system (control mass) undergoing a cycle or for a
change of state of a system.

Stated for a system undergoing a cycle, the cyclic integral of the work is proportional to the cyclic integral
of the heat.

Mathematically stated, for a control mass undergoing a cyclic process such as in Joule’s experiment and
for consistent set of units
∫dQfrom system= ∫dWon system

or ∫dQfrom system- ∫dWon system = 0

The important thing to remember is that the first law states that the energy is conserved always.

Sign convention The work done by a system on the surroundings is treated as a positive quantity.

Similarly, energy transfer as heat to the system from the surroundings is assigned a positive sign. With the
sign convention one can write,

∫dQ = ∫dW

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3.1 Consequences of the first law

Suppose a system is taken from state 1 to state 2 by the path 1-a-2 and is restored to the initial state by the
path 2-b-1, then the system has undergone a cyclic process 1-a-2-b-1. If the system is restored to the initial
state by path 2-c-1, then the system has undergone the cyclic change 1-a-2-c-1. Let us apply the first law
of thermodynamics to the cyclic processes 1-a-2-b-1 and 1-a-2-c-1 to obtain

∫1-a-2dQ+ ∫2-b-1dQ - ∫1-a-2dW - ∫2-b-1dW =0

∫1-a-2dQ+ ∫2-c-1dQ - ∫1-a-2dW - ∫2-c-1dW=0

Subtracting, we get

∫2b1dQ- ∫2c1dQ –( ∫2b1dW - ∫2c1dW) =0

We know that the work is a path function and hence the term in the bracket is non-zero. Hence we find

∫2b1dQ = ∫2c1dQ

That is heat is also a path function.

3.2 Energy is a property of the system

By rearranging we can have
∫2b1 (dQ - dW) = ∫2c1 (dQ - dW)
It shows that the integral is the same for the paths 2-b-1 and 2-c-1, connecting the states 2 and 1. That is,
the quantity ∫ (dQ - dW) does not depend on the path followed by a system, but depends only on the initial
and the final states of the system. That is ∫ (dQ - dW) is an exact differential of a property. This property
is called energy (E). It is given by
dE = dQ-dW
E = KE + PE +U
where U is the internal energy. Therefore,
dE = d(KE) + d(PE) + dU = dQ-dW
Quit often in many situations the KE or PE changes are negligible.
dU = dQ – dW
An isolated system does not exchange energy with the surroundings in the form of work as well as heat.
Hence dQ = 0 and dW = 0. Then the first law of thermodynamics reduces to dE = 0 or E2 = E1 that is
energy of an isolated system remains constant.

3.3 Perpetual Motion Machine of the first kind

An imaginary device that delivers work continuously without absorbing energy from the surroundings is
called a Perpetual Motion machine of the first kind. Since the device has to deliver work continuously, it
has to operate on a cycle. If such a device does not absorb energy from its surroundings ∫dQ =0. From
the first law, it can be observed that ∫dW =0, if ∫ dQ = 0. Therefore such a device is impossible from first
law of thermodynamics.

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3.4 First law analysis of non-flow processes

The first law of thermodynamics can be applied to a system to evaluate the changes in its energy when it
undergoes a change of state while interacting with its surroundings. The processes that are usually
encountered in thermodynamic analysis of systems can be identified as any one or a combination of the
following elementary processes:
(i) Constant volume (isochoric) process
(ii) Constant pressure (isobaric) process
(iii) Constant temperature (isothermal) process.
(iv) Adiabatic process.

3.5 Constant volume process

Suppose a gas enclosed in a rigid vessel is interacting with the surroundings and absorbs energy Q as heat.

Since the vessel is rigid, the work done W due to expansion or compression is zero. Applying the first law,
we get
dU = dQ or Q = U2 –U1
That is, heat interaction is equal to the change in internal energy of the gas. If the system contains a mass
m equal of an ideal gas, then
Q = ΔU = mCv (T2 –T1)
The path followed by the gas is shown on a P-V diagram. Now consider the fluid contained in a rigid
vessel as shown. The vessel is rigid and insulated. Shaft work is done on the system by a paddle wheel.
Constant volume process involving electrical work:
- Ws = U2- U1

Since the vessel is rigid, the PdV work is zero. Moreover, the vessel is insulated and hence dQ = 0.
Application of the first law of thermodynamics gives
dU = dQ – dW = dQ – (dWpdv + dWs)
or dU = -dWs or – Ws = ΔU = U2 –U1
Where dWpdv is the compression /expansion work and dWs is the shaft work. That is increase in internal
energy of a system at a constant volume, which is enclosed by an adiabatic wall, is equal to the shaft work
done on the system.

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3.6 Constant pressure process

Several industrial processes are carried out at constant pressure. A few examples of constant pressure
processes are: (a) reversible heating/cooling of a gas (b) phase change (c) paddle wheel work (d) electrical
work. For a constant pressure process, the work done W is given by

W = ∫PdV = P (V2-V1)

Application of the first law of thermodynamics gives

dU = dQ – dW = dQ – PdV = dQ – d(PV)

or dQ = dU + d(PV) = d(U + PV) = dH

or Q = ΔH

That is in a constant pressure process, the heat interaction is equal to the increase in the enthalpy of the
system. Now consider the constant pressure processes in which the system is enclosed by an adiabatic
boundary. Application of the first law gives:

dU = dQ – dW = dQ – (PdV + dWs)

Here, the net work done (dW) consists of two parts – the PdV work associated with the motion of the
boundary and (-dWs), the shaft work (or electrical work) done by the surroundings. Since the system is
enclosed by an adiabatic boundary, dQ = 0 the equation can be written as
-dWs = dU + d(PV) = dH
That is, the increase in the enthalpy of the system is equal to the shaft work done on the system.

3.7 Constant temperature process

Suppose a gas enclosed in the piston cylinder assembly is allowed to expand from P1 to P2 while the
temperature is held constant. Then application of the first law gives:
dU = dQ – dW = dQ –PdV
It is not possible to calculate work and heat interactions unless the relationships between the
thermodynamic properties of the gas are known. Suppose the gas under consideration is an ideal gas
(which follows the relation Pv = RT and u = u(T) only) then for an isothermal process,
dU = 0
dQ = PdV = RTdv/v or Q =W = RTln(v2/v1)

3.8 Reversible adiabatic (Isentropic process)

Polytropic Process

W = ∫ cdv/ vn

w = (P1v1- P2v2)/(n-1)

du = dq – dw

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u2 – u1 = q - (P1v1- P2v2)/(n-1)

u2 – u1 = Cv (T2 – T1) = q – w

q = R(T2 – T1)/(γ-1) + (P1v1- P2v2)/(n-1)

= R (T1 – T2){1/(n-1) – 1/(γ-1)}

=(P1v1- P2v2)/(n-1) {(γ -n)/(γ-1)}

=w.{ (γ -n)/(γ-1)}

Example: Air (ideal gas with γ = 1.4) at 1 bar and 300K is compressed till the final volume is one-
sixteenth of the original volume, following a polytropic process Pv1.25 = const. Calculate (a) the final
pressure and temperature of the air, (b) the work done and (c) the energy transferred as heat per mole of
the air.

Solution: (a) P1v11.25 = P2v21.25

P2 = P1(v1/v2)1.25 = 1(16)1.25 = 32 bar

T2 = (T1P2v2)/(P1v1) = (300 x 32 x 1)/(1x16)
= 600K

(b) w = (P1v1- P2v2)/(n-1)

= Ru(T1 – T2)/(n-1)
= 8.314 (300 – 600)/(1.25-1) = -9.977 kJ/mol

(c) q = w.{ (γ -n)/(γ-1)}

= -9.977 (1.4 – 1.25)/(1.4-1)
= -3.742 kJ/mol

3.9 Control-Volume Analysis

Control volume is a volume in space of special interest for particular analysis. The surface of the control
volume is referred as a control surface and is a closed surface. The surface is defined with relative to a
coordinate system that may be fixed, moving or rotating.

Mass, heat and work can cross the control surface and mass and properties can change with time within
the control volume.

Examples: turbines, compressors, nozzle, diffuser, pumps, heat exchanger, reactors, a thrust-producing
device, and combinations of these.

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3.10 Steady state steady flow process

The first law of thermodynamics can be used to develop the so-called general energy equation for open
systems. Imagine a heat engine taking in a working substance (WS) in an initial state characterized by
the energies U1, KE1, and PE1.

The WS passes through the machine having Q units of heat supplied to it and giving a work output of
units. The WS then leaves the machine with energies U2, KE2, and PE2.
The work done to drive one unit mass of air through the system is given by:
Work done = F2l2 – F1l1 ………………………………………………………………… (1)

which can also be written, by taking into account that the force acting on a piston is F = P x A, as:
Work done = P2A2l2 – P1A1l1 ………………………………………………………………… (2)

Equation (2) can be written as:

Work done = P2V2 – P1V1…. ………………………………………………………………… (3)

where P is the pressure, and V the volume.

Applying the first law of thermodynamics, which states that the energy which enters the system equals
that which leaves the system and taking equation (3) into account, we can write that:
U1 + KE1 + PE1 + Q = U2 + KE2 + PE2 + W + (P2V2 – P1V1) ………………………………… (4)
Equation (4) can also be written as:

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(U1 + P1V1) + KE1+ PE1 + Q = (U2 + P2V2) + KE2+ PE2 + W…………………………….(5)

and is called the general energy equation.
The term (U + PV) is called enthalpy and is denoted with H. Thus, the general energy equation can also
be written as:
H1 + KE1+ PE1 + Q = H2 + KE2+ PE2 + W…………………………………………………. (6)

where H1 is the enthalpy characterizing the first state, while H2 is the enthalpy characterizing the second
state.
The form of the general energy equation can also be adapted to particular applications. For example, for
a petrol engine, the KE and PE terms are negligible, and thus equation (6) becomes:
H1 + Q = H2 + W………………………….…………………………………………………. (7)
from which we have that:
Q = W + (H2 – H1)…………………………………………………………………………… (8)
Therefore, in this case, the heat supplied to the WS equals the work done by the WS plus the gain in
enthalpy.
For a gas turbine, we can ignore only the PE terms, and thus equation (6) becomes:
H1 + KE1 + Q = H2 + KE2+ W………………………………………………………………... (9)

from which:
Q = W + (KE2 – KE1) + (H2 – H1) …………………………………………………………… (10)

Therefore, in this case, the heat supplied to the WS equals the work done by the WS plus the gain in
kinetic energy plus the gain in enthalpy.
For a non-flow process, there are no PV, KE, or PE terms. Thus, in this case, equation (5) becomes:
U1 + Q = U2 + W…………………………………………………..………………………… (11)
from which:
Q = W + (U2 – U1) …………………………………………………………………………… (12)

Hence, the heat supplied to the WS equals the work done by the WS plus the gain in internal energy.
We can further apply the general energy equation to more comprehensive particular cases.
1) Constant Volume Processes
In this case, the work output is zero, and the processes are invariably non-flow.

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Nearly all the terms in the general energy equation (5) are eliminated, leaving:
U1 + Q = U2 ………………………………………………………..………………………… (13)
or:
Q = U2 – U1…………………………………………………………………………………… (14)

Therefore, for constant volume processes, all the heat supplied goes into increasing the internal energy
of the WS.
2) Constant Pressure Processes
a) Non-Flow Processes
Consider that the WS experiences an isobaric change in volume as shown the in Figure:

As the force acting on the piston is given by:

F = P x A …………………………………………………………………………………… (15)
the work done:
W = F x l……………………………………………………………………………… …… (16)
becomes:
W = P x A x l …………………………………………………………………………… …. (17)
or, furthermore:
W = P (V2 – V1) ….………………………………………………………………………… (18)
In the general energy equation (5) most terms are eliminated, leaving:
U1 + Q = U2 + W……………………………………………………………………………… (19)

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which leads to:

Q = (U2 – U1) + W………………………………………………………………………….… (20)

Combining equations (18) and (19):

Q = (U2 – U1) + P (V2 – V1)……………………………………………………………….… (21)
or, furthermore:
Q = (U2 + P2V2) – (U1 + P1V1)…………………………………………………………….… (22)
Thus:
Q = H2 – H1 ……………………………………………………………………………….… (23)
Therefore, for constant pressure non-flow processes, the heat supplied to the WS equals the gain in
enthalpy.
b) Flow Processes
In this case, considering that all the changes to the kinetic and potential energies are negligible, the
general energy equation (6) becomes:
H1 + Q = H2 + W……………………………………………………………………………... (24)
which leads to:
Q = W + (H2 – H1) …………………………………………………………………………… (25)
However, it is impossible to devise a machine that operates a constant pressure flow process giving a
constant work output. Therefore, in all practical cases, the heat supplied to the WS equals the gain in
enthalpy.
3) Adiabatic Processes
These are processes during which there is no heat transfer between the WS and the surroundings.
a) Non-Flow Processes
For adiabatic non-flow processes, the general energy equation (5) becomes:
U1 = U2 + W …………………………………………………………………………………. (26)
Therefore, the work done is:
W = U1 – U2…………………………………………………………………………………. (27)

and it thus equivalates the loss of internal energy.

b) Flow Processes
This category includes all rotary turbines and compressors. The general energy equation (6) can be
written in this case as:
H1 = H2 + W …………………………………………………………………………………. (28)

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from which the work done becomes:

W = H1 – H2…………………………………………………………………………………. (29)
and it thus equivalates the loss of enthalpy.
4) Throttling Processes
Consider two points, and , which are far enough from the orifice so that the terms are negligible
(see Figure).

Furthermore, consider that there is no heat supplied and there is no work output. Therefore, the general
energy equation (6) becomes in this case:
H1 = H2…………………………………………………………………………………. (30)

Hence, for throttling processes, there is no change in enthalpy.

3.11 Turbine

A turbine is a rotary steady state steady flow machine whose purpose is the production of shaft power at
the expense of the pressure of the working fluid.

Two general classes of turbines are steam and gas turbines depending on the working substance used.

Usually, changes in potential energy are negligible, as is the inlet kinetic energy. Often the exit kinetic
energy is neglected (if in a problem, the flow velocities are specified, the kinetic energy term should
be included).

Normally, the process in the turbine is adiabatic and the work output reduces to decrease in enthalpy from
the inlet to exit states.

• •
Wsh = m (h − h )
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3.12 Compressor / pump

The purpose of a compressor (gas) or pump (liquid) is the same, to increase the pressure of a fluid by
putting in shaft work (power). There are two fundamentally different types of compressors:
1. The rotary type (either axial or centrifugal flow)
2. A piston/cylinder type compressor.

The first type is analyzed using control volume approach (steady state steady flow process). The working
fluid enters the compressor at low pressure and exits at high pressure.

Usually, changes in potential energy are negligible as is the inlet kinetic energy. Often, exit kinetic energy
is neglected as well (wherever, in a problem, velocities are specified, ke term should not be
neglected).
The compression process is usually adiabatic.

• •
Wsh = m [(h i − he ) + (Vi 2 − Ve2 ) / 2]

3.13 Nozzle

A nozzle is a steady state steady flow device to create a high velocity fluid stream at the expense of its
pressure. It is contoured in an appropriate manner to expand the fluid to a lower pressure.

Since the objective of the device is to increase the flow velocity, hence kinetic energy, the kinetic energy
term cannot be ignored. Usually, the process through the nozzle is treated as adiabatic.

Since there are no moving parts, shaft work is zero. The potential energy term (for gases) is negligible and
hence omitted.

( hi − he ) = (Ve2 − Vi 2 ) / 2

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3.14 Diffuser

A steady state steady flow device meant to decelerate high velocity fluid resulting in increased pressure of
the fluid. It is the opposite of a nozzle as far as the purpose is concerned. The assumptions are similar to
those for a nozzle.

3.15 A systematic approach to problem solving

Step 1. Identify the system and draw a sketch of it. The system that is about to be analyzed should be
identified on the sketch by drawing its boundaries using the dashed lines.

Step 2. List the given information on the sketch. Heat and work interactions if any should also be
indicated on the sketch with proper directions.

Step 3. State any assumptions:

The simplifying assumptions that are made to solve a problem should be stated and fully justified.
Commonly made assumptions:
(i) Assuming process to be quasi-equilibrium
(ii) Neglecting PE and KE
(iii) Treating gas as ideal
(iv) Neglecting heat transfer from insulated systems.

Step 5. Apply the conservation equations.

Step 6. Draw a process diagram.

Determine the required properties and unknowns.

Example 1: A 0.1 m3 rigid tank contains steam initially at 500 kPa and 200oC. The steam is now
allowed to cool until the temperature drops to 50oC. Determine the amount of heat transfer during this
process and the final pressure in the tank.

State 1: P1 = 500kPa, T1 = 200oC

v1 = 0.4249 m3/kg, u1 = 2642.9 kJ/kg

State 2: v2 = v1 = 0.4269 m3/kg

T2 = 50oC Æ vf = 0.001m3/kg
vg= 12.03 m3/kg
uf = 209.32 kJ/kg
ug = 2443.5 kJ/kg

P2 = Psat @50oc = 12.349 kPa

v2 = vf + x2vfg
0.4249 = 0.001 + x2(12.03 = 0.001)
x2 = 0.0352

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u2 = uf +x2ug
= 209.32 +(0.0352)(2443.5 – 209.32)
= 288.0 kJ/kg

m = V/u = (0.1 m3/kg)/(0.4249 m3/kg)

= 0.235 kg

-Qout = ΔU = m(u2 – u1)

Qout = m(u1 – u2)
= (0.235)(2642.9 – 288)
= 553.4 kg

Example 2: A piston/cylinder contains 50 kg of water at 200 kPa with a volume of 0.1 m3 . Stop in the
cylinder is placed to restrict the enclosed volume to 0.5 m3. The water is now heated until the piston
reaches the stops. Find the necessary heat transfer.

At 200 kPa,
vf = 0.001061 m3/kg
vfg = 0.88467 m3/kg
hf = 504.68 kJ/kg
hfg = 2201.96 kJ/kg

This is a constant pressure process. Hence,

Q = ΔH

The specific volume initially,

vi = 0.1 /50 = 0.002 m3/kg
v = vf + x vfg
= 0.001061 + x (0.88467)
Therefore, x = (0.002 – 0.001061) / 0.88467
= 0.001061

h = hf + x hfg
= 504.68 + 0.001061(2201.96)
= 507.017 kJ/kg

vfinal = 0.5 /50 = 0.01 m3/kg

v = vf + x vfg

Therefore, x = (0.01 – 0.001061) / 0.88467

= 0.01

hfinal = 504.68 + 0.01(2201.96)

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= 526.69 kJ/kg

Q = ΔH = 50 (526.69 - 507.017)
= 983.65 kJ/kg

Example 3: A rigid insulated tank is separated into two rooms by a stiff plate. Room A of 0.5 m3 contains
air at 250 kPa, 300 K and room B of 1 m3 has air at 150 kPa, 1000 K. The plate is removed and the air
comes to a uniform state without any heat transfer. Find the final pressure and temperature.

The system comprises of room A and B together. This is a constant internal energy process as there is no
heat and work exchange with the surroundings.

mA = PAVA / RTA
= (250 x 1000 x 0.5) / (287 x 300)
= 1.452 kg
mB = PBVB / RTB
= (150 x 1000 x 1.0) / (287 x 1000)
= 0.523 kg

ΔUA + ΔUB = 0

Let Tf be the final temperature at equilibrium

mA (Tf – 300) + mB (Tf – 1000) = 0

1.452 (Tf – 300) + 0.523 (Tf – 1000) = 0

Tf = 485.37 K

Pf = (1.452 + 0.523) x 287 x 485.37 / 1.5

= 183.41 kPa

Example 4: A piston / cylinder assembly contains 0.1m3 of superheated steam at 10 bar and 400oC. If the
steam is allowed to expand reversibly and adiabatically to a pressure of 3 bar, calculate the work done by
the steam.

At 10 bar and 400oC,

v = 0.3065 m3/kg
h = 3264.4 kJ/kg
s = 7.4665 kJ/kg K

At 3 bar,

sg = 6.9909 kJ/kg K

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This is an isentropic process as initial entropy value is greater than sg at 3 bar, the steam is superheated at
the end of the process.
At 3 bar and 200oC,
s = 7.3119 kJ/kg K and
at 300oC, s = 7.7034 kJ/kg K
therefore, the final state is having a temperature between 200oC and 300oC.
Equating si = sfinal,
Find the enthalpy and specific volume by interpolation. Then calculate ui and ufinal.

The work done = ΔU = m(ui – ufinal)

Example 1 (Nozzle)

Nitrogen gas flows into a convergent nozzle at 200 kPa, 400 K and very low velocity. It flows out of the
nozzle at 100 kPa, 330 K. If the nozzle is insulated, find the exit velocity.

Vi = 0
Adiabatic nozzle

The SSSF equation:

Ve2/2 = (hi – he) = Cp(Ti – Te)
= {γRu/M(γ-1)} (Ti – Te)
= {1.4 * 8314/(28*0.4)}(400-330)
= 72747.5 m2/s2

We get, Ve = 381.44 m/s

Example 2 (Diffuser)

Air at 10o C and 80 kPa enters the diffuser of a jet engine steadily with a velocity of 200 m/s. The inlet
area of the diffuser is 0.4 m2. The air leaves the diffuser with a velocity that is very small compared with
the inlet velocity. Determine (a) the mass flow rate of the air and (b) the temperature of the air leaving the
diffuser.

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Solution:
Assumptions: This is a steady flow process. Air is an ideal gas. The potential energy change is zero.
Kinetic energy at diffuser exit is negligible. There are no work interactions. Heat transfer is negligible.

To determine the mass flow rate, we need the specific volume of air.
v1 = RT1/ P1 = 0.287 * 283 / 80 = 1.015 m3/kg

m = 1/v1(V1A1) = (200 * 0.4)/ 1.015 = 78.8 kg/s

For steady flow, mass flow through the diffuser is constant.

(b) (h1 + V12/2) = (h2 + V22/2) (since Q = 0, W = 0, and ΔPE = 0)

h2 = h1 – (V22- V12)/2
The exit velocity of a diffuser is very small and therefore neglected.

h2 = h1 + V12/2
T2 = T1 + V12/2Cp

T2 = 283 + 2002/(2*1004)
= 302.92 K

3.16 Compressing air by a compressor

Air at 100 kPa and 280 K is compressed steadily to 600 kPa and 400 K. The mass flow rate of air is 0.02
kg/s and a heat loss of 16 kJ/kg occurs during the process. Assuming the changes in KE and

PE are negligible, determine the necessary power input to the compressor.

We take the compressor as the system. This is a control volume since the mass crosses the system
boundary during the process. Heat is lost from the system and work is supplied to the system.

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With similar assumptions as in the diffuser problem,

w = q + (h2 – h1)

The input power = m (q + (h2 – h1))

= 0.02 (16 + (1.004*(400 – 280))) = 2.73 kW

3.17 Power generation by a steam turbine

The power output of an adiabatic steam turbine is 5 MW, and the inlet and exit conditions of the steam are
as indicated in the figure.
a) Compare the magnitude of Δh, ΔKE, and ΔPE
b) Determine the work done per unit mass of the steam flowing through the turbine
c) Calculate the mass flow rate of the steam.

We take the turbine as a system. The control volume is

shown in the figure. The system, the inlet and exit velocities do work and elevations are given and thus the

kinetic and potential energies are to be considered.

At the inlet, the steam is in superheated vapor state.

h1 = 3247.6 kJ/kg.
At the turbine exit, we have a saturated liquid-vapor mixture at 15 kPa pressure. The enthalpy at this state

is

h2 = hf + x2hfg
= 225.94 + 0.9 * 2373.1
= 2361.73 kJ/kg
Δh = h2 – h1
= 2361.73 – 3247.6 = -885.87 kJ/kg

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Δke = (V22- V12)/2 = (1802-502)/2*1000

= 14.95 kJ/kg

ΔPe = g(Z2-Z1) = 9.807 * (6 –10)/1000

= -0.04 kJ/kg

wout = -[( h2 – h1) +(V22- V12)/2 + g(Z2-Z1)]

= -[-885.87 + 14.95 – 0.04]
= 870.96 kJ/kg

d) The required mass flow rate for a 5MW power output is 5000/870.96 = 5.74 kg/s

3.18 Heat exchangers

Heat exchangers are devices where two moving fluid streams exchange heat without mixing.

Heat is transferred from the hot fluid to the cold one.

Under steady operation, the mass flow rate of each fluid stream flowing through a heat exchanger remains
constant.

w = 0, Δke = 0, Δpe = 0

Heat exchangers are intended for heat transfer between two fluids within the device.

Usually, the entire heat exchanger is selected as the control volume and Q becomes zero.

3.19 Throttle
Throttle is any kind of flow restricting device that causes a significant pressure drop in the fluid.

The pressure drop does not involve any work.

A large drop in temperature often accompanies the pressure drop in the fluid.

Throttling devices are commonly used in refrigeration and air-conditioning applications.

q = 0, w = 0, Δke = 0, Δpe = 0

Hence across a steady flow throttling device,

h2 = h1

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Internal energy + flow energy = constant

3.20 Thermal Reservoir
A thermal reservoir is a large system (very high mass x specific heat value) from which a quantity of
energy can be absorbed or added as heat without changing its temperature. The atmosphere and sea are
examples of thermal reservoirs.
Any physical body whose thermal energy capacity is large relative to the amount of energy it supplies or
absorbs can be modeled as a thermal reservoir.

A reservoir that supplies energy in the form of heat is called a source and one that absorbs energy in the
form of heat is called a sink.

3.21 Heat Engine

It is a cyclically operating device which absorbs energy as heat from a high temperature reservoir,
converts part of the energy into work and rejects the rest of the energy as heat to a thermal reservoir at low
temperature.

The working fluid is a substance, which absorbs energy as heat from a source, and rejects energy as heat
to a sink.

3.21.1 Thermal Power Plant

Schematic representation of Heat Engine

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Schematic representation of Refrigerator and Heat pump.

Working Fluid ------- Water

Q1 – Heat received from hot gases

WT – Shaft work by turbine

Q2 – Heat rejected to cooling water in condenser

WP – Work done on the pump

Wnet=WT-WP
W = Q1 – Q2

Thermal Efficiency,
Wnet W Q1 − Q2
η= = =
Q1 Q1 Q1

QL – Heat absorbed from low temperature thermal reservoir

QH – Heat rejected to a high temperature thermal reservoir when work (W) is done on it.

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QL QL
( COP ) R = =
W QH −Q L

QH QH
( COP ) HP = =
W QH −Q L

In a reversible, isothermal expansion of an ideal gas, all the energy absorbed as heat by the system is
converted completely into work. However this cannot produce work continuously (not a cycle).

Single reservoir heat engine (1 T engine) is not possible.

4.0 SECOND LAW OF THERMODYNAMICS

Engineering thermodynamics is based on two main principles namely the First and Second Laws
of Thermodynamics.

4.0.1 Kelvin-Planck Statement: - It is impossible to devise a cyclically operating device, which produces
no other effect than the extraction of heat from a single thermal reservoir and delivers an equivalent
amount of work.

Heat engine with single thermal reservoir is not possible.

For a 1-T engine the thermal efficiency η=W/Q=1. No heat engine can have efficiency equal to unity.

Clausius Statement: - It is impossible to construct a device that operates in a cycle and produces no effect
other than the transfer of heat from a lower-temperature body to higher-temperature body.

Equivalence of the two statements

To prove that violation of the Kelvin-Planck Statement leads to a violation of the Clausius Statement, let
us assume that Kelvin-Planck statement is incorrect.

Consider a cyclically working device 1, which absorbs energy Q1 as heat from a thermal reservoir at TH.
Equivalent amount of work W(W=Q1) is performed.
Consider another device 2 operating as a cycle, which absorbs energy QL as heat from a low temperature
thermal reservoir at TL and rejects energy QH (QH=QL+W). Such a device does not violate Clausius
statement.
If the two devices are now combined, the combined device (enclosed by the dotted boundary) transfers
heat QL from the low temperature reservoir at TL to a high temperature reservoir at TH with out receiving
any aid from an external agent, which is the violation of the Clausius statement.
Likewise let us assume that the Clausius statement is incorrect. So we have a device 1, cyclically working
transferring heat Q from a low temperature reservoir at TL to a high temperature thermal reservoir at TH .
Consider another device 2, which absorbs heat Q1 from a high temperature reservoir at TH does work W
and rejects energy Q as heat tot the low temperature reservoir at TL as shown in figure. If the two devices
are combined (shown in figure by a dotted enclosure), then the combined device receives energy (Q1-Q) as
heat from a thermal reservoir and delivers equivalent work (W=Q1-Q) in violation of the Kelvin-Planck
statement.

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Therefore violation of Clausius statement leads to the violation of the Kelvin-Planck statement. Hence,
these two statements are equivalent.

Perpetual Motion Machines

A device that violates the First law of thermodynamics (by creating energy) is called a Perpetual Motion

Machine of the first kind.

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A device that violates the Second law of thermodynamics is called a Perpetual Motion Machine of the
Second kind.

The first device supplies continuously energy with out receiving it. So this is a system creating energy and
therefore violating the first law.

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The second device exchanges heat with a single reservoir and thus a net amount of work. This need not
violate the first law, but violates the second law and therefore will not work.

4.2 Reversible and Irreversible Processes

A process is said to be reversible if both the system and the surroundings can be restored to their

respective initial states, by reversing the direction of the process. A reversible process is a process that can

be reversed without leaving a trace on the surroundings. Processes that are not reversible are called

Irreversible processes.

Irreversibilities
The factors that cause a process to be irreversible are called irreversibilities. Examples:

1. Friction
2. Unrestrained expansion
3. Mixing of two gases
4. Heat transfer across a finite temperature difference
5. Spontaneous chemical reactions
6. Expansion or Compression with finite pressure difference
7. Mixing of matter at different states

4.3 Carnot Cycle

The Carnot cycle uses only two thermal reservoirs – one at high temperature T1 and the other at two
temperature T2.

If the process undergone by the working fluid during the cycle is to be reversible, the heat transfer must
take place with no temperature difference, i.e. it should be isothermal.

The Carnot cycle consists of a reversible isothermal expansion from state 1 to 2, reversible adiabatic
expansion from state 2 to 3, a reversible isothermal compression from state 3 to 4 followed by a reversible
adiabatic compression to state 1.

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The thermal efficiency, η is given by

η = Net work done / Energy absorbed as heat

During processes 2-3 and 4-1, there is no heat interaction as they are adiabatic.

2 2
dv
Q1− 2 = ∫ Pdv = ∫ RT1 = RT1 ln(v 2 / v1 )
1 1
v
Similarly for the process 3-4,
4 4
dv
Q3−4 = ∫ Pdv = ∫ RT2 = RT2 ln(v 4 / v3 )
3 3
v
Net heat interaction = Net work done

= RT1ln(v2/v1) + RT2ln(v4/v3)

= RT1ln(v2/v1) - RT2ln(v3/v4)

The processes 2-3 and 4-1 are reversible, adiabatic and hence

T1v2γ-1 = T2v3γ-1

Or, v2/v3 = (T2/T1)1/(γ-1)

And T2v4γ-1 = T1v1γ-1

Or, v1/v4 = (T2/T1)1/(γ-1)

v2/v3 = v1/v4 or v2/v1 = v3/v4

η = {RT1ln(v2/v1) - RT2ln(v3/v4)} / RT1ln(v2/v1)

η = (T1 – T2)/T1
= 1- T2/T1

4.3.1 The Carnot Principles

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1.The efficiency of an irreversible heat engine is always less than the efficiency of a reversible one
operating between same two thermal reservoirs.
2.The efficiencies of all reversible heat engines operating between the same two thermal reservoirs are the
same.

Lets us assume it is possible for an engine I to have an efficiency greater than the efficiency of a reversible
heat engine R.

ηI > ηR

Let both the engines absorb same quantity of energy Q1. Let Q and Q2 represent the energy rejected as
heat by the engines R, and I respectively.

WI = Q1 - Q
WR= Q1 – Q2

ηI = WI / Q1 = (Q1 - Q)/Q1 = 1-Q/Q1

ηR = WR/Q1 = (Q1 - Q2)/Q1 = 1-Q2/Q1

Since ηI > ηR,

1-Q/Q1 > 1-Q2/Q1

or, Q < Q2

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Therefore, WI (= Q1-Q) > WR (=Q1 – Q2)

Since the engine R is reversible, it can be made to execute in the reverse order. Then, it will absorb
energy Q2 from the reservoir at T2 and reject energy Q1 to the reservoir at T1 when work WR is done on it.

If now engines I and R are combined, the net work delivered by the combined device is given by

WI – WR = Q1 – Q – (Q1 – Q2) = Q2 – Q

The combined device absorbs energy (Q2 – Q) as heat from a single thermal reservoir and delivers an
equivalent amount of work, which violates the second law of thermodynamics.

Hence, ηR ≥ ηI

4.3.1.1Carnot principle 2

Consider two reversible heat engines R1 and R2 , operating between the two given thermal reservoirs at
temperatures T1 and T2.

Let ηR1 > ηR2

Q1= energy absorbed as heat from the reservoir at T1 by the engines R1 and R2, separately.

Q = energy rejected by reversible engine R1 to the reservoir at T2

Q2 = energy rejected by reversible engine R2 to the reservoir at T2.

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WR1 = Q1 - Q = work done by a reversible engine R1 .

WR2 = Q1 –Q2 = work done by a reversible engine R2

According to assumption,

ηR1 > ηR2

Or, 1 – Q/Q1 > 1- Q2/Q1

Q1 –Q >Q1-Q2 or WR1 >WR2

WR1 – WR2 = (Q1 –Q) – (Q1- Q2) = Q2 – Q

Since the engine R2 is reversible, it can be made to execute the cycle in the reverse by supplying WR2.

Since WR1 > WR2 the reversible engine R2 can be run as a heat pump by utilizing part of the work
delivered by R1.
For the combined device,

WR1 – WR2 = Q2 – Q, by absorbing energy Q2 – Q from a single thermal reservoir which violates the
second law of thermodynamics.

Hence ηR1 > ηR2 is incorrect.

By similar arguments, if we assume that ηR2 > ηR1 then,

ηR1 ≥ ηR2

Therefore, based on these two equations,

ηR1 = ηR2

The efficiency of a reversible heat engine is also independent of the working fluid and depends only on
the temperatures of the reservoirs between which it operates.

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The Carnot cycle uses only two thermal reservoirs – one at high temperature T1 and the other at two
temperature T2.

If the process undergone by the working fluid during the cycle is to be reversible, the heat transfer must
take place with no temperature difference, i.e. it should be isothermal.

The Carnot cycle consists of a reversible isothermal expansion from state 1 to 2, reversible adiabatic
expansion from state 2 to 3, a reversible isothermal compression from state 3 to 4 followed by a reversible
adiabatic compression to state 1.

The thermal efficiency, η is given by

η = Net work done / Energy absorbed as heat

During processes 2-3 and 4-1, there is no heat interaction as they are adiabatic.

2 2
dv
Q1− 2 = ∫ Pdv = ∫ RT1 = RT1 ln(v 2 / v1 )
1 1
v
Similarly for the process 3-4,
4 4
dv
Q3− 4 = ∫ Pdv = ∫ RT2 = RT2 ln(v 4 / v3 )
3 3
v

Net heat interaction = Net work done

= RT1ln(v2/v1) + RT2ln(v4/v3)

= RT1ln(v2/v1) - RT2ln(v3/v4)

The processes 2-3 and 4-1 are reversible, adiabatic and hence

T1v2γ-1 = T2v3γ-1

Or, v2/v3 = (T2/T1)1/(γ-1)

And T2v4γ-1 = T1v1γ-1

Or, v1/v4 = (T2/T1)1/(γ-1)

v2/v3 = v1/v4 or v2/v1 = v3/v4

η = {RT1ln(v2/v1) - RT2ln(v3/v4)} / RT1ln(v2/v1)

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η = (T1 – T2)/T1
= 1- T2/T1

The Carnot Principles Cont’d

3.The efficiency of an irreversible heat engine is always less than the efficiency of a reversible one
operating between same two thermal reservoirs.
4.The efficiencies of all reversible heat engines operating between the same two thermal reservoirs are the
same.

Lets us assume it is possible for an engine I to have an efficiency greater than the efficiency of a reversible
heat engine R.

ηI > ηR

Let both the engines absorb same quantity of energy Q1. Let Q and Q2 represent the energy rejected as
heat by the engines R, and I respectively.

WI = Q1 - Q
WR= Q1 – Q2

ηI = WI / Q1 = (Q1 - Q)/Q1 = 1-Q/Q1

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ηR = WR/Q1 = (Q1 - Q2)/Q1 = 1-Q2/Q1

Since ηI > ηR,

1-Q/Q1 > 1-Q2/Q1

or, Q < Q2

Therefore, WI (= Q1-Q) > WR (=Q1 – Q2)

Since the engine R is reversible, it can be made to execute in the reverse order. Then, it will absorb
energy Q2 from the reservoir at T2 and reject energy Q1 to the reservoir at T1 when work WR is done on it.

If now engines I and R are combined, the net work delivered by the combined device is given by

WI – WR = Q1 – Q – (Q1 – Q2) = Q2 – Q

The combined device absorbs energy (Q2 – Q) as heat from a single thermal reservoir and delivers an
equivalent amount of work, which violates the second law of thermodynamics.

Hence, ηR ≥ ηI

Carnot principle 2

Consider two reversible heat engines R1 and R2 , operating between the two given thermal reservoirs at
temperatures T1 and T2.

Let ηR1 > ηR2

Q1= energy absorbed as heat from the reservoir at T1 by the engines R1 and R2, separately.

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Q = energy rejected by reversible engine R1 to the reservoir at T2

Q2 = energy rejected by reversible engine R2 to the reservoir at T2.

WR1 = Q1 - Q = work done by a reversible engine R1 .

WR2 = Q1 –Q2 = work done by a reversible engine R2

According to assumption,

ηR1 > ηR2

Or, 1 – Q/Q1 > 1- Q2/Q1

Q1 –Q >Q1-Q2 or WR1 >WR2

WR1 – WR2 = (Q1 –Q) – (Q1- Q2) = Q2 – Q

Since the engine R2 is reversible, it can be made to execute the cycle in the reverse by supplying WR2.

Since WR1 > WR2 the reversible engine R2 can be run as a heat pump by utilizing part of the work
delivered by R1.
For the combined device,

WR1 – WR2 = Q2 – Q, by absorbing energy Q2 – Q from a single thermal reservoir which violates the
second law of thermodynamics.

Hence ηR1 > ηR2 is incorrect.

By similar arguments, if we assume that ηR2 > ηR1 then,

ηR1 ≥ ηR2

Therefore, based on these two equations,

ηR1 = ηR2

The efficiency of a reversible heat engine is also independent of the working fluid and depends only on
the temperatures of the reservoirs between which it operates.

5.0 ENTROPY

dQ
1. ∫ T has the same value irrespective of path as long as path is reversible
⎛ dQ ⎞
2. ⎜ ⎟ is an exact differential of some function which is identical as entropy
⎝ T ⎠R
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2 2
⎛ dQ ⎞
∫
3. S 2 − S1 = ΔS = dS = ⎜
1
∫⎝ T
1
⎟
⎠R

⎛ dQ ⎞
4. dS = ⎜ ⎟ for reversible process only
⎝ T ⎠R

Calculation of Entropy change

1.Entropy is a state function. The entropy change is determined by its initial and final states only

2.In analyzing irreversible process, it is not necessary to make a direct analysis of actual reversible
process.

Substitute actual process by an imaginary reversible process. The entropy change for imaginary reversible
process is same as that of an irreversible process between given final and initial state.

(a) Absorption of energy by a constant temperature reservoir

Energy can be added reversibly or irreversibly as heat or by performing work.

⎛ dQ ⎞
ΔS = ∫ ⎜ ⎟
⎝ T ⎠R

Example:-

The contents of a large constant-temperature reservoir maintained at 500 K are continuously stirred by a
paddle wheel driven by an electric motor. Estimate the entropy change of the reservoir if the paddle wheel
is operated for two hours by a 250W motor.

Paddle wheel work converted into internal energy- an irreversible process. Imagine a reversible process
with identical energy addition

⎛ dQ⎞ Q 0.25× 2(3600)

ΔS = ∫ ⎜ ⎟ = = = 0.6kJ
⎝ T ⎠R T 500

(b) Heating or cooling of matter

Q = ΔU for constant volume heating

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Q = ΔH for constant pressure heating

⎛T ⎞
2 T
dQ dT
ΔS = ∫ = m ∫ Cp = mC p ln⎜⎜ 2 ⎟⎟
T T1
T ⎝ T1 ⎠
, for constant pressure

⎛T ⎞
2 T
dQ dT
ΔS = ∫ = m ∫ Cv = mCv ln ⎜⎜ 2 ⎟⎟
T T1
T ⎝ T1 ⎠

, for constant volume process

Example: -

Calculate entropy change if 1kg of water at 300 C is heated to 800C at 1 bar pressure. The specific heat of
water is 4.2kJ/kg-K

⎛T ⎞ ⎛ 273 + 80 ⎞
ΔS = C p ln ⎜⎜ 2 ⎟⎟ = 4.2 × 10 3 × ln ⎜ ⎟
⎝ 1⎠
T ⎝ 273 + 30 ⎠
kJ
= 0.6415
kg .K

(c) Phase change at constant temperature and pressure

dQ hsf
S sf = ∫ T = Tsf
dQ h fg
S fg = ∫ =
T T

Example:-

Ice melts at 00C with latent heat of fusion= 339.92 kJ/kg. Water boils at atmospheric pressure at 1000C
with hfg= 2257 kJ/kg.

334.92 kJ
S sf = = 1.2261
273.15 kg.K

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2257 kJ
S fg = = 6.0485
373 .15 kg .K

Change of state for an ideal gas

If an ideal gas undergoes a change from P1, v1, T1 to P2, v2, T2 the change in entropy can be calculated by
devising a reversible path connecting the two given states.

Let us consider two paths by which a gas can be taken from the initial state, 1 to the final state, 2.

The gas in state 1 is heated at constant pressure till the temperature T2 is attained and then it is brought
reversibly and isothermally to the final pressure P2.

Path 1-a: reversible, constant-pressure process.

Path a-2: reversible, isothermal path

Δs1-a = ∫dq/T = ∫Cp dT/T = Cp ln(T2/T1)

Δsa-2 = ∫dq/T = ∫(du+Pdv)/T = ∫(Pdv)/T = Rln(v2/va)

(Since du = 0 for an isothermal process)

Since P2v2 = Pava = P1va

Or, v2/va = P1/P2

Or, Δsa-2 = -Rln(P2/P1)

Therefore, Δs = Δs1-a + Δsa-2

= Cp ln(T2/T1) – Rln(P2/P1)

Path 1-b-2: The gas initially in state 1 is heated at constant volume to the final temperature T2 and then it
is reversibly and isothermally changed to the final pressure P2.

1-b: reversible, constant volume process

b-2: reversible, isothermal process

Δs1-b = Cv ln(T2/T1)

Δsb-2 =Rln(v2/v1)

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or, Δs = Cv ln(T2/T1)+ Rln(v2/v1)

2

The above equation for Δs can also be or , ∫ dS > ∫ dQ / T deduced in the following manner:
1 2 C1

ds = (dq/T)R = (du + Pdv)/T = (dh – In general, vdP)/T

dS ≥ dQ / T
or,

2 2
(d u + p d v ) C d T R d v
Δ s = ∫ 1
T
= ∫
1
v

T
+
v
T 2 v2
= C v ln + R ln
T1 v1
S im ila rly ,
2
(d h − vd p ) T2 P2
Δ s = ∫ 1
T
= C p ln
T1
− R ln
P1

Principle of increase of entropy

Let a system change from state 1 to state 2 by a reversible process A and return to state 1 by another
reversible process B. Then 1A2B1 is a reversible cycle. Therefore, the Clausius inequality gives:

1 A 2 B1
∫ dQ / T = ∫ dQ / T + ∫ dQ / t = o
1 A2 2 B1

If the system is restored to the initial state from 1 to state 2 by an irreversible process C, then 1A2C1 is an

irreversible cycle. Then the Clausius inequality gives:

∫
1 A 2C1
dQ / T = ∫ dQ / T + ∫ dQ / t = o
1A2 2 C1

Subtracting the above equation from the first one,

∫ dQ / T > ∫ dQ / T
2 B1 2 C1

Since the process 2B1 is reversible,

2 B1
∫ dQ / T = ∫ dQ / T
1
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Where the equality sign holds good for a reversible process and the inequality sign holds good for an
irreversible process.

Now let us apply the above result to evaluate the entropy change of the universe when a system interacts
with its surroundings and exchanges energy as heat with the surroundings.

Let Tsur and Tsys be the temperatures of the surroundings and the system such that Tsur >Tsys. Let dQ
represent the energy transfer as heat from t he surroundings to the system during the given irreversible
process.

dSsys = dQ/Tsys
dSsur = -dQ/Tsur
dSuni = dSsys + dSsur = (dQ/T)sys – (dQ/T)sur >0

ΔSuni >0 (since Tsur>Tsys)

If the system is isolated, there is no change in the entropy of the surroundings and
ΔS ≥ 0, for an isolated system

Therefore the entropy of an isolated system either increases or, in the limit, remains constant.

The equality sign holds good when the process undergone by the system is reversible, the inequality sign
holds good if there is any irreversibility present in the process. This statement is usually called the
principle of entropy increase.

Irreversible or spontaneous processes can occur only in that direction for which the entropy of the
universe or that of an isolated system, increases. These processes cannot occur in the direction of
decreasing entropy.

For an isolated system,

ΔS > 0, for irreversible processes

ΔS = 0, for reversible processes
ΔS < 0, the process is impossible

Example:

One kg of superheated steam at 0.2MPa and 2000C contained in a piston cylinder assembly is kept at
ambient conditions of 300K till the steam is condensed to saturated liquid at constant pressure. Calculate
the change in the entropy of the universe with this process.

Solution:

Initial state of the steam: superheated at 0.2 MPa and 200oC

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h1= 2870.4 kJ/kg; and s1 = 7.5033 kJ/kgK

Final state: saturated liquid at 0.2 MPa.

h2 = 504.52 kJ/kg and s2 = 1.5295 kJ/kgK

Hence ΔSsteam = s2 – s1 = 1.5295 – 7.5033 =

-5.9738 kJ/kgK

For a constant pressure process: q = Δh

Therefore, q = h2 – h1 = 504.52 – 2870.4 =

-2365.68 kJ

Entropy change of the surroundings = ΔSsur = Q/Tsur = 2365.88/300 = 7.886 kJ/K

Hence, ΔSuni = ΔSsys + ΔSsur = -5.9738 +7.886 = 1.9122 kJ/K

ΔSuni > 0 and hence the process is irreversible and feasible.

Temperature-Entropy diagram

Entropy change of a system is given by dS = (dQ/T)R. during energy transfer as heat to the system from
the surroundings is given by

dQ = TdS. Hence if T and S are chosen as independent variables, then the integral ∫ TdS is the area
under the curve.

The first law of thermodynamics gives

dU = dQ - dW
also for a reversible process,

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6.0 THERMODYNAMIC RELATIONS

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Gibbs Function and Helmoltz Function

Gibbs equation is

du = Tds - Pdv

The enthalpy h can be differentiated,

dh = du + pdv + vdP

Combining the two results in

dh = Tds + vdP

The coefficients T and v are partial derivative of h(s,P),

⎛ ∂h ⎞
⎜ ⎟ = T
⎝ ∂s ⎠ P

⎛ ∂h ⎞
⎜ ⎟ = v
⎝ ∂P ⎠ s
Since v > 0, an isentropic increase in pressure will result in an increase in enthalpy.

We introduce Helmholtz function

a = u – Ts

Combine Gibbs equation with the differential of a,

da = -Pdv – sdT

The coefficient –P and –s are the partial derivatives of f(v,T), so

⎛ ∂ a ⎞
⎜ ⎟ = − P
⎝ ∂ v ⎠ T
⎛ ∂ a ⎞
⎜ ⎟ = − s
⎝ ∂ T ⎠ v

Similarly, using the Gibbs function

g = h – Ts

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dg = vdP – sdT

Consequently,
⎛ ∂ g ⎞
⎜ ⎟ = v
⎝ ∂ P ⎠ T

⎛ ∂ g ⎞
⎜ ⎟ = − s
⎝ ∂ T ⎠ P

Note:

1. The decrease in Helmholtz function of a system sets an upper limit to the work done in any process
between two equilibrium states at the same temperature during which the system exchanges heat only with
a single reservoir at this temperature. Since the decrease in the Helmholtz potential represents the potential
to do work by the system, it is also a thermodynamic potential.

2. The decrease in Gibbs function of a system sets an upper limit to the work, exclusive of “pdv” work in
any process between two states at the same temperature and pressure, provided the system exchanges heat
only with a single reservoir at this temperature and that the surroundings are at a constant pressure equal
to that in the end states of the pressure.

The maximum work is done when the process is isothermal isobaric. Gibbs function is also called
Chemical Potential.

Some important property relations

dz(x,y) = Mdx + Ndy

⎛ ∂z ⎞ ⎛ ∂Z ⎞
where, M = ⎜ ⎟ N= ⎜⎜ ⎟⎟
⎝ ∂x ⎠ y ⎝ ∂y ⎠ x

Mathematically, we would say that dz is an exact differential, which simply means that z is a continuous
function of the two independent variables x and y. Since the order in which a second partial derivative is
taken is unimportant, it follows that,

⎛ ∂M ⎞ ⎛ ∂P ⎞
⎜⎜ ⎟⎟ = ⎜ ⎟
⎝ ∂y ⎠ x ⎝ ∂x ⎠ y
Maxwell’s relations:

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⎛ ∂T ⎞ ⎛ ∂P ⎞
⎜ ⎟ = −⎜ ⎟ [From equation du = Tds − Pdv]
⎝ ∂v ⎠ s ⎝ ∂s ⎠ v
⎛ ∂T ⎞ ⎛ ∂v ⎞
⎜ ⎟ = ⎜ ⎟ [From equation dh = Tds + vdP]
⎝ ∂P ⎠ s ⎝ ∂s ⎠ P
⎛ ∂P ⎞ ⎛ ∂s ⎞
⎜ ⎟ = ⎜ ⎟ [From equation da = − Pdv − sdT ]
⎝ ∂T ⎠ v ⎝ ∂v ⎠T
⎛ ∂v ⎞ ⎛ ∂s ⎞
⎜ ⎟ = −⎜ ⎟ [From equation dg = vdP − sdT ]
⎝ ∂T ⎠ P ⎝ ∂P ⎠T

Mnemonic Diagram

The differential expressions for the thermodynamic potentials and Maxwell relations can be remembered
conveniently in terms of a thermodynamic Mnemonic diagram.

The diagram consists of a square with two diagonal arrows pointing upwards and the thermodynamic
potentials in alphabetical order clockwise on the sides as shown in figure. The natural variables associated
with each potential are placed in the corners.

Diagonal arrows indicate the coefficients associated with the natural variables in the differential
expression of the potential. The sign of the coefficient depends on whether the arrow is pointing towards
(- ve) or away from the natural variable (+ ve).
For example,

du = (sign)(coeff.) ds + (sign)(coeff.) dv

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du = (sign)Tds + (sign)Pdv

du = +Tds - Pdv

To write the Maxwell relations we need to concentrate on the direction of the arrows and the natural
variables only.

If both the arrows pointing in the same direction, there is no need to change the sign, otherwise the
equation should carry a negative sign.

The internal energy

u = u(T,v)

For a simple compressible substance,

⎛ ∂u ⎞
du = C v dT + ⎜ ⎟ dv
⎝ ∂v ⎠T
C v 1 ⎡⎛ ∂ u ⎞ ⎤
ds = dT + ⎢⎜ ⎟ + P ⎥ dv
T T ⎣⎝ ∂ v ⎠T ⎦

Taking entropy as a function of temperature and volume,

⎛ ∂s ⎞ Cv
⎜ ⎟ =
⎝ ∂T ⎠v T
Using thrid Maxwell's relation,
⎛ ∂s ⎞ ⎛ ∂P ⎞ 1 ⎡⎛ ∂u ⎞ ⎤
⎜ ⎟ =⎜ ⎟ = ⎢⎜ ⎟ + P ⎥
⎝ ∂v ⎠T ⎝ ∂T ⎠v T ⎣⎝ ∂v ⎠T ⎦
From this we obtain
⎛ ∂u ⎞ ⎛ ∂P ⎞
⎜ ⎟ =T ⎜ ⎟ −P
⎝ ∂v ⎠T ⎝ ∂T ⎠ v

This important equation expresses the dependence of the internal energy on the volume at fixed
temperature solely in terms of measurable T, P and v. This is helpful in construction of tables for u in
terms of measured T, P and v.

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For a perfect gas,

Pv = RT

⎛ ∂P ⎞ R
⎜ ⎟ =
⎝ ∂T ⎠v v
⎛ ∂u ⎞ R
⎜ ⎟ =T −P = P−P =0
⎝ ∂v ⎠T v

This implies that, for a perfect gas, internal energy is independent of density and depends only on T.

C v ⎛ ∂P ⎞
ds = dT + ⎜ ⎟ dv
T ⎝ ∂T ⎠ v

Similarly it can be shown using Fourth Maxwell’s relation that

C P ⎛ ∂v ⎞
ds = dT + ⎜ ⎟ dP
T ⎝ ∂T ⎠P
Using the above two equations and solving for dP,

CP − Cv (∂P / ∂T )v
dP = dT − dv
T (∂v / ∂T ) P ( ∂u / ∂T ) P

Considering P as a function of T and v, we see that

CP − Cv ⎛ ∂P ⎞
=⎜ ⎟
T (∂v / ∂T ) P ⎝ ∂T ⎠v

Two thermodynamic properties can be defined at this stage,

1 ⎛ ∂v ⎞
β≡ ⎜ ⎟ 1 ⎛ ∂v ⎞
v ⎝ ∂T ⎠ P
κ ≡− ⎜ ⎟
β is called the isobaric compressibility and κ is called the v ⎝ ∂P ⎠T isothermal
compressibility.

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http://www.unaab.edu.ng
Federal University of Agriculture, Abeokuta

From calculus, it can be shown that,

⎛ ∂P ⎞ ⎛ ∂T ⎞ ⎛ ∂v ⎞
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ = −1
⎝ ∂T ⎠ v ⎝ ∂v ⎠ P ⎝ ∂P ⎠T
or,
⎛ ∂P ⎞ (∂v / ∂T ) P β
⎜ ⎟ = − =
⎝ ∂T ⎠v ⎛ ∂v ⎞ κ
⎜ ⎟
⎝ ∂P ⎠T

Therefore,

T ⎡⎣( ∂v / ∂P ) P ⎤⎦
2

CP − Cv = −
( ∂v / ∂P )T

Since ( ∂v / ∂P )T is always negative for all stable substances, C

P is always greater that Cv

BIBLIOGRAPHY
1. www.codecogs.com/reference/engineering/thermodynamics/first_law_of_thermodynamics.php
2. http://www.engineersedge.com/thermodynamics/second_law.htm
3. http://en.wikipedia.org/wiki/Thermodynamics
4. Osore O.A. (1999). Essentials of Classical Thermodynamics. IPS Educational Press, P.M.B 173, Ilaro,
Ogun state, Nigeria.

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