2 Thermodynamics of
Chemical Reactions
2.0 INTRODUCTION
The science of chemical kinetics is concerned
primarily with chemical changes and the energy
and mass fluxes associated therewith. Thermo-
dynamics, on the other hand, is concerned with
equilibrium systems . . . systems that are under-
going no net change with time. This chapter
will remind the student of the key thermo-
dynamic principles with which he should be
familiar. Emphasis is placed on calculations of
equilibrium extents of reaction and enthalpy
changes accompanying chemical reactions.
Of primary consideration in any discussion
of chemical reaction equilibria is the constraints
on the system in question. If calculations of
equilibrium compositions are to be in accord
with experimental observations, one must in-
clude in his or her analysis all reactions that
occur at appreciable rates relative to the time
frame involved. Such calculations are useful in
that the equilibrium conversion provides a
standard against which the actual performance
of a reactor may be compared. For example, if
the equilibrium yield of a given reactant system
is 75%, and the observed yield from a given
reactor is only 30%, it is obviously possible to
obtain major improvements in the process
yield. On the other hand, if the process yield
were close to 75%, the potential improvement
in the yield is minimal and additional efforts
aimed at improving the yield may not be
warranted. Without a knowledge of the equili-
brium yield, one might be tempted to look for
catalysts giving higher yields when, in fact, the
present catalyst provides a sufficiently rapid
approach to equilibrium.
The basic criterion for the establishment of
chemical reaction equilibrium is that
I yifk = 0 (2.0.1)
i
where the fit are the chemical potentials of the
various species in the reaction mixture. If r
reactions may occur in the system and equilib-
rium is established with respect to each of these
reactions, it is required that
= 0 k = 1, 2,. . . , r (2.0.2)
These equations are equivalent to a requirement
that the Gibbs free energy change for each
reaction (AG) be zero at equilibrium.
AG = Y^t^i = 0 at equilibrium (2.0.3)
2.1 CHEMICAL POTENTIALS AND
STANDARD STATES
The activity at of species i is related to its
chemical potential by
. = tf + RT En a{ (2.1.1)
where
R is the gas constant
T is the absolute temperature
fii is the standard chemical potential of species
i in a reference state where its activity is taken
as unity
The choice of the standard state is largely
arbitrary and is based primarily on experimental
convenience and reproducibility. The tempera-
ture of the standard state is the same as that of
the system under investigation. In some cases,
the standard state may represent a hypothetical
condition that cannot be achieved experi-
mentally, but that is susceptible to calculations
giving reproducible results. Although different
standard states may be chosen for various
species, throughout any set of calculations it is
important that the standard state of a component
be kept the same so as to minimize possibilities
for error.
Certain choices of standard states have found
such widespread use that they have achieved

the status of recognized conventions. In parti-
cular, those listed in Table 2.1 are used in cal-
culations dealing with chemical reaction equili-
bria. In all cases the temperature is the same as
that of the reaction mixture.
Table 2.1
Standard States for Chemical Potential Calculations
(for Use in Studies of Chemical Reaction Equilibria)
State of
aggregation Standard state
Gas
Pure gas at unit fugacity (for an ideal
gas the fugacity is unity at 1 atm
pressure; this is a valid approx-
imation for most real gases).
Liquid Pure liquid in the most stable form at
1 atm
Solid
Pure solid in the most stable form at
1 atm.
Once the standard states for the various
species have been established, one can proceed
to calculate a number of standard energy
changes for processes involving a change from
reactants, all in their respective standard states,
to products, all in their respective standard
states. For example, the Gibbs free energy
change for this process is
AG = (2.1.2)
where the superscript zero on AG emphasizes
the fact that this is a process involving standard
states for both the final and initial conditions
of the system. In a similar manner one can
determine standard enthalpy (AH0) and stan-
dard entropy changes (AS0) for this process.
2.2 ENERGY EFFECTS ASSOCIATED
WITH CHEMICAL REACTIONS
Since chemical reactions involve the formation,
destruction, or rearrangement of chemical
bonds, they are invariably accompanied by
Thermodynamics of Chemical Reactions
changes in the enthalpy and Gibbs free energy
of the system. The enthalpy change on reaction
provides information that is necessary for any
engineering analysis of the system in terms of
the first law of thermodynamics. It is also useful
in determining the effect of temperature on the
equilibrium constant of the reaction and thus
on the reaction yield. The Gibbs free energy is
useful in determining whether or not chemical
equilibrium exists in the system being studied
and in determining how changes in process
variables can influence the yield of the reaction.
In chemical kinetics there are two types of
processes for which one calculates changes in
these energy functions.
1. A chemical process whereby reactants, each
in its standard state, are converted into
products, each in its standard state, under
conditions such that the initial temperature
of the reactants is equal to the final tem-
perature of the products.
2. An actual chemical process as it might occur
under either equilibrium or nonequilibrium
conditions in a chemical reactor.
One must be very careful not to confuse
actual energy effects with those that are asso-
ciated with the process whose initial and final
states are the standard states of the reactants
and products respectively.
In order to have a consistent basis for
comparing different reactions and to permit
the tabulation of thermochemical data for var-
ious reaction systems, it is convenient to define
enthalpy and Gibbs free energy changes for
standard reaction conditions. These conditions
involve the use of stoichiometric amounts of
the various reactants (each in its standard state
at some temperature T). The reaction proceeds
by some unspecified path to end up with com-
plete conversion of reactants to the various
products (each in its standard state at the same
temperature T).
The enthalpy and Gibbs free energy changes
for a standard reaction are denoted by the
2.2 Energy Effects Associated with Chemical Reactions
symbols AH0 and AG, where the superscript
zero is used to signify that a "standard" reaction
is involved. Use of these symbols is restricted
to the case where the extent of reaction is 1 mole
for the reaction as written. The remaining
discussion in this chapter refers to this basis.
Because G and H are state functions, changes
in these quantities are independent of whether
the reaction takes place in one or in several
steps. Consequently, it is possible to tabulate
data for relatively few reactions and use this
data in the calculation of AG and AH0 for other
reactions. In particular, one tabulates data for
the standard reactions that involve the forma-
tion of a compound from its elements. One may
then consider a reaction involving several
compounds as being an appropriate algebraic
sum of a number of elementary reactions, each
of which involves the formation of one com-
pound. The dehydration of n-propanol
CH3CH2CH2OH(/) ->
CH3CH=CH2(<7)
may be considered as the algebraic sum of the
following series of reactions.
CH 3 CH 2 CH 2 OH(0 3C( graphite) + 4H2(#)
3C(j3 graphite) + 3H2(g) CH 3 CH=CH 2 (#)
H2O(/)
CH3CH2CHOH(0 -> H2O(/) + CH3CH=CH2(#)
For the overall reaction,
AH0 = A//? + AH2 + AH3 (2.2.1)
AG = AG? + AG2 + AG^ (2.2.2)
However, each of the individual reactions
involves the formation of a compound from
its elements or the decomposition of a com-
pound into those elements. The standard en-
thalpy change of a reaction that involves the
formation of a compound from its elements is
called the enthalpy (or heat) of formation of the
compound and is denoted by the symbol AHf.
Thus,
Ai/? veralI = AiJwalert/, + A//propvlene - AiJpropanoI(/,
(2.2.3)
and
AGoverall = AGwalert/) + AGpropyIenc - AGpropanol(/l
(2.2.4)
where AG refers to the standard Gibbs free
energy of formation.
This example illustrates the principle that
values of AG and AH0 may be calculated from
values of the enthalpies and Gibbs free energies
of formation of the products and reactants. In
more general form,
AH0 = YJvi AHfJ (2.2.5)
i
ACJ = > Vj ACJJ- i yZ.l.b)
i
When an element enters into a reaction, its
standard Gibbs free energy and standard en-
thalpy of formation are taken as zero if its state
of aggregation is that selected as the basis for
AH AG?
AH2 AG?.
AH3 AG?
AH0 AG
the determination of the standard Gibbs free
energy and enthalpy of formation of its com-
pounds. If AH0 is negative, the reaction is said
to be exothermic; if AH0 is positive, the reaction
is said to be endothermic.
It is not necessary to tabulate values of AG
or AH0 for all conceivable reactions. It is
sufficient to tabulate values of these parameters
only for the reactions that involve the formation
of a compound from its elements. The problem
of data compilation is further simplified by the

fact that it is unnecessary to record AGf and
AHf at all temperatures, because of the rela-
tions that exist between these quantities and
other thermodynamic properties of the reactants
and products. The convention that is commonly
accepted in engineering practice today is to
report values of standard enthalpies of formation
and Gibbs free energies of formation at 25 C
(298.16 K) or at 0 K. The problem of calculat-
ing a value for AG or AH0 at temperature T thus
reduces to one of determining values of AGJ
and AH at 25 C or 0 K and then adjusting
the value obtained to take into account the
effects of temperature on the property in ques-
tion. The appropriate techniques for carrying
out these adjustments are indicated below.
The effect of temperature on AH0 is given by
(2.2.7)
where Cpi is the constant pressure heat capacity
of species i in its standard state.
In many cases the magnitude of the last term
on the right side of equation 2.2.7 is very small
compared to AH%9%A6. However, if one is to be
able to evaluate properly the standard heat of
reaction at some temperature other than
298.16 K, one must know the constant pressure
heat capacities of the reactants and the products
as functions of temperature as well as the heat
of reaction at 298.16 K. Data of this type and
techniques for estimating these properties are
contained in the references in Section 2.3.
The most useful expression for describing
the variation of standard Gibbs free energy
changes with temperature is:
AG
T AH0
(2.2.8)
dT
In Section 2.5 we will see that the equilibrium
constant for a chemical reaction is simply
Thermodynamics of Chemical Reactions
related to AG/T and that equation 2.2.8 is
useful in determining how this parameter varies
with temperature. If one desires to obtain an
expression for AG itself as a function of tem-
perature, equation 2.2.7 may be integrated to
give AH0 as a function of temperature. This
relation may then be used with equation 2.2.8
to arrive at the desired relation.
The effect of pressure on AG and AH0
depends on the choice of standard states em-
ployed. When the standard state of each com-
ponent of the reaction system is taken at 1 atm
pressure, whether the species in question is a
gas, liquid, or solid, the values of AG and AH0
refer to a process that starts and ends at 1 atm.
For this choice of standard states, the values of
AG and AH0 are independent of the system
pressure at which the reaction is actually carried
out. It is important to note in this connection
that we are calculating the enthalpy change for
a hypothetical process, not for the actual process
as it occurs in nature. This choice of standard
states at 1 atm pressure is the convention that is
customarily adopted in the analysis of chemical
reaction equilibria.
For cases where the standard state pressure
for the various species is chosen as that of the
system under investigation, changes in this
variable will alter the values of AG and AH0.
In such cases thermodynamic analysis indicates
that
(2.2.9)
where Vt is the molal volume of component i in
its standard state and where each integral is
evaluated for the species in question along an
isothermal path. The term in brackets represents
the variation of the enthalpy of a component
with pressure at constant temperature (dH/dP)T.
It should be emphasized that the choice of
standard states implied by equation 2.2.9 is not
that which is conventionally used in the analysis
of chemically reacting systems. Furthermore,
2.4 The Equilibrium Constant and its Relation to A(7
in the vast majority of cases the summation term
on the right side of the equation is very small
compared to the magnitude of AH,dim and,
indeed, is usually considerably smaller than the
uncertainty in this term.
The Gibbs free energy analog of equation
2.2.9 is
AGg = AG? atm + (2.2.10)
where the integral is again evaluated along an
isothermal path. For cases where the species
involved is a condensed phase, Vt will be a very
small quantity and the contribution of this
species to the summation will be quite small
unless the system pressure is extremely high.
For ideal gases, the integral may be evaluated
directly as RT In P. For nonideal gases the
integral is equal to RT In / ? , where / ? is the
fugacity of pure species i at pressure P.
2.3 SOURCES OF THERMOCHEMICAL
DATA
Thermochemical data for several common spe-
cies are contained in Appendix A. Other useful
standard references are listed below.
1. F. D. Rossini, et al., Selected Values of Physical and
Thermodynamic Properties of Hydrocarbons and Related
Compounds, Carnegie Press, Pittsburgh, 1953; also loose-
leaf supplements. Data compiled by Research Project 44
of the American Petroleum Institute.
2. F. D. Rossini, et al., "Selected Values of Chemical
Thermodynamic Properties," National Bureau of Stan-
dards, Circular 500 and Supplements, 1952.
3. E. W. Washburn (Editor), International Critical Tables,
McGraw-Hill, New York, 1926.
4. T. Hilsenrath, et al., "Thermal Properties of Gases,"
National Bureau of Standards Circular 564, 1955.
5. D. R. Stull and G. C. Sinke, "Thermodynamic Properties
of the Elements," Adv. Chem. Ser., 18, 1956.
6. Landolt-Bornstein Tabellen, Sechste Auflage, Band II,
Teil 4, Springer-Verlag, Berlin, 1961.
7. Janaf Thermochemical Tables, D. R. Stull, Project Direc-
tor, PB 168370, Clearinghouse for Federal Scientific and
Technical Information, 1965.
The following references contain techniques for
estimating thermochemical data.
1. R. C. Reid and T. K. Sherwood, The Properties of Gases
and Liquids, Second Edition, McGraw-Hill, New York,
1966.
2. S. W. Benson, Thermochemical Kinetics, Wiley, New
York, 1968.
3. G. J. Janz, Estimation of Thermodynamic Properties of
Organic Compounds, Academic Press, New York, 1958.
2.4 THE EQUILIBRIUM CONSTANT AND
ITS RELATION TO AG
The basic criterion for equilibrium with respect
to a given chemical reaction is that the Gibbs
free energy change associated with the progress
of the reaction be zero.
AG = = 0 (2.4.1)
The standard Gibbs free energy change for a
reaction refers to the process wherein the
reaction proceeds isothermally, starting with
stoichiometric quantities of reactants each in its
standard state of unit activity and ending with
products each at unit activity. In general it is
nonzero and given by
AG = v^ 0 (2.4.2)
i
Subtraction of equation 2.4.2 from equation
2.4.1 gives
AG - AG = X MfjLt - /i?) (2.4.3)
i
This equation may be rewritten in terms of the
activities of the various species by making use of
equation 2.1.1.
AG - AG = RT X vf In at = RT In (]J a]*
(2.4.4)
where the \\ symbol denotes a product over i
i
species of the term that follows.
10 Thermodynamics of Chemical Reactions

For a general reaction of the form of the influence of temperature changes is

readily obtained by combining equations 2.2.8
(2.4.5)
and 2.4.7.
the above equations become:
AG"
AG - AG = RT n (2.4.6) T Rd In Kt AH0
abBacc (2.5.1)
dT dT
For a system at equilibrium, AG = 0, and
or
AG = -RT In 4-^ = ~RT tn K
'd In Ka\ AH0
(2.5.2)
dT RT2
(2.4.7)
and
where the equilibrium constant for the reaction
(Ka) at temperature T is defined as the term in dlnK AH0
(2.5.3)
brackets. The subscript a has been used to R
emphasize that an equilibrium constant is
properly written as a product of the activities
raised to appropriate powers. Thus, in general, For cases where AH0 is essentially indepen-
a =
1 1 Qi ~ e
(Z.4.0) dent of temperature, plots of ta Ka versus \jT
i are linear with slope (AH/R). For cases
As equation 2.4.8 indicates, the equilibrium where the heat capacity term in equation 2.2.7
constant for a reaction is determined by the is appreciable, this equation must be substituted
temperature and the standard Gibbs free energy in either equation 2.5.2 or equation 2.5.3 in order
change (AG) for the process. The latter quantity to determine the temperature dependence of the
in turn depends on temperature, the definitions equilibrium constant. For exothermic reactions
of the standard states of the various components, (AH0 negative) the equilibrium constant de-
and the stoichiometric coefficients of these creases with increasing temperature, while for
species. Consequently, in assigning a numerical endothermic reactions the equilibrium constant
value to an equilibrium constant, one must be increases with increasing temperature.
careful to specify the three parameters men- For cases where the standard states of the
tioned above in order to give meaning to this reactants and products are chosen as 1 atm,
value. Once one has thus specified the point of the value of AG is pressure independent.
reference, this value may be used to calculate Consequently, equation 2.4.7 indicates that Ka
the equilibrium composition of the mixture in is also pressure independent for this choice of
the manner described in Sections 2.6 to 2.9. standard states. For the unconventional choice
of standard states discussed in Section 2.2,
equations 2.4.7 and 2.2.10 may be combined to
2.5 EFFECTS OF TEMPERATURE AND
give the effect of pressure on Ka.
PRESSURE CHANGES ON THE
EQUILIBRIUM CONSTANT FOR A
REACTION 'd In Kt
(2.5.4)
dP IT RT
Equilibrium constants are quite sensitive to
temperature changes. A quantitative description where the Vt are the standard state molal
2.6 Determination of Equilibrium Compositions
volumes of the reactants and products. However,
this choice of standard states is extremely rare
in engineering practice.
2.6 DETERMINATION OF EQUILIBRIUM
COMPOSITIONS
The basic equation from which one calculates
the composition of an equilibrium mixture is
equation 2.4.7.
AG = -RT lnKn
(S) (2.6.1)
In a system that involves gaseous components,
one normally chooses as the standard state the
pure component gases, each at unit fugacity
(essentially 1 atm). The activity of a gaseous
species B is then given by
aB = (2.6.2)
JB,
B,SS J partial pressure. Thus
where fB is the fugacity of species B as it exists
in the reaction mixture and fBSS is the fugacity
of species B in its standard state.
The fugacity of species B in an ideal solution
pf ga'ses is given by the Lewis and Randall rule
(2.6.3)
where yB is the mole fraction B in the gaseous
phase and fB is the fugacity of pure component
B evaluated at the temperature and total
pressure (P) of the reaction mixture. Alterna-
tively,
(2.6.4)
where {f/P)B is the fugacity coefficient for pure
component B at the temperature and total
pressure of the system.
11
If all of the species are gases, combination of
equations 2.6.1, 2.6.2, and 2.6.4 gives
ps +t-b-c (2.6.5)
The first term in parentheses is assigned the
symbol Ky, while the term in brackets is assigned
the symbol Kf/P.
The quantity Kf/P is constant for a given
temperature and pressure. However, unlike the
equilibrium constant Ka, the term Kf/P is
affected by changes in the system pressure as
well as by changes in temperature.
The product of Ky and ps + t~b~c is assigned
the symbol KP.
KP = s+t_6_c _
(2.6.6)
since each term in parentheses is a component
= Kf/PKP (2.6.7)
For cases where the gases behave ideally, the
fugacity coefficients may be taken as unity and
the term KP equated to Ka. At higher pressures
where the gases are no longer ideal, the KfjP
term may differ appreciably from unity and
have a significant effect on the equilibrium
composition. The corresponding states plot of
fugacity coefficients contained in Appendix- B
may be used to calculate Kf/P.
In a system containing an inert gas / in the
amount of nr moles, the mole fraction of reac-
tant gas B is given by
n n n
B + C + l
(2.6.8)
Combination of equations 2.6.5 to 2.6.7 and
defining equations similar to equation 2.6.8 for
12 Thermodynamics of Chemical Reactions

the various mole fractions gives:

+t-b-c
K K (2.6.9)
c
cj \nB + nc + nnTT
ris -r -f

This equation is extremely useful for cal- 264.2 atm. Assume that the only significant
culating the equilibrium composition of the chemical reaction is
reaction mixture. The mole numbers of the
various species at equilibrium may be related to H2O(g) + C 2 H 4 (0) ^ C 2 H 5 OH(#)
their values at time zero using the extent of Use only the following data and the fugacity
reaction. When these values are substituted into coefficient chart.
equation 2.6.9, one has a single equation in a
single unknown, the equilibrium extent of re-
action. This technique is utilized in Illustration Compound Tc (K) Pc (atm)
2.1. If more than one independent reaction is
occurring in a given system, one needs as many H2O(g) 647.3 218.2
equations of the form of equation 2.6.9 as there C2H4(g) 283.1 50.5
are independent reactions. These equations are C 2 H 5 OH(#) 516.3 63.0
then written in terms of the various extents of
reaction to obtain a set of independent equa-
tions equal to the number of unknowns. Such a
system is considered in Illustration 2.2.
Compound AGj 298 16 (kcal) A//? 298 . 16 (kcal)

H2O(g) -54.6357 -57.7979

ILLUSTRATION 2.1 CALCULATION OF C2RM 16.282 12.496
EQUILIBRIUM YIELD FOR A CHEMICAL C2H5OH(g) -40.30 -56.24
REACTION

Problem The standard state of each species is taken as

the pure material at unit fugacity.
Calculate the equilibrium composition of a
mixture of the following species.
Solution
N2 15.0 mole percent
H2O 60.0 mole percent Basis: 100 moles of initial gas
C2H4 25.0 mole percent In order to calculate the equilibrium compo-
sition one must know the equilibrium constant
for the reaction at 527 K.
The mixture is maintained at a constant tem- From the values of AGf and AHf at 298.16 K
perature of 527 K and a constant pressure of and equations 2.2.5 and 2.2.6:
2.6 Determination of Equilibrium Compositions 13

AG 98 = 40.30) + (-1)(16.282) + ( - (-54.6357) = -1.946 kcal/mole

AH298 = 56.24) + (-1)(12.496) + ( - (-57.7979) = -10.938 kcal/mole

The equilibrium constant at 298.16 K may be rewritten as

determined from equation 2.4.7.
AG = -RT In Ka [
i s OH
(-1946)
(1.987)(298.16)
= 3.28 f\ If
C2H4J
The equilibrium constant at 527 K may be
found using equation 2.5.3. The fugacity coefficients {f/P) for the various
0 species may be determined from the generalized
AH chart in Appendix B if one knows the reduced
R temperature and pressure corresponding to the
species in question. Therefore,

Reduced temperature at Reduced pressure at

Species 527 K 264.2 atm f/P

H2O 527/647.3 = 0.815 264.2/218.2 - 1.202 0.190

C2H4 527/283.1 = 1.862 264.2/50.5 = 5.232 0.885
C 2 H 5 OH 527/516.3 = 1.021 264.2/63.0 = 4.194 0.280

If one assumes that AH0 is independent of From the stoichiometry of the reaction it is
temperature, this equation may be integrated to possible to determine the mole numbers of the
give various species in terms of the extent of reaction
and their initial mole numbers.

l
= ni
2

For our case, Initial moles Moles at extent <

10,938 ( \ 1 N2 15.0 15.0

n Xfl>2 - 3.28 == - H2O 60.0 60.0 -
1 ^ y (^-^ -
C2H4 25.0 25.0 -
= -8.02 C 2 H 5 OH 0.0
Total 100.0 100.0 -
or
Knl = 8.74 x 1 0 " 3 a t 5 2 7 K
The various mole fractions are readily deter-
Since the standard states are the pure mate- mined from this table. Note that the upper limit
rials at unit fugacity, equation 2.6.5 may be on is 25.0.
14 Thermodynamics of Chemical Reactions

Substitution of numerical values and expres- 2.7.1 Effect of Temperature Changes

sions for the various mole fractions in equation A
The temperature affects the equilibrium yield
gives:
primarily through its influence on the equilib-

100.0 - (0.280) 1
;.74 x 10~ 3 =
/ 60.0 - A / 25.0 - (0.190)(0.885) (264.2)
\ 100.0 - U 1100.0 -

or
(100.0 -
(60.0 - 0(25.0 _

This equation is quadratic in . The solution is rium constant Ka. From equation 2.5.2 it follows
= 10.8. On the basis of 100 moles of starting that the equilibrium conversion is decreased as
material, the equilibrium composition is as the temperature increases for exothermic reac-
follows. tions. The equilibrium yield increases with in-
creasing temperature for .endothermic reactions.
Temperature changes also affect the value of
Mole numbers Mole percentages
Kf/p. The changes in this term, however, are
N2 15.0 16.8 generally very small compared to those in Ka.
H2O 49.2
C2H4 14.2 15.9 2.7.2 Effect of Total Pressure
C 2 H 5 OH 10.8 12.1
Total 89.2 100.0 The equilibrium constant Ka is independent of
pressure for those cases where the standard states
are taken as the pure components at 1 atm. This
2.7 THE EFFECT OF REACTION
case is the one used as the basis for deriving equa-
CONDITIONS ON EQUILIBRIUM YIELDS
tion 2.6.9. TJie effect of pressure changes then
Equation 2.6.9 is an extremely useful relation for appears in the terms Kf/P and _p + t+--*-*-^
determining the effects of changes in process The influence of pressure on KffP is quite small.
parameters on the equilibrium yield of a given However, for cases where there is no change in
product in a system in which only a single gas the total number of gaseous moles during the
phase reaction is important. It may be rewritten reaction, this is the only term by which pressure
as changes affect the equilibrium yield. For these

s+t-b-c
K
a nc ns (2.7.1)
nbBncc K f/p

Any change that increases the right side of cases the value of Kf/P should be calculated
equation 2.7.1 will increase the ratio of products from the fugacity coefficient charts for the sys-
to reactants in the equilibrium mixture and thus tem and conditions of interest in order to deter-
correspond to increased conversions. mine the effect of pressure on the equilibrium
2.8 Heterogeneous Reactions
yield. For those cases where the reaction pro-
duces a change in the total number of gaseous
species in the system, the term that has the
largest effect on the equilibrium yield of products
is Ps + t+ b-c--\ Thus, if a reaction produces a
decrease in the total number of gaseous com-
ponents, the equilibrium yield is increased by an
increase in pressure. If the total number of gas-
eous moles is increased by reaction, the equilib-
rium yield decreases as the pressure increases.
2.7.3 Effect of Addition of Inert Gases
The only term in equation 2.7.1 that is influenced
by the addition of inert gases is nl. Thus, for
reactions in which there is no change in the total
number of gaseous moles, addition of inerts has
no effect on the equilibrium yield. For cases
where there is a change, the effect produced by
addition of inert gases is in the same direction as
that which would be produced by a pressure
decrease.
2.7.4 Effect of Addition of Catalysts
The equilibrium constant and equilibrium yield
are independent of whether or not a catalyst is
bB(g) + cC(g) + dD (/ or s) +
present. If the catalyst does not remove any of
the passive restraints that have been placed on
the system by opening up the possibility of addi-
tional reactions, the equilibrium yield will not
be affected by the presence of this material.
2.7.5 Effect of Excess Reactants
If nonstoichiometric amounts of reactants are
present in the initial system, the presence of
excess reactants tends to increase the equilib-
rium fractional conversion of the limiting re-
15
agent above that which would be obtained with
stoichiometric ratios of the reactants.
2.8 HETEROGENEOUS REACTIONS
The fundamental fact on which the analysis of
heterogeneous reactions is based is that when a
component is present as a pure liquid or as a pure
solid, its activity may be taken as unity, provided
the pressure on the system does not differ very
much from the chosen standard state pressure.
At very high pressures, the effect of pressure on
solid or liquid activity may be determined using
the Poynting correction factor.
p V dP
(2.8.1)
RT
where V is the molal volume of the condensed
phase. The activity ratio is essentially unity at
moderate pressures.
If we now return to our generalized reaction
2.4.5 and add to our gaseous components B, C,
S, and T a pure liquid or solid reactant D and a
pure liquid or solid product U with stoichio-
metric coefficients d and u, respectively, the re-
action may be written as
sS(g) + tT(g) + uU(/ or s) (2.8.2)
The equilibrium constant for this reaction is
(2.8.3)
4CB
When the standard states for the solid and
liquid species correspond to the pure species at
1 atm pressure or at a low equilibrium vapor
pressure of the condensed phase, the activities of
the pure species at equilibrium are taken as unity
at all moderate pressures. Consequently, the gas
phase composition at equilibrium will not be
16
affected by the amount of solid or liquid present.
At very high pressures equation 2.8.1 must be
used to calculate these activities. When solid or
liquid solutions are present, the activities of the
components of these solutions are no longer
unity even at moderate pressures. In this case
one needs data on the activity coefficients of the
various species and the solution composition in
order to determine the equilibrium composition
of the system.
2.9 EQUILIBRIUM TREATMENT OF
SIMULTANEOUS REACTIONS
The treatment of chemical reaction equilibria
outlined above can be generalized to cover the
situation where multiple reactions occur simul-
taneously. In theory one can take all conceivable
reactions into account in computing the com-
position of a gas mixture at equilibrium. How-
ever, because of kinetic limitations on the rate of
approach to equilibrium of certain reactions,
one can treat many systems as if equilibrium is
achieved in some reactions, but not in others. In
many cases reactions that are thermodynami-
cally possible do not, in fact, occur at appreciable
rates.
In practice, additional simplifications occur
because at equilibrium many of the possible re-
actions occur either to a negligible extent, or
else proceed substantially to completion. One
criterion for determining if either of these condi-
tions prevails is to examine the magnitude of
the equilibrium constant in question. If it is many
orders of magnitude greater than unity, the re-
action may be said to go to completion. If it is
orders of magnitude less than unity, the reaction
may be assumed to go to a negligible extent. In
either event, the number of chemical species that
must be considered is reduced and the analysis is
thereby simplified. After the simplifications are
made, there may still remain a group of reactions
whose equilibrium constants are neither very
small nor very large, indicating that appreciable
amounts of both products and reactants are
Thermodynamics of Chemical Reactions
present at equilibrium. All of these reactions
must be considered in calculating the equilib-
rium composition.
In order to arrive at a consistent set of relation-
ships from which complex reaction equilibria
may be determined, one must develop the same
number of independent equations as there are
unknowns. The following treatment indicates
one method of arriving at a set of chemical reac-
tions that are independent. It has been adopted
from the text by Aris (1).*
If R reactions occur simultaneously within a
system composed of S species, then one has R
stoichiometric equations of the form
v ^ . = 0 fc= 1 , 2 , . . . , / * (2.9.1)
i= 1
where vki is the stoichiometric coefficient of
species i in reaction k.
Since the same reaction may be written with
different stoichiometric coefficients, the impor-
tance of the coefficients lies in the fact that the
ratios of the coefficients of two species must be
identical no matter how the reaction is written.
Thus the stoichiometric coefficients of a reaction
are given up to a constant multiplier X. The
equation
foktA, = 0 (2.9.2)
i
has the same meaning as equation 2.9.1, pro-
vided that X is nonzero. If three or more reactions
can be written for a given system, one must test
to see if any is a multiple of one of the others and
if any is a linear combination of two or more
others. We will use a set of elementary reactions
representing a mechanism for the H 2 Br2
reaction as a vehicle for indicating how one
may determine which of a set of reactions are
independent.
* Rutherford Aris, Introduction to the Analysis of Chemical
Reactors, copyright 1965, pp. 10-13. Adapted by permis-
sion of Prentice-Hall, Inc., Englewood Cliffs, NJ.
2.9 Equilibrium Treatment of Simultaneous Reactions 17

Br2 -> 2Br In the present example the revised coefficient

Br + H 2 -> HBr + H matrix becomes
H + Br2 -> HBr + Br (2.9.3) 1 - 2 0 0 0
H + HBr -+ H 2 + Br 0 - 1 -1 1 1
2Br -> Br2 0 - 1 0 - 1 1 (2.9.9)
0 1 i _ i _ i
If we define
0 0 0 0 0
^ = Br2 A2 = Br /43 = H 2 The next step is to ignore the first row and
A4 = H A5 = HBr (2.9.4) the first column of this matrix and repeat the
then the above reactions may be written as above reduction on the resultant reduced matrix
containing R 1 rows. Thus, equation 2.9.9
-Ax+ 2A2 =0 becomes
1 - 2 0 0 0
=0 (2.9.5) 0 1 1 - 1 - 1
0 0 1 - 2 0 (2.9.10)
Ax- 2A2 =0 0 0 0 0 0
To test for independence, form the matrix of 0 0 0 0 0
the stoichiometric coefficients of the above re- This procedure may be repeated as often as
actions with vki in the fcth row and the ith column. necessary until one has l's down the diagonal as
far as possible and zeros beneath them. In the
- 1 2 0 0 0
present case we have reached this point. If this
0 - 1 - 1 1 1 had not been the case, the next step would have
-1 1 0 - 1 1 (2.9.6) been to ignore the first two rows and columns
0 1 1 - 1 - 1 and to repeat the above operations on the re-
sultant array. The number of independent reac-
1 - 2 0 0 0
tions is then equal to the number of l's on the
Next, take the first row with a nonzero ele- diagonal.
ment in the first column and divide through by Once the number of independent reactions has
the leading element. If v n / 0, this will give a been determined, an independent subset can be
new first row of chosen for subsequent calculations.

1 (2.9.7) ILLUSTRATION 2.2 DETERMINATION OF

EQUILIBRIUM COMPOSITIONS IN THE
This new row may now be used to make all other PRESENCE OF SIMULTANEOUS
elements of the first column zero by subtracting REACTIONS [ADAPTED FROM
vkl times the new first row from the corre- STRICKLAND-CONSTABLE (2)]
sponding element in the fcth row. This row then Consider a system that initially consists of 1 mole
becomes of CO and 3 moles of H 2 at 1000 K. The system

0 Vi Vfc3 - Vkl - Vfcl ' (2.9.8)

18 Thermodynamics of Chemical Reactions

pressure is 25 atm. The following reactions are The values of KP for reactions A and B are
to be considered. given by
2CO + 2H 2 ^ CH 4 + CO 2 (A)
p2 p2 ,,2 ,,2 p2
CO + 3H 2 - CH 4 + H 2 O (B) r
COrH2
CO 2 + H 2 ^ H 2 O + CO (C)
r.tf p p3
When the equilibrium constants for reactions CO H

A and B are expressed in terms of the partial The mole fractions of the various species may
pressures of the various species (in atmospheres), be expressed in terms of A and B so that the
the equilibrium constants for these reactions
above expressions for KP become
have the following values.
ZA
KPA = 0.046 KPB = 0.034
4 - 2^ - 2 4 - 2^ -
Determine the equilibrium composition of the
mixture.

Solution

The first step in the analysis is to determine if the

chemical equations A to C are independent by
applying the test described above. When one ( *-
(,4-2 ~ 2 ^ - 2c^B/)
does this one finds that only two of the reactions
are independent. We will choose the first two UA-ZB V3 \3p2
for use in subsequent calculations. Let the vari- (,4-2 1
ables A and B represent the equilibrium de-
(ZA~
grees of advancement of reactions A and B,
respectively. A mole table indicating the mole
numbers of the various species present at equilib- Substitution of numerical values for F, KPyA
rium may be prepared using the following form and KP B gives two equations in two unknowns.
of equation 1.1.6. The resultant equations can be solved only by
trial and error techniques. In this case a simple
n. = ni0 + vAiA + vBiB
graphical approach can be employed in which
one plots A versus B for each equation and
Initial mole Equilibrium notes the point of intersection. Values of A =
Species number mole number 0.128 and ,B = 0.593 are consistent with the
CO 1 1 - 2^ - SB
H2 3 3 It
CH 4 0 Species Mole number Mole fraction
CO 2 0
H2O 0 ZB CO 0.151 0.059
Total 4 4 - 14A - KB H2 0.965 0.377
CH 4 0.721 0.282
CO 2 0.128 0.050
The fact that none of the mole numbers can H2O 0.593 0.232
ever be negative places maximum values of 1/2
Total 2.558 1.000
on A and 1 on I
Problems
2.10 SUPPLEMENTARY READING
REFERENCES
The following texts contain adequate discussions
of the thermodynamics of chemical reactions;
they can be recommended without implying
judgment on others that are not mentioned.
1. K. G. Denbigh, The Principles of Chemical Equilibrium,
Third Edition, Cambridge University Press, Cambridge,
1971.
2. O. A. Hougen, K. M. Watson, and R. A. Ragatz, Chemical
Process Principles, Part I, Material and Energy Balances
and Part II, Thermodynamics, Second Edition, Wiley,
New York, 1954, 1959.
3. I. Prigogine and R. Defay, Chemical Thermodynamics,
translated by D. H. Everett, Wiley, New York, 1954.
4. F. T. Wall, Chemical Thermodynamics, Second Edition,
W. H. Freeman, San Francisco, 1965.
5. K. S. Pitzer and L. Brewer, revision of Thermodynamics,
by G. N. Lewis and M. Randall, McGraw-Hill, New
York, 1961.
6. M. Modell and R. C. Reid, Thermodynamics and Its
Applications, Prentice-Hall, Englewood Cliffs, N. J., 1974.
LITERATURE CITATIONS
1. Aris, R., Introduction to the Analysis of Chemical Reactors,
Prentice-Hall, Englewood Cliffs, N J , copyright 1965.
Used with permission.
2. Strickland-Constable, R. F., "Chemical Thermodynam-
ics," in Volume 8 of Chemical Engineering Practice,
edited by H. W. Cremer and S. B. Watkins, Butterworths,
London, 1965. Used with permission.
PROBLEMS
1. In the presence of an appropriate catalyst, ac-
etone reacts with hydrogen to give isopropanol.
CH3COCH3 + H 2 ^ CH3CHOHCH3
Standard enthalpies and Gibbs free energies of
formation at 25 C and 101.3 kPa are as follows.
AHf (kJ/mole) AGf (kJ/mole)
Acetone (g) -216.83 -152.61
Isopropanol (g) -261.30 -159.94
19
Tabulate the effects of the changes below on:
(a) Reaction velocity.
(b) Equilibrium constant.
(c) Equilibrium degree of conversion.
(d) Actual degree of conversion obtained in a
very short time interval at the start of the
reaction.
Variables:
(1) Increase in temperature.
(2) Increase of pressure.
(3) Substitution of a less active catalyst.
(4) Dilution with argon at constant total
pressure.
(5) Increase in the Reynolds number of the fluid
in the reactor.
Appropriate tabular entries are: (increases), (de-
creases), (no effect), (indeterminate).
2. Consider the ammonia synthesis reaction
being carried out at 450 C and 101.3 MPa.
IN2 + | H 2 - NH 3
The feed stream consists of 60 mole percent
hydrogen, 20% nitrogen, and 20% argon. Calcu-
late the composition of the exit gases, assuming
equilibrium is achieved in the reactor. Make
sure that you take deviations from the ideal gas
law into account. The equilibrium constant ex-
pressed in terms of activities relative to standard
states at 1 atm may be assumed to be equal to
8.75 x 10" 3 . Thefugacity of pure H 2 at 450 C
and 101.3 MPa may be assumed to be equal to
136.8 MPa.
3. A new process for the manufacture of acety-
lene has been proposed. The process will involve
the dehydrogenation of ethane over a suitable
catalyst (yet to be found). Pure ethane will be
fed to a reactor and a mixture of acetylene,
hydrogen, and unreacted ethane will be with-
drawn. The reactor will operate at 101.3 kPa
total pressure and at some as yet unspecified
temperature T.
The reaction
C 2 H 6 -> C 2 H 2 2H 2
20 Thermodynamics of Chemical Reactions

may be assumed to be the only reaction occur-
ring in the proposed reactor. The following data
on the heats of formation of ethane and acety-
lene are available.
is obtained, what is the composition of the
effluent mixture? The reactor may be as-
sumed to operate isothermally at 101.3 kPa
total pressure. Neglect any other reactions
that may occur.

AG/298 AHf2Q8
(kJ/mole) (kJ/mole)
4. As a thermodynamicist working at the Lower
Slobbovian Research Institute, you have been
Ethane -32.908 -84.724 asked to determine the standard Gibbs free en-
Acetylene 209.340 226.899 ergy of formation and the standard enthalpy of
formation of the compounds ds-butene-2 and
raws-butene-2. Your boss has informed you that
The standard states of these materials are taken the standard enthalpy of formation of butene-1 is
as the pure components at 298 K and a pressure 1.172 kJ/mole while the standard Gibbs free
of 101.3 kPa. The following data on the absolute energy of formation is 72.10 k J/mole where the
entropies of the hydrocarbons at 298 K are standard state is taken as the pure component
available. at 25 C and 101.3 kPa.
Your associate, Kem Injuneer, has been
testing a new catalyst for selective butene isom-
Entropy
erization reactions. He says that the only re-
(J/mole K)
actions that occur to any appreciable extent over
Ethane 229.65 this material are:
Acetylene 200.95
butene-1 ^ ds-butene-2
ds-butene-2 ^ trarcs-butene-2
(a) What is the standard Gibbs free energy
change at 25 C for the reaction as written? He has reported the following sets of data from
(b) What is the standard enthalpy change at his system as being appropriate for equilibrium
25 C for the reaction as written? conditions.
(c) What is the absolute entropy of gaseous
hydrogen at 25 C and a pressure of 101.3 Run I
kPa? Use only the above data in evaluating Reactor pressure 53.33 kPa
this quantity. Reactor temperature 25 C
(d) What is the equilibrium constant for the Gas composition (mole percent):
reaction at 25 C? butene-1 3.0
(e) If the standard enthalpy change may be as- cis-butene-2 21.9
sumed to be essentially independent of tem- trans-butene-2 75.1
perature, what is the equilibrium constant
for the reaction at 827 C? Run II
Reactor pressure 101.3 kPa
(f) If we supply pure ethane at 827 C and a
Reactor temperature 127 C
pressure of 101.3 kPa to the reactor de-
Gas composition (mole percent):
scribed above and if equilibrium with respect butene-1 8.1
to the reaction cis-butene-2 28.8
trans-butQnQ-2 63.1
C 22 H 6 C2H2 2H 2
Problems
Kem maintains that you now have enough data
to determine the values of AGf and AHf for
the two isomers of butene-2 at 25 C.
Proceed to evaluate these quantities. State
specifically what assumptions you must make
in your analysis and comment on their validity.
Use only the above data.
5. Hydrogen can be manufactured from carbon
monoxide by the water gas shift reaction
H2
CO + H 2 O ^ CO 2
At 900 F the equilibrium constant for this re-
action is 5.62 when the standard states for all
species are taken as unit fugacity. If the reaction
is carried out at 75 atm, what molal ratio of
steam to carbon monoxide is required to pro-
duce a product mixture in which 90% of the
inlet CO is converted to CO 2 ?
6. (a) What is the composition of an equilib-
rium mixture of N O 2 and N 2 O 4 at 25 C
and 101.3 kPa? It may be assumed that
the only chemical reaction involved is:
N2O4(</) - 2NO2(g)
(b) Calculate values of the Gibbs free energy
of mixtures of these two substances at
25 C and 101.3 kPa for several different
compositions from 0 to 1.0 mole fraction
N 2 O 4 . Base your calculations on a mix-
ture containing 2 gram atoms of nitrogen.
Plot the results versus composition. Com-
pare the composition at the minimum
with that determined in part (a).
7. At 25 C the standard Gibbs free energy
change for the reaction
so2 so 3
is 70.04 kJ/mole where the standard states are
taken as the pure components at 101.3 kPa and
25 C. At 227 C and a total system pressure of
1.013 kPa, the following equilibrium compo-
sition was determined experimentally.
21
Component Mole percent
O2 0.10
so 2 0.12
so 3 78.18
Helium 21.60
(a) What is the equilibrium constant for the
reaction at 25 C and 1.013 kPa?
(b) What is the equilibrium constant for the
reaction at 227 C and 1.013 kPa?
(c) What is the standard enthalpy change for the
reaction if it is assumed to be temperature
independent?
(d) Will the equilibrium constant for the re-
action at 25 C and 101.3 kPa be greater
than, equal to, or less than that calculated in
part (a)? Explain your reasoning.
8. A company has a large ethane (C 2 H 6 ) stream
available and has demands for both ethylene
(C 2 H 4 ) and acetylene (C 2 H 2 ). The relative
amounts of these two chemicals required varies
from time to time, and the company proposes to
build a single plant operating at atmospheric
pressure to produce either material.
(a) Using the data below, calculate the maxi-
mum temperature at which the reactor may
operate and still produce essentially ethylene
(not more than 0.1% acetylene).
(b) Calculate the minimum temperature at
which the reactor can operate and produce
essentially acetylene (not more than 0.1%
ethylene).
(c) At what temperature will one produce
equimolal quantities of acetylene and
ethylene?
Data and Notes: Assume that only the following
reactions occur.
C2H6 H2
Neglect the effect of temperature on AH0.
9. A gas mixture containing only equimolal
quantities of CO 2 and H 2 is to be "reformed" by
22 Thermodynamics of Chemical Reactions

flowing it over a powerful catalyst at 1000 K 11. Methanol may be synthesized from hydro-
and at various pressures. Over what range of gen and carbon monoxide in the presence of an
pressures may carbon deposit on the catalyst? appropriate catalyst.
Over what range of pressures will it not deposit?
CO + 2H 2 ^ CH 3 OH
Note. Assume that only the reactions given in
the table occur, and that equilibrium is attained. If one has a feed stream containing these gases in
stoichiometric proportions (H 2 /CO = 2) at 200
X atm and 275 C, determine the effluent composi-
tion from the reactor:
3.16 (a) If it operates isothermally and equilibrium
C + 2H 2 O ^ CO 2 + 2H 2 5.01 is achieved.
CO 2 + C ^ 2CO 2.00 (b) If it operates adiabatically and equilibrium
CO + H 2 O ^ C O 2 + H 2 1.58 is achieved. (Also determine the effluent
temperature.)
For an initial ratio of CO 2 to H 2 of unity, what Data:
must the pressure be if exactly 30% of the carbon (1) AH0 = -17,530 - 18.19T + 0.0141T2 for
present in the feed can precipitate as solid AH0 in calories per gram mole and T in
carbon? degrees Kelvin.
The equilibrium constants are based on a (2) Molal heat capacities at constant pressure
standard state of unit fugacity for the gaseous H2 Cp = 6.65 + 0.00070 T
species and on a standard state corresponding CO Cp = 6.89 + O.OOO38 T
to the pure solid for carbon.
CH3OH Cp = 2.0 + 0.03T
10. Butadiene can be produced by the dehydro- for Cp in calories per gram mole-degree
genation of butene over an appropriate catalyst. Kelvin.
C4H8 (3) Equilibrium constant expressed in terms of
H2 C4H6
fugacities
In order to moderate the thermal effects asso-
ciated with the reaction, large quantities of 3835
Kf = - 9.150 l o g 1 0 T
steam are usually injected with the butene feed.
Steam/butene ratios of 10 to 20 are typical of the
+ 3.08 x 10" 3 T + 13.20
conditions employed in many industrial reac-
tors. If equilibrium is achieved within the reactor, (4) Note that in part (b) a trial and error solu-
determine the effluent composition correspond- tion is required. (Hint. The effluent tempera-
ing to the conditions enumerated below. ture will be close to 700 CK.)

Effluent temperature 820 K

Effluent pressure 101.3 kPa
Feed composition (mole percent)
Steam (H2O) 92%
Butene
Thermodynamic data at 800 K AGf (kJ/mole) AHf (kJ/mole)
H 2 O (g) -203.66 -246.53
Butene (g) 207.04 -21.56
Butadiene (g) 228.10 97.34
0 0
Problems
12.* In a laboratory investigation a high-pres-
sure gas reaction A ^ 2B is being studied in a
flow reactor at 200 C and 10.13 MPa. At the end
of the reactor the gases are in chemical equilib-
l
rium, and their composition is desired.
Unfortunately, to make any analytical mea-
surements on this system, it is necessary to bleed
off a small side stream through a low-pressure
conductivity cell operating at 1 atm. It is found
that when the side stream passes through the
sampling valve, the temperature drops to 100 C
arid the conductivity cell gives compositions of
yA = 0.5 and yB = 0.5 (mole fractions).
: (4) The flow through the sampling valve is a true
Adapted from Michael Modell and Robert C. Reid,
Thermodynamics and Its Applications, copyright 1974.
Reprinted by permission of Prentice-Hall, Inc. Englewood
Cliffs, N. J.
23
From these experimental data and the physi-
cal properties listed below:
(a) Calculate the composition of the gas stream
before the sampling valve.
(b) Are the gases at, near, or far from chemical
equilibrium after the sampling valve? (Show
definite proof for your answer.)
Data and Allowable Assumptions:
(1) Heat of the reaction, AH = 29.31 kJ/mole of
A reacting, independent' of temperature.
(2) Heat capacities: 58.62 J/mole-K for A
and 29.31 J/mole-K for B, independent of
temperature.
(3) The gas mixture is ideal at all pressures,
temperatures, and compositions.
Joule-Thompson expansion.
(5) Assume no heat loss in the sampling line or
across sampling valve.