CAMBRIDGE SCHOOL SRINIVASPURI NEW DELHI

UNIT : CHEMICAL THERMODYNAMICS

Sub-Topic : SOME BASIC TERMS AND CONCEPTS.
LEARNING OBJECTIVES : The students will learn about the Basic Terms and Concepts.
GENERAL INTRODUCTION : The branch of Science which deals with the study of different
forms of energy and the quantitative relationships between them is known as Thermodynamics.
The importance of thermodynamics lies in the following facts.
(i) It helps us to predict whether any given chemical reaction can occur under the given set of
conditions.
(ii) It helps in predicting the extent of reaction before the equilibrium is attained
(iii) It helps to deduce some important laws like the laws of chemical equilibrium.
The limitations of thermodynamics ie where it fails to give any information are as follows.
(i) It helps to predict the feasibility of a process but does not tell anything about the rate at which the
process takes place.
(ii) It deals only with the initial and final states of a system but does not tell anything about the
mechanism of the process.
(iii) It deals with the properties like temperature, pressure etc of the matter in bulk. But does not tell
anything about the individual atoms and molecules.(microscopic properties)
SOME BASIC TERMS AND CONCEPTS :
1 System and Surroundings. The part of the universe chosen to study the effect of
temperature,pressure etc ) is called a system.
The remaining part of the universe excluding the system, is called surroundings.
2Types of System : Open, closed and isolated systems.
(a) Open system: A system is said to be an open system if it can exchange both matter and energy
with the surroundings. eg if reaction takes place between marble and HCl exchange of energy takes
place between the system and surroundings.
(b) Closed system. If a system can exchange only energy with the surroundings but not matter it is
called a closed system. For example, if some water is placed in a closed metallic vessel or if some
reaction is allowed to take place in a cylinder enclosed by a piston then as the vessel is closed, no
exchange of matter between the system and surroundings can take place. However if the vessel has
conducting walls, exchange of energy can take place between the system and surroundings.
If the reaction is exothermic heat is given by the system to the surroundings.
If the reaction is endothermic heat is given by surroundings to the system.
(c) Isolated system. If a system can neither exchange matter nor energy with the surroundings it is
called an isolated system. Tea placed in thermos flask is an example of an isolated system.
3State of a system and State variables. The state of a system means the condition of the system
which is described in terms of certain observable properties such as temperature(T)pressure (P)
volume (V) of the system . If any of these properties of the system changes, the system is said to be in
a different state. These are known as state variables.
A Process is said to occur when the state of the system changes. The first and last state of a system
are called the initial state and final state respectively.
4.State function. A physical quantity is said to be a state function if the change in its value during the
process depends only upon initial state and the final state of the system and does not depend upon the
path or route by which this change has been brought about.
Examples of physical quantities which are state function include pressure, volume ,
temperature, internal energy , enthalpy entropy, free energy
5.Macroscopic system and Macroscopic Properties( Extensive and Intensive Properties)
If a system contains a large number of chemical species, atoms, ions or molecules it is called a
Macroscopic system.
(i) Extensive properties. These are those properties which depend upon the quantity of the matter
contained in the system. The common examples of these properties are mass, volume and heat
capacity, internal energy, enthalpy, entropy ,Gibbs free energy etc.
(ii) Intensive properties. These are those properties which does not depend upon the quantity of the
matter contained in the system. The common examples of these properties are temp, pressure ,
refractive index , viscosity ,density , specific heat, freezing point ,boiling point, emf of a cell,
mole fraction, molarity etc.
6.Thermodynamic equilibrium. A system is said to be in thermodynamic equilibrium if its
macroscopic properties like temperature, pressure etc do not change with time.
7.Thermodynamic processes. A thermodynamic process is said to occur when the system changes
from one state(initial state) to another (final state)
(i) Isothermal process. When a process is carried out in such a manner that the temperature remains
constant throughout the process, it is called an isothermal process.
(ii) Adiabatic process . When a process is carried out in such a manner that no heat can flow from the
system to the surroundings or vice versa
(iii)Isochoric process. It is a process during which the volume of the system is kept constant.
(iv) Isobaric process. It is a process during which the pressure of the system is kept constant

8.Reversible and Irreversible Processes.

A reversible process is a process which is carried out infinitesimally slowly so that all changes
occurring in the direct process can be exactly reversed and the system remains almost in a state
of equilibrium with the surroundings at every stage of the process.
An irreversible process is defined as that process which is not carried out infinitesimally
slowly(instead it is carried out rapidly ) so that the successive steps of the direct process cannot
be retraced and any change in the external conditions disturbs the equilibrium.

A gas confined within a cylinder provided with a friction less piston upon which is piled very fine
sand . The pressure exerted by the gas on the piston is equal to the combined pressure exerted by the
weight of the piston , the pile of sand and the atmospheric pressure. Thus under these conditions the
piston does not move at all and a state of equilibrium is said to exist.
Now if one pile of sand is removed the gas will expand very slightly but the equilibrium will be
restored almost immediately. Such a change is called an infinitesimal change. If the particle of sand
is replaced the gas will return to its original volume .
By the continued removal of the particles of sand the gas can be allowed to go a finite expansion but
step in this expansion is an infinitesimal one and can be reversed by an infinitesimal change in the
external conditions. At all times the equilibrium is restored immediately.
Thus the necessary condition for reversible compression is : P external = Pinternal + dp
Thus the necessary condition for reversible expansion is : P external = Pinternal - dp
9(a) Internal energy. The energy thus stored within a substance (or a system) is called its
internal energy. It is sum of different types of energies associated with atoms and molecules
Internal energy change. If the internal energy of a system in the initial state is U1 and in the final
state, it is U2, then the change in internal energy (∆U) may be written as
∆U= U2 –U1
∆U= UP –UR UR = Internal energy of reactants
U p = Internal energy of products
The internal energy of a system changes when
(i) heat passes in or out of the system.
(ii) work is done on or by the system
(iii) matter enters or leaves the system
Sign of ∆U. : If UR > Up The extra energy possessed by the system would be given out and ∆U will
be negative. Similarly if UR < Up energy will be absorbed in the process.
The internal energy of an ideal gas is a function of temperature only. For an isothermal process there
is no change in internal energy ∆U=0 . There is no intermolecular force of attraction between gas
molecules. No work is done in overcoming the intermolecular forces when the ideal gas expands.