Internal energy and comparison between ∆H and ∆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.

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.

The first law of thermodynamics states that “The total energy of an isolated thermodynamic

system is constant”.

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 Internal energy and comparison between ∆H and ∆E

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.

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.

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 Internal energy and comparison between ∆H and ∆E

Mathematically derivation of enthalpy: From the 1st law of thermodynamic equation, 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

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.

the enthalpy changes for a process equal to the heat exchange in a system at constant

pressure qp=∆H

∆H=∆E+P∆V

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 Internal energy and comparison between ∆H and ∆E

THE COMPARISON BETWEEN ∆H AND ∆E

The following are 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

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,

N2(g) +O2(g) →NO2(g)

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 H 2, 3

mole of gas yield 2 mole.

2H2(g)+O2(g) →2H2O(g)

In this reaction ∆H=-483.6kjmole-1 and the P∆V=-2.5kjmole-1, so from equation we gat

∆E=∆H-P∆V=-483.6+(-2.5) =-481.1 kjmole-1

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 Internal energy and comparison between ∆H and ∆E

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.

REFERENCES

Physical chemistry fifth edition by P.W. Atkins

Chemistry Zumdahl fifth edition by S. Zumdahl & Susan A. Zumdahl

Essentials of physical chemistry by Arun Bahl &B.S. Bahl & G.D. Tuli

Chemistry part 1 textbook for class XI

Chemistry tenth edition by Raymond Chang