Chemical Engineering

Thermodynamics-II

Chemical-Reaction Equilibrium

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 Outline
• To define what is extent of reaction and relate it to the
mole fraction(composition).
• To derive the equilibrium criteria for chemical reaction.
• Using equilibrium criteria to derive equilibrium
constant(K) and able to calculate K.
• To relate K to mole fraction and able to calculate the
equilibrium conversion for gas phase reaction
• Analyze the effect of T and P on K and equilibrium
composition endothermic and exothermic reactions.
• Phase rule for reacting systems
 Introduction
• Previously we studied the equilibrium
behavior of non-reacting systems.
• Here, we examine equilibrium when there are
reactions present.

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 Chemical Reaction
• Chemical reaction is the heart of chemical processes
• Take place in a reactor.
• Main requirement: Design of reactors
• A value-added process.
– Transform raw materials into products of greater value
– Economic or Gross profit must be positive. i.e. Main
products have a higher price than the raw
materials(reactants).
– Gross profit is based on price of reactants and products ,
excluding the equipment and operating costs.
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• Study of how rapidly reactions proceed - rate of reaction
• Details of process from reactants to products - mechanism

• Thermodynamics determines the direction in which reactions

proceed spontaneously and equilibrium conditions, but not the
rate at which equilibrium is reached.

• For a complete picture of a chemical reaction need information

on both the thermodynamics and kinetics of a reaction.
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 Study of chemical reaction
• Reaction kinetics
– Study of rates of reaction
• i.e., How fast is the reaction?
• Thermodynamics
– Determination of maximum possible conversion
or equilibrium conversion in a chemical reaction.
– Evaluation of equilibrium constant

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CH4003 Lecture Notes 6 (Erzeng Xue)

Chemical Reaction - The Rate

• What is reaction rate?
– The rate of a chemical reaction refers to the reactant consumption or the product
formation per unit time.
– It is a quantitative measure of how fast a reaction can proceed.
• some reactions proceed very fast, other reactions may proceed very slow
• In thermodynamics where only the starting and ending states are characterised
• Why study the reaction rate?
– in industry we need to know how long do we need to produce a certain product
• the size and type of a reactor
– we also need to know what is the best reaction conditions we should apply
• using proper conditions such as T, P, concentration etc. to speed up the desired reaction
• to suppress undesired side reactions
• when apply a catalyst how effective it is on the desired / undesired reaction
– A study of reaction rate often reveal information on the reaction mechanism
• A good understanding of reaction mechanism helps us to find a more effective way to
carry out a reaction and sometimes leads to discovery of new means of reaction

A study of reaction rate is often referred as a study of Reaction Kinetics

Thermodynamics of chemical reaction systems

–Study the energy transfer process in chemical reactions

–Predict the direction of a chemical reaction and the
energy transfer associated with the reaction
–Predict the final state (equilibrium) of a chemical reaction
system, and Study factors that affect the characteristics of
the final state of a reaction system

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 Chemical reaction
• Both the rate and equilibrium conversion of a
chemical reaction depend on the temperature,
pressure, and composition of reactants.
– Although reaction rates are not susceptible to
thermodynamic treatment, equilibrium conversions
are.
– To determine the effect of temperature, pressure, and
initial composition on the equilibrium conversions of
chemical reactions.

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 Example
• Basic properties to be considered: T, P and composition

• Can continue without any catalyst at appreciable T but to

get desired rate use of catalyst in there, V2O5 at 3000C will
give desired results and rate will increase by increasing T.
• If rate is the only parameter to be considered then one
would operate it at higher T but when the question comes
for conversion it is 90% at 5200C and falls rapidly at 50% at
6800C regardless of catalyst or rate.
• Main purpose of using this chapter to get the effect of T , P
and ratios of reactants on equilibrium conversion of
chemical reactions. 13
 Reaction coordinate

• Reaction coordinate(e) characterizes the

extent or degree to which a reaction has taken
place.
• Also known as.
– The extent of reaction
– Progress variable
– Degree of advancement
– Degree of reaction

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 Reaction coordinate

• Extent of reaction is a quantity that measures

the extent in which the reaction proceeds.
• It is usually denoted by the Greek letter ξ.
• The extent of a reaction has units of amount
(moles).
• For a reaction, the changes in the number of
moles(ni) of the species present in the
reaction chamber are in direct proportion to
the stochiometric numbers(vi).
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Reaction coordinate
• A general chemical reaction:
v1 A1  v2 A2  ...  v3 A3  v4 A4  ...
dn1 dn2 dn3 dn4
    ...  d
v1 v2 v3 v4
Reaction coordinate, which characterizes the extent or
degree to which a reaction has taken place.

– A differential change in the number of moles of a

reacting species:
ni 
dni  vi d (i  1, 2, ..., N ) ni 0
dni  vi  d
0
(i  1, 2, ..., N )

ni ni 0  vi
yi   ni  ni 0  vi (i  1, 2, ..., N )
n n0  v n   ni  n0  v 17
i
For a system in which the following reaction occurs,
CH4  H 2O  CO  3H 2
assume there are present initially 2 mol CH4, 1 mol H2O, 1 mol CO and
4 mol H2. Determine expressions for the mole fractions yi as functions
of ε.
ni ni 0  vi
yi  
n n0  v
   i  1  1  1  3  2
i

n0   ni 0  2  1  1  4  8
i

2
yCH 4 
8  2
1 
yCO 
8  2
1  4  3
y H 2O  yH 2 
8  2 8  2 18
 Example-2
Consider a vessel which initially contains only n0 mol of water
vapor. If decomposition occurs according to the reaction,
1
H 2O  H 2  O2
2
Find expressions which relate the number of moles and the mole
fraction of each chemical species to the reaction coordinate ε.

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Solution :
ni ni 0  vi
yi  
n n0  v
1 1
   i  1  1  
i 2 2
n0   ni 0  n0
i

n 
1
 
y H 2O  0 yH 2 
1 yO2  2 1
n0  
n0   1
n0   2
2 2
nH 2  
nH 2O  n0   1
nO2  
2 20
 Multireaction
• Two or more independent reactions proceed
simultaneously
– νi,j : the stoichiometric number of species i in reaction j.
– the change of the moles of a species ni:

dni   vi , j d j
j

integration

ni  ni 0   vi , j  j
j
ni 0   vi , j  j
total stoichiometric number:
summation
yi 
j  j   i , j
n0   v j  j n  n0   v j  j  
n  n0     vi , j   j
i

j  i 
j j
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Consider a system in which the following reactions occur,

CH4  H 2O  CO  3H 2 CH4  2H 2O  CO2  4H 2

if there are present initially 2 mol CH4 and 3 mol H2O, determine expressions for the yi as
functions of ε1 and ε2 .

i CH4 H2O CO CO2 H2

j νj
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2
2  1   2
yCH 4 
5  2 1  2 2
ni 0   vi , j  j
3   1  2 2
yi 
j
y H 2O 
n0   v j  j 5  2 1  2 2
j
1
yCO 
5  2 1  2 2
2 3 1  4 2
yCO2  yH 2 
5  2 1  2 2 5  2 1  2 2
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Criteria of Chemical Reaction Equilibrium
• As the process proceeds the total Gibbs free
energy of a closed system in an actual process
must decrease at constant temperature and
pressure(during an irreversible process).

• A chemical reaction must proceed in the direction

of decreasing G.
• Hence the reaction will ultimately stop and the
equilibrium will be reached when Gibbs free
energy G attains the minimum value.
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Criteria of Chemical Reaction Equilibrium
• At the equilibrium state,
(dG)T,P = 0
• This is the equilibrium condition or criterion in
a chemical reaction.
• So the change occurs in a system at constant
temperature and pressure, produces no
change in G of the system.

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 Prove
• We know that Gibbs free energy,
G=H-TS
dG=dH-TdS-SdT
dG = dU+PdV + VdP-TdS-SdT
(dG)T,P = dU +PdV-TdS
(dG)T,P = TdS –PdV+PdV-TdS
(dG)T,P = 0

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• At constant temperature and pressure,
(i)
• For a reaction, aA +bB  rR+sS

or

• Substituting the value of dni into eq. (i),

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• This is the criterion of equilibrium of a chemical
reaction.
Physical significance:
• Consider a simple chemical reaction equilibrium:
A B
• Let the extent of reaction be ԑ.
• The change in number of moles of A = -dԑ and the
change in number of moles of B= dԑ.
• The change in free energy at constant temperature
and pressure is found out by,

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• This gives the slope of the curve obtained when the
Gibbs free energy is plotted against extent of reaction.
• The change in Gibbs free energy with extent of
reaction can be graphically represented as,

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• The slopes given by the eq. are not constant because
the chemical potentials are functions of composition,
which caries as the extent of reaction changes.
• Reaction proceeds in the direction of decreasing Gibbs
free energy G, the forward reaction takes place if
and the backward reaction proceeds if
• When , the slope of the curve is zero.
• This occurs at the minimum of the curve and
corresponds to the position of chemical equilibrium.
• If the system not in chemical equilibrium, the reaction
occurring must be irreversible and the total Gibbs free
energy must decrease at constant temperature and
pressure.

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 Equilibrium Constants (Keq)
• In order to quantify the chemical equilibria,
equilibrium constants are determined.
• The equilibrium constant (Keq) is the ratio of
product concentration to the reactant
concentration at equilibrium,

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 Equilibrium Constants
• A good quantitative indicator of the feasibility
of a reaction, which is determined to quantify
the chemical equilibria.
• the equilibrium constants provide valuable
information, such as whether products or
reactants are favored:
if Keq > 1, products favored at equilibrium
if Keq < 1, reactants favored at equilibrium

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Relation between the standard Gibbs energy
change and the equilibrium constant
Fundamental property relation for single phase system;
d(nG) = (nV)dP – (nS)dT + idni
Replacing dni,
d(nG) = (nV)dP – (nS)dT + iid

ii = [∂(nG)/∂]T,P
Where ii = rate of change of the total Gibb’s energy of system with respect
to reaction co-ordinates at constant T and P. and at equilibrium this value will
become 0.

ii = 0

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As,
dĜi = di = RTdln fˆi
Integrating the above equation, at const. T from the standard state
of species i to a state of species i in solution gives
i – G0i = RTln( fˆi /ƒ0i)

Here the ratio fˆi /ƒ0i is called as ACTIVITY of species i in the

solution and is symbolized by âi.
i = G0i + RTln(âi)
 (G0i + RTln(âi))i = 0
 G0ii +  RTi lnâi = 0
G0ii +  RT ln(âi)i = 0
 = exp{- G0i i / RT} = K
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 -RT lnK = G0ii = ΔG0 or
Here;
G0i is the property of pure chemical species i in its standard state at fixed
Pressure which is the function of Temperature.
K is the equilibrium constant for any reaction
ΔG0 standard Gibb’s energy change of reaction.
For the gas phase considered as the ideal gas has the value of activity is
given by the equation;
âi = ƒi/ƒ0i = ƒi because for an ideal gas the value of ƒ0i is equal to 1bar.

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• This is a useful relation between Gibbs free
energy change and equilibrium constant, by
which equilibrium constant can be determined
at the given Gibbs free energy change and the
temperature.

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 Feasibility of chemical reaction
• Criterion for feasibility of a chemical reaction
from values of standard free energy change.
• If the reaction is not thermodynamically
feasible, there is no point in pursuing a long
and expensive experimental investigation on
improving the rate of reaction, searching for
catalysts, or other conditions to cause the
reaction

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 Feasibility of chemical reaction
-RT lnK = ΔG0
Conditions for feasibility of a reaction can be represented as:
then K>1.
The reaction is spontaneous and feasible

then K =1.
The system has attained a state of equilibrium

then K<1.
The reaction proceeds spontaneously in the reverse direction.

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 Feasibility of chemical reaction
Approximate criterion for the feasibility of chemical reactions:

the reaction is promising.

The reaction may or may not be possible.

the reaction is very unfavorable .

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EFFECT OF TEMPERATURE ON THE EQUILIBIRUM
CONSTANT (K)(Van’t Hoff ‘s equation)
Go and Ho = (T)

 H o d G o RT

 (1)
2
RT dT

G o
  ln K (2)
RT
d ln K H o (3)

dT RT 2
There are two possibilities:
•H is negative and so the reaction is exothermic. K decreases with
increase in T
•H is positive and so the reaction is endothermic. K is increase
with increase in T.
•Van’t Hoff’s equation predicts the effect of temperature on the
equilibrium constant.
For the integration of equation (3), again there are two possibilities:
H is independent of T and H is dependent of T. 39
Case I H is independent of T
K H o  1 1 
ln     (4)
K1 R  T T1 
lnK vs. 1/T plot is straight line and the slop and intercept is used to predict the
approximate values of K and K1.
Case II H is dependent of T
H o
ln K   2
dT  I (5)
RT


Where H  J  C p dT
o 0 (6)

I and J are integration constants

After proper integration of equation (6)

H o J B 2 C 3 D (7)
  AT  T  T 
R R 2 3 T
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from equation (5) and (7),
J B C 2 D
ln K   A ln T  T T  2
I (8)
RT 2 6 2T
G o
According to equation   ln K
RT

 B C 2 D 
G  J  RT  Aln T 
o
T T  I (9)
 
2
2 6 2T

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 Temperature effect on KP
 G o  Ho S o
lnK P   
RT RT R
Exothermic (Ho < 0);
take d/d(1/T)
Kp large; as T, Kp
reactant side favored
d ln K P Ho
lnKp
  const.
d (1/ T ) R
Van’t Hoff equation
Endothermic (Ho > 0)
Kp small; as T, Kp 
product side favored

1/T
Increasing T
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Equilibrium constants as a function of temperature for some common reactions 43
HOW TO EVALUATE THE EQUILIBRIUM CONSTANT?

• For any given reaction at particular temperature conditions

requires the knowledge of heat capacity and enough data to
evaluate constants J and I.

• For J or J/R take equation no (7), T = 298.15K where the value

of H 0 is known.

• For I take equation no (9), T =298.15K where the value of G0

is known.

• Finally use equation no (8) to calculate the value of K from

known values of I and J.

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Conclusions:
•According to equation
d ln K H o

, dT RT 2
•If H is positive and so the reaction is endothermic.
•K is increase with increase in T. (Const P)
•Reaction is shifted right and causing increase in εe.
•If H is negative and so the reaction is exothermic.
•K is decrease with increase in T. (Const P)
•Reaction is shifted left and causing decrease in εe.

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Thank you

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