CH 211: Chemical Thermodynamics

Thermodynamics

The branch of science dealing with the relations between energy, heat, and work and
accompanying changes in the nature and behavior of various substances around us is called
thermodynamics. The word thermodynamics stems from the Greek words therme (heat) and
dynamics (force). The formal study of thermodynamics began in the early nineteenth century
through consideration of the motive power of heat: the capacity of hot bodies to produce work.
Today the scope is larger, dealing generally with energy and with relationships among the
properties of matter. 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.

MACROSCOPIC AND MICROSCOPIC VIEWS OF THERMODYNAMICS

Systems can be studied from a macroscopic or a microscopic point of view. The macroscopic
approach to thermodynamics is concerned with the gross or overall behavior. This is
sometimes called classical thermodynamics. No model of the structure of matter at the
molecular, atomic, and subatomic levels is directly used in classical thermodynamics.
Although the behavior of systems is affected by molecular structure, classical thermodynamics
allows important aspects of system behavior to be evaluated from observations of the overall
system.

The microscopic approach to thermodynamics, known as statistical thermodynamics, is

concerned directly with the structure of matter. The objective of statistical thermodynamics is
to characterize by statistical means the average behavior of the particles making up a system
of interest and relate this information to the observed macroscopic behavior of the system. For
applications involving lasers, plasmas, high-speed gas flows, chemical kinetics, very low
temperatures (cryogenics), and others, the methods of statistical thermodynamics are essential.

CHEMICAL THERMODYNAMICS:

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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.

Aim of the study of 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.

In practice, the primary objective of chemical thermodynamics is to establish a criterion for

determining the feasibility or spontaneity of a given physical or chemical transformation. Once
the spontaneous direction of a natural process is determined, we may wish to know how far
the process will proceed before reaching equilibrium. Thermodynamic methods provide the
mathematical relations required to estimate such quantities.

Although the main objective of chemical thermodynamics is the analysis of spontaneity and
equilibrium, the methods also are applicable to many other problems. For example, the study
of phase equilibria, in ideal and nonideal systems, is basic to the intelligent use of the
techniques of extraction, distillation, and crystallization; to metallurgical operations; to the
development of new materials; and to the understanding of the species of minerals found in
geological systems. Similarly, the energy changes that accompany a physical or chemical
transformation, in the form of either heat or work, are of great interest, whether the
transformation is the combustion of a fuel, the fission of a uranium nucleus, or the transport of
a metabolite against a concentration gradient. Thermodynamic concepts and methods provide
a powerful approach to the understanding of such problems.

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Various forms of energy involved in the study of chemical thermodynamics

In the study of chemical thermodynamics most frequently we deal with the interconversions
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. As
a result of breaking and formation of bonds the energy equivalent to 286 kJ is released. The
changes are described by the equation.

H – H + ½ O = O → ⎯H – O – H + 286 kJ

Conversion of chemical energy into other forms

Depending upon the conditions under which the reaction proceeds, the chemical energy
released can be made to appear as thermal energy, mechanical energy or electrical energy. If
the reaction takes place in a closed vessel immersed in a water bath, the chemical energy will
appear as thermal energy (heat), which would warm the vessel, the reaction mixture and the
bath. If the reaction proceeds in a cylinder fitted with a movable piston, the chemical energy
released can be made to produce mechanical work (work of expansion) by forcing the piston
to move in the cylinder against an external pressure. If the reaction is allowed to take place in
an appropriate electrochemical cell, the chemical energy can be converted into electrical
energy.

Thermodynamic terms

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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. 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.

Or

The system is whatever we want to study. It may be as simple as a free body or as complex as
an entire chemical refinery.

A thermodynamic system

A thermodynamic system is a device or combination of devices containing a quantity of

matter that is being studied.

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.

Or

Everything external to the system is considered to be part of the system’s surroundings.

Boundary: The space that separates the system and the surroundings is called the boundary.
The system and surroundings interact across the boundary. The boundary may be real or even
imaginary 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.

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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

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(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
(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
is not permissible. 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 thermos flask is an example of an isolated system.

PROPERTY, STATE, AND PROCESS

A property is a macroscopic characteristic of a system such as mass, volume, energy, pressure,

and temperature to which a numerical value can be assigned at a given time without knowledge
of the previous behavior (history) of the system.

state

The word state refers to the condition of a system as described by its properties.

Process

When any of the properties of a system change, the state changes and the system is said to have
undergone a process. A process is a transformation from one state to another.

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However, if a system exhibits the same values of its properties at two different times, it is in
the same state at these times. A system is said to be at steady state if none of its properties
changes with time.

Extensive and intensive properties

Some of the properties of a system depend on its size whereas others do not depend on its size.
Therefore, the properties of a system are grouped as extensive property and intensive property.

Extensive property: A property which depends directly on the size of the system is called
extensive property. Volume, mass and amount (mole) are extensive properties.

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.

Intensive property: A property which does not depend on the size of the system is called
intensive property. Density, temperature and molarity 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.

List of extensive and intensive properties

Extensive properties Intensive properties

Volume, mass, amount (mole), energy, Molar volume, density, molar mass,
enthalpy, entropy, free energy, heat capacity molarity, mole fraction, molality, specific
heat capacity

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

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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

(2) Molarity is an intensive property

State properties of the system and state functions

“A property of the system which depends only on the state variables is called state property or
state function”.

The change in a state property depends only on the initial and final states of the system. A state
property is independent of the manner in which the change is brought about. This means that
the state property does not depend on the path followed by the system.

Thermodynamic properties namely energy (U), enthalpy (H), entropy (S), work function (A)
free energy (G), volume (V), pressure (P) and temperature (T) are state functions. A state
function say energy (U) may be mathematically represented as U = U (T, V, n). The
mathematical representation is stated as U is a function of T, V, and n. That is, energy of the
system depends on the state variables T, V and n. Similarly; volume of the system is a function
of temperature (T), pressure (P) and amount (n). That is, V = V (T, P, n). For a system of

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constant composition (for a constant value of n) the volume of a gas is a function of temperature
and pressure only i.e., V = V (T, P).

VOLUME IS A STATE PROPERTY– demonstration by calculation

Ex: Consider a given amount of an ideal gas in its initial state TI = 300 K, PI = 1 bar, VI = 20
dm3. Let us suppose that the state variables of the gas are changed to a final state T2 = 600 K,
P2 = 0.8 bar, so that its final volume is V2. The change in the state of the gas (system) may be
made in the following ways.

Solution

Method 1. The gas is heated and allowed to expand simultaneously from the initial state T1 =
300 K, P1 = 1 bar, V1= 20 dm3 to the final state T2 = 600 K, P2 = 0.8 bar, so that final volume
is V2. Now in this case the gas equation P1 V1/ T1 = P2 V2 /T2 gives

Thus change of volume = ∆V (1) = V2 – V1 = 50 dm3 – 20 dm3 = 30 dm3

Method 2.

Step (a). The gas is heated at constant pressure from 300 K, 1 bar, 20 dm3 to 600 K, 1 bar so
that its volume is Va as given by Charles’s law:

∆V (2 a) = (40 – 20) dm3 = 20 dm3

Step 2(b) The gas is allowed to expand at constant temperature from 600 K, 1 bar, 40 dm3 to
600 K, 0.8 bar so that its final volume is V2 as given by Boyle's law

∆V (2 b) = (50 dm3 – 40 dm3) = 10 dm3

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Net change of volume in step 2 =∆V (2 ) = ∆V (2a) + ∆V (2b) = (20 dm3 + 10 dm3) = 30 dm3

Method 3.

Step (a) The gas is allowed to expand at constant temperature from 300 K, 1 bar, 20 dm 3 to
300 K, 0.8 bar so that its final volume is Va as given by Boyle's law

∆V (3a) =(25 dm3– 20 dm3) = 5 dm3

Step (b) The gas is heated at constant pressure from 300 K, 0.8 bar, 25 dm3 to 600 K, 0.8 bar
so that its final volume V2 is given by Charles’s law:

∆V (3b) =(50 dm3 – 25 dm3) = 25 dm3

Net change of volume in step 3 =∆V (3 ) = ∆V (3a) + ∆V (3b) = (5 dm3 + 25 dm3) dm3= 30
dm3

Discussion: The final state of the system is reached in three different ways but the final volume
in each process is the same V2 = 50 dm3 and the net volume change for all the three paths is
also the same. This proves that volume is a state function and V = V (T, P)

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).

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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. Combustion of a fuel in a
bomb calorimeter is an example of isochoric process. (the term chore is used for space,
therefore, isochoric means same space or same volume)

Quick view of the process and its condition

Process Isothermal Adiabatic Isobaric Isochoric

Condition dT = 0 q=0 dP=0 dV=0

Reversible process:

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

Illustrations of a reversible process

Let us consider a gas taken in a cylinder which is fitted with a movable piston. Suppose that
an external pressure (Pext) is applied on the gas by keeping sufficient quantity of sand grains
on the piston. In this situation the pressure of the gas (P1) is balanced by the external pressure
on the gas, that is, P1 = Pext

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Suppose that one grain of the sand is removed from the piston. The removal of the sand grain
will cause a very small decrease in the external pressure. Now the pressure of the gas becomes
slightly greater than the external pressure. Because of this difference of pressure the gas will
expand till the pressure of the gas becomes equal to the pressure on the gas. This expansion
will result in an infinitesimally small work done by the gas on the surroundings.

The work is so small that no appreciable change is observed in the properties of the system or
surroundings. On the other hand, if the same grain of sand is placed again on the piston, the
external pressure will increase and the gas will be compressed to its initial stage. In this case
also infinitesimally small work will be done by the surroundings on the system, which will not
cause any appreciable change in the properties of the system and surroundings. Therefore, the
change is said to be reversible. However, by removing the sand grains continuously from the
piston (by lowering the pressure) the gas will expand by a definite volume

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 Path. Path is the representation of steps of changes starting
from initial state and then reaching the final state through various intermediate states (if any).

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Path: Path is the representation of steps of changes starting from initial state and then reaching
the final state through various intermediate states (if any).

ENERGY

Energy is the capacity to do work. The total energy of a particle is the sum of its kinetic and
potential energies. The kinetic energy of a particle is the energy it possesses as a result of its
motion. The potential energy of a particle is the energy it possesses as a result of its position.

For a body of mass m travelling at a speed v

The potential energy, equation or more commonly V, of a body is the energy it possesses as a
result of its position. For a particle of mass m at an altitude h close to the surface of the Earth,
the gravitational potential energy is

Where g is the acceleration of free fall (g=9.81 m s−2). The total energy of a particle is the sum
of its kinetic and potential energies

E = EK + EP

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