Chapter 19

Rates and Equilibrium

19.1 INTRODUCTION
We havc learned (Chap. 7) that sorne reactions occur under one
set of conditions while an opposite reaction occurs under anothcr set
of conditions. For example, we learned that sodium and chlorine
combine when treated with each other, but that molten NaCI dccomposcs
when treated with electricity:
2Na + Cl2--
+ 2NaCI
elect
ricity
----+
2NaCl(molten)
2Na + Cl2
However, sorne sets of reactants can undergo both a forward and a
reverse reaction under the same set of conditions. This circumstance
leads to a state called chemical equilibrium. Before we take up
equilibrium, however, we have to leam about the factors that affect the
rate of a chemical reaction.

19.2 RATES OF CHEMICAL

REACTION
Sorne chernical reactions procced vcry slowly, others with explosive
speed, and still others somewhcre in between. The "dissolving" of
underground limestone deposits by water containing carbon dioxide to
forro cavems is an example of a slow reaction: it can take ccnturies. The
explosion of TNT is an example of a very rapid reaction.
The rate of a reaction is defined as the change in concentration of any
of its reactants or products
per unit time. There are six factors that atfect the
rate of a reaction:
l. The nature of the reactants. Carbon tetrachloride (CCl4) does not
bum in oxygen, but rnethane (CH) burns very well indeed. In fact,
CCl4 used to be used in fire extinguishers. while CH-1 is the major
componen! of natural gas. This factor is least controllable by the
chemist, and so is of least interest here.
2. Temperature. In general, the higher the ternpcrature of a systern,
the faster the chemical reaction will proceed. A rough rule of thumb is
that a lOºC rise in temperature will about double the rate of a
rcaction.
3. Thc prcscnce of a catalyst. A catalyst is a substance that can
accelerate (or slow down) a chemical reaction without undcrgoing a
permanent change in its own composition. For example, the
decornposition of KCl0_1 by hcat is accelerated by thc presencc of
a small quantity of Mn02. After thc reaction. the KCI0_1 has been
changed to KCI and 02, but thc Mn02 is still Mn02.
4. Thc concentration of thc reactants. In general, the higher the
concentration of the rcactants. the
faster thc reaction.
5. The pressurc of gaseous reactants. In general, the higher the
pressure of gascous rcactants. the faster thc reaction. This factor is
merely a corollary of factor 4, since the higher pressure is in effect a
highcr concentration.
6. Statc of subdivision. The smaller the pieces of a solid
reactant-the srnaller the state of subdivision-thc fastcr the
rcaction. Wood shavings bum fastcr than solid wood. for exarnple,
because they have more surfacc arca in contact with the oxygen with
which they are combining (for a givcn mass of wood). In a sense, this
is also a corollary of factor 4.
Most of the factors that affcct the rate of a reaction are qualitative or
scmiquantitative, but the
dcpendcncy of thc ratc on conccntration (or prcssure, which is a
measure of concentration) may be

283
284
CHAP. 19] RATES AND
RATES ANO EQUILIBRIUM [CHAP.285
19

stated as a rate law expression . For the reaction

a A + b B --->
products thc rate law gcnerally has the
following form:
rate = 1

k[A]'[B]
The proportionality constant k , called the rute constant , has a constant
value for a given reaction at a given temperature. The terms in square
brackets are concentration terrns (compare Chap. 14), and x and y are
exponents which are oftcn integral. The exponent x is called the order
with respect to A, and y is called the order with respect ro B. Thc sum x
+ y is called thc overa// order of the reaction. The valúes for x and y
can be O, 1, 2, 3 or 0.5, 1.5, or 2.5, but never more than 3. These values
must be determined by cxperirnent, and do not ncccssarily equal the
values of a and b in the chemical equation.

EXAMPLE 19.1. In a ccrtain rcaction, doubling thc initial

conccntration of thc only rcactant doublcs thc initial ratc of the
rcaction. What is thc ordcr of thc rcaction?
Sincc thc ratc doublcs as thc conccntration doublcs, the rcaction
mus! be first ordcr.
ratc = k[Aj'

2 = k[A)i: =
2 = rate
([Ah)·'= 2., ratc ,
.r mus! k[A]1 (A]1
cqual 1.

EXAMPLE 19.2. In a ccrtain rcaction, doubling thc initial

conccntration of thc only rcactant quadruplcs thc initial rate of the
rcaction. What is thc ordcr of the rcaction?
Sincc thc ratc quadruples as thc cunccntration doubles, thc reaction
rnust be sccond ordcr.
ratc =
k[A]'
ratc ,
k(A],'
4 = -- =
---- = 2 .l
rutc ,
k[A)¡'
x must cqual 2.

EXAMPLE 19.3. Thc ratc of a givcn rcaction changos as thc rcaction

procccds, Explain why.
285
CHAP. 19] RATES AND
RATES ANO EQUILIBRIUM [CHAP.285
19

Thc conccntrations of thc rcactants changc as the reaction

progrcsscs, and so thc ratc changes becausc it dcpends on thc
conccntrations. An illustration of thc cffcct of time on thc ratc of a
first-ordcr proccss is the dccay of a radioactivo substancc,
considcrcd in Scc, 22.3.

EXAMPLE 19.4. Considcr thc following data about thc rcaction

A + B --+
products
lnitial lnitial
Concentr Concentr
Run Initial
ation
O.IOof A ation
I.O of2.1 X 10-
1
2 0.20 I.O 8.4X 10
3 0.20 2.0 8.4 X 10
M rcspcct to M
Determine thc ordcr with ·1 M/s
A and with rcspect to B. as wcll
as the overall ordcr,
ratc = 1

k[A]'[B]
Whcn thc initial conccntrarion of A doubles and that of B stays
thc sarnc (compare runs I and 2), the ratc mercases by a factor
of 4. The value of x must be 2. Whcn thc conccntration of B
doubles with constan! A
concentration (as in runs 2 and 3), thc ratc <loes not chango. Thc valuc
of y is O.
ratc ,
k[A)/
4=-- x must cqual 2
=-- =2 r
ratc¡ k[A]¡'
-2'
(--rate-, k[B],'-
y must cqual O
- ratc , - k[B]/ -
Thc overall ordcr is
2 + O = 2.

EXAMPLE 19.5. What can you determine about thc rcaction from just
runs I and 3 of thc table in Example
19.4?
You cannot tell if thc chango in ratc stcms from thc changc in
A conccntration, the change in B conccntration, or both. Kceping ali
but onc of the factors constant during a series of rcactions, and using
thc effect of that onc changc. is thc characteristic of a controlled
experiment .

EXAMPLE 19.6. From the following data, calculare the valuc of k for
the reaction
A + B ----+
products
Initi lniti
Concentrat Concentrat
Run of of Initial
A B Rate
0.4 1. I.IXI0
2 0.8 1. 2.2 X
3 0.8 3. 4.4 X
0 0 10 .¡
Doubling each concentration. with thc othcr constant, doublcs thc
ratc. and so thc rcaction is first ordcr with respect to each reactant. The
rate law thcn has thc form
ratc =
k[Al[B]
Substituting thc values from run I of this set of data yiclds
1.1 x 10
4M/s=k(0.40M}
(l.5M)
( .8 X
I.IXIO.iM/s
k= 0.60M" 10 4
M·
s
 The rate law equation gives sorne insight into the actual steps by
which thc reaction takes place-the reaction mechanism.

19.3 CHEMICAL EQUILIBRIUM

Many chemical reactions convert practically ali the reactant(s) (at least
the limiting quantity) into products under a given set of conditions.
These reactions are said to go to completion. In other reactions, as
the products are formed they in turn react to form the original
rcactants again. This situation-two opposing reactions occurring at the
same time-leads to formation of sorne products, but none of the
reactants is completely converted to products. A state in which two
exactly opposite reactions are occurring at the same rate is called
chemícal equilibrium, (In fact, ali chemical reactions are equilibrium
reactions, at least theoretically.) For example, nitrogen and hydrogen
gases react with each other at 500 ºC and high pressure to form
ammonia; under the samc conditions. ammonia decampases to
produce hydrogcn and nitrogen:
3H2+N2---
+2NH3
2NH_1---
+3H2+N2
To save effort, we often write these two exactly opposite equations as
one, with doublc arrows:
or
We call the reagents on the right of the chemical equation as it is
written the products and those on the Ieft the reactants, despite the fact
that we can write the equation with eithcr set of reagents on the left side.
With the reaction just above, if you start with a mixture of nitrogen and
hydrogen and allow it to
come to 500 ºC at 200 atm pressure, sorne nitrogen and hydrogen
combine to form ammonia. If you heat ammonia to 500 ºC at 200 atm
pressure, sorne of it decomposes to nitrogen and hydrogen. Both
reactions can occur in the same vessel at the same time.
What happens when we first place hydrogen and nitrogen in a
container at 500 ºC and allow them
to react? At first, there is no ammonia present, and so the only reaction
that occurs is the combination of the two elements. As time passes, there
is less and less nitrogen and hydrogen, and thc combination reaction
therefore slows down (factor 4 or 5, Sec. 19.2). Meanwhile, the
concentration of ammonia is building up, and the decomposition of the
ammonia therefore increases in rate. There comes a time when both
the combination reaction and the decomposition reaction occur at thc
same rate. Whcn that happens, the concentration of ammonia will not
change any more. Apparently. the rcaction stops. However. in reality both
the combination reaction and the dccomposition reaction continuc to
occur; their effects merely cancel each other. A state of equilibrium has
been achicvcd.

Le Chátelíer's
Principie
lf we change the conditions on the N2, H 2, NH3 system at
equilibrium, such as changing thc temperature, we can get sorne further
reaction-either combination or decomposition. Soon, howcver, the
system will achieve a new equilibrium at the new set of conditions.
Le Chátelier's principie states that if a stress is applied to a systcm
at equilibrium, the equilibrium will shift in a tendency to reduce that
stress. A stress is something done to the system (not by thc equilibrium
reaction). The stresses that we consider are change of temperature,
change of pressure. change of concentration(s), and addition of a
catalyst. Lct us consider the effect on a typical equilibrium by each
of thesc strcsses.
Temperature
Change
To consider the cffect of temperaturc change, let us rewrite one of
thc equations including thc heat involved:

How do we get the temperature of the system to rise? By adding

heat. When we add heat, this equilibrium system reacts to reduce that
stress, that is, to use up sorne of the added hcat. lt can use up heat in
the reverse reaction, the decomposition of ammonia to hydrogen and
nitrogen. When the substances written as products of the reaction (on
the right sidc of the equation) react to produce more reactants (on the
left side of the equation), we say that the reaction has shifted to the left.
Whcn the opposite process occurs, we say that the equilibrium has
shifted to the right. Thus, raising the temperature on this system
already at equilibrium causes a shift to the left; sorne of the ammonia
decomposes without being replaced.

EXAMPLE 19.7. What would happcn to thc above systern at

cquilibrium if thc ternpcraturc wcre lowcrcd?
Wc lower the tcmperaturc of a systcm by rcmoving hcat. The
equilibrium tries to minimizc that chango by rcstoring sorne hcat: it can
do that by shifting to thc right. Thus, more nitrogcn and hydrogcn are
convcrtcd to ammoma.
287
CHAP. 19] RATES
RATES ANO
AND EQUILIBRIUM
EQUILIBRJUM [CHAP.287
19

The Effect of Pressure

Pressure affects the gases in a system much more than it affects
the liquid or solids. We will investigate the same ammonia, hydrogen,
nitrogen system discussed above. lf the system is at equilibrium,
what will an increase in pressure by the chemist do to the equilibriurn?
The system will shift to try to reduce the stress, as required by Le
Chátelier's principie. How can this system reduce its own pressure? By
reducing the total number of moles present. It can shift to the right to
produce
2 mol of gas for every 4 mol used up:
3H2 + N2
2NH3
Of course, it need not shift much. For example, if 0.0030mol H2 reacts
with 0.0010mol N2 to produce
0.0020 mol NH 3, the total number of moles will have been reduced (by
0.0020 mol), and the pressure
will therefore have been reduced.

EXAMPLE 19.8. What will be thc effect of increased pressure on the

following system at cquilibriurn?
2NH,
3H2+N2

Again sorne nitrogen and hydrogen will be converted to ammonia. This

time, sincc thc equation is writtcn in thc reverse of the way it was
writtcn above, the equilibrium will shiít to thc left. Of coursc, the samc
physical effect is produced: More ammonia is formcd. But the answcr in
terms oí the dircction of the shiít is diffcrent since the equation is
written "backward."

EXAMPLE 19.9. What effect would a decrease in volumc havc on thc

following system at cquilibrium at SOOºC, where ali the reagents are
gases?
H 2 + 12
2HI
Thc decreasc in volume would increase the pressurc on each of the
gases (Chap. 11 ). Thc equilibrium would not shift, however, because
there are equal numbers of moles of gases on the two sides. Neither
possible shift would cause a reduction of pressure.

The Effect of
Concentration
288
CHAP. 19] RATES
RATES ANO
AND EQUILIBRIUM
EQUILIBRJUM [CHAP.288
19

An increase in concentration of one of the reactants or products of the

equilibrium will cause the equilibrium to shift to try to reduce that
concentration increase.

EXAMPLE 19.10. How will addition oí hydrogen gas affect

the following equilibrium system?
3H2+N2
2NH,
Addition of hydrogen will at first increase the concentration of
hydrogen. The equilibrium will thcrefore shift to reduce sorne of that
increased concentration; it will shift right. Sorne of the added hydrogen
will react with sorne of the nitrogen originally present to produce more
ammonia. Note especially that the hydrogen concentra- tion will be above
thc original hydrogen concentration but bclow the concentration it would
havc if no shift had taken place.

EXAMPLE 19.11. Suppose that, under a ccrtain set of conditions,

a mixture of nitrogcn, hydrogen. and ammonia is at equilibrium. The
concentration of hydrogen is 0.250mol/L; that of nitrogen is
O.lOOmol/L, and that of ammonia is 0.200 mol/L. Now 0.003 mol of
hydrogen is added to 1.00 L of the mixture. What is the widest possible
tange of hydrogen concentration in the new equilibrium?
Before addition of the extra hydrogen, its concentration was 0.250
mol/L. After addition oí the extra hydrogcn, but before any
equilibrium shift could take place, there would be 0.253 rnol /L. Thc
shift of the equilibrium would use up sorne but not ali oí the added
hydrogen, and so the final hydrogen concentration must be above 0.250
mot¡L and below 0.253 mol/L. Sorne nitrogen has been used up, and its
final concentration must be less than its original concentration, O. IOO
mot¡L. Sorne additional ammonia has been formed, and so its final
concentration has becn increased over 0.200 mol/L. Notice that Le
Chátclier's principie does not tell us how much of a shift there will be,
but only qualitatively in which direction a shift will occur.
289
CHAP. 19] RATES
RATES ANO
AND EQUILIBRIUM
EQUILIBRJUM [CHAP.289
19

Presence of a Catalyst
Addition of a catalyst to a system at cquilibriurn will not cause any
change in the position of the equilibrium: it will shift neither left nor
right. Addition of the catalyst speeds up both thc forward reaction and
the reverse reaction equally.

19.4 EQUILIBRIUM CONSTANTS

Although Le Chátelier's principie docs not tell us how much an
equilibrium will be shifted, there is a way to determine thc position of
an cquilibriurn once data have been dcterrnincd for the equilibrium
experimentally. The ratio of concentrations of products to reactants,
each raised to a suitable power, is constant for a given equitibrium
reaction. The Ictters A, B, C, and O are used herc to stand for general
chemical species. Thus, for a chemical reaction in general.
aA+hB
cC+dD
it is true that the following ratio always has thc sarne valuc al a given
temperature:
[c]'[oJ
"
K=--
--
[A]"[B]1'
Here the square brackcts indicate the concentration of the chernical
species within the bracket. That is, [Al means the concentration of A, and
so forth. [A]" means thc concentration of A raised to the a power, where
a is the value of the coetficient of A in the balanced equation for
the chcmical equilibrium. The value of the ratio of concentration terms
is symbolizcd by the lcttcr K, callcd thc equilibrium constant. Far example,
for the reaction of nitrogen and hydrogen referred to in Sec. 19.3.
3H2+N2
2NH,
the ratio
is [NH,f
K=----
[H2fíN2]
The exponents 2 and 3 are the coetficients of ammonia and hydrogen,
rcspcctively, in the balanccd equation.
Please note thc following points about such an cquation:
l. This is a mathcmatical equation. lts valucs are nurnbers,
involving the concentrations of the chemicals.
2. Each concentration is raised to thc corrcct power, given by thc
coctficicnt in the chernical
290
CHAP. 19] RATES
RATES ANO
AND EQUILIBRIUM
EQUILIBRJUM [CHAP.290
19

equation. (Contrast this exponent with that in Sec. 19.2.)

3. The concentrations of the products of the rcaction are written in thc
numerator of thc right-hand side of the equilibrium constant
cxprcssion; thc conccntrations of thc rcactants are in the
denominator.
4. The tcrms are multiplicd togcther, not added.
5. Each equilibrium constant cxprcssion is associated with a particular
chcmical reaction written in a given direction.

EXAMPLE 19.12. Writc the cquilibrium constant cxprcssion for thc

rcaction
2NH,
3H2 + N2

For this cquation, thc tcrrns involving thc conccntrations uf thc

clcrncnts are in thc numcrator. bccause thcy
are thc products:
[H,f(N,
]
- K= -
[NH,]
2
289
CHAP. 19] RATES
RATES ANO
AND EQUILIBRIUM
EQUILIBRIUM [CHAP.289
19

There are a great many types of equilibrium problems. We will try to

start with the easiest and work to the hardcr ones as wc go.

EXAMPLE 19.13. Calculate the valuc of thc cquilibrium constant for

thc followíng rcaction íf at cquilibriurn thc conccntration of A is 2.00 M,
that of B is 3.50 M, that of C is 0.500 M, and that of D is 1..50 M.
A + B ;::::::::!
C+D
Sincc ali thc coefficients in thc balanced equation are cqual to 1, thc
valuc of thc cquilibrium constan! is
[C]
(D]
K=
[Al[B]
Wc mcrely substituto thc cquílíbríum concentratíons into this cquation to
determine thc valuc of thc cquilíhrium
constant:
(0.500 M )(
1.50 M)
K=
= O 107
(2.00M)
(3.50M) .
One way to make Example 19.13 hardcr is by giving nurnbers of
moles and a volumc instcad of concentrations at equilibrium. Since the
equilibrium constan! is defined in terms of conccntrations, we must first
convert the numbcrs of moles and volume to concentrations. Note
cspecially that the volume of ali the reactants is thc same, since they
are ali in the same system.
EXAMPLE A+B C+D
19.14.

Calculare the valuc of the equílibrium constan! if at cquílibrium thcrc

are 1.00 mol A, 1.7.5 mol 8, 0.250 mol C. and 0.750 mol D in 500 mL of
solution,
Since nurnbers of moles and a volurne are givcn, ít is casy to calculare
thc cquilibriurn conccntrations of thc spccics. In thís case. [AJ= 2.00 M, [B]
= 3.50 M, [C] = 0.500 M. and [D] = 1.50 M. which are cxactly thc concen·
trations given in thc last example. Thus, this problcrn has cxactly thc
sarnc answcr.

lt is somewhat more difficult to determine the value of the

equilibrium constan! if sorne initial concentrations are given instead of
equilibriurn concentrations,
 290
CHAP. 19] RATES
RATES ANO
AND EQUILIBRIUM
EQUILIBRIUM [CHAP.290
19

EXAMPLE 19.15. Calculatc the valué of thc equilibrium constan! in the

following reaction if J.(){Jmol of A and
2.00 mol of 8 are placed in 1.00 L of solution and allowcd to come to
equilibrium. The equilibrium concentration of C is found to be 0.20 M.
A+B
C+D
To determine the equilibrium concentrations of ali the reactants and
products. wc must deduce the changos that have occurred. We can
assume by the wording of the problcm that no Cor D was addcd by thc
chcrnist, that sorne A and B have bccn used up, and that sorne D has
also bccn produccd. lt is perhaps casicst to tabulare thc various
coneentrations. Wc will use thc chcrnical equation as our table
headings. and entcr thc valucs that we know now:

Initial concentrations 1.00 2.00 0.00 0.00

Changos produced by
the rcaction 0.20
Equilibrium
concentrations
We deduce that to produce 0.20 M C it takes 0.20 M A and 0.20 M B.
Moreovcr. wc know that 0.20 M D was also produced. The magnitudes
of the valúes in the second row of the table-the changes produced
by the reaction-are always in the same ratio as the coefficients in the
balanced chemical equation.
A + B e + D
Initial conccntrations 1.00 2.00 0.00 o.oo
Changes produccd by the rcaction -0.20 -0.20 +0.20 +0.20
Equilibrium concentrations 0.20
We merely add the columns to find the rest of the equilibrium
concentrations:
--+ e + D
A + 8 -
Initial concentrations 1.00 2.00 0.00 0.00
Changes produced by the reaction -0.20 -0.20 +0.20 +0.20
Equilibrium concentrations 0.80 1.80 0.20 0.20

Now that we have calculated the equilibrium concentrations we can

substitute these valucs into the cquilibrium constan! expression:
(C)[D]
(0.20)(0.20)
K= -- =
= 0.028 [A](B]
(0.80)( 1.80)

When the chemical equation is more complex, thc equilibrium

constan! cxprcssion is also more complex and the deductions about the
equilibrium concentrations of reactants and products are more involved
too.

EXAMPLE 19.16. Calculate the value of the equilibrium constant for thc
following reaction if l.Oílrnol of A and
2.00 mol of B are placed in l .00 L of solution and allowed to come to
equilibrium. The cquilibrium conccntration of C is found to be 0.20 M.
2A+B

C+D The equilibrium constant

expression for this equation is

[C]
(D]
K=-
--
[A}2[
B]
2 A + B .::==! C + D

lnitial concentrations 1.00 2.00 0.00 0.00

Changes produced by 0.20
the reaction
Equilibrium
conccntrations

The changes brought about by the chemical reaction are a littlc different
in this case. Twicc as many moles pcr liter of A are used up as moles
per liter of C are produccd. Note that the magnitudes in thc middle row
of rhis table and the cocfficients in thc balanced chcmical equation are
in the same ratio.
2A + 8 e + D
lnitial concentrations 1.00 0.00
 Changes produced by -0.40 +0.20
the rcaction -0.20 +0.20
Adding the columns:
2A + B e +
D
lnitial concentrations 1.00 0.00
Changes produced by -0.40 +0.20
Equilibrium 0.60 0.20
concentrations 1.80 0.20
The equilibrium values are substituted into the equilibrium constant
cxpression:
[Cl[D]
(0.20)(0.20)
K= = = 0.062
[A]2[B] (0.60)2( 1
.80)

The next type of problem gives the initial concentrations of the

reactants (and products) plus the value of the equilibrium constant and
requires calculation of one or more equilibrium concentrations. We use
algebraic quantities (such as x) to represent at least one equilibrium
concentration, and solve for the others if necessary in terms of that
quantity.
292
CHAP. 19] RATES
RATES AND
AND EQUILIBRIUM
EQUILJBRIUM [CHAP.291
19

EXAMPLE 19.17. For A+B C+D

thc reaction

1.50 mol of A and 2.25 mol B are placed in a 1.00-L vessel and allowed to
come to cquilibrium. Thc value of thc equilibrium constant is 0.0010.
Calculate the concentration of C at equilibrium.
A + B C + D
1.50 2.25 0.00 0.00
lnítíal concentratíons
Changes produced by
the reaction X
Equilibrium
concentrations

The changes due to the chemical reaction are as easy to

determine as before, and therefore so are thc equilibríum
concentrations:
A + B e + D
Initíal conccntrations 0.0 0.0
Changes produced by -x X X
the reaction -x
We could substitute these equilibrium concentrations in the equilibríum
constant expression, and solve using the quadratic equation. However, it
is more conveníent to attempt to approximate the equilibríum
= =
concentratíons by neglectíng a small quantity (x) when added to or
subtracted from a larger quantíty (such as 2.25 or 1.50). We do not neglect
small quantities unless they are added to or subtracted from larger
quantities! Thus, we approximate the equílibríum concentratíons as [AJ
1.50 M and (B] 2.25 M. The equílibrium constant expression is thus
[C][D] (x)(x)
x2
K= -- =
= - =0.0010 (A][B]
(1.50)(2.25) 3.38
x = 0.058 M
Next we must check whether our approximation was valíd. Is it true that
1.50 - 0.058 = l.50 and 2.25 - 0.058 =
2.25? Consídering the limits of accuracy of the equílibrium constant
expression, results within 5% accuracy are
considered valid for the general chemistry course. These results are
thus valid. The equilíbrium conccntrations are
[A]= 1.50 - 0.058
= 1.44 M [B] =
2.25-0.058 =
292
CHAP. 19] RATES
RATES AND
AND EQUILIBRIUM
EQUILJBRIUM [CHAP.292
19

2.19M [C] = [D] =

0.058 M
If the approxímation had caused an error of 10% or more, you would not
be able to use it. You would havc to
solve by a more rígorous method, such as the quadratic equation.

EXAMPLE 19.18. Rcpeat the last example, but with an cquílibríum

constan! value of 0.100.
The problem is done in cxactly the same manner until you
find that the value of x is 0.581 M.
x
-o
-
=0.100
3.3
8
X=
0.581
When that value is subtracted from 1.50 or 2.25, the answer is not
nearly thc original 1.50 or 2.25. The approximation is not valid. Thus,
we must use the quadratic equation.
K= (x)2
= 0.100 (J.50-x)
(2.25 -x)
x2 = (0.100)(1.50-x)(2.25 -x) =
O.IOO(x2 - 3.75x + 3.38)
0.900x2 + 0.375x -
0.338 = O
2
-b ± �(b - 4ac) -0.375 ± V(0.375)2 - 4(0.900)
(-0.338)
x= 2a 2(0.900)
Two solutions for .r , one positive and one negative, can be obtaincd from
this equation, but only eme will havc
physical meaning. Thcrc cannot be any ncgativc concentrations.
X = o .439 M = [
C] = [DI
The conccntrations of A
and B are then [A] = l .50 - O .439 = 1 .06 M
[B) = 2.25 - 0.439 = 1.81 M
The value from thc cquilibrium constant expression is thcrcfore cqual to
the valuc of K given in thc problcm.
(0.43
9)2
K=
= 0.HXl
( 1.06 )(
1.81 )

Solved Problems
RATES OF CHEMICAL
REACTION
19.1. Under what conditions does a glowing lump of charcoal react
faster: in air or in pure oxygen?
Explain.
Ans. lt will rcact Iaster in purc oxygen, since thc conccntration of
oxygcn is grcater thcrc.

19.2. Does sugar dissolve faster in hot coffee or in lukewarm coffee?

Explain.
Ans. In hol coffee. The higher thc tempcraturc. the faster thc
proccss.

19.3. Does lump sugar or granular sugar dissolve faster in water, all
other factors being cqual?
Explain.
Ans. Granular sugar dissolvcs fastcr; it has more surfacc arca in
contact with thc liquid.

19.4. At the same temperature, which sample of a gas has more

molecules per unit volume-one at high pressure or one at lower
pressure? Which sarnple would react fastcr with a solid
substance, ali other factors being equal?
Ans. The high prcssure gas has more molecules per unit volurne
and therefore reacts faster.
19.5. Write arate law equation for each of thc following: (a) A reaction
first order with respect to A and second order with respect to B. (b)
A reaction zero arder with respect to A and second order with
respect to B. (e) A reaction first ordcr with respect to A and first
order with respect to B. ( d) A reaction sccond order with respect to
B, its only reactant.
Ans.
(a) rate = k[A][Bf

(b) ratc = k[B)2

(e) ratc = k[A)[B]
(d) rate = k[B)2

19.6. Calculate the value of k for part (a) of the last problem if the rate
is 1.6 X 10-4 moly'L · s when
(A] = 1.00 M and (B] = 2.00 M.
Ans.
1.6 X 10-4 mol/L · s = k( l.00mol/L)
{2.00mol/L)"
k = 4.0 X w-5 . L2/mol2 s
294
CHAP. 19) RATES
RATES AND
ANO EQUILIBRIUM
EQUILIBRIUM [CHAP.293
19

19.7. What are the units of k for part (b) of Problem 19.5?
Ans. L/mol · s. The rarc is always in M /s (or mol/L · s). The
units of k change depending on the overall order of the
rcaction. Check:
tate =
k[Bf
mol/L · S = (L/mol · s)( mol ' /L2) = mol/L · s
CHEMICAL EQUILIBRJUM
19.8. Write an "equation" for the addition of heat to a water-ice
mixture at OºC to produce more liquid water at OºC. Which
way does the equilibrium shift when you try to raise thc
temperature?
H20(s) + heat
Ans.
H20(1)
Thc cquilibrium shifts toward liquid water as you add heat in an
attcmpt to raise the temperature. (Howevcr, the temperature
docs not change until ali the ice is rnclted and this cquilihrium
systcm is destroyed.)

19.9. What does Le Chátelier's principie state about the etTect of an

addition of NH., on a mixture of
N2 and H 2 befare it attains equilibrium?
Ans. Nothing. Le Chátelier's principie applies only to a system
already at equilibrium.

19.IO. What effect would a decrease in volume have on the following

system at equilibrium at 500 ºC?
2C(s) + 02
2CO
Ans. The equilibrium would shift to the left. Thc dccrcasc in
volumc would incrcasc the pressure of each of thc gases, but
not of the carbon, which is a solid. The numhcr of moles of gas
would be decreased by the shift to the left.
19.11. For the A+ B C + heat
reaction

does a rise in temperature increase or decrease the rate of

(a) the forward reaction? (b) the reverse reaction? (e) Which
effect is greater?
294
CHAP. 19) RATES
RATES AND
ANO EQUILIBRIUM
EQUILIBRIUM [CHAP.293
19

Ans. (a) Incrcase and (h) increase. (An increase in tempcrature

mercases all rates.) (e) The addcd heat shifts thc equilibrium to
the left, That mcans that the reverse reaetion was spccdcd up
more than the forward reaction was speedcd up.

19.12. Hydrogen gas is added to an equilibrium system of hydrogen,

nitrogen, and ammonia. The equilibrium shifts to reduce the stress
of the added hydrogen. How much hydrogen will he present at the
new equilibrium compared with the old equilibrium-more. less, or
the same concentration?
Ans.
N2+3H2 2NH,+hcat
Thcrc will be more hydrogen and more ammonia prcsent
at the new cquilibrium, and lcss nitrogcn. The conccntration
of hydrogen is not as great as thc original conccntration plus
that which would have resultcd from thc addition of more
hydrogcn, howcvcr. Sorne of the total has becn uscd up in thc
cquilibrium shift.
EQUILIBRJUM
CONSTANTS
3H2+N2 2NH_1
19.13. The balanced
chemical equation
mcans which one(s) of the following: (a) One can place H 2 and
N 2 in a rcaction vessel only in the ratio 3mol to 1 mol. (b) If
one places NH3 in a reaction vesscl, one cannot pul any N2
 and/or H 2 in with it. (e) lf one puts 3 mol of H 2 and l mol of N2
into a reaction vessel, it wíll produce 2 mol of NH 3• (d) For every 1
mol of N 2 that reacts, 3 mol of H 2 will also react and
2mol of NH3 will be produced. (e) For every 2mol of NH3 that
decornposes, 3mol of H2 and
1 mol of N2 are produced.
Ans. Only parts (d) and (e) are correct. The balanced equation
governs the reacting ratios only. It cannot determine how
much of any chemical may be placed in a vessel-(a) and
(h)-or if a reaction will go to completion-(c ).

19.14. Write equilibrium constant expressions for the following equations.

Tell how they are related.
(a) N2 04 N02 + N02
( b) N204 2 N02
Ans.
K = [N02 J[N02]
(a)
[N204]
[NO,)
(b} "
K=-
--
[N204]
The equilibrium constant expressions are the same because
the chemical equations are the samc. lt is easy to see why
the coefficients of the chcrnical equation are uscd as
exponcnts in the equilibrium constant expression by writing out
the equation and cxpression as in part (a).

19.15. Write an equilibrium constant expression for

cach of the following:
(a) PCl3(g) + Cl2(g) PCl,(g)
(b) 2N0+02 2N02
(e) S02 + Cl2
(d) S02Cl2
(e) 2NH3
N2+3H2
2 HBr(g) H2 +
Br2(g)

Ans.
(a) (b) (e) (d)
(e) [P [NO,f
CI, K= -
[NOJ2[0
K ] 2]
=
. [SO,CI
[
P K = ,) - -
C [S02H
I Cl2]
3
] K=
[ [N2HH
C 2J'
l
2 [NH,f
]
K= [H2l[Br2]
[HBr]
2
19.16. Write an equilibrium constant expression for each of the following:
(a S02 + � 02
S03
) (
2N02+�02
b) N205
(e CH3COCH2COCH3
CH3C(OH)=CHCOCH3
)
296
CHAP. 19) RATES ANO
RATES ANO EQUILIBRIUM
EQUILIBRIUM 29519
[CHAP.

Ans. [S01
(a K= ].
) 112

[S02ll
ü2]
(b) 112
K=
[N20s ]
.
[N02]2[02]
[CH
(e) K= . .
1C(OH)=CHC
OCH 11
[CH1COCH2C
OCH1]

19.17. Write equilibrium constant expressions for the following equations.

Tell how these expressions are related.
(a) 2 N02 N204
( b) N204 2N02
(e) N02 f N204
Ans. (N204]
(a K=--
[N02J"
)

[N02
(b) f
K=-
-
[N204]
[Nz04)
(e) 1;2
K=
[N02
]

The K in part (b) is thc reciproca! of that in part (a). Thc K in

part (e) is thc square root of that in part (a).
19.18. In the
reaction X+Y Z

1.0 mol of X, 1.3 mol of Y, and 2.2 mol of Z are found at

equilibrium in a l.0-L reaction mixture. (a) Calculate the value for
K. (b) If the same mixture had been found in a 2.0-L reaction
mixture, would the value of K have been the same? Explain.
296
CHAP. 19) RATES ANO
RATES ANO EQUILIBRIUM
EQUILIBRIUM 29519
[CHAP.

A
ns
.
[Z]
(a) (2.2)
K=--=
[X][Y] (1.0)(J.3) =17
.
( 1.1
(b) )
K=
= 3.4
(0.50)
(0.65)
The value is not the samc. Thc valuc of K is rclatcd to thc
concentrations of thc rcagcnts, not to their numbers of moles.

19.1 A+B
9. C+D
If 1.00 mol of A and 2.00 mol of B are placed in a 1.00-L vessel
and allowed to achieve equilibrium, 0.20mol of C is found. In
order to determine the value of the equilibrium constant,
determine (a) the quantity of C produced, (b) thc quantity of D
produced, (e) the quantities of A and B used up, (d) the quantity
of A remaining at equilibrium, by considering
 the initial quantity and the quantity uscd up, (e) the quantity of B
remaining at cquilibrium, and ( f) the valuc of the cquilibriurn constan t.
A11s. (a). ( b l. and ( c) 0.20 mol cae h.
(d) 1 .00 - O 20 = 0.80 mol
( e) 2.00 - 0.20 =
I .HOmol
( f)
[C](D] (0.20)"
K = --- =
[A](B]= 2.H (0.80)(
X 10 1.80)

19.20. In which line of thc table used to calculate thc equilibrium

concentrations are thc values in the ratio of the coefficicnts of the
halanced chemical cquation? Are othcr lincs?
Ans. The tcrms in the sccond linc are in that ratio, sincc it
describes thc changcs rnadc by the reaction.
Thc terms in the othcr lines are not gcncrally in that ratio.

19.21. 2A + B C+2D
lf 0.75 mol of A and 1.30 mol of B are placed in a l.00-L vcssel
and allowcd to achieve equilibrium, 0.15 mol of C is found. Use a table
such as shown in Examplc 19.15 to determine the value of the
cquilibriurn constant.
Ans. 2A + B e +
20 lnitial 0.75
1.30 () o Change
-(UO -0.15 + 0.15 +
0.30
Equilibrium 0.45 1.15 0.15
<UO
[C](Df (0.15)(0.30)"
K= =5.8X 10-c
[Af(B] (0-
45)"( 1.15)

19.22. For the following rcaction, K = 1.0 X I0-5

.

W+Q
R+Z
lf 1.0 mol of W and 3.0 mol of Q are placed in a 1.0-L vesset and
allowed to come to equilibrium, calculate the equilibrium conccntration
of Z using the following steps: (a) lf the equilibrium concentration of Z
is equal to x, how much Z was produccd by the chemical reaction?
(b) How much R was produced by the chemical reaction? (e) How
much W and Q were used up by the reaction? (d) How much W is lcft
at equilibriurn? (e) How much Q is left at equilibrium? (f) With the
value of the equilibrium constant given, will x (equal to the Z
concentration at equilibrium) be significan! whcn subtractcd from 1.0? (g)
Approximately what conccntrations of W and Q will be present at
equilibrium? (/z) What is the value of x? (i) What is the conccntration
of R at cquilibrium? (j) Is thc answcr to part (f) justificd?
Ans. (a) x. (Thcrc was neme prcscnt originally, so ali that is
thcrc must havc come from the reaetion.) (b) x. (Thc Z and
R are produccd in cqual mole quantitics, and thcy are in
the same volumc.) (e)
.r cach. (Thc rcacting ratio of W to Q to R to Z is 1: 1: 1: l.)
(d) 1.0 - x. (The original conccntration rninus the
concentration uscd up.) (e) 3.0 - x. (Thc original
conecntration minus thc conccntration
uscd up.) ( J) No. (Wc will try it first anti scc that this is
truc.) (g) 1.0 mol/L and 3.0 rnoí z l.,
rcspcctively.
(R](Z] x2
( h) K = = = 1.0 X 10
(W](O) ( 1.0)(3.0)
x"=3.0x 10 5
x=5.5x10·-'
( i)
(j) Ye�. [R) =x = 5.5 X 10- ·1 moljl
1.0 - (5.5 X 10 1) � 1.0.
CHAP. 19]
298 RATES
RATES AND
ANO EQUILIBRIUM
EQUJLIBRIUM [CHAP.297
19

19.23. For the following reaction of gases, K = 1.0 X 10-9

:

W + 20 3R
+Z
Determine the concentration of Z at equilibrium by repeating cach
of the steps in Problcm
19.22. Calculate the equilibrium concentration of R if 1.0 mol of W
and 3.0 mol of Q are placed m a 1.0-L vesscl and allowed to attain
equilibrium.
Ans. (a) x; (h) 3x; (e) W: .r, O: 2x; (d) 1.0 -x; (e) 3.0 - 2x;
(f) no; (g) 1.0mol/L and 3.0mol/L. rcspcctively,
[R]"'[Z] (3x )"'(x)
(h) K= ,= ,=3.0x4=l.Oxl0-9
[W][o]- (i.0)
(3.0f
x=4.3X 10-1=[2]
(i)
(j) Yes. [R] = 3x = U X 10 · 2 mol/L

Supplementary Problems

19.24. Identify or explain cach of the following terms: (a)

equilibrium, (h) rate of reaction, (e) catalyst. (d) completion,
(e) Le Chátclicrs principie, (f) stress, (g) shift, (h) shift to
the right or left, (il equilibrium constant, and (j) equilibrium
constant cxpression.
Ans. (a) Equilihrium is a state in which two exactly
opposite processes occur at equal rates. No apparent
change takes place at equilihrium. (b) Ratc of reaction is
the number of moles per liter of reactant that reacts pcr
unit time. (e) A catalyst is a substance that alters the rate
of a chemical reaction without pcrmancnt changc in its
own composition. (d) A reaction goes to completion when
one or more of the reactants is cntirely uscd up. In
contrast, a reaction at equilihrium has sorne of each
reactant formed again from products, and no rcactant or
product concentration gocs
to O. (e) Le Chátclicr's principie states that when a stress
is applied to a systcm al equilibrium, thc
cquilibrium tcnds to shift to reduce thc stress. (f) Stress is
a change of conditions imposed on a systcm at equilibrium.
(g) Shift is a change in thc concentrations of reactants
CHAP. 19]
298 RATES
RATES AND
ANO EQUILIBRIUM
EQUJLIBRIUM [CHAP.298
19

and products as a result of a stress. (h) Shift to the right

is production of more products with thc using up of
reactants; shift to the left is exactly thc opposite. (i) An
cquilibrium constant is a set value of the ratio of
conccntrations of products to concentrations of rcactants,
each raiscd to the appropriatc power and multiplied
together. ( j) An equilibrium constant cxpression is thc
cquation that relates the equilibrium constant to thc
concentration ratio.

19.25. Compare and contras! the function of a catalyst in a chcrnical

reaction with that of a marriage hroker-a matchmaker.

19.26. Nitrogen and sulfur oxides undergo thc following rapid

rcactions in oxygen. Determine the overall reaction. What is thc
role of NO?
2NO + 02-
>2N02
N02 + S02 --+
NO + so_,
Ans. Combining the first rcaction with twicc the second yields the
following rcaction. That rcaction will procccd only slowly in thc
absence of the NO and N02.
2S02 + 02
- 2S0_1
The NO is a catalyst. It spccds up thc convcrsion of S02 to
S01 and is not changcd pcrmanently in the process.

19.27. What is thc bcst set of tcrnpcraturc and prcssurc conditions for
the Haber proccss=-thc industrial proccss to convcrt hydrogcn and
nitrogcn to arnrnonia?
Ans. To get thc equilibrium to shift as much as possiblc toward
ammonia. you should use a high prcssure and a low
tcmpcrature. Howcvcr, thc lowcr thc tcmpcrature. thc
slower the rcaction, Thcrcforc, a high prcssurc, 200 atrn,
and an intermediare ternpcraturc, 500 ºC, are actually used
in thc industrial proccss, Naturally, a catalyst to spccd up
thc rcaction is also uscd.
19.28. What happens to the position of the equilibrium in cach of
thc following cases?
N2+3H2
2NH,+heat
(a) Nitrogen is added and the volume is reduced. (b) Hcat is
addcd and ammonia is added. (e) Arnrnonia is taken out and a
catalyst is added. (d) Nitrogcn and ammonia are both added.
Ans. (a) Each strcss-addition of nitrogen and
incrcase in pressurc (by reduction of the volume)-
causes a shift to the right, and so the equilibrium will
shift to the right when both strcsses are applied. (b)
Addition of ammonia and addition of heat will each cause
thc cquilibrium to shift to the left; addition of both will also
cause shift to the lcft. (e) Addition of a catalyst will cause
no shift, but removal of ammonia will cause a shift to the
right, and so thesc stresses together will cause a shift to the
right. (d) You cannot tell, because addition of the nitrogen
would cause a shiít to the right and addition of ammonia
would cause a shift to the left. Since no data are given and
Le Chátelicr's principie is only qualitativc, no conclusion is
possible.

19.29. Considera chango in total volurne of the cquilibria described.

In each case, calculatc K for a 1.0-L total volume and again for
a 2.0-L total volurne, and explain in each case why thcrc is or is
not a diffcrence.
(a) In the rcaction
B
C+ D
1.3 mol of B, 2.4 mol of C, and 2.4 mol of D are found in a 1.0-L
reaction mixture at equilibrium. Calcula te the value of K. If the
same mixture were found in a 2.0-L rcaction mixture at
cquilibrium, would K be different?
(b) In thc reaction
A+B
C+D
1.0 mol of A, l.3 mol of 8, 2.4 mol of C. and 2.4 mol of D are
found in a 1.0-L rcaction mixture at cquilibrium. Calculate the
value of K. If the same mixture wcrc found in a 2.0-L
rcaction mixture at equilibrium, would K be ditferent? Compare
this answcr and that in part (a), and cxplain.
 Ans. (a) In the two
reactions we havc
(2.4)(2.4) ( 1.2)(
1 K = (1.3) = 4 .4 1.2)
K, =
- = 2.2
(0.65)
and the valúes are different. (h) In the two reactions wc
havc
(2.4)(2.4) (1.2)
K1 = (1.2)
K,=
( 1.00 =
)( 4.4
1.3) =4.4
- (0.50)(0.65)
The values are thc samc. In part (h ). 2.0 L appears
twice in thc numerator and twicc in the dcnominator, so
that it canccls out. In part (a), it appears only once in the
denominator and twice in the numcrator, and so the
constan! in the 2.0-L volume would be half as large as that
in thc
1.0-L volumc, Note that in part (a), thc sarne mixture
would not appear in thc 2.0-1. mixture,
because thc value of K docs not
changc with volumc,

19.30. Calcula te the units of K in Problem l 9. l 7(a) and (d. Can you
tell from the units whieh of the equations is rcferrcd to?
Ans. The units for part (a) are L/mol; those. If a valuc is givcn
for part (e) are (L/mol)112 in L/mol
for thc reaction, the equation in part (a) is thc one to be
used. If the units are the square root of thosc, the
equation of part (e) is to be used.

19.31. What is the sequence of putting valúes in the table in the

solution of Problem 19.21?
Ans. The superscript numbcrs bcfore thc table entries givc thc
sequence.
2A + B e + 20
Initial 0.75 1.30 o o
Change - 0.30 -0.15 +0.15 +0.30
4 4 4
Equilibrium 0.45 1.15 0.15 0.30
19.32. For the A+ B C + hcat K = 1.0 X 10-4
rcaction

would an increase in temperaturc raisc or lower thc value of K?

Ans. According to Le Chátelier's principie, raising the
temperature would shift this equilibrium to the left. That
means that there would be lcss C and more A and B present
al the new equilibrium tcmperature. The value of the
equilibrium constan! al that temperature would therefore be
lower than the one al the original tcmpcrature.
[e]
K = [A)
[B]

19.33. Calculate the value oí the equilibrium constan! for the reaction
below if there are present al equilibrium
7.0mol of N2• 9.0mol of 02, and 0.130mol of N02 in 2.0L.
N2+202
2N02
Ans.
[N2] = 7.0mol/2.0L=
3.5mol/L
(02] = 9.0mol/2.0 L = 4.5 mol/L
[N02 J = 0.130mol/2.0 L =
0.065 rnol /L
[N0,)2 (0.065)2
= 5
K= • 2 ,=6.0x10-
[N2H02]
(3.5)(4.5)"
19.34. For the 2N02 N20�
reaction

calculatc the value of the equilibrium constan! if initially 1.00mol

of N02 and l.OOmol of N204 are placed in a 1.00-L vessel and
at equilibrium 0.75 mol of N204 is lcft in thc vessel,
Ans.

lnitial 1.0 1.0

0 0
Changc
0.5 -
Equilibrium 0 0.2
1.5 5
0 0.7
5
 [N204]
(0.75)
K= -- =
-- =0.33
[N02 ]2 (
1.50)"

19.35. Calculate the numbcr oí moles oí Cl2 produced al equilibrium in

a 10.0-L vesscl whcn l.OOmol of PCl5 is hcatcd to 250ºC. K = 0.041
mol/L.
Ans.
PCl5
PCl3 + Cl2
[PCI 3 )[ CI 2 ) x2
K=0.041 = = ---
[PCl5] 0.100-x
x2 = 0.0041 -
0.041x
2
x + 0.04lx -
0.0041 = O
-0.041 + V(0.041 )2 +
4(0.0041)
X=---------
---= 0.047
2
(0.047mol/L)( 10.0L)
= 0.47mol
300
CHAP. 19) RATES ANO EQUILIBRIUM
RATES AND EQUILIBRIUM [CHAP.303
19

19.36. In a 10.0-L vessel at 448 ºC, H 2 and I i{g) rcact to form HI. K = 50.
If 0.500 mol of each reactant is used, how many moles of 12 remain at
equilibrium?
Ans. The inítíal concentration of each reagcnt is 0.500mol/10.0L =
0.0500mol/L. Lct the equilibrium concentration of HI be lx for
conveniencc.
H2 + 12 2H
Initial 0.05 0.0500 o
Change -x -x 2x
Equilibrium 0.0500 -x
0.0500 -x 2x
(lx
)2
-----
=50 (0.0500
-x )2
Taking the square root of each side of thc last equation yíelds
2
x
----
=7.1
0.0500
-x
2x = 7.1(0.0500)
- 7.lx
9.lx =
7.1(0.0500)
X=
0.039
[12] = 0.0500 - 0.039 =
0.011 mol /L
In 10.0L, there is then O.llmol 12.

19.37. Calculatc the equilibrium ca2 concentration if 1.00mol of ca

and l.OOmol of H2a are placed in a
1.00-L vessel and allowed to come to cquilibrium at 975 ºC.
ca+ H2a(g) co, + H2
K = 0.63
Ans.

x
2
K= =0.63 (
2
J.00 - X)
Taking the square root of this exprcssion yields:
300
CHAP. 19) RATES ANO EQUILIBRIUM
RATES AND EQUILIBRIUM [CHAP.304
19

X
---
=0.79
1.00
-x
X= 0.79
- 0.79x
1.79x =
0.79
x = 0.44
mol/L

19.38. What effect would a decrease in volumc have on thc following

system at equilibrium at 500 ºC?
H2+12
2HI
Ans. The equilibrium would not shift. The decreasc in volumc would
increasc the prcssure of cach of the gases, but at 500 ºC, ali of
these reagents are gases. The total number of moles of gas would
not be affected by either shift, so no shift takes place.

19.39. What is the difference between the concentration ratio in the

equilibrium constant expression and that in the Nernst equation (Chap.
14)?
Ans. In a reaction at equilibrium, the ratio can have only onc value at
any given temperature. In the Nernst equation, the value can
changc, since the reaction can be stopped short of equilibrium
simply by disconnecting a wire or the salt bridge.
300
CHAP. 19) RATES ANO EQUILIBRIUM
RATES AND EQUILIBRIUM [CHAP.305
19

19.40. From the following data, calculatc the order of the rcaction
A +B-
products

I l
i i
Ru l
n n
1 1 4
2 1 6
3 3 2. 1
4 3
.
Ans. 00 00
The reaction is first order with respect to each reactant.
Sincc the 1.50 factor increase in [B] causes a 1.50 factor
increase in rate, the reaction is first order with respect to
B. Sincc the 3.00-fold increase in A concentration causes a
3.00-fold increase in rate, it is also first order with rcspcct to
A.

19.41. Substitute the values from runs 2 and 3 in Examplc 19.6 and
compare the results for k with the rcsult from run l.
Ans.
2.2 X 10-4 M/s 4.4 X 10-
k=------- 1.8 X
(0.80 M)(l.5 M) 4 M/s 10-4
The answcrs are the same
each time. (0.80 M) M·
(3.0 M) s