CHAPTER ONE

1.0 Introduction to Thermodynamics

The branch of science dealing with the relations between energy, heat, and work and
accompanying changes in the nature and behaviour of various substances around us is called
thermodynamics. It can also be defined as a branch of science that deals with the study of
energy and its transformations. The principles of thermodynamics have been enunciated in the
form of a few laws of thermodynamics called zeroth law, first law, second law and third law.
These laws find applications in physics, chemistry, engineering, medicine, biotechnology,
biochemistry, geology and space sciences. The branch of chemistry dealing with the
investigation of energetics and feasibility of chemical reactions and physical changes is called
chemical thermodynamics. Its principles are simple, and its predictions are powerful and
extensive.

The predictive power of chemical thermodynamics is based on the characteristics of

thermodynamic properties namely internal energy (U), enthalpy (H), entropy (S) and free
energy functions (A and G) and their variations with variables like temperature, pressure,
volume and amount. The changes in these properties depend only on the initial and final states
of the system, and are independent of the path followed for the system Therefore; these
thermodynamic properties are called state functions. This aspect will be discussed later in this
unit.

1.1 Aim of studying chemical thermodynamics

The main aim of the study of chemical thermodynamics is to learn (i) transformation of energy
from one form into another form, (ii) utilization of various forms of energy and (iii) changes in
the properties of systems produced by chemical or physical effects. Therefore, this branch of
science is called chemical energetics also.

1.2 Various forms of energy involved in the study of chemical thermodynamics

In the study of chemical thermodynamics most frequently we deal with the inter conversions

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of four forms of energy namely, electrical energy, thermal energy, mechanical energy, and
chemical energy. The energy involved in the chemical processes is called chemical energy.
That is, it is the energy liberated or absorbed when chemical bonds are formed, broken or
rearranged. For example, when hydrogen and oxygen combine water is formed and a large
quantity of chemical energy is released. When one mole H–H and half mole O = O bonds are
broken, two moles of O–H bonds are formed as H–O–H. In the process energy is required to
break H – H and O = O bonds whereas energy is liberated in the formation of O – H bonds.

Thermodynamics comes from two Greek words (i) thermo which means heat and (ii) dynamics
which means motion combining these two to an ordinary man thermodynamics means heat in
motion which conquer with our definition the study of energy and its transformations.

1.3 Thermodynamic terms

In order to understand and appreciate the power of thermodynamics it is necessary to become
familiar with the commonly used terms in thermodynamics.

System. A system is a portion of the universe which is selected for investigations in which the
researcher has interest. The system may be water taken in a beaker, a balloon filled with air, an
aqueous solution of glucose, a seed, a plant, a flower, a bird, animal cell etc.

Surroundings. The rest of the universe, which can interact with the system, is called
surroundings. For practical purposes the environment in the immediate vicinity of the system is
called the surroundings. The boundary may be real or even imaginary

Boundary. The space that separates the system and the surroundings is called the boundary. The
system and surroundings interact across the boundary.

Surroundings
(Thermostat)
Boundary
System

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 Fig. 1.1. Illustration of system, surroundings and boundary

Let us suppose that water is taken in a beaker and kept in a constant temperature bath (called
thermostat) as shown in Fig. 1. Here water is the system. Each wall of the beaker is a boundary
(water-air surface is another boundary). The constant temperature bath is the surroundings.
Types of boundary: Depending upon the nature of the walls of the container boundary can be
classified as follows.
(a) Rigid boundary. It is a wall whose shape and position are fixed
(b) Impermeable boundary: It is a wall that prevents the passage of the matter but
permits the passage of energy.
(c) Permeable boundary. It is a wall that permits the passage of matter and energy
(d) Adiabatic boundary. It is a wall that prevents the passage of mass or energy.
(e) Diathermic boundary. It is a wall that allows the passage of energy but prevents the
passage of matter. That is, a diathermic boundary is impermeable but not adiabatic

Types of system

Depending upon the nature of the boundary the system can be identified as open, closed
or isolated.

(i) An open system. It is a system which has permeable boundary across which the
system can exchange both the mass (m) and energy (U) with the surroundings.
Thus in an open system mass and energy may change. In terms of symbolic
notation it may be stated that in an open system ∆m ≠ 0 and ∆U ≠0

(ii) A closed system. It is a system with impermeable boundary across which the
system cannot exchange the mass (m) but it can exchange energy (U) with the
surroundings. Thus in a closed system mass remains constant but energy may
change. In terms of symbolic notation it may be stated that in an open system ∆m
= 0 but ∆U ≠0.The best example of such a system is the condenser.

Open system Closed system Isolated

system Fig. 1.2. Types of systems
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(iii) An isolated system. It is a system with rigid and adiabatic boundary across which neither
exchange of mass (m) nor energy (U) between the system and the surroundings. Thus in an
isolated system mass and energy remain unchanged. In terms of symbolic notation it may be

stated that in an isolated system ∆m = 0 and ∆U =0 Milk kept in a perfect thermos flask is an
example of an isolated system.

1.4 State of a System

We describe the state of a system by its measurable properties. For example, we can describe
the state of a gas by specifying its pressure, volume, temperature, enthalpy etc. These
variable properties are called state variables or state functions. Their values depend only on
the initial and final state of the system and not on the path taken by the system during the
change. When the state of a system changes, the change depends only on the initial and the
final state of the system
We can understand it by considering another example. We travel from one point to another. The
distance travelled depends on the path or the route we take. But the separation between these two
points on the earth is fixed. Thus, separation is a state function, but not the distance travelled.

Properties of a System

As stated earlier, the measurable properties of a system are called state variables. They may be further
divided into two main types.

(i) Extensive property (variable) is one whose value depends upon the size of the
system. For example, volume, weight, heat, etc.

Characteristics of an extensive property

An extensive property of the entire system is greater than any of its smaller parts.
The sum of the properties of subsystems is equal to the same property of the entire
system. This means that the extensive properties are additive.

(ii) Intensive property (variable) is one whose value is independent of the size of the
system. For example, temperature, pressure, refractive index, viscosity, density,

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 surface tension, etc. You may note that an extensive property can become an intensive
property by specifying a unit amount of the substance concerned. For example, mass
and volume are extensive properties, but density (mass per unit volume) and specific
volume (volume per unit mass) are intensive properties.
Characteristics of an intensive property
An intensive property of a homogeneous system is the same as that of any of its smaller parts.The
intensive properties are nonadditive.

Illustration that volume is an extensive property but temperature is an intensive

property

Take 100 mL of water in a beaker (main system A) and note its temperature (say it is 25
°C). Now divide water (the main system) into four parts as subsystems A1 (10 mL), A2 (20 mL),
A3 (30 mL), and A4 (40 mL). Here we observe that the volume of the main system A is larger
than the volume of any individual subsystem. But the sum of the volumes of subsystems
(10 mL + 20 mL + 30 mL+ 40 mL) is equal to the volume of the main system (100 mL). So
volume is an extensive property.

Record the temperature of each subsystem. It is observed that the temperature of each subsystem
A1, A2, A3, and A4 is the same as it was for the main system. Therefore, temperature is
an intensive property.

A general statement: The ratio of two extensive properties is an intensive property. For
example:

(1) Density is an intensive property

Mass (extensive property)

= Density (intensive property)
Volume (extensive property)

(2) Molarity is an intensive property

Mole of the solute (extensive property)

= Molarity ( intensive property )
Volume of solution (extensive property)

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 Examples of intensive and extensive properties.

Temperature, pressure, and specific volume of both systems are intensive properties. Total mass
and total volume of each system are extensive property. At 100 oC and 1 atm, the specific
volume v of each system is 1.674 m3/kg. The mass of system (1) is m1 = 2 kg and that of system
(2) is m2 = 5 kg. The total volume of system (1) is V1 = m1v = (2 kg) (1.674 m3/kg) =

3.348 m3. The total volume of system (2) is V2 = m2v = (5 kg) (1.674 m3/kg) = 8.37 m3. An
intensive property might be obtained from an extensive property by dividing the extensive
property by the mass of the system.

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Units
The SI units (System International Units, translated Internal System of Units) are used in this
text. It happens that seven primary quantities are needed to completely describe all natural
phenomena. The decision as to which quantities are primary is arbitrary. The units of the
primary quantities and their symbols are listed in Table 1.1 and are defined arbitrarily as
follows:
Meter: the length of the trajectory traveled by light in a vacuum per 1/299,792,458 s,
Kilogram: the mass of the platinum cylinder deposited at the International Office for
Weights and Measures, Sèvres, France,
Second: 9,192,631,770 times the period of radiation in energy level transitions in the fine
spectral structure of 133Cs,
Kelvin: 1/273.16 of the triple point temperature of water with naturally occurring amounts of
H and O isotopes,
Amperes: the current which, on passing through two parallel infinite conducting wires of
negligible cross section, separated by 1 m and in vacuum, induces a force (per unit length) of
2×10-7 N/m,
Mole: the amount of a matter containing the number of particles equal to the number of
atoms in 0.012 kg of the pure isotope 12C,
Candela: the amount of perpendicular light (luminosity) of 1/60×10-6 m2 of the surface of an
absolute black body at the melting temperature of platinum and a pressure of 101,325 Pa.

Table 1.1: The seven primary quantities and their units in SI

Primary quantity Unit

Length Meter (m)
Mass Kilogram (kg)
Time Second (s)
Temperature Kelvin (K)
Electric current Ampere (A)
Amount of matter Mole (mol)
Amount of light Candela (cd)

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Several of the derived quantities with units are listed in Table 1.2 a derived unit is a
quantity expressed in terms of a product and/or quotient of two or more primary units.

Table 1.2. The derived quantities and their units in SI

Derived quantity Unit

Cp, specific heat capacity J/kg·K
E, energy J = N·m, joule
F, force N = kg·m/s2, newton
k, thermal conductivity W/m·K
p, pressure Pa = N/m2, pascal
q, heat transfer rate W = J/s = kg·m2/s3, watt
q", heat flux W/m2 = J/s·m2
q′′ , heat generation rate per unit volume W/m3
μ, viscosity N/m2=kg/s·m
ρ, density kg/m3

Pressure
Any force acting on a surface consists of a component perpendicular to the surface and a
component parallel to the surface. These two components are called normal force and shear
force as shown in Figure 1.4-1. Pressure is defined as a normal force per unit area on which
the force acts. The SI pressure unit, N/m2, is called a Pascal (Pa). Pressure at any point is a
fluid is the same in any direction.

Consider a hole in the wall of a tank or a pipe as shown in Figure 1.2. The fluid pressure p may
be defined as the ratio F/A, where F is the minimum force that would have to exerted on a

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frictionless plug in the hole to keep the fluid from emerging

The pressure at a given position measured relative to absolute zero pressure or absolute
vacuum is called the absolute pressure. Most pressure-measuring devices are calibrated to
read zero in the atmosphere as shown in Figure 1.3. These pressure gages indicate the
difference between the absolute pressure and the local atmospheric pressure. Pressures below
atmospheric pressure are called vacuum pressures and are measured by vacuum gages that
indicate the difference between the atmospheric pressure and the absolute pressure.
Absolute, gage, and vacuum pressures are all positive quantities and are related to each other
by

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 Two common pressure units are the bar and standard atmosphere:

1 bar = 105 Pa = 0.1 Mpa = 100 kPa

1 atm = 101,325 Pa = 101.325 kPa = 1.01325 bar = 14.696 psi

Temperature
When two objects are brought into contact and isolated from the surrounding, energy tends to
move spontaneously from one to the other. The object that gives up energy is at a higher
temperature, and the object that receives energy is at a lower temperature. We would be able to
observe that the electrical resistance of the warmer object decreases with time, and that of the
colder block increases with time; eventually there would be no change in the electrical
resistances of these objects. The two objects are then in thermal equilibiurm. They are at the
same Temperature. We could then define temperature as a measure of the tendency of an object
to spontaneously give up energy to its surroundings.
Any object with at least one measurable property that changes as its temperature changes can be
used as a thermometer. Most thermometers operate on the principle of thermal expansion:
Materials tend to occupy more volume at a given pressure when they are at a higher temperature.
A mercury thermometer is just a convenient device for measuring the volume of a fixed amount
of mercury. To define actual units for temperature we arbitrary assign 0 to the freezing point and
100 to the boiling or steam point of water. We then mark these two points on our mercury
thermometer, measure off a hundred equally spaced intervals in between, and declare that this
thermometer now measures temperature on the Celsius (or centigrade) scale, by definition.
The Kelvin scale is an absolute temperature scale that measures temperature from absolute zero
instead of from the freezing point of water. The relationship between these two temperature
scales is given by
T(oC) = T(K) − 273.15. By definition, the Rankin scale, is related to the Kelvin scale by a
factor of 1.8:
T(oR) = 1.8T(K)
A degree of the same size as that on the Rankine scale is used in the Fahrenheit scale but the
zero point is shifted according to the relation
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T(oF) = T(oR) − 459.67 .
The Fahrenheit scale can be related to the Celsius scale by

T(oF) = 1.8T(oC) + 32

1.5 Thermodynamic process

The method of operation which can bring about the change in the system is called thermodynamic
process. Heating, cooling, expansion, compression, fusion, vaporization etc., are some
examples of thermodynamic process.

Types of process

A change can be carried in different ways and under different conditions. Therefore, the processes
can be classified as follows:

Isothermal process. A process is said to be isothermal when the temperature of the system is
kept constant during various operations. That is, there is no change of temperature (dT = 0) in an
isothermal process. Isothermal condition is attained either by supplying heat to the system
or by removing heat from the system. For this purpose the experiment is performed in a
thermostat (constant temperature bath).

Adiabatic process. A process is said to be adiabatic if there is no exchange of heat (q) between
the system and surroundings during various operations. That is, q = 0 in an adiabatic process.
This condition is attained by thermally insulating the system. In an adiabatic process if work is
done by the system its temperature decreases, if work is done on the system its temperature
increases.

Isobaric process. A process is said to be isobaric if the pressure remains constant during the
change. That is, dP = 0 in an isobaric process. (Bar is the SI unit of pressure; therefore, isobaric
means same pressure)
Isochoric process. A process is said to be isochoric if the volume of the system remains constant
during the change. That is, dV = 0 in an isochoric process.

Reversible process. A process is said to be reversible if the change can take place in both the

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forward and back directions by a small change in its state variables. In a reversible change the
system can be brought back to its initial state without altering the properties of surroundings to
an appreciable extent. In a reversible process the change takes place very slowly so that the
system and surroundings are nearly at equilibrium (called quasi equilibrium).
Irreversible process. A process is said to be irreversible if the change takes place in one
direction. In an irreversible process the system cannot be brought back to its original state without
affecting the surroundings. All the natural changes are irreversible and hence spontaneous.

Cyclic process. It is a process in which the initial state of the system is restored after undergoing
a series of changes

1.6 Concept of internal energy (U)

Internal energy is a characteristic property of a system which decides its nature and
behaviour. It is denoted by symbol U or E. Internal energy of a system is equal to the energy
possessed by all its constituents namely atoms, ions and molecules. The energy of a molecule is
equal to translational energy (Ut), vibrational energy (Uv), rotational energy (Ur), bond energy
(Ub), electronic energy (Ue), energy due to molecular interactions (VT) etc.

The total energy of all the molecules of the system is called internal energy or intrinsic energy.
The internal energy is the cause of existence of various types of distinct substances. In
thermodynamic studies one is more concerned with the change in internal energy (∆U) rather
than the absolute value of energy. This is because internal energy of a system cannot be
practically measured but what can be measured is the change in internal energy ΔU.

Importance of internal energy: The internal energy possessed by a substance differentiates it

from other substances. For example, the allotropes of carbon namely graphite (C) and diamond
(C), differ from each other because they possess different internal energies and have different
structures. This is the reason that internal energy is also called inherent energy or hidden energy
or more appropriately intrinsic energy.

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