CHAPTER FOUR: THERMODYNAMICS

4.0 Introduction
Thermodynamics is a branch of physics that deals with heat and flow of energy. Thermodynamics
is the study of the effects of work, heat, and energy on a system. It deals only with the large-scale
response of a system, which can be observed and measured in an experiment, of heat and work.
The basic idea is that objects are made up of atoms and molecules, which are in ceaseless motion.
The faster the motion the hotter the object. However, thermodynamics deals only with the large-
scale response of a system, i.e., response that can be observed and measured, to heat flow. This
unit examines the basic concepts of thermodynamics as a way of introducing the course.

Learning Objectives
At the end of this chapter, the student should be able to:
1. explain what thermodynamics is;
2. mention all thermodynamics coordinates and explain change of state;
3. describe all thermodynamics processes;
4. write equation of state and its usefulness, and differentiate between a system and its surrounding;
and
5. solve problems on thermodynamics.

4.1. Definition of basic thermodynamics parameters

System is a restricted region of space or a finite portion of matter one has chosen to study. Or the
part of the universe, with well-defined boundaries, one has chosen to study.

Surrounding is the rest of the universe outside the region of interest (i.e., the rest of space outside
the system).

Boundary or wall is the surface that divides the system from the surroundings. This wall or
boundary may or may not allow interaction between the system and the surroundings.

Thermodynamic properties/coordinates: These are macroscopic coordinates or properties used

to describe or characterise a system. Because they are macroscopic properties or coordinates, they
can be observed and measured. Some examples are Temperature (T), Pressure (P), Volume (V),
density (ρ), mass (m), specific heat capacity at constant volume (CV), specific heat capacity at
constant pressure (CP), thermal conductivity (k), thermal diffusivity (α), and chemical potential
(µ).

Thermodynamic system: This is a system that could be described in terms of thermodynamic

coordinates or properties. Thermodynamic Systems can be categorised into the followings
depending on the type of boundary:
Open system: This is a system that its boundary allows transfer of mass and energy into or out of
the system. In other words, the boundary allows exchange of mass and energy between the system
and the surrounding.

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Closed system: This is a system that its boundary allows exchange of energy alone (inform of
heat) between the system and its surrounding (i.e., the boundary allows exchange of energy alone).
This type of boundary that allows exchange of heat is called diathermal boundary.
Isolated system: This is a system that its boundary allows neither mass nor energy between it and
the surrounding. In other words, the boundary does not allow exchange of mass nor energy.

Thermodynamic processes: A system undergoes a thermodynamic process when there is some

sort of energetic change within the system, generally associated with changes in pressure, volume,
internal energy, temperature, or any sort of heat transfer.
There are several specific types of thermodynamic processes that happen frequently enough (and
in practical situations) that they are commonly treated in the study of thermodynamics. Each has
a unique trait that identifies it, and which is useful in analyzing the energy and work change related
to the process.

Adiabatic process: This is a thermodynamic process in which there is no heat transfer into or out
of the system. For this process, change in quantity of heat is zero (i.e., ∆Q = 0 during this process)

Isochoric process: This is a thermodynamic process that occurs at constant volume (i.e., ∆V = 0
during this process). This implies that during this process no work is done on or by the system.

Isobaric process: This is a thermodynamic process that occurs at constant pressure (i.e., ∆p = 0
during this process).

Isothermal process: This is a thermodynamic process that takes place at constant temperature
(i.e., ∆T = 0 during this process).
It is possible to have multiple processes within a single process. A good example would be a case
where volume and pressure change during a process, resulting in no change in temperature and no
heat transfer. This kind of a process would be both adiabatic and isothermal.

Cyclic processes: These are series of processes in which after certain interchanges of heat and
work, the system is restored to its initial state.
For a cyclic process ∆U = 0, and if this is put into the first law
Q=W
This implies that the net work done during this process must be exactly equal to the net amount of
energy transferred as heat; the store of internal energy of the system remains unchanged.

Reversible process: A reversible process can be defined as one which direction can be reversed
by an infinitesimal change in some properties of the system.

Irreversible process: An irreversible process can be defined as one which direction cannot be
reversed by an infinitesimal change in some properties of the system

Quasi-static process: This is a process that is carried out in such a way that at every instant, the
system departs only infinitesimal from an equilibrium state (i.e., almost static). Thus, a quasi-static
process closely approximates a succession of equilibrium states.

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Non-quasi-static process: This is a process that is carried out in such a way that at every instant,
there is finite departure of the system from an equilibrium state.

4.2 Work done by gas

Imagine a hydrostatic system contained in a cylinder with a movable piston like the one shown in
Figure 4.1. From the diagram, suppose an external force F acted in the direction shown by moving
the piston from initial point 1 to final point 2 through a distance dx. Suppose that the cylinder has
a cross section area A, that the pressure exerted on the system at the piston face is p, and that the
force is pA. The system also exerts an opposing force on the piston. The work done dW on the
system in the process described above is;
dW = pAdx 4.1
But Adx = dV
Therefore,
dW = −pdV 4.2
The negative sign in the last equation indicates negative change in volume (i.e., a decrease in
volume).

Point 2 Point 1
dx

Force F

Figure 4.1: The work done on a system compressed by external force

In a finite quasi-static process in which the volume changes from Vi to Vf , the work done is
W = − ∫pdV 4.3
Note the sign convention, work done on a system is positive work, and work done by system is
negative work.
4.2.1. Work in quasi-static process
For a quasi-static isothermal expansion of compression of an ideal gas
W = − ∫ pdV 4.4
Note that an ideal gas is the one which equation of state is PV = nRT, where n and R are constant.

4.3. Internal energy of a gas

When an adiabatic work (dWad) is done on or by the system, the internal energy of the system
changes. The change in internal energy (∆U) is equal to the adiabatic work done.
dU = dWad 4.5

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If a system changes from state 1 to state 2 by doing adiabatic work, and if the states are differed
by a finite amount, then
2
U = U2 – U1 = ∫1 𝑝𝑑𝑉
dU=dWad = −Wad 4.6
Suppose the work done is mechanical work (i.e., mechanical adiabatic work), then
2
U2 – U1 = − ∫1 𝑝𝑑𝑉 4.7
When heat flows in or out of a system from its surroundings, the temperature of the system
increases or decreases. And the internal energy of the system changes from initial state (Ui) to final
state (Uf). This change in internal energy ∆U must be equal to the heat flow i.e.
∆U = Uf − Ui = Q 4.8
Q is positive when there is a flow of heat into the system, Q is negative when there is a flow of
heat from the system

4.4 First and second law of thermodynamics

We have learnt that the internal energy of a system can change only if:
a. there is flow of heat into the system or out of the system.
b. work is done on the system or by the system.
Hence, the change in internal energy ∆U of a system is
∆U = Uf − Ui = Q −W OR 𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 4.9
where Q is the heat and W is work. Equation 4.9 is the first law of thermodynamic.
The differential form of first law of thermodynamics is
dU = dQ −PdV 4.10

The statement of first law of thermodynamics

The first law states that the total amount of energy in an isolated system is conserved.
i.e., The internal energy of a system tends to increase if energy is added as heat Q and
tends to decrease if energy is lost as work W done by the system.
Special Cases of First Law of Thermodynamics are considered for four different thermodynamic
processes in which certain restriction is imposed on the system and the corresponding implication
when apply to the first law.
Adiabatic process, dQ = 0, and equation of first law reduces to
dU = dW = PdV 4.11
Isochoric process, dV = 0, and the equation of the first law becomes
dU = dQ = CV dT 4.12
Cyclic process, dU = 0, and the equation of the first law becomes
Q=W 4.13
Free expansion, Q = W = 0, and the equation of the first law becomes
dU = 0 4.14

The Second Law of Thermodynamics

The change in entropy ∆S for a process occurring in a closed system is zero for reversible process
and greater than zero for irreversible process. This is one of the statements of the second law of
thermodynamics.

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The second law of thermodynamics gives the direction in which the natural process will take place.

The statement of second law of thermodynamics

If a process occurs in a closed system, the entropy of the system increases for irreversible processes
and remains constant for reversible processes.
The second law of thermodynamics is a consequence of entropy (amount of disorderliness in a
system of particles).

Mathematical statement of the Second law of thermodynamics

∆S ≥ 0 4.15
The second law can also be defined in these ways:
a. No process is possible whose sole result is the absorption of heat from a reservoir at a single
temperature and the conversion of this heat completely into mechanical work
b. Kelvin’s statement of second law of thermodynamics (in terms of engines) states that no
heat engine, reversible or irreversible, operates in a cycle can take in heat from its
surroundings and totally convert it into work.

4.5 Heat engines

A heat engine is a device used to convert thermal energy (i.e., heat) into mechanical work and then
exhausts the heat which cannot be used to do work.

T H QH QC TC
hot reservoir working cold reservoir
body

Figure 4.2: Basic operation of heat engine

The working body absorbed heat from the hot reservoir at relatively high temperature. Part of the
absorbed heat is used by the working body to do mechanical work. The unused energy is then
ejected as heat at lower temperature. Some examples of real engines are Otto engine, Stirling
engine, and steam engine. The process of converting thermal energy to mechanical work by heat
engine is shown in Figure 4.2.
Heat engine as shown in the Figure 4.2 above comprises of two heat reservoirs, one hot at TH and
the other cold at TC. The interaction between these two reservoirs and the working body leads to
the conversion of heat energy to mechanical work. Another explanation is that the working body
absorbs heat QH at temperature TH, uses part of it do mechanical work, and then ejected the unused
heat energy (QC) at temperature TC through the cold reservoir.
4.5.1. Thermodynamic efficiency ε of real engines
The efficiency of a heat engine is
W Work output
E=Q = (in one cycle) 4.16
H heat in

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The efficiency E measures the fraction of heat pumped into the working body that is converted to
mechanical work by the working body. The efficiency of real heat engines is always less than
unity. The Changes in energy of the working body are related to the changes in the thermodynamic
properties. Using the combined first and second laws of thermodynamics,
dU = TdS − PdV = dQ − dW 4.17
where dQ is the heat into the working body and dW is the mechanical work (i.e., work output). But
the working body operates in a cycle (i.e., cyclic process), returning the system back to its initial
state. We can integrate 16 over a complete cycle.
0 = ∮ 𝑑𝑈 = ∮ 𝑇𝑑𝑆 − ∮ 𝑃𝑑𝑉 4.18
where ∮ 𝑑𝑈 = Ufinal – Uinitial = 0 since the system returns to its initial state.
∫ 𝑃𝐷𝑉 = W is the work done in a cycle ∮ 𝑑𝑄.
∮ 𝑑𝑄 = QH – QC = Q the total heat transfer to the working body in a cycle. Equation 4.18 becomes
0 = QH – QC – W 4.19
Rearrange to have
W = QH − QC 4.20
Inserting equations 4.20 into 4.16
𝑄𝐻 −𝑄𝐶 𝑄
E= = 1 − 𝑄𝐶 4.21
𝑄𝐻 𝐻
Therefore,
𝑄 heat released
E = 1 − 𝑄 𝑐 = 1 – heat absorbed 4.22
𝐻
Equation 4.22 is the generalized form of efficiency for heat engine.

4.6. Concept of isothermal and adiabatic processes

Isothermal process
Temperature is strictly kept constant. That pressure, P x volume, V = constant; PV = constant
(Boyle’s law). The other changes in the thermodynamic coordinates, pressure and volume must be
carried out slowly and heat must be transferred. None of the quantities W, Q and dU is zero. For
an ideal gas and ideal paramagnetic substance, Q = W (isothermal). Entropy changes in isothermal
process. The work done by an expanding or compressing gas is the area under the P-V curve and
it depends on the path taken. Work done, W in an isothermal process is given by
𝑅𝑇
pdV = dV
𝑉
For a change of volume from V1 to V2,
𝑉 𝑑𝑉 𝑉
W = RT∫𝑉 2 = RT ln𝑉2 4.23
1 𝑉 1
𝑃 𝑉
But P1V1 = P2V2 and 𝑃1 = 𝑉2
2 1
𝑉2 𝑃1
W = RT ln𝑉 = RT ln𝑃 (for one moles) 4.24
1 2
𝑉 𝑃
W = nRT ln𝑉2 = nRT ln𝑃1 (for n moles)
1 2

Adiabatic process
Heat content is a constant as no heat enters or leaves the system; dQ = 0. It is a process with
constant entropy (isentropic). Since dQ = 0, dU = -dW. When the internal energy change of the

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system decreases, then work is done by the system and this causes a drop in temperature but when
the internal energy change increases, then work is done on the system and this causes a temperature
rise. Thus, dU and dW changes in such a way that their sum is equal to zero at any point in time
during the process.
Work done W in an adiabatic process is given by
W = PdV, but P𝑉 𝛾 = constant for adiabatic process
𝑉2
𝑉 𝑑𝑉 𝑉 1−𝛾 𝐾 1−𝛾 1−𝛾
W = ∫𝑉 2 𝑉 𝛾 = 𝐾 ( 1−𝛾 ) = 1−𝛾 (𝑉2 − 𝑉1 ) 4.25
1 𝑉1
𝛾 𝛾
But P1𝑉1 = P2𝑉2 = K
1
W = 1−𝛾(P2V2 – P1V1) = mcv(T2 – T1)
A comparison between isothermal and adiabatic process is shown in Table 4.1 and Figure 4.2.

Table 4.2: Comparison between isothermal and adiabatic process

Isothermal process Adiabatic process

Temperature is constant, ∆𝑇 = 0 Heat change is constant, ∆𝑄 = 0

1 1
The pressure, P𝛼 𝑉, PV=K The pressure, P𝛼 𝑉 𝛾 , P𝑉 𝛾 =K

𝑉 1
Work done, 𝑊 = 𝑛RTln 𝑉2 Work done, W=1−𝛾 (𝑃2 𝑉2 − 𝑃1 𝑉1 )
1

Figure 4.2: Comparison between isothermal and adiabatic process

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EXCERCISES 4

4.1. Calculate the heat added to a system if at atmosphere pressure, water of volume 1.00cm3
changes to steam of volume 1671.00cm3
Solution
V1 = 1.00cm3 = 1x106m3 and V2 = 1671.00cm3 = 1671x106m3
W = P(V2 – V1) = 1.013x105(1671x106 – 1x106) = 196.5J

4.2. 500cm3of helium gas at 300K is expanded at a constant pressure of 2 atmospheres to 700cm3.
Calculate (i) the work done by the gas in the expansion. (ii) the new temperature of the gas.
Solution
V1 = 500cm3, T1 = 300K, P = 2 atmospheres and V2 = 700cm3
(i) Work done = PdV = 2(1.01x105)(700x10-6 – 500x10-6) = 40.4J
V
(ii) At constant pressure, T = constant
V1 V
= T2
T1 2
T1 V2 300 𝑥 700
∴ T2 = = = 420K
V1 500

4.3. A kilogram of water is boiled until it is completely converted into steam. If work done is
1.68x105J, calculate the increase in internal energy when heat of vaporization is 2250Jg-1.
Solution
W = 1.68x105J and Lv = 2250Jg-1
Q = mLv = (1000 x 2250) = 22.5x105J
U = Q – W = 22.5x105 – 1.68x105 = 2.08x106J

4.4. A carnot engine whose high temperature reservoir at 500K takes in 600J of heat at this
temperature in one cycle and gives up 240J to the low temperature of the reservoir. Calculate (i)
the low temperature of the reservoir (ii) efficiency of the cycle.
Solution
T2 = 500K, Q2 = 600J and Q1 = 240J
𝑇 𝑄
(i) 𝑇2 = 𝑄2
1 1
𝑄1 𝑇2 500 x 240
T1 = = = 200K
𝑄2 600
𝑇 𝑄 240
(ii) Efficiency = 1− 𝑇1 = 1 – 𝑄1 = 1 – 500 = 0.6 = 60%
2 2

4.5. One kilogram of ice at 0oC is melted and converted to water at 0oC. Calculate the change in
entropy.
Solution
m = 1kg and T = 0 + 273 = 273K
Q = mLf = 1 x 3.3x105 = 3.3x105J
𝑑𝑄
dS = 𝑇

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 𝑑𝑄 𝑄 3.3×105
dS = S2 – S1 = ∫ = = = 1.2x103JK-1
𝑇 𝑇 273

Summary of Chapter 4
1. Heat engines are devices used to convert heat to mechanical work.
𝑄𝑐 heat released
2. The efficiency of heat engine is E = 1 – = 1 – heat absorbed.
𝑄𝐻
3. The first law of thermodynamics gives an insight to the internal energy of a system i.e., work
and heat as the only means by which the internal energy of a system can change.
4. The expression for work done a mechanical system is PdV and similar expression can be derived
for work done under different systems. The differential form of first law is dU = dQ − PdV.

SELF-ASSESSMENT QUESTIONS FOR CHAPTER 4

4.1. State the first law of thermodynamics.

4.2. If there are 2 moles of gas kept at a constant temperature of 20ºC and if this gas is compressed
from a volume of 4m3 to 2m3, calculate the work done on the gas. (Take R= 8.31J/mol.K)

4.3. When one gram of boiling water is converted into steam at a pressure of one atmosphere, the
steam occupies a volume of 1671 cm3. The heat input is 2255J. Compute the external work done
by the system and the increase in its internal energy.

4.4. Consider that 200J of work is done on a system and 293.3J is extracted from the system as
heat. In the sense of the first law of thermodynamics, what is the value of ∆U?

4.5. The expression dQ = dU + dw is a statement of the

A. Second law of thermodynamics B. Zero law of thermodynamics
C. Third law of thermodynamics D. First law of thermodynamics

4.6. Internal energy of an ideal gas depends on I. the volume of the ideal gas II. the pressure of the
ideal gas III. the absolute temperature of the ideal gas
A. I B. I and II C. III D. I, II and III

4.7. Derive the corresponding equation of the first law of thermodynamics under the following
processes: (i) adiabatic process (ii) isochoric process and (iii) cyclic process.