Chemical Equilibrium

Charles D. Mickey
Texas A&M University at Galveston
Galveston, TX 77553

Many chemical reactions do not proceed to completion;

instead, they establish a dynamic equilibrium in which two
opposing reactions occur at the same rate.1 For example,
mixing solutions containing cerium(IV) and iodide ions gives
rise to the reaction

2Ce?a+q) + 3lraq, -
2Ce&> + I7(aq)
On the other hand, when cerium(III) is added to a solution of
triiodide ion, significant quantities of cerium(IV) and iodide s
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ions are produced. The extent of either reaction is easily E

gauged by the intensity of the orange-red color of the triiodide C
ion. The concentration of this colored ion rapidly reaches a
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constant level that is independent of the route by which it is o

formed. It makes no difference whether Ce4+ and I- or Ce3+ N
and 17 are selected as the original reactants; the same condi- The variation in concentration of reactants and products as a function of lime,
D
(a) initially, stoichiometric amounts of Ce4+ and I- are mixed and allowed to reach
tion of equilibrium will result. In the beginning, if Ce4+ and
I~ are the original reactants, the concentrations of Ce4+ and equilibrium, (b) Stoichiometric amounts of Ce3+ and 17 are allowed to react at A
the same temperature. In both instances, the final equilibrium concentrations
I- will be high, and consequently the forward reaction will R
of all species are the same.
proceed rapidly. No reverse reaction is possible at the start, Y
since Ce3+ and I:7 are not yet present. As Ce3+ and 17 are
the other to the left (called the reverse reaction), in which D
formed, the reverse reaction will begin slowly and gradually and E react to form A and B. According to the Law of Mass
increase in rate as Ce3+ and I7 accumulate. Meanwhile the g
forward reaction is slowing down as Ce4+ and I- are being used Action, the rate of the forward reaction is proportional to the q
concentrations of the reactants A and B, while the rate of the
up, as shown in Figure I, reverse reaction is proportional to the concentration of D and H
Conditions of chemical equilibrium that most chemical E. Thus, the forward reaction has the rate
reactions can attain may be compared to a person running on O
a treadmill, which moves faster as the runner increases his Rate{ £fjA)[B]
= O
speed. When the runner and the treadmill are in equilibrium, ^
the runner is apparently stationary to an observer. If the and the reverse reaction has the rate
runner increases his speed, he advances a short distance. A,[D][E]
Rate, =

However, as the treadmill also moves faster, the runner again c

where brackets, [ ], represent the molar concentrations of the
appears to be stationary; although, his position is in advance H
enclosed substances, and k[ and kT are proportionality con-
of his previous stationary position. E
In a reversible reaction, such as stants called specific rate constants.
Guldberg and Waage assumed that equilibrium results M
2N0te) + 02(g) ^ 2N02(gl When the rates of the forward and reverse reactions are equal,
I
the equilibrium amounts of NO, O2, and NO2 remain constant; i.e.,
S
yet like the runner and the treadmill, the reactions proceed Rate =
Rater
in opposite directions at the same rate.
f
T
Therefore, at equilibrium, R
The Law of Mass Action
fef[A][B] =
MD][E] Y
In 1864, the Norwegian chemists Cato M. Guldberg and
Peter Waage proposed that the rate of a chemical reaction is Writing this equation in a more useful form gives
proportional to the active masses of the reacting substances; if=MM
the molecular concentration of a substance in solution or in kr [A] [B]
the gas phase is used as a measure of its active mass.2 The Inasmuch as k( and kr are both constants, their ratio kjkr is
significance of this statement, which is called the Law of Mass also a constant, hence
Action (the rate law in kinetics) is more apparent as the
quantitative notions of chemical equilibrium are developed. hi_K JD][E]
For example, consider the general reversible reaction in which kT~ e\ [A] [Bj
an equilibrium exists between four substances A, B, D, and
in which Keq is called the equilibrium constant. Although the
E kinetic arguments used for the derivation of this equilibrium
constant are not applicable to complex multistep reactions,
A+ D+ E they are valid for simple one-step bimolecular reactions.
Two reactions are proceeding, one to the right (called the
forward reaction), in which A and B react to form D and E and This feature is aimed as a review of basic chemical principles
and as a reappraisal of the state of the art. Comments, sug-
1
Mickey, C. D., J. CHEM. EDUC., 57,659 (1980) gestions for topics, and contributions should be sent to the
2
Glasstone, S., “Textbook of Physical Chemistry,” D. Van Nos- feature editor.
trand Company, Inc., New York, 1946, p. 817.

Volume 57, Number 11, November 1980 / 801

 The Equilibrium Constant and Ideal Behavior and at equilibrium,
The expression
Ri “
Rt
,
eq
=ID][E] therefore,
[A|[B]
is only rigorously valid in situations where all reactants and fef[C02l[H20]3 =
fer|H;,O+]2[C0M
products behave like ideal gases or are components of an ideal hence
solution. For example, just as conductivity in concentrated
solutions of strong electrolytes fails to indicate complete k(_,, eq _ [h3o+]2[com
ionization, because of the interference of ions with the motions kr [C02][H20]3
of other ions, the presence of high concentrations of ions in- Alternately, assume that the reaction proceeds by the fol-
terferes with the reactions of any ion. If the rates of reactions lowing two-step mechanism:
in concentrated solutions of strong electrolytes are calculated
C02(aq) + 2H20(1) —
HsOjiq) + HC03(aq) (Step 1)
and compared with the measured rates of these same reac-
tions, there are discrepancies which increase with the increase HCO^q, + H20(1) H30,+aq) + C03faq)
-

(Step 2)
in concentration. Moreover, these discrepancies will be re- For the first step
flected in the equilibrium constant. If the activity of the re- Rf =
fcf[C02](H20]2
acting particle is substitued for its concentration or partial
Rr Ar[H30+J[HC03-]
=

pressure a correct rate of reaction is found and the equilibrium

constant will be rigorously valid. The correction factor used At equilibrium, Rf =
Rr, and since the ratio of two constants
s as a multiplier of the actual pressure or concentration to is a third constant
E produce the activity is called the activity coefficient (7). The kf_u 1 [H30+][HC03]
experimentally determined value of the activity coefficient
_

C kr [C02J[H20]2
varies, not only from one substance to another, but also with Similarly, for the second step:
o pressure, concentration, and temperature. The magnitude of
N the activity coefficient is always less than one and approaches R'{= *j[HC03][H20]
D unity as the partial pressure or concentration decreases. The K =
*;[H30+][C0|-]
activity (a) of a reaction component is its molar concentration
A or partial pressure times an activity coefficient (7), or a yM = At equilibrium, R{ =
R,' and
R for solutions and a =
7P for gases. The activity of a pure k'<=K 2 - [H3Q+|[COn
Y liquid or a pure solid, at constant temperature, is defined as Vr [HC03-][H20]
unity. The product of two constants is a third constant; therefore,
One of the great theoretical outcomes of chemical thermo-
the product
S dynamics was the rigorous derivation of equilibrium constants
C using activities, rather than molarities or partial pressures. KX X K2 =
Keq
=
[H30+][HC03]
H Although it is not possible within the scope of this article, it [C02][H20]2
can be shown that the thermodynamic analog of the preceding [H30+][C0n [H30+]2[C0n
x _

0 equilibrium-constant expression is [HC03][H20] [C02][H20]3

0 apCB
q
= Consequently, the equilibrium-constant expression turns out
L oa°b to be the same; whether based on kinetic arguments or the
Frequently, as in this discussion, equilibrium constants are balanced equation. Thus, for the general reaction:
based on molarities or partial pressures instead of the more
C exact activities, for three reasons: (1) the measurement of rA + sB ==: xD + 2E
H reagents are usually made in grams and put into solutions in in which r, s, x, and 2 represent the coefficients of A, B, D, and
E terms of grams or moles per liter; (2) the activity coefficient E, respectively, in the balanced equation, the formulation of
of any ion changes not only with its own concentration, but Keq is
M with that of other ions in the solution; (3) all substances for
1 which equilibria are calculated are either in dilute solutions K eq _ [D]x[Ep
of their kinds of ions and molecules or are weak electrolytes, [A]r[B]s
S
so the approximations secured by the use of molarities or There are several different but interrelated types of equi-
T
partial pressures instead of activities are sufficiently accu- librium constants, with the symbol Keq generally used to
R rate.
represent any of the various kinds. However, special desig-
Y nations for equilibrium constants are frequently used to
General Form of the Equilibrium Constant
characterize a particular equilibrium system. The symbol Kp,
Fortunately, it is not necessary to know the mechanism or for example, indicates a particular equilibrium constant in
rate laws for a reversible reaction to be able to write the
which the quantities of gaseous reactants and products are
equilibrium-constant expression. Even if a reversible reaction
proceeds through a series of complicated steps, each individual expressed in terms of their partial pressures. Concentrations
can be related to partial pressures through the ideal gas law
step is reversible and, at equilibrium, the reversible reactions
(PV nRT)\ therefore, the partial pressure for any gaseous
=

proceed at the same rate in both directions. Thus, the equi-

librium-constant expression can be derived from the balanced reactant or product, that behaves ideally, is proportional to
its concentration. Hence, for the gas phase equilibrium:
equation for the overall reaction. Consider the reaction
N2(g) + 3H2(E) ^
2NH3(g)
C02(aq) + 3H20(]) —>
2^)0^) + C03^q)
If the forward reaction is a single-step termolecular reaction, the equilibrium-constant expression is
its rate will be expressed as:
kp = =
3.52 X 10-7 at 1000°K
Ratef =
fef[C02][H20]'!
The symbol Kc represents a particular equilibrium constant
Likewise, if the reverse reaction is a single-step trimolecular in which the quantities of reactants and products are ex-
reaction, its rate will be given by the equation:
pressed in terms of their molarities. The Kc value for the
Rate, =
/MHsO+PICOM previous reaction is
802 / Journal of Chemical Education

Kc =
rirTTTTTi =
IN2IIH2I
Two different reactions will generally have different equi-
librium constants. At 1000°K the reaction involving carbon
monoxide, oxygen, and carbon dioxide
2CO(g) + 02(B)
has the equilibrium constant value
= 224 x
TUSFffcl=
The fact that in the latter reaction Kc is greater than Kc in the
former reaction means that at 1000°K carbon monoxide and
oxygen are more completely converted to carbon dioxide than
nitrogen and hydrogen are to ammonia. Thus, the magnitude
of the equilibrium constant may be used to gauge the extent
to which a given reaction progresses toward completion. If all
other factors are equal, a value of Keq > 1 indicates a high
degree of conversion of reactants to products and a value of
Keq < 1 indicates a low degree of conversion.
The Forward and Reverse Reactions
Since equations for chemical reactions may be written in
a variety of different but equivalent ways, each value for an
equilibrium must always be accompanied by the specific
equation which it represents. For example, in the reaction
Cu?„ + 2Agfaql
-
2.37 * 10-3 at 1000° K
concentration, which affect the rate of any reaction will also
affect the equilibrium; that is, these same parameters can
change the balance between the two opposing reactions. To
understand the problem more clearly, again consider the
analogy between a chemical system in equilibrium and a
person running on a treadmill which increases its speed as the
5=1
2C02(E)
person advances. If the person while running and apparently
remaining stationary with respect to some fixed point, in-
creases his speed he advances; but as he does so the speed of
treadmill also increases and again the runner comes to an
1022 atl000°K
apparent stationary position. For the second time, the runner
and the treadmill are in a state of equilibrium, but the runner
has now occupied a position farther forward. If, on the other
hand, the runner tires he runs slower. Momentarily he shifts
his position backward; but since the treadmill is readjusted
to a slower rate, the runner will soon assume a new position
of equilibrium. During the short interval that the runner ad-
vances or falls back, the position of equilibrium is shifted.
In a analogous manner, the equilibrium position of a
chemical reaction may be shifted; and it is customary to speak
of a shift in equilibrium to the right or to the left with refer- s
ence to the chemical equation for the reaction taking place. E
Thus, in the equilibrium between nitrogen, hydrogen, and C
ammonia as represented by the equation
0
N2(g) + 3H2(b) 2NH3(B) N
all these substances are present in definite amounts and the D

Cufo, + 2Ag(s) reaction is proceeding in both directions. If now, by some in- A

fluence, the equilibrium is affected so that more ammonia is
The equilibrium constant is R
formed; the equilibrium is shifted to the right. During the
rCu2+l
Kc =
tFzw = 2 X 1015 at 298° K change from one equilibrium position to another, the reaction Y
[Ag+J2 proceeds momentarily faster from left to right than from right
to left. This situation is analogous to the momentary shift in
Suppose the reaction is written as S
the position of the runner on the treadmill when he is inspired
Cufa+q) + 2Ag(’s) ^
Cu®a) + 2Agfaq) to run faster. C
consistency is maintained and ambiguity avoided, if the Le Chateiier’s Principle and Chemical Equilibrium H
equilibrium constant is written as Extensive studies of reversible reactions and the equilibria O

Kc = = 5 X 10~16 at 298°K associated with them led the French chemist, Henri Louis Le 0
Chatelier (1888), to make a simple generalization, commonly L
referred to as Le Chateiier’s Principle:
Quantitatively, for any reversible reaction the value of the
equilibrium constant for the reverse reaction is the reciprocal A system at equilibrium, when subjected to any stress (such as C
of the equilibrium constant for the forward reaction. In other change in temperature, pressure, or concentration of matter) so that
H
words, equilibrium is disturbed, will tend to adjust itself so as to remove the
stress and re-establish equilibrium. E
K( reverse) =
T7
Of the three stresses, only a change in temperature will affect M
(forward)
the magnitude of the equilibrium constant. For example,
As illustrated in the last two equations, it is customary to
1

exclude the concentration terms for solids from the equilib- Reaction Temp (°K) K S
rium expression. The concentrations of the silver and copper N2(b, + 3H2(B) ^
2NH3(b, 623 2.66 X 10“2 T
solids are constant, hence the respective equilibrium-constant N2(b) + 3H2(g) 2NHa(B) 723 6.59 X 10"3
N2(b) + 3H2(g) —
2NHa(B) 1000 2.37 X 10~3 R
expressions are simplified by combining the constants. Sim-
The Effect of Temperature on an Equilibrium Y
ilarly, the concentration of a pure liquid is constant, hence its
concentration term is also excluded from the equilibrium- All chemical reactions are accompanied by energy changes.
constant expression. For example, consider the reaction Some reactions are exothermic—produce heat during the
reaction; others are endothermic—absorb heat from the sur-
NH4(aq) + HN02(aq) N2(aq) + 2H20(() + H+(aq)
“

roundings. In the reaction

the equilibrium constant is expressed by N2(b) + 3H2(b) —
2NH3 + 22.08 kcal
nitrogen and hydrogen, in combining to from ammonia, pro-
_ [N2][H20]2[H+| duce heat. When ammonia decomposes into nitrogen and
eq
[NHJ][HN02] hydrogen (the reverse reaction), an equivalent amount of heat
must be absorbed. When this system is at equilibrium, no heat
Combining the two constants in this equation gives
change occurs.
JO, c
_ [N2][H+] A quantitative relationship between the equilibrium con-
[H20]2 [NH4+][HN02] stant and temperature can be derived from the Arrhenius
Factors Influencing Equilibrium equation for the specific rate constant, since the equilibrium
constant, Ksq, is equal to the ratio kf/kt. The specific rate
At equilibrium a chemical reaction is proceeding in the constant for the forward reaction is
forward and reverse directions with equal velocities, thus it
is expected that the parameters, such as temperature and kf =
Afe~EalRT

Volume 57, Number 11, November 1980 / 803

 while the corresponding expression for the reverse reaction the position of the equilibrium shifts to the left.
is Conversely, removal of a component from an equilibrium
system favors the reaction which replaces it. For example, the
kr =
AIe~E°'IiT removal of sulfur trioxide from the equilibrium system shifts
Substitution shows the temperature dependence of Keq< the position of equilibrium to the right. The forward rate will
momentarily be greater than the reverse rate; the system is
Km kf_ Ase-Ea/RT _

e-(.Ea)f-IEa),/RT temporarily out of equilibrium and sulfur trioxide molecules

hr Are~Ea/RT Ar will be produced faster than they are used up in the reverse
reaction. Similarly, if part of the sulfur dioxide or oxygen is
and
removed, the reverse reaction, forming more sulfur dioxide
Keq
=
Ze~AF-n/RT and oxygen, will be favored.
The Effect of Pressure on Equilibrium: A Special Case of
(where Z, a constant, is the ratio of A[/Ar). Thus, for exo- Changing Concentration
thermic reactions /veq decreases as temperature increases, and
for endothermic reactions ffeq increases as temperature in- Change of pressure is insignificant for liquids and solids
creases. In other words, increasing the temperature will shift
because of their low compressihility, but it is extremely im-
the position of equilibrium to the left for an exothermic re- portant for gases because the molarity of a gas, at constant
action; whereas, increasing the temperature will shift the temperature, is directly proportional to its partial pressure
position of equilibrium to the right for an endothermic reac- {PV nRT). Therefore, as the external pressure on a gaseous
=

tion. This simplified derivation supports the generalization system increases, the substances undergo compression and
of Le Chatelier. the molarity increases. Le Chatelier’s principle indicates that,
s if a stress is placed on a reversible system by increasing the
E According to Le Chatelier’s principle, if heat is added to the
nitrogen, hydrogen, ammonia system (increase of tempera- pressure, that chemical change will be favored which will tend
C to reduce the pressure. For a gaseous system, the increase in
ture), the system will change in such a way as to minimize the
0 stress. To relieve the stress (increase of temperature), the pressure is achieved by increasing the total number of mole-
cules per unit volume. This process will favor the net chemical
N system will absorb heat, i.e., the formation of nitrogen and
hydrogen from ammonia will be favored since this reaction change that will reduce the total number of molecules per unit
D absorbs heat. In reality, part of the heat is used to increase the volume.
A Consider the reversible reaction
temperature of the system and part is used to shift the equi-
R librium. 2CO(g) + 02(g) =5
2C02(g)
Y The Effect of Changing Concentration on the Position of A total of three moles of carbon monoxide and oxygen form
Equilibrium only two moles of carbon dioxide. The formation of carbon
Another way to put a stress on a system is to alter the con- dioxide will therefore decrease the total number of molecules
S in the system, and the total gaseous pressure will therefore be
centration of one or more of the components. This can be ac-
C reduced. Thus, increasing the total external pressure on the
complished by adding or removing one or more of the equi-
H librium species. For example, consider the equilibrium system will favor the conversion of carbon monoxide and
0 oxygen to carbon dioxide. Conversely, a decrease in the total
2S02(g> + 02(g) —-
2803(g) external pressure will favor the dissociation of carbon dioxide
0 where to carbon monoxide and oxygen.
L If PC15 is injected into a closed system at 523° K, it disso-
,, _ [S03P ciates to an equilibrium state:
eq
C [so2ho2] PCl5(g) ^
PCl3(g) + Cl2(e)
H A stress can be placed on this system by adding sulfur dioxide, Since there are two moles of gaseous product compared to only
oxygen, or both. In either event, the product of the molar one mole of gaseous reactant, an increase in the external
E
concentrations in the denominator of the equilibrium-con- pressure will cause a shift in the equilibrium to the left, i.e.,
M stant expression exceeds the equilibrium value, and the ratio less PCI5 dissociates; whereas a decrease in the external
1 of the molar concentrations is now less than Keq. If the molar pressure will favor the dissociation of PClr,. In other words,
concentration of sulfur dioxide is increased, the reaction rate there is a shift in the equilibrium to the right.
S
to the right will increase, and the change which tends to use Certain gaseous reactions are not affected by changes in
T pressure, for example:
up sulfur dioxide and oxygen and thus remove the stress will
R be favored. This conforms to Le Chatelier’s principle which
indicates that the equilibrium system will shift so as to min- H2(e) + C12W ^
2HCl(g)
Y
imize the stress. Sulfur dioxide and oxygen will be used up In this case there are two moles of reactants and two moles of
faster than they are formed, and the molar concentration of product. Changes in the external pressure have no effect on
sulfur trioxide will increase. However, as the molarity of sulfur this system because there are equal numbers of molecules on
trioxide increases, the rate of its dissociation into sulfur both sides of the equation.
dioxide and oxygen will also increase. Eventually, the forward
Catalysts and Equilibrium
and reverse reactions will attain equal rates and equilibrium
will be re-established. The stress placed on the system, when While catalysts are used to increase the rate of a reaction,
the concentration of sulfur dioxide was increased, will have they cannot change the numerical value of the equilibrium
been removed by changes in the molarites of all the substances constant and hence cannot change the relative amounts of
such that the value of Keq is restored. Note that when the reactants and products present at equilibrium. However, the
concentration of sulfur dioxide is increased, the net changes catalyst may greatly reduce the time necessary for the estab-
which occur in the system are such that the concentration of lishment of equilibrium. This is extremely important from an
oxygen is decreased while the concentration of sulfur trioxide
industrial viewpoint, since the rate at which a product can be
is increased. In other words, oxygen can be used up more produced is a primary consideration. Catalysts may be used
completely and sulfur trioxide can be produced more effi- effectively in many reactions which allow conversion of only
a small percentage of reactants into products (position of
ciently by increasing the concentration of sulfur dioxide. On
the other hand, the introduction of more sulfur trioxide into equilibrium shifted far to the left) because, from a production
the system favors the reverse reaction, more sulfur dioxide and standpoint, it is far more important to obtain a small yield in
a few minutes than to obtain a large yield in several days.
oxygen are formed while some sulfur trioxide is consumed, i.e.,
804 / Journal of Chemical Education