Chemical Process Technology

 Qualitative concepts of First and Second Law

of thermodynamics
 Le Chatelier Principle: A principle stating that if
a constraint (such as a change in pressure,
temperature, or concentration of a reactant) is
applied to a system in equilibrium, the
equilibrium will shift so as to tend to counteract
the effect of the constraint
 Examples
 Application
Qualitative Concepts of I and II law of
Thermodynamics
 Le Chatelier Principle
 A reaction always shifts in such a manner as to
restore the initial conditions
 the position of equilibrium moves in such a way as
to tend to undo the change that you have made
 Suppose you have an equilibrium established between
four substances A, B, C and D..

 if you decrease the concentration of C, for example,

the position of equilibrium will move to the right to
increase the concentration again.
Qualitative Concepts of I and II law of
Thermodynamics
 Explanation in terms of the constancy of the
equilibrium constant
 The equilibrium constant, Kc for this reaction looks like
this:

 If you decrease the concentration of C, the top of the

Kc expression gets smaller.
 That would change the value of Kc. In order for that not
to happen, the concentrations of C and D will have to
increase again, and those of A and B must decrease.

 The position of equilibrium moves - not because

Le Chatelier says it must - but because of the need
to keep a constant value for the equilibrium
constant
Qualitative Concepts of I and II law of
Thermodynamics
 If you decrease the concentration of C:
Qualitative Concepts of I and II law of
Thermodynamics
 Changing pressure
 The position of equilibrium may be changed if you
change the pressure. According to Le Chatelier's
Principle, the position of equilibrium moves in such a
way as to tend to undo the change that you have
made.
 That means that if you increase the pressure, the
position of equilibrium will move in such a way as
to decrease the pressure again - if that is possible.
 It can do this by favoring the reaction which produces
the fewer molecules
 If there are the same number of molecules on each
side of the equation, then a change of pressure
makes no difference to the position of equilibrium
Qualitative Concepts of I and II law of
Thermodynamics
 Suppose you have an equilibrium established between four substances
A, B, C and D

 Replacing all the partial pressure terms by mole fractions and total
pressure gives you this

 When No. of moles of reactants are higher than no. of moles of product
molecules, Increase in Pressure favors the reaction
Qualitative Concepts of I and II law of
Thermodynamics
 Changing Temperature
 Equilibrium constants are changed if you change the
temperature of the system. Kc or Kp are constant at constant
temperature, but they vary as the temperature changes.
 Look at the equilibrium involving hydrogen, iodine and
hydrogen iodide:

 The Kp expression is:

 Two values for Kp are: Temperature Kp

500 K 160
700 K 54
Qualitative Concepts of I and II law of
Thermodynamics
 You can see that as the temperature increases, the
value of Kp falls.
 The position of equilibrium also changes if you
change the temperature. According to Le Chatelier's
Principle, the position of equilibrium moves in such a
way as to tend to undo the change that you have
made.

 If you increase the temperature, the position of

equilibrium will move in such a way as to reduce
the temperature again

 It will do that by favoring the reaction which

absorbs heat
Qualitative Concepts of I and II law of
Thermodynamics
 In the equilibrium we've just looked at, that will be the back
reaction because the forward reaction is exothermic.

 So, according to Le Chatelier's Principle the position of

equilibrium will move to the left.

 Less hydrogen iodide will be formed, and the equilibrium

mixture will contain more unreacted hydrogen and iodine.

 That is entirely consistent with a fall in the value of the

equilibrium constant.
Qualitative Concepts of I and II law of
Thermodynamics
 If you increase the temperature of an
Exothermic Reaction
Qualitative Concepts of I and II law of
Thermodynamics
 Suppose the system is in equilibrium at 300°C, and
you increase the temperature to 500°C.

 How can the reaction counteract the change you

have made? How can it cool itself down again?
 To cool down, it needs to absorb the extra heat that
you have just put in. In the case we are looking at,
the back reaction absorbs heat.
 The position of equilibrium therefore moves to the
left. The new equilibrium mixture contains more A
and B, and less C and D.
Qualitative Concepts of I and II law of
Thermodynamics

 Increasing the temperature of a system in

dynamic equilibrium favours the endothermic
reaction. The system counteracts the change you
have made by absorbing the extra heat.

 Decreasing the temperature of a system in

dynamic equilibrium favours the exothermic
reaction. The system counteracts the change you
have made by producing more heat.
 Applications
 The preferred condition for any reaction is
ambient condition.
 For any reaction to take place
 Kinetics and thermodynamics should be
favorable
 If for a reaction
 Thermodynamics Favorable
 Kinetics Unfavorable
 Increase the temperature such that rate of
reaction (kinetics) favorable
 Applications
 If kinetics not favorable at any temperature
 Need to find the suitable catalyst

 If thermodynamics of any reaction is not favorable

 It is called unfamiliar or unfavorable reaction

 Example
 NaCl + H2O NaOH
 Both reactants are readily available but It is an
unfavorable reaction
 So electrolysis is used to break the energy barrier and
to carry out the reaction
 Qualitative Concepts of I and II law of
Thermodynamics
 Graphical Illustration of Temperature effects

Exothermic Endothermic

Fraction
Converted

Adiabatic
Temperature Temperature
Intermediate
Isothermal
 Qualitative Concepts of I and II law of
Thermodynamics
 Graphical Illustration of Temperature effects

Exothermic

Fraction
Converted

Temperature
 Applications
 Coupling of Reactions
 FeO Fe + ½ O2 Unfavorable
 C + ½ O2 CO Highly Fav
 FeO + C Fe + CO

 N2 + 3H2 2NH3 can be made

favorable by increasing pressure very high
 C4H10 C4H8 + H2 can be made
favorable by decreasing pressure
 Applications
 NaCl + CaCO3 Na2CO3 + CaCl2
 Above reaction is Unfavorable
 Even with Electrolysis or Coupling, it is unfavorable
 Solvay Process
 CaCO3 CaO + CO2
 CaO + H2O Ca(OH)2
 2NH3 + 2H2O 2NH4OH
 2NH4OH + CO2 + 2NaCl 2NH4Cl + 2NaHCO3
 2NaHCO3 Na2CO3 + CO2 + H2O
 Ca(OH)2 + 2NH4Cl 2NH3 + CaCl2 + H2O
 Applications
 Process Design using T effect of Rxn Kinetics
 2CH4 C2H2 + 3H2 ΔH = +ve
 Equilibirium Conversion diagram

ye

Fractional
Conversion

Temperature
T0 T2
Thank You
Qualitative Concepts of I and II law of
Thermodynamics
 Another Example