THERMODYNAMIC

INTENNAL ENERGY AND COMPARISON BETWEEN

ENTHALPY ∆H AND INTERNAL ENERGY ∆E
INTERNAL ENERGY
• Internal energy is the sum total of all kinetic and potential
energy within the system.
It denoted as U or E. The internal energy of the system has two
components according to definition, these are kinetic energy
and potential energy.
• Kinetic energy component K.E consist of various types of
the molecular motion and the movement of electron within
the molecule.
• Potential energy component P.E determined by attraction
interaction between electron and nuclei and by repulsion
interaction between electron and nuclei in individual
molecules
 Cont…
It is impossible to measure all these contributions accurately, so
we cannot calculate the total energy of the system with any
certainty. Changes in energy, on other hand, can be determined
experimentally.
Changes in the value of e and its relationship to other
thermodynamic quantities are therefore used.
E is a state function, as a specific system has a specific value at
any given temperature and pressure. Thermodynamics therefore
only deals with changes in E, denoted as ∆E.
 Cont…
The first law of thermodynamics states that “the total
energy of an isolated thermodynamic system is constant”.
The law is often referred to as the conservation of
energy, and implies the popular interpretation of the first
law, namely that “energy cannot be created or
destroyed”. In other words, energy may be lost from a
system in only two ways, either as work or as heat.
Cont...
As a result of this, it is possible to describe a change in the total
internal energy as the sum of energy lost or gained as work and heat,
since ∆E cannot change in any other way. Thus, for a finite change:
∆E=q + w
Where
q is the heat supplied to the system
w is the work done on the system.
Internal energy ∆E is the sum of heat exchange between the system
and the surrounding and the work done on or by the system
 ENTHALPY
• The enthalpy change is the heat exchanged by the system under conditions of constant
pressure. For a reaction involving a perfect gas, in which heat is generated or taken up, ∆H
is related to ∆E by:
∆H=∆E+P∆V
• Enthalpy is a state function because it depends only in the initial and final state or
internal energy, pressure and volume are state function.
Mathematically: Consider the process carried out at constant P where the only work allowed
is pressure-volume work w=-P∆V
∆E=q+w
∆E=qp-P∆V
qp=∆E+P∆V
Cont…
Where
the subscript “p” denoted as constant pressure condition. We
introduce a new thermodynamic function of a system called enthalpy
(H). In a chemical reaction, the enthalpy change is equal to the
difference in enthalpy between the reactants and products:
∆H(Reaction)=ΣH(Products)
−ΣH(Reactants).
The heat exchanged by a system at constant pressure is equal to the
sum of the internal energy change of that system and the work done
by the system in expanding against the constant external pressure.
Cont…

The enthalpy changes for a process equal to the heat

exchange in a system at constant pressure qp=∆H
∆H=∆E+P∆V
 THE COMPARISON BETWEEN ∆H AND ∆E
i. Reaction that do not involve gases. Gases do not
appear in many reactions (precipitation, many acid-
base and many redox reaction)
For example,
2KOH (aq) +H2SO4(aq)→K2SO4(aq)+H2O(l)
Since liquids and solids undergo very small volume
changes, ∆V≈0, so P∆V≈0 and ∆H=∆E
Cont…
ii. Reaction in which the amount (mole) of gas
does not changes. When the total amount of
gaseous reactant equal to the amount of
gaseous product, ∆V=0, so P∆V=0 and
∆E=∆H.
For example,
N2g +O2g →NO2g
Cont…
iii. Reaction in which the amount of gases does change.in this cases,
P∆V≠0. however, qp is usually much larger than P∆V.
foresentences, in the combustion OF H2, 3mole of gas yield 2mole.
2H2g+O2g →2H2Og
In this reaction ∆H=-483.6kjmole-1 and the P∆V=-2.5kjmole-1, so from
equation we get
∆E=∆H-P∆V=-483.6+(-2.5) =-481.1 kjmole-1
Obviously most of ∆E occurs as interfere, so ∆H≈∆E. The key point to
realize from three cases is that for many reaction ∆H is equals, or is very
close to ∆E. 
END