University Of Mauritius

BEng (Hons.) Chemical and Environmental

Engineering - E400

Chemistry &Basic
Chemical Engineering
CHE 1001Y (3)

Assignment 3:
Explain the Hesss Law while calculating heat of reaction.
Tutor: Dr D. Surroop
Name: Fanilo Antra Tia Razafindralambo
Index number: 1312636

TABLE OF CONTENTS
2. INTRODUCTION..............................................................................................3
3. APPLICATION OF HESSS LAW....................................................................3
Evaluating Enthalpy changes...................................................................................................3
Calculating Heat of Reaction.....................................................................................................3
Finding Lattice Energy..............................................................................................................3

4. CONCLUSIONS................................................................................................3
5. REFERENCES...................................................................................................3

1. INTRODUCTION
Germain Henri Hess (1802 - 1850) is important primarily for his thermochemical studies. Hess'
Law states that the heat evolved or absorbed in a chemical process is the same whether the
process takes place in one or in several steps. This is also known as the law of constant heat
summation. According to this law, it is permissible to write stoichiometric equations, together
with the enthalpy changes, and to treat them as mathematical equations, thereby obtaining
thermochemically valid result.

2. APPLICATION OF HESSS LAW

Few reactions occur on a simple manner, following a simple chemical equation, with the result
that the enthalpy changes corresponding to a simple chemical equation cannot be measured
directly. For many of these the enthalpy changes can be calculated from the values for other
reactions by making use of Hesss Law. To illustrate Hess's law, the simplified thermal equations
and the energy level diagrams are shown below:
For example, suppose that a substance A reacts with B according to the equation
1.

2.

3.

A+BX
DH1= -10kJ mol-1
Suppose that X reacts with an additional molecule of A to give another product Y:
A+XY
DH2= -20 kJ mol-1
Then according to Hesss Law, it is permissible to add these two equations and obtain:
2A + B Y
DH3= DH1 + DH2 = -30 kJ mol-1

DHn= Enthalpy change for reaction n.

The law follows at once from the Principle of conservation of Energy and from the fact that
enthalpy is a state function. Thus, if reactions 1 and 2 occur, there is a net evolution of 30 kJ,
when 1 mole of Y is produced. In principle we could reconvert Y into 2A + B by the reverse
of reaction 3. If the heat required to do this were different from 30 kJ, we should have
obtained the starting materials with a net gain or loss of heat, and this would violate the
principle of conservation of Energy.

Evaluating Enthalpy changes

The majority of reactions and processes that we encounter will be conducted at constant
pressure, Enthalpy describes the energy changes at constant pressure, represented with the
symbol H. Although we are interested we are interested in enthalpy changes during chemical
processes, the knowledge of how much heat a reaction needs-or how much it evolves-can be
much more significant (at a larger scale).
As a straightforward example, let us consider the oxidation of carbon monoxide (at room
conditions). We could conduct the reaction directly and measure DH.
(1)

CO(g) + O2(g) CO2(g)

DH1= -283.0 kJ mol-1
Alternatively, the reaction of graphite with oxygen could be carried out under two
different stoichiometries:

(2)

C(graph.) + O2(g) CO(g)

C(graph.) + O2(g) CO2(g)

(3)

DH2= -110.5 kJ mol-1

DH3= -393.5 kJ mol-1

Hesss Law allows us to treat the chemical equations and the enthalpy changes in the same way
as algebraic equations. Subtracting (2) from (3) gives the equivalent of (1) and leads to the same
result for DH.
[C(graph.) + O2(g)] - [C(graph.) + O2(g)] [CO2(g)] [CO(g)]
CO(g) + O2(g) CO2(g)
DH = (-393.5) - (-110.5)= -283.0 kJ mol-1
DH3 = DH1 + DH2

Or

Another method of displaying these enthalpy changes and performing the calculations is to use
graphical methods of the energy levels. This method has a number of important applications in
chemistry. The most obvious consequences of Hesss law (and the First Law of
Thermodynamics) is that, for a reaction, DHforward= -DHreverse. A more important use is that, the
calculation of enthalpy changes for reactions which would be experimentally difficult or even
impossible to carry out in practice,
Calculating Heat of Reaction
The enthalpy of reaction is sometime called heat of reaction, especially for combustion reactions.
It is the heat evolved when a combustion reaction occurs.
As an example, let us consider the enthalpy change when methane is formed from both its
elements, both reactants and product being in their standard states. This is called the Standard
enthalpy of Formation and written DHf0.
C(s) + 2H2(g) CH4(g)
The standard state of each element is the most stable form at 1 atm and the temperature specified
(usually 298 K).
The direct reaction cannot conveniently be carried out, it is relatively easy to measure the
enthalpy of combustion of methane in an apparatus called a flame calorimeter.
As DH = (q) (heat), when methane is burnt with oxygen the heat produced gives the enthalpy of
combustion directly (Heat of reaction).
CH4(g) + O2(g) CO2(g) + 2H2O(l);

DH = - 890.4 kJ mol-1

C(s) + O2(g) CO2(g);

DH= - 393.5 kJ mol-1

H2(g) + O2(g) 2H2O(l);

DH= -571.6 kJ mol-1

2O2
Combining the enthalpy of combustion of+ methane
with that of carbon and hydrogen enables us
to apply Hesss law to the problem. We can see that D Hf0 =CH
DH4(g)
1 DH2, in the figure below.
DH

DHf0

CO2(g) + 2H2O(l)

+ 2O2
DH1

C(s) + 2H2(g)

DH1 is the enthalpy of combustion of one molecule of carbon and two moles of hydrogen.
Therefore
DHf0(CH4) = [- 393.5 571.6 + 890.4] kJ mol-1
=- 74.7 kJ mol-1
Note: If reverse chemical reaction is considered, the enthalpy change reverses its sign.

Finding Lattice Energy

Many substances are composed of ions. These exist in a three-dimensional array called Lattice.
The Lattice Energy is a measure of the energetic stability of the crystal with respect to the ions
from which it is made when they are present in gaseous state.
The procedure of finding lattice energy using Hesss law is called Born-Haber cycle. This
method makes use of energy level diagrams for better understanding.
We choose Potassium fluoride, KF, as an example illustrated below

Energy/ kJ mol-1

K+(g) + F-(g)

-600
Atomisation of F
K

-500

Electron
affinity of
fluorine

+ F2 (g)

Ionisation
energy of
potassium

-400

-300

+
(g)

K+(g) + F-(g)

K+(g) + F-(g)

-200
K(g) + F2 (g)
-100
Atomisation of K
-0

K(s) + F2 (g)

Lattice
energy

- -100

- -200

K(s) + F2 (g)

Heat of
formation

Lattice
energy

Heat of formation

- -300

- -400

- -500
KF(s)

KF(s)
- -600
(a)

(b)

This method simplifies significantly the calculation of lattice energy. The principle is easy,
positive enthalpy changes move upwards while negative value downwards. Knowing each value
of enthalpy from tables, we can find the value of lattice energy with minimal effort.
Or simply by using
- (lattice energy) = - (heat of formation)
+heats of atomization
+ionization energies
+electron affinities

3. CONCLUSIONS
We can, therefore, conclude that Hesss law is an important consideration in thermochemistry,
whether in organic or non-organic. It can be used to find (a) The heat of reaction (b) The
Enthalpy of reaction (c) Lattice energy and even more.

4. REFERENCES
1) Graham Hill, J. H., 1995. Chemistry in Context. 4th ed. Surrey: Thomas Nelson & Sons
Ltd.
2) Keith Laidler, J. M., 1995. Physical Chemistry. 2nd ed. New Jersey: Houghton Mifflin
Company.
3) Matthews, P., 1997. Advanced Chemistry. Cambridge: Cambridge University Press.
4) Price, G., 1998. Thermodynamics of Chemical Processes. New York: Oxford University
Press.
5) Smith, B., 2004. Basic Chemical Thermodynamics. 5th ed. London: Imperial College
Press.