Discuss with concrete example the factors and irreversibilities which could occasion

the incomplete conversion of a limiting reactant in a chemical reaction.

1. THE COLLISION THEORY

The collision theory was developed to describe reactions in the gas phase. It is known
from experience that most reactions go faster when the temperature is raised. Reaction
happens twice as fast at 30 °C than at 20 °C. As the temperature rises the average energy of
the molecules increases and the rate of reaction increases. It seems logical to deduce that
the two observations are connected: molecules need energy in order to react. The collision
theory proposes that molecules must first collide in order to react. If they collide at low
speed - and low energy - they bounce apart again without reacting. If they collide at
higher speed, with more than a certain energy, then bonds can be broken and new bonds
made. The minimum energy which colliding molecules need in order to react is called the
activation energy of the reaction, EA.

Figure 1 shows activation energy as a barrier between the reactants and the products. A
graph of this kind, showing the progress of the reaction is called a reaction profile. The
activation energy EA is the difference between the potential energy of the reactants and the
potential energy at the height of the barrier. As the reactant molecules approach, their
potential energy (energy due to position) increases. It reaches a maximum as the molecules
collide and bonds are distorted. It decreases as the atoms rearrange to form molecules of
products the product molecules separate. If the reactant molecules have energy less EA, they
cannot pass over the barrier; they roll down the left-hand side again and separate. If they have
energy EA or greater, they pass over the top of the barrier and roll down the right-hand side to
form the products.

Figure 1:

EA = activation energy

1|Page
The energy of colliding molecules:

1. The colliding molecules have kinetic energy Jess than EA. They bounce apart without
reacting

E<EA

2. The colliding molecules have kinetic energy equal to (or greater than) EA. They react to
form the products.

 Minimum amount of energy (Ea)

Molecules which have energy lower then Ea will collide and bounce back. There will be
no reaction.

 Proper orientation
If orientation is wrong, the molecules will bounce back. But if correctly oriented, the
reaction may ‘’occur’’.

2|Page
 2. FREE ENERGY (ΔG)

There is a condition for changes to proceed spontaneously - to happen without external

help. The condition is that the change involves a decrease in free energy ΔG. The value of
the standard free energy, ΔGᶿ is given by:

ΔGᶿ = ΔHᶿ - T ΔSᶿ

Where ΔGᶿ = Change in standard free energy

ΔSᶿ= Change in standard entropy

ΔHᶿ= Change in standard enthalpy

 If ΔGᶿ for a reaction is negative, we say that the reactants are thermodynamically
unstable with respect to the reaction: the reaction can occur.
 If ΔGᶿ for a reaction is positive, we say that the reactants are thermodynamically
stable with respect to the reaction: the reaction cannot occur.
We say the reaction is under thermodynamic control. Thermodynamic instability (ΔGᶿ
negative) is not the only condition necessary for a change to occur. The molecules must
possess enough energy to climb the energy barrier between reactants and products (Figure
1). For example methane is a fuel; the oxidation of methane is thermodynamically
unstable with respect to the products of oxidation:
CH4 (g) + 2O2 (g) CO2 (g) + 2H20(l) ΔGᶿ = -580 kJmol-1
Yet oxidation does not proceed at room temperature because at room temperature very,
very few molecules of methane and oxygen collide with energy equal to the activation
energy. As a result, the reaction takes place so slowly as to be unobservable, and we say
the reaction is under kinetic control. At higher temperatures the fraction of molecules
which collide with enough energy to react increases and the reaction takes place more
rapidly.

3|Page
 3. ENTROPY
Entropy is a macroscopic property of a system that is a measure of the microscopic disorder
within the system. It is an important part of the second law of thermodynamics. Thermodynamic
systems are made up of microscopic objects, e.g. atoms or molecules, which "carry" energy.
According to the second law of thermodynamics, the thermodynamic entropy is a measure of the
amount of energy which does no work during energy conversions. In applied thermodynamics, as
a matter of convention, entropy is measured in units of energy per temperature (SI: joules per
Kelvin). If thermodynamic systems are described using thermal energy instead of temperature,
then entropy is just a number by which the thermal energy in the system is multiplied. The
resulting energy is an energy for which no information is available which would be required to
convert the energy in technical systems from one form into another form.
The concept of entropy may even be applied to human beings. Efficient people are those who
lead low entropy lives. Its takes minimum energy for them to find anything they need.
Disorganised people however lead high entropy lives and are highly inefficient. Its takes them
hours to find something they need in a hurry instead of seconds.
The Clausius Inequality is expresses as:

‘’ The cyclic integral of is always less than or equal to zero’’, that is, .

Entropy is equally essential in predicting the extent of complex chemical reactions, i.e. whether a
process will go as written or proceed in the opposite direction. For such applications, ΔS must be
incorporated in an expression that includes both the system and its surroundings, ΔStotal=
ΔSsurroundings + ΔS system.
> 0 Irreversible processes

ΔStotal =0 Reversible processes

< 0 impossible processes

4|Page
REFERENCES

E.N Ramsden. 2000. A-level Chemistry. 4th ed. Cheltenham: Nelson Thornes 287-295

S.K. Som and A. Datta .Thermodynamic irreversibilities and exergy balance in combustion
processes. Progress in Energy and Combustion Science, Volume 34, Issue 3, June 2008, Pages
351-376

W. R. Dunbar and N. Lior. Combustion; Energy & Fuels; Thermodynamics; Combustion

Science and Technology, Volume 103, Issue 1 - 6 1994 , pages 41 - 61

A. Datta and S. K. Som. Thermodynamic Irreversibilities and Second Law Analysis in a Spray
Combustion Process.  Combustion Science and Technology, Volume 142, Issue 1 - 6 July 1999 ,
pages 29 – 54

http://www.engineeringarchives.com/les_thermo_irreversibleprocess.html

Lucia U. 2009, Irreversibility, entropy and incomplete information, Physica A: Statistical

Mechanics and its Applications, 388, pages 4025-4033

Grazzini G. and Lucia U. 1997. Global analysis of dissipations due to irreversibility,Revue

Gènèrale de Thermique, 36, pages 605-609

John D and Johnson, Kenneth, J et all (1998). Physics, 4th edition. John Wiley and Sons, Inc

Y. A. Çengel and M. A. Boles. (2006) Thermodynamics: An Engineering Approach, 5th ed,

McGraw-Hill. Chapter 7: Entropy, pages 331-350

5|Page