THERMODYNAMICS

The word thermodynamics means ‘Flow of heat’. It deals with energy changes accompanying all

types of physical and chemical processes. Thermodynamics is based on three generalizations

called the first, second, and third laws of thermodynamics.

 The first law of thermodynamics (also known as law of conservation of energy) states that

‘energy can neither be created nor destroyed, although it can be transformed from one

form to another’.

 The second law of thermodynamics states that ‘the state entropy of the entire universe, as

an isolated system, will always increase over time’. In other words, the changes in the

entropy in the universe can never be negative.

 The third law of thermodynamics states that ‘the entropy of a closed at thermodynamic

equilibrium approaches a constant value when its temperature approaches absolute zero’.

The above-mentioned laws are based on human experience, thus there is no formal proof for the

laws. On the other hand, nothing contrary to these laws has been known to happen whenever we

consider the behavior of matter in bulk.

IMPORTANCE OF THERMODYNAMICS

Thermodynamics is of great importance in physical chemistry due to the following reasons;

 Most of the generalizations of physical chemistry including Van’t Hoff law of dilute

solution, Raoult’s law of vapour pressure lowering, Distribution law, Law of chemical

equilibrium, the phase rule, and the laws of thermochemistry, can be deduced from the laws

of thermodynamics.
  Thermodynamics helps to lay down the criteria for predicting feasibility or spontaneity of

a process, including chemical reactions under a given set of conditions.

LIMITATIONS OF THERMODYNAMICS

Thermodynamics have the following limitations;

 The laws of thermodynamics apply only to a matter in bulk and not to individual atoms or

molecules.

 Thermodynamics can only predict whether a given process including chemical reactions is

feasible under a given set of conditions. In other words, it does not tell anything about the

rate at which a given process may proceed. It shades light on initial and final states of a

system.

For example, thermodynamics predicts that hydrogen and oxygen gases would react at

ordinary temperatures to yield liquid water. But it does not tell whether the reaction will be

fast or slow. We only know from the experiment that in the absence of oxygen the reaction

is extremely slow.

TERMINLOGY OF THERMODYNAMICS

The following terms are frequently used in the thermodynamics:

 System: A system can be defined as any specified portion of matter under study which is

separated from the rest of the universe with a bonding surface. A system may consist of

one or more substances.

 Surroundings: The rest of the universe which might be in a position to exchange energy

and matter with the system is called surroundings. Examples of surroundings includes air,

or water-bath, in which a system under examination is immersed.

surroundings is called an isolated system.

 Closed systems: A system which can exchange energy but not matter with its surroundings

is called a closed system.

 Open system: A system which can exchange matter as well as energy with its surroundings

is said to be an open system.

 Macroscopic properties: The properties associated with a macroscopic system (consisting

of a large number of particles) are called macroscopic properties. These properties are

pressure, volume, temperature, composition, density, viscosity, surface tension, refractive

index, colour, etc.

 Homogeneous and Heterogeneous systems: A system is said to be homogeneous when it

is completely uniform throughout, e.g pure solid or liquid, or a solution, or a mixture of

gases. Thus, a homogeneous system consists of only one phase.

On the other hand, a system is said to be heterogeneous when it is not uniform throughout.

In other words, a heterogeneous is one which consists of two or more phases, eg two or

more immiscible liquids, or solid in contact with liquid in which it does not dissolve, or

liquid in contact with its vapour.

 Phase: A phase is defined as a homogeneous and physically distinct part of a system which

is bounded by a surface and is mechanically separable from other parts of the system.

 State of a system: When macroscopic properties of a system have definite values, the

system is said to be in a definite state. Thus, the state of a system is fixed by its macroscopic

properties.
 State of variables: Since the state of a system changes with change in any of the

macroscopic properties, these properties are called state variables.

It also follows that when a system changes from one state (initial state) to another state

(final state) there are invariably a change in one or more of the macroscopic properties.

Pressure, temperature, volume, mass, and composition, are the most important variables.

 Independent and Dependent variables: Consider an ideal gas equation PV=RT, where R

is the universal gas constant. Evidently, if only two of the three variables (P, V, and T) are

known, the third can easily be calculated. The two variables generally specified are

temperature and pressure. These are called independent variables. The third variable

generally volume, is said to be dependent variable as its value depends upon the values of

P, and T.

 Thermodynamic equilibrium: A system in which the macroscopic properties do not

undergo any change with time is said to be in thermodynamic equilibrium.

The term implies the existence of three kinds of equilibria in the system namely; thermal,

mechanical, and chemical equilibrium.

A system is said to be in thermal equilibrium if there is no flow of heat from one portion

of the system to another. This is possible if the temperature remains the same throughout

in all parts of the system.

A system is said to be in mechanical equilibrium if no mechanical work is done by one

part of the system on another part of the system. This is possible if the pressure remains

the same throughout in all parts of the system.

A system is said to be in chemical equilibrium if the composition of the various phases in

the system remains the same throughout.

depends upon the amount of the substance or substances present in the system, eg mass,

volume, and energy.

An intensive property of a system is that which is independent of the amount of substance

present in the system, eg temperature, pressure, density, concentration, viscosity, refractive

index, surface tension, and specific heat.

PROCESSES AND THEIR TYPES

The operation by which a system changes from one state to another is called a process.

Whenever a system changes from one state to another it is accompanied by the change in

energy. In the case of open systems, there may be change in the matter as well.

There are four different types of processes:

1. Isothermal process: A process is said to be isothermal if the temperature of the system

remains constant during each stage of the process.

2. Adiabatic process: A process is said to be adiabatic if no heat enters or leaves the

system during any step of the process.

3. Isobaric process: A process is said to be isobaric if the pressure of the system remains

constant during each step of the process.

4. Reversible and Irreversible processes: A process carried out infinitesimally slowly

so that the driving force is only infinitesimally greater than the opposing force is called

reversible process.

Any process which does not take place infinitesimally slowly is said to be an

irreversible process.