Chemical Reaction Equilibria

Chapter 14

The Reaction Coordinate

Application of Equilibrium Criteria to Chemical Reactions
The Standard G and the Equilibrium Constant
Effect on Temperature on the Equilibrium Constant
Evaluation of the Equilibrium Constant
Relation of Equilibrium Constant to Composition
Equilibrium Conversion for Single Reactions
 Introduction
• Transformation of raw materials into products having commercial use and value
is a major industry.
Raw Materials → Products
{crude oil, minerals, etc..} {Gasoline, NaOH, H2SO4, ammonia, etc..}
• This often involves chemical reactions and subsequent separation of the products.
• The rate and maximum (or equilibrium) conversion of chemical reaction are of
important concern in its commercial development.
• Both of these aspects depend on the T, P, and composition of the reactants.

• We can often increase reaction rates by the

use of CATALYST, but we can not change  Uultimate
Degree of reaction
st
the equilibrium (or ultimate) conversion by With cataly conversion

using catalyst. ly st
at a
u tc
tho
Wi

Time
Chemical Engineering Thermodynamics II ChE 304 14-2
 • Chemical Reaction Course concerns on study of reaction rate and equilibrium,
where the following tasks are often considered:
• Design and operation of reaction equipment
• Effect of controllable variables upon conversion
• Extent of reaction as t → ∞
In general:
Reaction Equilibrium is governed by THERMODYNAMICS
while,
Reaction Rate is governed by REACTION KINETICS
Objectives:
• Definitions of reaction stoichiometry and criterion of reaction equilibrium.
• Dependence of equilibrium constant on temperature and its evaluation.
• Development of connection between equilibrium constant and composition.
• Calculation of equilibrium conversion for single reactions.

Chemical Engineering Thermodynamics II ChE 304 14-3

 The Reaction Coordinate
The general chemical reaction can be written as:
ν1 A1 + ν2 A2 + ........ → ν3 A3 + ν4 A4 (I)
where |i| are stoichiometric coefficients and Ai denotes the chemical formulas of
species.
 i themselves are stoichiometric numbers

Sign Convention
For products: i is positive (+) For reactants: i is negative (-)
• N.B. The reaction, as written above, does not represent any mechanisms. It
represents only the overall macroscopic picture. It does not tell us what is happening
at the microscopic level.
Example:
CH4 = -1 H2O = -1
CH4 + H2O → CO + 3H2
CO = +1 H2 = +3
• The stoichiomertric number of an inert species is zero.

Chemical Engineering Thermodynamics II ChE 304 14-4

• In all reactions, the change in the number of moles of the species present are related
to each other through the stoichiometric number.
 For example, for the reaction CH4 + H2O → CO + 3H2, if 0.5 mole CH4
reacts, then 1.5 moles H2 and 0.5 mol CO generated, that’s ratio of change in
number of moles to the stoichiometric number of CH4 is the same as that for H2.
Thus, in general for reaction (I), we can write:
dn2 dn1 ,
dn3 dn1
= = , etc…
ν2 ν1 ν3 ν1
or, in general:
dn1 dn2 dn3
= = = ......... = dε (II)
ν1 ν2 ν3
where d = the “amount of reaction”.
• It will be observed that the sign of i allows for the fact that:
dni > 0 for the product & dni < 0 for the reactants
 The preceding equation provides the definition for , the Reaction Coordinate; a
quantity characterizes the extent, or degree, to which chemical reaction has taken place.
•  is also called the Degree of Reaction

Chemical Engineering Thermodynamics II ChE 304 14-5

 From II, we can write,
dni = νi dε (III)
moles moles
dimensionless
By convention,  = 0 at the initial state (before the reaction occurs). Integration yields:
ni ε
 = f(t)
∫ dni = ∫ νi dε
ni 0 0

ni = ni0 + νi ε
Summing over all N species (reactant and products) yields: n = ∑ ni = ∑ ni0 + ε ∑ νi
or, n = n0 + νε where, n0 = ∑ ni0 & ν = ∑ νi
• The quantity  tells us whether there is a net increase or decrease in the total number
of moles in the system.
 The mole fraction of species i at any time, or stage of reaction, is by:
ni ni0 + νi ε This expression is very useful, since it provides us
yi = = with a relationship between species concentration
n n0 + νε and the progress of the reaction.

Chemical Engineering Thermodynamics II ChE 304 14-6

Example: Consider the chemical reaction, CH4 + H2O → CO + 3H2
Initially there present 2 moles CH4, 1 mole H2O, 1 mole CO and 4 moles H2.
Obtain yi = f().
  = ∑i = -1 -1 + 1 + 3 = 2 n0 = ∑n0i = 2 + 1 + 1 + 4 = 8 moles
ni0 + νi ε
Application of the equation: yi =
n0 + νε
2-ε 1- ε 1+ ε 4 + 3ε
yCH 4 = y H 2O = yCO = yH 2 =
8 + 2ε 8 + 2ε 8 + 2ε 8 + 2ε

Definition of a “Mole of Reaction”

This means that  has changed by a unit amount (i.e. 1 mol).
• When  = 1 mole, the reaction proceeds to such an extent that the change in
mole numbers for each reactant and product species is equal to its stoichiometric
numbers, that’s:
ni = i 

Chemical Engineering Thermodynamics II ChE 304 14-7

Multireaction Stoichiometry
• In this case, we allocate a reaction coordinate, j, to each reaction (j = 1, 2, 3, …R),
where R = number of separate reactions.
• The stoichiometric numbers are now identified as:

i,j Stoichiometric number of species i in reaction j

 ni may change because of the involvement of species i in several reactions.
 The general equation analogous to Eq. (III) for single reactions is:
dni = ∑ νi , j dε j (i = 1, 2, ….N; j = 1, 2, …. , R)
j
Integration yields; ni = ni0 + ∑ (νi , j ε j )
j
Summing over all species: n = ∑ ni = n0 + ∑∑ (νi , j ε j ) = n0 + ∑∑ (νi , j ε j )
i j j i
Similarly, v j = ∑ νi , j n = n0 + ∑ (ν j ε j )
i j
ni0 + ∑ (νi , j ε j )
n
yi = i
j
Mole fraction, = (i = 1, 2, …. , N)
n n0 + ∑ ν j ε j
j

Chemical Engineering Thermodynamics II ChE 304 14-8

Example: Consider the following reactions,
CH4 + H2O → CO + 3H2 (1) j=1
CH4 + 2H2O → CO2 + 4H2 (2) j=2
There are present 2 mol CH4 and 3 mol H2O. Obtain expressions for yi = f(1, 2).
Construct the following table for i,j:

i= CH4 H 2O CO CO2 H2
j j
1 -1 -1 1 0 3 1 = 2
2 -1 -2 0 1 4 2 = 2
∴n = n0 + ∑ (ν j ε j ) = 5 + 21 + 22
j
2 - ε1 - ε2 3 - ε1 - 2ε2 ε1
yCH 4 = y H 2O = yCO =
5 + 2ε1 + 2ε2 5 + 2ε1 + 2ε2 5 + 2ε1 + 2ε2
ε2 3ε1 + 4ε2
yCO2 = yH 2 =
5 + 2ε1 + 2ε2 5 + 2ε1 + 2ε2
Chemical Engineering Thermodynamics II ChE 304 14-9
Application of Equilibrium Criterion to Chemical Reactions
As noted previously, in a closed system at equilibrium (constant T &P):
(dGt)T,P = 0
• Recalling that Gt decreases during an irreversible process (eg. Mixing process,
chemical rxn, etc…)
 If a mixture is not in equilibrium, any reaction that occurs at constant T and P must
lead to a decrease in the total energy of the system
•  is the single variable that characterizes
the progress of the reaction.
• Recall that  is related to the
composition of the system
 Criterion for equilibrium:
1. (dGt)T,P = 0
2. Gt() is minimim
• N.B. Equilibrium expression can also be
used for OPEN SYSTEM at constant T & P.
Chemical Engineering Thermodynamics II ChE 304 14-10
The Standard Gibbs Energy Change and the Equilibrium Constant
Recall the fundamental property relation for single-phase system:
d ( nG ) = ( nV ) dP - ( nS ) dT + ∑ μi dni
i
If changes in ni occur as a result of single reaction in a closed system, then:
dni = νi dε
∴d ( nG ) = ( nV ) dP - ( nS ) dT + ∑ νi μi dε
i
∂ ( nG ) At equilibrium state,
⇒[ ]T , P = ∑ μi νi = 0.0
∂ε according to the previous
 The criterion for chemical reaction equilibriumfigure.
can be expressed as:
∑ μi νi = 0 .0
Since μi = G i

Recall that i  i (T )  RT ln f i (A)
Write this equation for pure species in its standard state at the same temperature
Gio = Γi (T ) + RT ln f i o (B)

Chemical Engineering Thermodynamics II ChE 304 14-11

 See section 4.3 (p. 136) for the definition of standard state:
Gases: pure species in ideal gas state at 1 bar (or 1 atm)
Liquids or solids: actual pure liquid or solid at 1 bar (or 1 atm)
Subtracting (B) from (A):

i  G  RT ln f i / f i o  RT ln ai
i
o


where ai is the activity of species i in solution.
 
• N.B. a ≠ the activity coefficient ( i  f i / xi f i )
i

Now, i  Gio  RT ln ai &


∑ μi νi = 0 .0
  i
∑[ i Gi0   i RT ln ai ]  0 or ∑[ i Gi0 ]  RT ∑ ln(ai )  0

ln Π ( ai ) v -
∑ i Gi0
or i
where   product over all species
RT

Π ( ai ) v  Exp[-∑ i Gi0 / RT ] = K
i

Goi = f(T) only, independent of pressure; K = the “equilibrium constant” = f(T) only
- RT ln K = ∑ νi Gio = ΔG o where G o  the “Standard Gibbs
Energy Change of Reaction”.
Chemical Engineering Thermodynamics II ChE 304 14-12
 Note: For a specific species the standard state represented by G o must be the same
i

state represented by fio upon which the activity coefficient ai is specified
Case of Gases
• The standard state is the ideal gas state of pure species at a pressure of 1 bar.
 fio = 1 bar for each species in has phase reaction
Λ + for product, - for reactant
Λ f i Λ
 K = Π
Λ v
(f i ) i
ai = o = f i must be measured in bar
fi
Example: A + 2B + 3C  D + 4 E
Λ v Λ -1 Λ -2 Λ -3 Λ Λ
 K = Π (f i ) i = (f A ) (f B) (f C) (f D) (f E)4
Λ Λ
or K = (f D) (f E)4
Λ Λ 2 Λ 3
(f A ) (f B) (f C)
Case of liquids and solids
• The usual standard state is pure liquid or pure solid at 1 bar and T of the system.
Λ
• for this state, fio is not generally equal to 1 bar, thus Λ f i
ai =
f io
Chemical Engineering Thermodynamics II ChE 304 14-13
 Other “Standard Property Change of Reaction”
For the general property, M, we can write
Mo = ∑i Mio
For example: Ho = ∑i Hio
f(T) only
CPo = ∑i CPio

Relationship between Hio and Gio

Previously, we have derived:
H ∂ (G / RT )
= -T [ ]P
RT ∂T
Therefore, in the standard state for species i:
d (Gio / RT ) Why we removed
H io = - RT 2
= f(T) the partial derivative?
dT Recall that at the standard state,
Summing over all species: P is fixed
d ∑ νi Gio
∑ νi H io = - RT 2 [ ]
dT RT

Chemical Engineering Thermodynamics II ChE 304 14-14

 o d ΔG o 2
ΔH = - RT [ ] Relationship between Ho and Go
dT RT
o d ln K ΔH o Highly important
But, ln K = -ΔG / RT =
dT RT 2 relation

Note: If Ho is negative (exothermic reactions)  K  as T 

Special case: Assuming Ho is independent of T,
ΔH o 1 1 A plot of lnK vs. 1/T should
ln( K / K1 ) = - [ - ]
R T T1 be a straight line

• See the next slide for plot of K versus 1/T for several reactions.

Chemical Engineering Thermodynamics II ChE 304 14-15

 Important Remarks:

• This figure allows determination of K

at any temperature.

• If K1 is known at T1  K can be
determined at any temperature for a
given Ho.

• Slope of the lines are –ve or +ve;

• -ve for endothermic reactions
• +ve for exothermic reactions

Chemical Engineering Thermodynamics II ChE 304 14-16

 Determination of Go
• K can be determined from the previous figure at a given temperature for certain
reactions if Ho is constant ( ≠ f(T))
• Another alternative method, when Ho = f(T), for determination of K is by using:
ΔG o
ln K = - = f(T)
Recall that
RT
If an estimate of Go is available  K can be determined Go = f(T)

• Go can be calculated by using the general relation: Go = ∑iGio

ΔG o = ΔH o - TΔS o (A) Ho = ∑iHio
So = ∑iSio
Recalling (from Chapter 4 and 5): CPo/R = ∑iGPio/R
T T
C Po C Po dT
ΔH  ΔH 0  R  ΔS  ΔS  R 
o o o o
dT or: 0
T
R T
R T
o o

Where H0o and S0o is the standard enthalpy and entropy changes at a reference
temperature T0, respectively.
Substituting in (A) gives:

Chemical Engineering Thermodynamics II ChE 304 14-17

 T T
C Po C Po dT
ΔG  ΔH  R 
dT  TΔS 0 - RT 
o o o
0
T
R T
R T
o o

According to (A):
ΔH 0o - ΔG0o
ΔS 0o =
T0
whence: T T
C P0 T C P0 dT
ΔG  ΔH  R 
dT  ( ΔH 0 - ΔG0 ) - RT 
o o o o
0
T
R T0 T
R T
o o

Division by RT:
T T
ΔG o ΔH 0o ΔG0o - ΔH 0o 1 C Po C Po dT
RT

RT

RT0

TT R 
dT -
T

R T
o o

• CPio/R = f(T) …… presented in Tables C.1-C.3 (pp. 684/685)

• Go and Ho values are tabulated for many formation reactions at standard conditions
• Gof298 and Gof298 (G0o and H0o) for a number of chemical compounds are listed
in Table C.4 (pp. 686/687)
Go/RT can be determined after determining the two integrals in the above
equations
Hence, K can be determined
Chemical Engineering Thermodynamics II ChE 304 14-18
 Example: calculate the equilibrium constant for the vapor-phase hydration of ethylene
at 145 & 320oC from data given in Appendix C
C2H4(g) + H2O(g)  C2H5OH(g)
Data: Species i
Ho298 Go298 Ai Bi  103 Ci  105
C2H4(g) -1 52510 68460 1.424 14.394 - 4.392
H2O(g) -1 -241818 -228572 3.47 1.45 -----
C2H5OH(g) +1 -235100 -168490 3.518 20.001 - 6.002
where Cpi/R = Ai + Bi T + Ci T2
o
ΔH 298 = ∑ νi H io, 298 = (-1)(52510) + (-1)(-241818)+(1)(-235100) = - 45792 J/mol
o
ΔG298 = ∑ νi Gio, 298 = (-1)(52510) + (-1)(-241818)+(1)(-235100)= - 45792 J/mol
ΔC Po / R = ∑ νi (C Po ,i / R ) = ∑ νi Ai + (∑ νi Bi )T + (∑ νi Bi )T 2
= [(-1)(1.424) + (-1)(3.47) + (1)(3.518)] + [(-1)(14.39) + (-1)(1.45) + (1)(20.0)]10-3T
+ [(-1)(-4.392) + (-1)(0.0) + (1)(-6.002)]  10-5T2
= -1.376 + 4.157  10-3T - 1.61  10-6T2

Chemical Engineering Thermodynamics II ChE 304 14-19

 @ T = 145oC = 418 K:
418
ΔG o - 45792 - 8378  45792 1
RT

(8.314)(418)

(8.314)(298)

418 298 ∫
[-1.376  4.157  10 -3 - 1.61 10 -6 T 2 ] dT

418
dT
- ∫
298
[-1.376  4.157  10 -3 - 1.61 10 -6 T 2 ]
T
o
ΔG
@ T = 145oC = 418 K: = 1.936
RT
o
ΔG
ln K = -  K = exp(-1.936) = 0.1443 K  with T
RT
Exothermic rxn
Similarly @ T = 320oC = 593 K  K = 0.00294

Chemical Engineering Thermodynamics II ChE 304 14-20

 Relationship between Equilibrium Constant and
Composition
Gas-Phase Reactions Λ
For the gas phase reactions: aΛ = f i = fΛ ( where fio = Po = 1 bar)
i o i

 fi
 K Π
i ( fi )
i

But K = f(T) only


& fi  f (T , P, yi ) Reflects nonideality of the equilibrium mixture
This means that for a given T, the composition at eqm must change

with P in such away that Π( fi ) remains constant
i

  
Now, fi   yi P
i  K  i ( yi P )
i
i


Separate P term, ⇒ K i Π (i yi ) [ P ]
i
where  = ∑i
K P   i (i yi )

i Relates K to e for a given T and P
Or, i
(recalling that yi can be related to e)

Complicated problem because:  i  f (T , P, yi )  iterative solution is needed
Chemical Engineering Thermodynamics II ChE 304 14-21
 Special cases:

• For equilibrium mixture as an ideal solution  i  i
-ν νi
whence, K P = Π
i ( φ y
i i )

• For sufficiently low pressure, equilibrium mixture behaves as an ideal gas


i  1
 T, P, and composition-dependent terms are
whence, K P -ν = Πi ( yi ) νi distinct are separate, thus solution for any one of
e, T or P given the other two is straightforward
Conclusion remarks
- Dependence of T can be seen through K:
• If Ho +ve, ENDO rxn, K  with T  П(yi)i  for a fixed P  e 
 rxn shifts to the right
• If Ho -ve, EXO rxn, K  with T  П(yi)i  for a fixed P  e 
 rxn shifts to the left
- • If  (∑i) -ve,   P @ constant T  П(yi)i  rxn shifts to the right, e 
• If  (∑i) +ve,   P @ constant T  П(yi)i   rxn shifts to the left, e
Chemical Engineering Thermodynamics II ChE 304 14-22
 Example: Consider the water-gas shift reaction
CO(g) + H2O(g)  CO2(g) + H2(g)
Assuming ideal gas mixture, what is the fraction of the steam reacted in each of the
following cases: (Hint: fraction of steam converted = (ni0 – nie)/ni0 = -ie/ni0)
(a) n0,H2O = 1, n0, CO = 1 mol, T = 1100 K, P = 1 bar
 n0 = 2 mol &  = 0.0
From Fig. 13.2: @ 1/T = 1/(1100 K) = 9.09  10-4 for the above rxn  lnK = 0 or K = 1.0
∧ 0 νi y CO y H 2
∴φi =1 K (1) = Πi ( yi ) = 1 ⇒ =1
yCO y H 2O
0 + εe εe 1- ε ε 1- ε
yCO2 = = , yCO = , y H 2 = e , y H 2O =
2+0 2 2 2 2
εe2
Substituting:
2 = 1  e = 0.5 fraction of steam reacts = 0.5
4(1 - εe ) / 4
(b) n0,H2O = n0, CO = 1 mol, T = 1100 K, P = 10 bar Since  = 0  P has no effect; e = 0.5
(c) n0,H2O = n0, CO = 1 mol, n0,N2 = 2 mol, T = 1100 K, P = 1 bar
As an inert  N2 = 0 Does not affect the calculations, e remains the same.
Chemical Engineering Thermodynamics II ChE 304 14-23
(d) n0,H2O = 2, n0, CO = 1 mol, T = 1100 K, P = 1 bar
εe 1- ε εe 1- ε
 n0 = 3 mol yCO2 = , yCO = , yH 2 = , y H 2O =
3 3 3 3
εe2
Substituting: = 1  e = 0.667 fraction of steam reacts = 0.667/2 = 0.33
( 2 - εe )(1 - εe )
(e) n0,H2O = 1, n0, CO = 2 mol, T = 1100 K, P = 1 bar
εe 2-ε εe 1- ε
 n0 = 3 mol yCO2 = , yCO = , yH 2 = , y H 2O =
2 3 3 3
εe2
Substituting: = 1  e = 0.667 fraction of steam reacts = 0.667
( 2 - εe )(1 - εe )
(f) n0,H2O = 2, n0, CO = 1 mol, n0, CO2 = 1 mol, T = 1100 K, P = 1 bar
1 + ε 1- ε εe 1- ε
 n0 = 3 mol yCO2 = e
, yCO = , y H 2 = , y H 2O =
3 3 3 3
εe (1 + εe )
Substituting: = 1  e = 0. 33 fraction of steam reacts = 0.33
(1 - εe ) 2
(g) n0,H2O = 1, n0, CO = 1 mol, T = 1650 K, P = 1 bar
From Fig. 13.2: @ 1/T = 1/(1650 K)  lnK = -1.15 or K = 0.316
εe2
∴ 2 = 0.316  e = 0.36
(1 - εe )
Chemical Engineering Thermodynamics II ChE 304 14-24
 Liquid-Phase Reactions ∧
∧ fi where fio  0
For the liquid phase reactions: a i = o
fi
∧
Then K remains as K = Π ( ai ) vi ∧
∧ ∧ fi fi
For liquid: fi = γi xi f i ai = o = γi xi o
fi fi
Determination of fi/fio:
@ T and P: Gi = Γi (T ) + RT ln f i
o o
@ T and Po: Gi = Γi (T ) + RT ln f i
Subtracting: Gi - Gio = RT ln f i / f i o (A)
But: dGi = Vi dP - Si dT P
o
Integration at constant T from Po to P: Gi - Gi = ∫oVi dP (B)
P
fi P
Substitute (B) in (A): RT ln o = ∫ Vi dP
fi Po fi
For liquids Vi is weak function of P  upon integration RT ln o = Vi ( P - P o )
fi fi
o
or o = exp[Vi ( P - P ) / RT ]
fi
Chemical Engineering Thermodynamics II ChE 304 14-25
 ∧
a i = γi xi exp[Vi ( P - P o ) / RT ]
νi
and K = Π[ γi xi exp{Vi ( P - P o ) / RT }]
Vi ( P - P o )
= Π ( γi xi ) νi Π[e RT ]νi
 
Vii ( P - P o ) 
 Π ( i xi ) Πe i 
RT


 ( P 0 - P) 
 i
Π( i xi )  K exp 
 RT
  iVi 
i 
Special cases
• At low P:  exp[{(P0-P)/RT}{∑iVi}] ≈ 1.0 (or when P  Po)

K = Π ( γi xi ) νi Requires determination i, but i = f(xi)

i
 xi can be found in this case iteratively.
• For the case of ideal solution:  i = 1.0

K = Π ( xi ) νi Law of Mass Action

i

xi = f(e)

Chemical Engineering Thermodynamics II ChE 304 14-26

 Example: Esterification of acetic acid in the liquid phase at 100 oC and 1 atm:
CH3COOH(l) + C2H5OH(l)  CH3COOC2H5(l) + H2O(l)
Species i i Hof298 (J) Gof298 (J)

CH3COOH(l), i=1 -1 -484,500 -389,900

C2H5OH(l), i=2 -1 -277690 -174,780
CH3COOC2H5(l), i=3 +1 -480,000 -332,200
H2O(l), i=4 +1 -285,830 -273,129
n0,acetic acid = n0,C2H5OH = 1 mol
Estimate the mole fraction of ethyl acetate (x3) at equilibrium. Assuming ideal solution and
that Ho does not change significantly with from 25oC to 100oC.
∴K = Π ( xi ) νi
i
First, determine K:
o
ΔH 298 = ∑ νi H io, 298 = 484,500 + 277,690 – 480,00 – 285,830 = - 3640 J
o
ΔG298 = ∑ νi Gio, 298 = 389,990 + 174,780 -332,200 – 273,129 = - 4650 J
lnK = -Go/RT K298 = exp[-4650/(8.314)(298)]  K298 = 6.527

Chemical Engineering Thermodynamics II ChE 304 14-27

 For constant Ho, apply the following,
ΔH o 1 1 3640 1 1
ln( K / K1 ) = - [ - ] ln( K 373 / 6.527) = - [ - ]
R T T1 8.314 373 298
K373 = 4.859
x4 x3
Now: K =
x1 x2
K = 4.859, n0 = 2,  = 0
n0i + νi εe 1 - εe 1 - εe εe εe
xi = x1 = , x2 = , x3 = , x4 = ,
n0 2 2 2 2
εe2 / 4
∴ 2 = 4.859  e = 0.6879
(1 - εe ) / 4
x3 = 0.344

(see other examples in the textbook)

Chemical Engineering Thermodynamics II ChE 304 14-28

 HW
14.3
14.9
14.20

Chemical Engineering Thermodynamics II ChE 304 14-29