Prepared By Dr.

Rupa Dey
rdschemistry@gmail.com
Mob No. +918638155244
Concept of Heat Energy in Thermodynamics

INTERNAL ENERGY In terms of thermodynamics, the total energy possessed by any kind of system
(open, closed or isolated) is known as Internal Energy (designated by U).
System performs work with the cost of internal energy. For example: electrons revolve around the
nucleus due to nuclear force of attraction with the expense of nuclear energy.

∆U = q + w

It has been observed that not the whole amount of internal energy is used to do work (w). A portion of
energy is wasted or transferred to the surrounding which is represented by q.
Any mechanical work (w=PV) like expansion or contraction of gases at constant P may be
represented by

w = ± P∆V

We know that energy can neither be created nor be destroyed instead it transforms one to another form.
For example: internal energy converts to work or exchanged as heat to another system or surrounding.
This is known as law of conservation of energy.
The law of conservation of energy is another statement of First law of thermodynamics. It also
states that the energy can’t be completely converted into work during chemical or physical changes. A
portion of energy is wasted to the surrounding or another system. According to first law of
thermodynamics,
∆U = q ± P∆V

Where, positive sign signifies work done on the system by the surrounding and negative sign signifies
work done by the system.

At constant volume, ∆V = 0, ∆U = qv

ENTHALPY Let us consider a condition under which no work is done by the system on its surrounding
or vice versa. For example: a chemical reaction taking place in a beaker. Under this particular condition,
heat absorbed or eliminated by the reaction mixture is equal to the change in internal energy provided
there is no appreciable change in the volume so that ∆V = 0 i.e. ∆(PV) or w = 0.
Practically, reactions can’t be run at constant volume in an open flask or beaker since some
amount of gas can either leave or enter the reaction container. Moreover, most of the chemical reactions
and physical changes occur under constant pressure (i.e. atmospheric pressure).
The change in heat energy of a system during a chemical or physical change at constant pressure is
known as enthalpy (designated by H). For example: the energy change involved in melting of ice is called
enthalpy of fusion. Thus enthalpy of a system may be expressed as

H = U + PV
It is not possible to determine the enthalpy of the system directly but it is possible to determine the change
in enthalpy i.e. ∆H. Also, the reaction runs at constant pressure, therefore, the mathematical expression
for ∆H would be
∆H = ∆U + P∆V

Substituting the expression of ∆U from first law of thermodynamics in the above expression considering
work done by the system (e.g. expansion of the reacting gas during the reaction), we have

∆H = qp - P∆V + P∆V = qp

SUMMARY The relationship between the change in the internal energy (∆U) and enthalpy (∆H) during
a chemical reaction can be summarized as follows.

The heat exchanged during a reaction at constant volume is equal to the change in the internal
energy of the system. ∆U = qv

The heat exchanged in a reaction running at constant pressure is equal to the change in the
enthalpy of the system. ∆H = qp

Relation between internal energy & enthalpy of a chemical reaction ∆H = ∆U + (PV)

The difference between U and H for the system is small for reactions that involve only liquids
and solids because there is little change in the volume of the system during the reaction. The
difference is relatively large, however, for reactions that involve gases, if there is a change in the
number of moles of gas in the course of the reaction.

To be continued