CHAPTER 6
CHEMICAL-REACTION
EQUILIBRIA
6.1 The Reaction Coordinate
The general chemical reaction :
where | vi | is a stoichiometric coefficient and Ai
stands for a chemical formula.
For vi :
Positive ( + ) for product Negative ( - ) for
reactants
6.1 The Reaction Coordinate
Example :
CH4 + H2O CO + 3H2
The stoichiometric numbers are:
The stoichiometric number for an inert species is
zero
6.1 The Reaction Coordinate
Since
dni = vi d ( i = 1 , 2 ,.N)
is called the reaction coordinate, it characterizes the
extent or degree to which a reaction has taken place.
or (i = 1,2, N)
6.1 The Reaction Coordinate
Sum over all species
or
where
Example (page 486)
Consider a vessel which initially contains only no
mol of water vapor. If decomposition occurs
according to the reaction,
H2O H2+ 0.5 O2
find expressions which relate the number of moles
and the mole fraction of each chemical species to the
reaction coordinate e.
Example (page 486)
Solution
Application of equation (13.4) and (13.5) yields
Example (page 486)
The fractional decomposition of water vapor is:
when n0=1, is directly related to the fractional
decomposition of the water vapor.
Multireaction Stoichiometry
When two reactions occur simultaneously
(i = 1, 2, N)
Integration from ni0 and 0 to ni and j yields
(i = 1, 2, N)
Summing over all species yields
Multireaction Stoichiometry
The definition of a total stoichiometric number for
a single reaction has its counterpart in the definition
,
Combining with equation (13.6) gives the mole
fraction
(i = 1, 2, N)
6.2 APPLICATION OF EQUILIBRIUM
CRITERIA TO CHEMICAL REACTIONS
At the equilibrium state:
( dGt )T , P = 0
The total Gibbs energy Gt is at minimum
Its differential = 0
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
The fundamental property relation for single-phase
systems, provides an expression for the total
differential of the Gibbs energy:
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
If changes in mole numbers ni occur as the result of a
single chemical reaction in a closed system , then
each dni may be replaced by the product vi d .
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
Since nG is a state function , the right side of this
equation is an exact differential expression:
For chemical-reaction equilibrium:
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
Recall the definition of the fugacity of a species
in solution:
For a pure species i in its standard start at the same
temperature :
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
The difference between both equations is
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
Also, by definition
K is a function of only temperature
In spite of its dependence on temperature , K is
called the equilibrium constant for the reaction; ,
represented by G , is called the standard Gibbs-
energy change of reaction.
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
The dependence of G on T :
which can be re-written as
The equation gives the effect of temperature on
equilibrium constant and hence on the equilibrium
conversion.
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
When H
negative = exothermic reaction
positive = endothermic reaction
If H is assumed independent of T, then:
a plot of ln K versus the reciprocal of absolute
temperature is a straight line.
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
The rigorous development of the effect of
temperature on the equilibrium constant is based on
the definition of the Gibbs energy , written for a
chemical species in its standard state:
Multiplication by vi and summation over all species
gives:
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
As a result of the definition of standard property
change of reaction, this reduces to:
where the standard heat of reaction and standard
entropy change is related to temperature:
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
However,
so,
and,
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
The preceding equation may be reorganized so as to
factor K into three terms , each representing a basic
contribution to its value :
K = K0 K1 K2
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT
K0 represents the equilibrium constant at reference
temperature T0 :
6.5 EVALUATION OF EQUILIBRIUM
CONSTANTS
Values of Go for many reactions are tabulated
No way to measure Gof experimentally
Gof are calculated using equation
Example (page 496)
Calculate the equilibrium constant for the vapor-
phase hydration of ethylene at 145 and at 320C from
data given in Appendix C.
Solution
First determine values for A, B, C, and D for
the reaction
Example (page 496)
The meaning of is indicated by: A = (C2H5 OH) -
(C2H4) - (H2O). Thus, from the heat-capacity data of
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 l0-3
C = (-6.002 + 4.392 - 0.000) x 10-6 = -1.610 x 10-6
D = (-0.000 - 0.000 - 0.121) x 105 = -0.121 x 105
Example (page 496)
Values of H298 and G298 at 298.15K for the
hydration reaction are found from the heat-of-
formation and Gibbs-energy-of-formation data of
Table C.4:
H298 = -235,100 - 52,510 - (-241,818) = -45,792 J/mol
G298 = -168,490 - 68,460 - (-228,572) -8,378 J/mol
Example (page 496)
For T = 145 + 273.15 = 418.15 K, values of the
integrals in Eq. (13.18) are:
IDCPH(298.15,418.15;-1.376,4.157E-3,-1.610E-6,-
0.121 E+5) = -23.121
IDCPS(298.15,418.15;-1.376,4.157E-3,-1.610E-6,-
0.121 E+5) = -0.06924
Example (page 496)
Substitution of values into Eq. for a reference
temperature of 298.15 gives:
G418
8,378 45,792 45,792 23.121
0.06924 1.9356
RT 8.314 298.15 8.314 418.15 418.15
For T = 320 + 273.15 = 593.15 K,
IDCPH(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-
0.121 E+5) = 22.632
IDCPS(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-0.121
E+5) = 0.01731
So,
G593
8,378 45,792 45,792 22.632
0.01731 5.8286
RT 8.314 298.15 8.314 593.15 593.15
Example (page 496)
Finally,
@418.15K: ln K = -1.9356 and K = 1.443 x 10-1
@593.15K: ln K = -5.8286 and K = 2.942x 10-3
Application of Eqs. (13.21), (13.22), and (13.24)
provides an alternative solution to this example. By
Eq. (13.21),
8,378 H 0 45,792
K 0 exp 29.366 18.473
8.314 298.15 RT0 8.314 298.15
Example(page496)
Moreover,
With these values, the following results are readily
obtained:
T/ K K0 K1 K2 K
298.15 1 29.366 1 1 29.366
418.15 1.4025 29.366 4.985x10-3 0.9860 1.443x10-1
593.15 1.9894 29.366 1.023x10-4 0.9794 2.942x10-3
Clearly, the influence of K1, is far greater than that of
K2. This is a typical result, and accounts for the fact
that the lines on Fig. 13.2 are nearly linear.
Example 13.7 (page 505)
In a laboratory investigation, acetylene is
catalytically hydrogenated to ethylene at
1120C and 1 bar. If the feed is an equimolar
mixture of acetylene and hydrogen, what is
the composition of the product stream at
equilibrium?
