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 THE REACTION COORDINATE

 APPLICATION OF EQUILIBRIUM CRITERIA TO CHEMICAL REACTIONS


 THE STANDARD GIBBS-ENERGY CHANGE AND THE EQUILIBRIUM CONSTANT
 EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT
 EVALUATION OF EQUILIBRIUM CONSTANTS
Course Learning Outcomes
The student should be able to :
• Describe the chemical reaction equilibria and it’s
importance in chemical engineering.
• Derive excess Gibbs energy equation to evaluate
equilibrium constant (K) for a given reaction and
conditions.
• Evaluate the equilibrium constant from diagram or excess
Gibbs energy for given reaction and conditions
• Apply the equilibrium constant to determine equilibrium
conversion and to calculate reaction mixture equilibrium
compositions.
• Calculate the equilibrium conversions for single reactions
THE REACTION COORDINATE
• General chemical reaction:
v1 A1 + v2 A2 + ... → v3 A3 + v4 A4 + ...
where;
vi = stoichiometric coefficient
Ai = chemical formula
vi = stoichiometric number
By the sign convention:
Positive (+) for a product Negative (-) for a reactant
• For reaction:
CH 4 + H2O → CO + 3H2

the stoichiometric numbers, νi are


ν CH =
4
−1 νH O =
−12
ν CO =
1 νH =
3 2

• As the reaction progresses, the changes in the


numbers of moles of species present are in direct
proportion to the stoichiometric numbers. This
principle provides the equations:
dn2 dn1 dn3 dn1
= = etc.
ν2 ν1 ν3 ν1
• The list continues to include all species.
dn1 dn2 dn3 dn4
= = = = ...
ν1 ν 2 ν3 ν4 4
• All terms being equal, they can be identified collectively by a
single quantity representing an amount of reaction.
• A definition of dε is given by the equation:
dn1 dn2 dn3 dn4
= = = = ... ≡ d ε (13.2)
ν1 ν2 ν3 ν4
• The general relation connecting the differential change dni
with dε is therefore
=dni ν=
i dε ( i 1, 2, ..., N) (13.3)

• ε is called the reaction coordinate, characterizes the extent or


degree to which a reaction has taken place.

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• Integration of eq. (13.3) from an initial unreacted state where
ε = 0 and ni = nio to a state reached after an amount of
reaction gives n ε
∫ dni = ν i ∫ d ε
i

ni 0 0
or
ni 0 + ν i ε
ni = (i =
1, 2, ..., N ) (13.4)

• Summation over all species yields


=n ∑
= n ∑n
i
i
i
i0 + ε ∑ν i
i
or n n0 + νε
=
where
n ≡ ∑ ni n0 ≡ ∑ ni 0 ν ≡ ∑ν i
i i i

• Thus the mole fractions yi of the species present are related to


ε by ni ni 0 + ν i ε
y= = (13.5)
n0 + νε
i
n 6
Example 13.1
For a system in which the following reaction occurs,
CH 4 + H2O → CO + 3H2
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.
Solution:
For the reaction,
For the given numbers of moles of species initially
present,
ν =∑ν i =−1 − 1 + 1 + 3 =2
i

n0 = ∑n
i
i0 = 2 + 1+ 1+ 4 = 8
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Equation (13.5) yields
ni ni 0 + ν i ε
y= =
n0 + νε
i
n

2−ε 1− ε
=y CH4 = y H2O
8 + 2ε 8 + 2ε
1+ ε 4 + 3ε
=y CO = y H2
8 + 2ε 8 + 2ε

The mole fractions of the species in the reacting mixture


are seen to be functions of the single variable ε .

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Example 13.2
Consider a vessel which initially contains only n0 mol of
water vapor. If decomposition occurs according to the
reaction,
H2O → H2 + 21 O2

find expression which relate the number of moles and


the mole fraction of each chemical species to the
reaction coordinate ε.
Solution:
For the reaction,
ν =−1 + 1 + 1
2
=21

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=
ni ni 0 + ν i ε (13.4)
ni ni 0 + ν i ε
y= = (13.5)
n0 + νε
i
n

Application of eqs. (13.4) and (13.5) yields


nH O =
2
n0 − ε nH = ε nO =
2
1
2
ε2

n0 − ε ε 2ε
1
=y H2O = y H2 = y O2
n0 + 2 ε
1
n0 + 2 ε
1
n0 + 21 ε
The fractional decomposition of water vapor is
n0 − nH O n0 − ( n0 − ε ) ε
= = 2

n0 n0 n0

Thus, when n0 = 1, ε is directly related to the


fractional decomposition of the water vapor.

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Multireaction Stoichiometry
• For multireaction, νi,j designates the stoichiometric number of
species i in reaction j.
• The general relation, eq. (13.3) becomes
=dni ∑
=ν dε ( i
j
i, j j 1, 2, ..., N )

• Integration from ni = ni0 and εj = 0 to ni and εj gives


ni 0 + ∑ν i , j ε j
ni = (i =
1, 2, ..., N ) (13.6)
j

• Summing over all species yields


 
∑i i 0 ∑∑
n= n +
i j
ν ε
i, j j =
n0 + ∑  ∑ i , j ε j
j  i
ν

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• The definition of a total stoichiometric number ν ( ≡ ∑ i ν i ) for
a single reaction has its counterpart here in the definition:
ν j ≡ ∑ν i , j whence n0 + ∑ν j ε j
n=
i j

• Combination of this last equation with eq. (13.6) gives the


mole fraction
ni 0 + ∑ j ν i , j ε j
=yi = ( i 1, 2, ..., N ) (13.7)
n0 + ∑ j ν j ε j

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Example 13.3
Consider a system in which the following reactions occur:
CH 4 + H2O → CO + 3H2 (1)
CH 4 + 2H2O → CO2 + 4H2 ( 2)
where the numbers (1) and (2) indicate the value of j, the
reaction index.
If there are present initially 2 mol CH4 and 3 mol H2O,
determine expressions for the yi as functions of ε1 and ε2.
Solution:
The stoichiometric numbers νi,j can be arrayed as follows:
i= CH4 H2O CO CO2 H2
j νj
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2 13
ni 0 + ∑ j ν i , j ε j
=yi = ( i 1, 2, ..., N ) (13.7)
n0 + ∑ j ν j ε j
Application of eq. (13.7) gives
2 − ε1 − ε 2 ε1
=y CH4 = y CO
5 + 2ε1 + 2ε 2 5 + 2ε1 + 2ε 2
3 − ε1 − 2ε 2 ε2
=y H2O = y CO2
5 + 2ε1 + 2ε 2 5 + 2ε1 + 2ε 2
3ε1 + 4ε 2
y H2 =
5 + 2ε1 + 2ε 2

The composition of the system is a function of independent


variables ε1 and ε2 .

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APPLICATION OF EQUILIBRIUM
CRITERIA TO CHEMICAL REACTIONS
• Total Gibbs energy of a closed system at constant T and P
must decrease during an irreversible process and equilibrium
is reached when Gt attains its minimum value.

• At this equilibrium state,


( dG t )
T ,P
=0

• If a mixture is not in equilibrium, any reaction at constant T


and P must lead to a decrease in the total Gibbs energy of the
system.
• Fig. 13.1 shows the relation of Gt and ε. The arrows along the
curve indicate the directions of changes in (Gt)T,P. The reaction
coordinate, ε has its equilibrium value, εe at the minimum of
the curve.
This figure indicates two distinctive
features of the equilibrium state for given
T and P,

a) Total Gibbs energy Gt is a minimum.


b) Its differential is zero.

(For a single chemical reaction)

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THE STANDARD GIBBS-ENERGY CHANGE
AND THE EQUILIBRIUM CONSTANT
• Equation (11.2) provides an expression for the total
differential of the Gibbs energy:
d ( nG ) = (nV )dP − (nS )dT + ∑ µi dni (11.2)
i
• If changes in the mole numbers ni occur as the result of a
single chemical reaction in a closed system, then by eq. (13.3)
each dni may be replaced by the product νi dε .
• Eq. (11.2) then becomes
d ( nG ) = (nV )dP − (nS )dT + ∑ν i µi d ε
i

• Because nG is a state function, the right side of this equation


is an exact differential expression,
 ∂ ( nG )   ∂ Gt( ) 
∑i i i =
= ν µ
∂ ε
 
 ∂ε 
 T ,P T ,P
• In general, the quantity ∑i
ν i µi represents, the rate of change
of total Gibbs energy of the system with respect to the
reaction coordinate at constant T and P.
• Fig. 13.1 shows that this quantity is zero at the equilibrium
state. A criterion of chemical reaction equilibrium is therefore
∑ν µ
i
i i =0 (13.8)

• Recall the definition of the fugacity of a species in solution:


Γ i (T ) + RT ln fˆi
µi = (11.46)

• In addition, eq. (11.31) may be written for pure species i in its


standard state at the same temperature:
Γ i (T ) + RT ln fi o
Gio =
A standard state is a particular state of a species at temperature T and at specified
conditions of pressure, composition and physical condition e.g. gas, liquid or solid.
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• The difference between these two equations is
fˆi
µi − G = o
RT ln o
i
(13.9)
fi

• Combining eq. (13.8) with eq. (13.9) to eliminate µi gives


for the equilibrium state of a chemical reaction:
∑ i i
ν
i
G o
+

RT ln fˆ fo  =
i i 0 ( )
or
( )
νi
∑ i
ν G + RT
i
o
∑ i i
ln fˆ fo =
0
or
i i

( ) ∑
νi ν Go
ln ∏ fˆi fi

o
= RTi i i

i
where Πi signifies the product over all species i.

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• In exponential form, this equation becomes

∏( )
νi
fˆi fi o =K (13.10)
i

where the definition of K and its logarithm are given by


 −∆G o  (13.11a)
K ≡ exp  
 RT 
−∆G o (13.11b)
ln K =
RT
• Also by definition,
∆G o ≡ ∑ i ν i Gio (13.12)

∆Go and K are functions of temperature.

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K is called the equilibrium constant for the reaction;
∑iνi Gio, represented by ∆Go, is called the standard
Gibbs-energy change of reaction.
• The function ∆Go ≡ ∑iνiGio in eq. (13.12) is the difference
between the Gibbs energies of the products and reactants
when each is in its standard state as a pure substance at the
standard state pressure, but at the system temperature.

• Other standard property changes of reaction are similarly


defined. For general property M:
∆M o ≡ ∑ν i Mio
i

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• For example, the relation between the standard heat of
reaction and the standard Gibbs energy change of reaction is
developed from Eq. (6.39) written for species i in its standard
state: o
d (Gi / RT )
H = − RT
i
o 2

dT

• Then, multiplication of both sides of this equation by vi and


summation over all species gives
d (∑i vi Gio / RT )
∑i i
v
i
H o
= − RT 2

dT
• Therefore, using Eq.4.14 and Eq. 13.12, relation written as
Eq.(4.14)
∆H =
o
−RT 2
d ∆(
G o
RT ) (13.13)
∆H = ∑ vi H
o
i
o
dT
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EFFECT OF TEMPERATURE ON THE
EQUILIBRIUM CONSTANT
• Because the standard state temperature is that of the
equilibrium mixture, the standard property changes of
reaction, such as ∆Go and ∆Ho, vary with the equilibrium
temperature.
• The dependence of ∆Go on T is given by eq. (13.13),
(
d ∆G o RT ) = −∆H o

dT RT 2
• In view of eq. (13.11b), this becomes
d ln K ∆H o (13.14)
=
dT RT 2
• If ∆Ho is negative, i.e., if the reaction is exothermic, the
equilibrium constant decreases as the temperature increases.
K increases with T for endothermic reaction.
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• If ∆Ho is assumed independent of T, integration of eq. (13.14)
from T’ to T leads to the simple result:
K ∆H o  1 1  (13.15)
ln ' =
−  − '
K R T T 

• A plot of ln K vs. (1/T) the reciprocal of absolute temperature


is a straight line.

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A plot of ln K vs. (1/T) for a number of common reactions

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• The rigorous development of the effect of temperature on
equilibrium constant is based on the definition of the Gibbs
energy at standard state:
G=
i
o
H i
o
− TSi
o

• Multiply by νi and summation over all species gives


∑i i

i
G o
∑i i ∑i i
i
ν H o
− T ν S o

• As a result of the definition of a standard property change of


reaction, this reduces to
∆G o =∆H o − T ∆S o (13.16)
• The standard heat of reaction is related to temperature:
T ∆Cpo
∆H0o + R ∫
∆H o = dT (4.18)
T0 R

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• The temperature dependence of the standard entropy
change of reaction is:
dT
dSio = C Poi
T
• Multiply by νi and summation over all species gives
dT
d ∆S o = ∆CPo
T
• Integration gives
∆CPo dT
T
∆S + R ∫
∆S = o o
0 (13.17)
T0 R T
where ∆So and ∆S0o are the standard entropy changes of
reaction at temperature T and at reference temperature T0.

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• Eqs. (13.16), (4.18) and (13.17) are combined to yield
∆CP oT T ∆C
o
∆G =∆H + R ∫
o o
0 dT − T ∆S0 − RT ∫
o P
dT
T0 R T 0 R
• However,
∆H o
− ∆G o
∆S0o = 0 0

T0
• Hence,
T ∆C T ∆C
o o
∆G o =
∆H0o −
T
T0
( )
∆H0o − ∆G0o + R ∫
T 0 R
P
dT − RT ∫
T 0 R
P
dT

• Finally, division by RT yields


∆G0o − ∆H 0o
o
∆G o
∆H0 1 ∆CP o
T T ∆C
o
P dT
=
RT RT0
+
RT T
+ ∫T0 R dT − ∫T0 R T
(13.18)

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• The first integral of eq. (13.18) is
∆CPo ∆B 2 2 ∆C 3 3 ∆D  τ − 1 
( ) ( ) ( ) ( )
T
∫T0 R dT = ∆A T0 τ − 1 +
2
T0 τ − 1 +
3
T0 τ − 1 +
T0  τ 
(4.19)
• The second integral is
∆CPo dT   ∆D   τ + 1  
∫T0 R T =∆A lnτ + ∆BT0 +  ∆CT0 + τ 2T0   2  (τ − 1) (13.19)
T
2

 
where
T
τ≡
T0

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• ∆Go/RT(= - ln K) as given in eq. (13.18) is readily calculated at
any temperature from the standard heat of reaction and the
standard Gibbs energy change of reaction at a reference
temperature (usually 298.15 K).
• Factor K may be organized into three terms:
K = K 0K1K 2 (13.20)

 −∆G0o  (13.21)
K 0 ≡ exp  
 RT 0 

 ∆H0o  T0  
K1 ≡ exp   1−  (13.22)
 RT0  T  
 1 T ∆CPo T ∆C dT 
o
K 2 ≡ exp  − ∫ dT + ∫ P
 (13.23)
 T T0 R T0 R T 

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• Temperature dependence of the heat capacity (eq. 4.4):
CP
=A + BT + CT 2 + DT −2
R
• The expression for K2 becomes:
  (τ ) (τ ) (τ ) (τ ) 
2 2 2
 τ − 1  1 − 1 1 − 1 + 2 1 ∆D − 1
K= exp ∆A lnτ −    + ∆BT0 + ∆CT02
+ 
2
   τ   2 τ 6 τ 2 T0
2
τ 2

(13.24)

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EVALUATION OF EQUILIBRIUM
CONSTANTS
• Values of ∆Go for many formation reactions are tabulated in
standard references.
• The reported values of ∆Gof are not measured experimentally,
but are calculated by Eq. 13.16.
∆G o =∆H o − T ∆S o
• Values of ∆Gof298 and ∆Hof298 for a limited number of chemical
compounds are listed in Table C.4 of App. C. These for a
temperature of 298.15K.
• Values of ∆Go for other reactions are calculated from
formation-reaction values.
• In more extensive compilations of data, values of ∆Gof and
∆Hof are given for a wide range of temperature. When data is
lacking, methods of estimation are available.
Example 13.4
Calculate the equilibrium constant for the vapor phase
hydration of ethylene at 145oC (418.15 K) and at 320oC
(593.15 K) from data given in App. C.
Solution:
First determine the values for ∆A, ∆B, ∆C and ∆D for the
reaction
C2H 4 ( g ) + H 2O ( g ) → C2H5OH ( g )

∆ = (C2H5OH) – (C2H4) – (H2O)


From Table C.1:
∆A = 3.518 – 1.424 – 3.470 = -1.376
∆B = (20.001 – 14.394 – 1.450) x 10-3 = 4.157 x 10-3
∆C = (-6.002 +4.392 – 0) x 10-6 = -1.610 x 10-6
∆D = (-0 – 0 – 0.121) x 105 = -0.121 x 105
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• Values of ∆Ho298 and ∆Go298 at 25oC (298.15 K) for the
hydration reaction are found from Table C.4:
∆H298
o
=−235100 − 52510 − ( −241818 ) =−45792 Jmol-1

∆G298
o
=−168490 − 68460 − ( −228572 ) =−8378 Jmol-1
• For T = 418.15 K, values of integrals in eq. (13.18) are
T ∆CPo
∫T0 R dT = −23.121
T ∆C dT
o

∫T0 R P T = −0.0692
• Substitute into eq. (13.18) for a reference temperature of
298.15 K gives:
∆G418
o
−8378 + 45792 −45792 −23.121
= + + +=
0.0692 1.9356
RT ( 8.314 )( 298.15 ) ( 8.314 )( 418.15 ) 418.15

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• For T = 593.15 K,
T ∆CPo
∫T0 R dT = 22.632
T ∆C dT
o

∫T0 R P T = 0.0173
∆G593
o
−8378 + 45792 −45792 22.632
= + + −=
0.0173 5.8286
RT ( 8.314 )( 298.15 ) ( 8.314 )( 593.15 ) 593.15

• Finally, by eq. (13.11b)


− ∆G o
ln K =
RT
At 418.15 K, ln K = -1.9356 and K = 1.443 x 10-1
At 593.15 K, ln K = -5.8286 and K = 2.942 x 10-3
• Alternative solution by using eq. (13.21), (13.22) and (13.24).

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