First Law of Thermodynamics

Introduction

The branch of chemistry, which deals with energy changes during

various physical processes and chemical reactions, is called chemical
energetics.

Important Thermodynamic Terms

'A specified part of the universe which is under investigation is called

the system'. The system is separated from the rest of the universe by a
definite (real or imaginary) boundary.

Energy Changes in Chemical Reactions

Every substance possesses a definite quantity of energy, under a

given set of factors such as chemical nature of the substance,
temperature and pressure. The total energy contained in a system or
substance is called its internal energy or intrinsic energy. It is
represented by the symbol 'E' or 'U'.

Enthalpy

The change in internal energy gives the heat change accompanying a

chemical reaction at constant volume. However, most of the chemical
reactions carried out in laboratories, are open to normal atmospheric
conditions. A chemical reaction in a laboratory may incur change in
volume but the pressure remains constant i.e. atmospheric pressure.

Exothermic reactions

When chemical reactions take place, energy is either absorbed or

evolved. A reaction is said to be exothermic, if heat is 'evolved'. The heat
energy produced during the reactions is indicated by writing + q or more
precisely by giving the actual numerical value on the products side.

Endothermic reactions

Reactions that are accompanied by absorption of energy from the

surroundings are called endothermic reactions. Since heat is added to
the reactants in these chemical reactions, it is indicated by either
putting +q or by writing the actual numerical value of heat on the
reactants side.

Laws of Thermodynamics - Zeroth Law

The 'zeroth law' states that 'if two bodies (say A and B) are in thermal
equilibrium with another body C, then the bodies A and B will also be in
thermal equilibrium with each other'. This law is important as it helps in
understanding the concept of temperature.

First Law of Thermodynamics or Law of Conservation of Energy

The total energy in the universe is present either as kinetic energy or

as potential energy. For example, the water stored in a dam possesses
potential energy by virtue of its height (position). When this water is
allowed to fall, its potential energy gets converted into kinetic
energy. Falling water can rotate the turbines and produces electricity,
due to its kinetic energy. In other words, the total energy remains
constant even when a body changes its position, because one form of
energy may be converted into another. This leads to an important
conclusion known as conservation of energy or the first law of
thermodynamics.

Heat Capacity

Heat capacity gives a measure of the quantity of heat absorbed by a

system. It is defined as the amount of heat required to rise the
temperature of the system through 1oC. If the quantity of heat required
is to raise the temperature of unit mass of the substance through 1oC
then it the specific heat of the substance. Whereas when the whole mass
of the substance is considered, it is the heat capacity.

Thermochemical Reactions

Chemical reactions involve energy changes. These changes can be

represented in a standard way called the thermochemical equation.

Heat or Enthalpy of Reaction

The amount of heat evolved or absorbed in a reaction is known as

heat of reaction. As the amount of heat evolved or absorbed at
constant temperature and pressure is called enthalpy, the heat
changes for various reactions may also be called enthalpy changes.
The heat change during a chemical reaction depends upon the amount of
substance (number of moles) that has reacted. Thus, heat of reaction
may be defined as 'the amount of heat evolved or absorbed in a reaction
when the number of moles of reactants react completely to give the
products as given by the balanced chemical equation'.

Standard Enthalpy of Reaction

As the heat of a reaction varies with temperature it is desirable to

fix up a standard or a reference state. A substance is said to be in
standard state when it is present in its most stable state at 298 K under
a pressure of one atmosphere.

Types of Heat (enthalpy) of Reactions

The heat or enthalpy changes taking place during the chemical

reactions are expressed in different ways depending upon the nature of
the reaction.

Measurement of Enthalpy of Reactions

The heat changes in chemical reactions are measured with the help of
calorimeters. Depending upon the requirements of experiments different
types of calorimeters are used. In general, reactions taking place at
constant volume and involving gases are carried out in a closed
container with rigid walls that can withstand high pressures such as a
bomb calorimeter. The body of the bomb calorimeter is made of heavy
steel. The steel vessel is coated inside with gold or platinum to avoid
oxidation of steel during the chemical reactions. The vessel is fitted
with a tight screw cap. There are two electrodes R1 and R2, which are
connected to each other through a platinum wire S, which remains dipped
in a platinum cup just below it.

Determination of Enthalpy Change

The calorimeter is kept open to the atmosphere in the determination

of change in enthalpy of a reaction. The calorimeter is immersed in an
insulated water bath fitted with stirrer and thermometer. The
temperature of the bath is recorded in the beginning and after the end
of the reaction and the change in temperature is calculated. Knowing
the heat capacity of water bath and calorimeter and also the change
in temperature the heat absorbed or evolved in the reaction is
calculated. This gives the enthalpy change (DH) of the reaction.

Laws of Thermochemistry

A.L.Lavoisier and P.S.Laplace gave this law in 1780 which states that
'the enthalpy of a reaction is exactly equal but opposite in sign for the
reverse reaction'.

Bond Energy or Bond Enthalpy

In chemical reactions the formation of a chemical bond is accompanied

by the release of energy. Conversely energy has to be supplied for the
breaking of a bond.

Sources of Energy

The Sun radiates energy in the form of heat and light. We utilize these
forms of energy either directly or indirectly, after conversion into some
other forms. Utilization of solar energy in various ways is as
represented. Besides the primary role of the Sun's energy, it is now
believed that elements have been formed from hydrogen by the process
of nuclear fusion occurring in stars, similar to the sun. In that sense,
everything that we see around us, including ourselves and the uranium
we use as nuclear fuel, are products of the star-dust. Hence, stars in
general and our sun in particular, are the ultimate source of energy.

Calorific Value of Foods and Fuels

Nutritional value of foods, and the usefulness of fuels is determined

by the heat (energy) they produce on heating. The energy released by
the combustion of foods or fuels is usually compared in terms of their
combustion energy per gram. It is known as calorific value. It is defined
as the amount of heat produced in calories (or joules) when one gram of
a substance (food or fuel) is completely burnt.

Conservation of Energy Sources

Fossil fuels are the major source of energy on Earth. With the
development of technology, the worlds consumption of the concentrated
sources of energy like coal, petroleum and natural gas and uranium has
increased. Very slow physical and chemical processes spread over many
thousand years form these fuels. It is estimated that the use of non-
renewable reserves of energy fuels at a faster rate than at which
they are getting formed will deplete the fossil fuels within 30 - 40
years. Their fast depletion in such circumstances has come to be known
as 'the energy crisis'.

Pollution Due to the Burning of Fossil Fuels (Additional)

Contamination of air with harmful toxic gases, smoke and particulate

matter (e.g., dust etc.) is called air pollution. The substances that
cause pollution are called pollutants. Combustion of fossil fuels is one
of the main causes of pollution of the atmosphere in our cities and towns.
Fossil fuels are mainly used in the generation of electricity (thermal
power plants), and as fuel for transport.