Thermochemistry is the study of the heat released or absorbed as a result of chemical

processes. The chemical processes may be either physical changes such as

vaporization of liquid or chemical reactions such as combustion of wax to form carbon
dioxide and water.

Thermochemistry deals with heat flow in the chemical reactions. Heat is a form of
energy. It is difference from temperature. Temperature is a measure of how much heat
can flow. Temperature does not measure the heat itself. Heat is measured in Joules. It
is energy that flows or transferred due to a temperature difference.

Chemical reactions occur when two or more reactants are brought together under the
right conditions. Reactions that release heat are called exothermic while those that
absorb heat are termed endothermic. For example, when fuel burn in excess oxygen,
results the formation of carbon dioxide and water and the release of large amount of
heat and light as energy. It is an example of exothermic reaction. On the other hand,
reaction of hydrochloric acid and Sodium hydrogen carbonate absorb heat to form
Sodium carbonate, carbon dioxide and water. In order to describe this, we describe the
reaction as the system. Everything else is the surroundings. When we talk about the
heat transferred, we always describe it from the system’s point of view.

Exothermic Endothermic

SYSTEM SYSTEM
SURROUNDINGS SURROUNDINGS

Fuel burn in excess oxygen  CO2 + H2O 2NaHCO3  NaCO3 +CO2 +H2O

Heat flows from the system into the surrounding. Heat flows from the surroundings
the reaction system
When heat flows from the system into the surroundings, the system loses heat. The
temperature of the surroundings will increase in this situation. This reaction would be
described as being exothermic. If the heat flows from the surroundings into the system,
it has a positive value. The temperature of the surroundings will decrease in this
situation. This reaction would be described as being endothermic.

The total heat absorbed or liberated in a chemical reaction is called heat of reaction. If
the heat of reaction is measured under constants pressure conditions, the heat of
reaction is same as the enthalpy change ∆H, of the reaction. We cannot measure the
absolute value of enthalpy or heat, but we can measure the change in enthalpy. In
exothermic reaction, the enthalpy change of the reaction, ∆H has negative value
because the heat content of the products is less than the heat content of the reactants.
If the reaction is endothermic, heat is absorbed and enthalpy change ∆H, has a positive
value because the heat content of the products is higher than the heat content of the
reactants.

Reactants Reactants

∆H < 0 ∆H > 0

Exothermic Endothermic

Products Products

If a reaction is carried out in series of steps, the enthalpy for the reaction is sum of the
enthalpies of all the steps. This is known as Hess’s law. Hess’s law is very important
especially for determining the values of ∆H for reactions that are difficult to carry out
experimentally. For example, the reaction between carbon and oxygen:
 C(s) + O2(g)

C(s) + 1/2O2(g)  CO(g)

∆H2 = -111 kJ mol-1

Route 1
Route 2

∆H1 = -393 kJ mol-1

CO(g) + 1/2O2(g)  CO2(g)

∆H3 = -282 kJ mol-

1

CO2(g)

∆H for route 1 = total of ∆H of route 2. Regardless of whether the reaction takes place in
one step or two steps when carbon is converted to carbon dioxide, the total heat
liberated is the same.

The standard conditions for measuring enthalpies are:

i) Temperature of 25 0C (298 K)
ii) Pressure of 1 atm (or 101 kPa)
iii) Solutions having a concentration of 1.0 mol dm-3

We can define the standard enthalpy changes of reaction as the amount of heat
liberated or absorbed when the quantities of reactants (in moles) react together.

There are many enthalpy changes in chemical processes such as enthalpy of formation,
enthalpy of combustion, enthalpy of neutralization and so on.