EXPERIMENT NO.

1: CALORIMETRY
Theoretical Discussion:
Generally the reactions taking place in the chemical sciences are breaking and making of chemical bonds.
This is accompanied by some heat effects. Formation of chemical bonds releases energy in the form of
heat and hence known as an exothermic reaction. The reaction which is accompanied absorption of heat is
known as endothermic reaction. Calorimetry is a scientific term dealing with the changes in energy of the
system by measuring the heat exchanged with the surroundings. In a broader sense it is defined to
determine the heat released or absorbed in a chemical reaction. A calorimeter is a device designed to
measure heat of reaction or physical changes and heat capacity. The device can be sophisticated and
expensive or simple and cheap.
 
A calorimeter consists of two vessels, outer vessel and an inner vessel. The space between these vessels
acts as a heat insulator and hence there is very little heat exchange in between the inner and outer vessels.
Thermometer measures the temperature of the liquid in the inner vessel. The stirrer functions in such a
way to stir the liquid to distribute the heat in the entire vessel. The fibre rings in the calorimeter helps to
hold the inner vessel hanging in the center of the outer vessel. It also has an insulating cover or lid with
holes for attaching the stirring rod and thermometer.

A calorimeter contains water or other substances with known heat capacity. The heat, denoted as
released by a reaction or process is absorbed by the calorimeter and any substances in the calorimeter. If
the only other substance in the calorimeter is water, the following energy balance exists:

 = The heat flow for the calorimeter.

   = The heat flow for the water.

 
 
The individual heat flow rate can be directly related to the heat capacity and temperature change for the
substance. This can be denoted by the equation
 

 = The heat capacity of the calorimeter.

    = The heat capacity of the water.

 
 

Since the water and calorimeter are in thermal equilibrium they exhibit same value.
The heat capacity, which is defined as the amount of heat required to raise the temperature of a given

quantity of a substance by one degree Celsius,( unit is J/  0 C) of the entire system, denoted by ,is
represented as the sum of the heat capacities for the individual components involved in the reaction
process.
 

 
Note: Since the calorimeter is insulated there is no heat exchange with the surroundings. This can be
shown as:
 

 
 
It is noted that the calorimeter exists as a fixed unit and thus its heat capacity is also thought to be having
a fixed value. In some cases, where the amount of substance is varying, an intensive measurement of heat
capacity, specific heat capacity is employed to study the reactions. Specific heat capacity is defined as the
heat required for raising unit mass of substance by one degree of temperature. It has the units J/g 0 C.

The relation between the heat capacity and specific heat of a substance is denoted as  .

= mass of substance in grams.

= Heat capacity.

= specific heat.
 
 
The magnitude of these heat effects depends on the following parameters:
1.      Pressure.
2.      Temperature.
3.      Physical state of the reactants and the products.
4.      Amount of substance involved in the reaction.

In a reaction the quantity of heat that raises the temperature of some substance by some amount, the same
quantity of heat can simultaneously raise the same temperature of a certain mass of water. The mass of
water is then termed as water equivalent.
 
Principle:
 
The heat change associated with a chemical reaction can be studied with the help of the calorimetric
techniques. In a specific reaction the quantity of heat that raises the temperature of some substance by
some amount, the same quantity of heat can simultaneously raise the same temperature of a certain mass
of water assuming the specific heat of water to be 1 calorie per gram. The mass of water is then termed as
water equivalent.
 
Where,

 = The initial temperature of water and calorimeter.

 = The initial temperature of cold water.

 = The final temperature of the mixture.

 = The water equivalent of calorimeter.