Chemical Kinetics: Reaction Rates

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

There is much information that can be derived from a tant. As a result, one should expect to find that reaction rates
chemical equation: for example, the products that can be ex- vary greatly with changes in molecular structure. This can be
pected from a given set of reactants and the stoichiometric seen by comparing the rate of reaction of iron(II) and per-
relationship between the substances involved in the reaction manganate ions with that of oxalic acid molecules and per-
(I). The equation, however, does not reveal anything about manganate
the conditions under which the reaction will take place, its 2Mn04-|aq) + 10Fe(aql2+ + 16H(aql+
efficiency, or the “rate” at which the reaction occurs. By rate (purple)
is meant the number of chemical changes which take place on
2Mn(aqj2+ + 10Fe(aq)3+ + 8H20(o
—

a molecular scale per unit of time (2). s

(pink)
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By examination of numerous chemical reactions, one ob- E

serves that certain types of chemical reactions proceed faster 2Mn04(aq)“ + 5H2C204<aq) + 6H(aqj+
than others. For example, the explosion of nitroglycerine C
(purple)
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proceeds rapidly, while the rusting of iron generally occurs so —*•

2Mn(aq)2+ + 10CO2(B) + 8H20(i) o
slowly that it is scarcely perceptible. Some reactions go es- (pink) N
sentially to completion (little or no reactant remains), whereas In both cases the purple permanganate disappears as the pink D
others are in a state of dynamic equilibrium, a situation in manganese(II) ion appears; however, in the first reaction the
which reactants form products at the same rate that products purple color disappears almost instantaneously upon addition A
are transformed into reactants. In chemical reactions, rates of a stoichiometric quantity of iron(II) indicating that the R
are usually measured in terms of how fast products appear or reaction occurs very rapidly. On the other hand, the disap- Y
how fast reactants disappear. Color, pressure, concentration, pearance of the purple color in the second reaction requires
and mass changes are some parameters that are frequently a much longer period of time; therefore, the reaction must
used to monitor a reaction’s progress. occur more slowly. Even at elevated temperatures the second S
Reaction rates and reaction efficiency are of great impor- reaction is slow unless catalyzed by manganese(II) ion. (This C
tance to the chemist; often the practicability of a chemical is an example of autocatalysis, i.e., Mn2+, a reaction product,
H
reaction, particularly a commercial process, depends on the serves to catalyze its own formation.) Everything is identical
reaction’s rate and efficiency. If the reaction is too slow or the in these two reactions except for the nature of one of the 0
equilibrium is not shifted in favor of the products, it may not reactants; iron(II) is an ion whereas oxalic acid is a molecule. 0
be economically feasible. Generally, ionic reactants are found to yield products at a L
The study of chemical equilibrium deals only with the limit much faster rate than covalent molecules.
or extent to which a reaction can occur; it is only concerned Two reasons can be suggested for the observed difference
with the initial and final states of the chemical system. in rate of reaction. First, the permanganate and iron(II) are C
Chemical kinetics, however, is concerned with the reaction both ions. Reactions occurring between ions of opposite charge H
mechanism, i.e., the sequence of steps by which a chemical and essentially spherical charge distribution are usually rapid
reaction proceeds, the rates of these steps, and the factors, like because effective interparticle contact can occur from any E
nature of reactants, concentration, temperature, and catalysis, relative direction of approach. That is, the influence of mo- M
which affect the rate. lecular size and geometry (4) on reaction rate, commonly re- 1

The Collision Theory of Reaction Rates ferred to as the “steric” effect, is minimal in ionic reac-
tions. S
A concept, known as the collision theory, has been devel- The second reason concerns the probability that properly T
oped to explain why certain factors, such as the nature of oriented oxalic acid molecules will collide with properly ori- R
reactants, concentration, and temperature, affect the rate of ented permanganate ions. The probability of a permanganate
a chemical reaction. This theory is based on the idea that for Y
ion colliding with a nonreactive part of the molecule is con-
a reaction to occur, there must be collisions between reactant
siderably greater for the oxalic acid molecule than for the
particles. Accordingly, the rate of reaction depends upon the iron(II) ion. Consequently, the rate of effective collision, and
number of collisions per unit of time and the fraction of these the rate of overall reaction, should be slower for the oxalic acid
collisions that are effective. By effective collisions is meant than for the iron(II) ion.
interparticle contacts between reactants that are successful
in the formation of products. Concentration of Reactants
Nature of Reactants From a kinetic standpoint, chemical change takes place as
a result of molecular collisions. The greater the number of
Substances differ in activity and hence in the rate with collisions per unit of time, the greater the probability of con-
which they react with other substances. For example, an active version of reactants into products per unit of time, i.e., the
metal like potassium will displace hydrogen vigorously and
greater the rate of reaction. By increasing the concentration
rapidly from acids, while less active metals, like lead or plat- of any or all of the reactants, each molecule has a greater
inum, react very slowly, if at all as in the case of platinum. A probability of colliding with another molecule and partici-
more detailed discussion of the relative activities of metals can
pating in a reaction.
be found in an earlier article in this series (3). To develop the quantitative notions of reaction rate, con-
Another factor to be considered is that a chemical reaction sider the reaction between gaseous iodine and bromine to form
is a process in which existing bonds are broken and new bonds
gaseous iodine monobromide
are formed. Therefore, the reaction rate will depend on the
specific bonds involved and hence on the nature of the reac- l2(g) + Br2(B)
—
2IBr(g)

Volume 57, Number 9, September 1980 / 659

 The progress of the reaction can be monitored by the disap- constant. The term k includes the effects of temperature,
pearance of the violet color of iodine vapor. For I2 and Br2 catalysts, and nature of reactants—all the parameters except
molecules to react, it is necessary that they collide. The concentration which influence the rate of a reaction. The
number of molecules reacting per unit of time will be pro- concentrations of the reactants, expressed in moles per liter,
portional to the number of collisions. If the number of colli- are represented by the term C.
sions between I2 and Br2 molecules in one case were twice as Now consider a case in which two molecules of the same
great as that in another in a given time, then twice as many I2 kind react with each other, for example,
and Br2 molecules would react. To determine the dependence
of the rate of the reaction upon the concentrations of I2 and 18% I2(g) + Br2(g>
2 ->-

Br2, it is necessary to determine the manner in which the Two molecules of iodine monobromide react with each other
number of collisions between I2 and Br2 molecules varies with to form one molecule of I2 and one of Br2.
their respective concentrations. To do this, consider a closed To determine the chance of collision between any two IBr
vessel containing only I2 and Br2 molecules and, for simplicity, molecules, consider a vessel containing six IBr molecules.
suppose that there are four I2 molecules and four Br2 mole- Counting the chances as was done in the previous examples,
cules in the vessel. The chance of I2 colliding with Br2 can be one finds that there are fifteen (5 + 4 + 3 + 2 + 1 lines, Figure
indicated by drawing lines between I2 and Rr2 molecules, as 2). That is, the first IBr molecule to be considered has five
shown in Figure 1. chances of collision, the next molecule has four chances (not
counting the same chance twice), the third molecule has three
chances, etc.
S By doubling the number of IBr molecules, the chance in-
E
C
0
N
D
A
R
Y

S
C Figure 2. A schematic representation of the effect of concentration on the col-
Figure 1. A schematic representation of the effect of concentration on the col-
H lision frequency between l2 and Br2. Increasing the concentration increases the
lision frequency between IBr molecules. Increasing the concentration increases
the collision frequency and, hence, the rate of reaction.
0 collision frequency and, hence, the rate of reaction.

0 creases to 66 (11 +10 + 9 + 8 + 7 + 6 + 5 + 4 + 3 + 2+1

L Under the conditions chosen, the chance that any I2 mole- lines). In general, for N molecules the chance for collision will
cule will collide with any Br2 molecule is 16 (16 lines). In other be (IV 1) + (IV
—

2) + (IV 3) +
— —
+1. The mathematical
...

words, each I2 molecule has four chances of colliding with a formula for determining the sum of such a series of combi-
C Br2 molecule; since there are four I2 molecules and four Br2 nations is
H molecules, the total chance becomes 4 X 4 = 16. Obviously, (N-l)N
c Uisions between like molecules are not to be included since
E 2
t ,ey do not lead to reactions.
M Consequently, the number of collisions is proportional to (N
By extension of the device used in Figure 1, it can be shown —

1)JV (5). N represents the number of molecules in the re-

I that by doubling the concentration of I2 molecules, that is, action vessel. In real chemical systems N is a very large
when there are eight I2 molecules and four Br2 molecules in 1 )N c=r N2. This reasoning
S number, so (N 1) TV, and (N
— —

the same vessel, the chance that any I2 molecule will collide is logical because the lowest possible vacuum probably con-
T with any Br2 molecule is 32 (8 X 4 lines). The number of I2
tains billions of molecules (remember Avogadro’s number)
R molecules in the second case is twice that in the first and the
chance for collision between I2 and Br2 molecules is doubled. per unit volume, obviously one molecule more or less will not
Y make any appreciable difference, and (N 1) = N. Accord- —

With eight I2 molecules and eight Br2 molecules, the chance the number of collisions in such cases is proportional
of collision between I2 and Br2 molecules is 64 (8 X 8 lines). ingly,
to N2. Since N can be expressed as the concentration of
For the general case
reactants, in this case IBr molecules, the number of collisions
A+ B —
D is proportional to the concentration of IBr molecules squared.
In other words
the chance of collision is equal to N a X IVb, where N a and IVb
represent the number of A and B molecules, respectively. In Rate of the IBr reaction =
kC'm,
all cases, the volume of the reaction vessel is constant, so the
Similar results can be obtained for the reaction
number of reactant molecules, expressed in proper units,
corresponds to the reactant concentrations. Therefore, the 2A + B-*-D + 2E
chance for collision of reactant molecules is proportional to
the product of the reactant concentrations. The effect of such By considering the collisions between two A molecules and one
B molecule, the rate of reaction would be proportional to the
manipulations can be expressed in terms of a rate law. For the number of B molecules times the number of collisions between
I2 and Br2 reaction the rate law is, two A molecules. Since the number of collisions between two
Rate of formation of IBr =
kC\JCRr2 A molecules is proportional to Na2, the number of collisions
between two A molecules and one B molecule will be propor-
and in the general case, the rate law is,
tional to Na2 X Nr. According to the arguments used previ-
Rate of formation of D =
kCACR ously, the rate of reaction is
where k is a proportionality constant called the specific rate Rate =
kCA2CR

660 / Journal of Chemical Education

 For, the general reaction: 2N02 *
2NO + 02 Rate —
AC

rA + sB — iD + zE Reactions of order higher than second are occasionally

found. This may be shown with the third-order reaction be-
in which r, s, x, and z represent the coefficients of A, B, D, and tween nitric oxide and chlorine, for which the balanced
E, respectively in the balanced equation, the formulation of equation is
the rate law is .

2NO + Cl2 —
2NOC1
Rate =
kC&'CBs
The rate of formation of nitrosyl chloride, based on experi-
Complex Reactions and the Collision Theory mental data, is proportional to the square of the nitric oxide
To illustrate the collision theory as applied to complex concentration times the concentration of chlorine. The rate
reactions it is instructive to consider the reaction: law for this third-order reaction is
A + 2B-»D + 2E Rate =
&Cno2Cci2
Based on the preceding arguments, one is tempted to write In general, the order of the reaction with respect to a reac-
the rate law for this reaction as tant is equal to its exponent in the rate law, and the overall
reaction order is given by the sunroof the exponents in the rate
Rate =
&CaCb2 law. The exponents in the rate law are usually single positive
However, testing this expression with the experimental data integers, but occasionally they may be fractional or even
may show that the proposed rate law is grossly inaccurate. negative, depending on the complexity of the reaction. Thus,
Why? Suppose the reaction A + 2B -* takes place in several for the reaction
S
steps, the first step resulting in the formation of some inter-
H2 + Br2 2HBr
mediate, for example B2, which in turn reacts with A. Such a E
mechanism could be represented as a series of reactions, C
the experimental rate law is (7)
2 B -*•
B2 (slow) kC H2CBr21/2 o
Rate =

and 1 + &'CHBr/CBr2 N
Occasionally, there are reactions in which the rate is unaf- D
A + B2 D + 2E (fast) fected by changes in the concentrations of any of the reactants.
If the first step occurs very slowly and the second step is very This type of behavior in a reaction is characterized as zero- A
rapid, then the measured rate for the overall reaction is ap- order kinetics. The first example of zero-order kinetics, the R
proximately equal to the rate of the first step. The slow step decomposition of ammonia on tungsten, was reported by C. Y
in the overall reaction is the rate-determining step. If the N. Hinshelwood and R. E. Burk (6). For this reaction, and
proposed mechanism is correct, then the rate of reaction is others in which the rate of reaction is affected by some limiting
factor other than concentration such as the quantity of light S
probably proportional to the concentration of B squared,
i.e., absorbed in a photochemical process, the rate is given by the C
expression H
Rate =
kCB2
Rate =
k 0
Alternatively, some other intermediate, such as AB, could be
formed by the reaction The order of a reaction is an empirical quantity whereas 0
A+ B —»
AB (slow)
molecularity is a theoretical concept which can be specified L
only through a knowledge of the reaction mechanism. The
which, in turn, reacts with B, molecularity of a reaction reflects the number of individual
molecules that participate in a particular step of the reaction C
AB + B — D + 2E (fast)
mechanism. The simplest type reaction is the process H
If the first step, resulting in the formation of AB, is the rate- E
B —
D+ E
determining step, the rate of reaction will probably be pro-
for which all that is needed is a molecule of B. No collision with M
portional to the concentration of A times the concentration
of B other species is necessary; the molecule of B decays sponta- 1

neously. Hence the rate is directly proportional to amount of S

Rate =
kCfjCn B, in other words the reaction is first-order in B:
The important point being emphasized is that rate laws must T
Rate =
kCB
be experimentally determined; they cannot be determined R
from the stoichiometric equation for the reaction. This is known as a unimolecular process, because only one Y
molecule is involved.
Order of Reaction and Molecularity Another case involves the collisions of A with B,
Generally, the rate of a chemical reaction is proportional
to the concentrations of the reactants. In the decomposition A+ B -
D
of nitrogen tetroxide In this single-step process, one molecule of A collides with one
molecule of B. Under these conditions, the rate law is ex-
N2O4 —*
2N02
pressed as
the rate of reaction is proportional to the concentration of just
one reactant and the rate = /eCN204; this is called a first-order Rate =
ACaCb
reaction. This reaction is first-order with respect to A and B, and sec-
When the rate of a reaction, as determined experimentally, ond-order overall. However, the reaction is bimolecular, be-
is proportional to the concentration of two reactants, the re- cause it involves the collision between two molecules. Alter-
action is called a second-order reaction. Alternately, a sec- nately, a reaction may occur because of the collisions of two
ond-order reaction occurs when the rate of reaction is pro- indentical molecules
portional to the square of the concentration of a single reac-
tant. Examples of second-order reactions include: 2 A —A2
The rate law is second-order in A and second-order overall.
NO + 03 -*
N02 + 02 pate =
&Cn02 Moreover, this is a bimolecular reaction since two molecules
I2 + Br2 —
2IBr Rate =
kCi2CBn of A had to collide to bring about the reaction. These examples

Volume 57, Number 9, September 1980 / 661

 represent the most important types of reactions that may form
the steps in a reaction mechanism. Moleeularites of multi-
plicity greater than three are unlikely, because the probability
of a four-body collision is extremely small.

Temperature Effects
Most chemical reactions proceed more rapidly as the tem-
perature is increased. Materials such as charcoal, wood, paper,
sulfur, and gasoline slowly oxidize when exposed to air. Heat
is produced during the oxidation, but so slowly that It is im-
perceptible. When this slow oxidation occurs in unventilated
places, the heat generated is likely to accumulate. Eventually
the temperature may reach the kindling point and rapid ox-
idation with a flame may begin. Many destructive fires have
resulted from this sort of spontaneous combustion.
Chemical reactions in living organisms are also temperature
dependent. One of the principles of food preservation involves
refrigeration. Chilled or frozen foods are preserved longer than
non-refrigerated foods, because of the temperature depen-
s dence of the oxidation-reduction reactions in microorganisms
E that cause the foods to spoil. Insects during the winter months
are very sluggish or become dormant, because their metabolic Figure 3. Potential energy profile. A reaction energy diagram for an exothermic
C reaction showing the energy required to overcome the potential energy barrier
rates decrease during cold weather.
0 Not all chemical reactions respond in the same way to separating reactants and products.
N temperature changes. However, many simple reactions follow
D the “rule of thumb” that the reaction velocity doubles for each
10°C increase in temperature. For example, the process of
A
cooking food involves chemical reactions, most of which pro-
R ceed at approximately 100°C, the boiling point of water. The
Y cooling process can be hastened by the use of a pressure
cooker. By not allowing the steam to escape, the pressure in-
creases and the temperature of the water can be increased
S beyond 100°C. When the vapor pressure of the water in the
C cooker is 1266 torr in excess of atmospheric pressure, the
H temperature of the water is about 130°C. If the increase in the
cooking rate doubles for every 10°C rise in temperature, the
0 cooking rate at 130°C should be approximately eight (2s)
0 times that at 100°C.
L Although many reactions proceed rapidly at elevated
temperatures, it is apparent that an energy barrier prevents
Figure 4. The effect of temperature on molecular kinetic energy distribution.
most reactions from proceeding rapidly at ordinary temper- As temperature increases the number of reactant molecules possessing kinetic
C atures. The nature of this barrier is revealed by considering
energy > the activation energy (£"„) increases.
H the requirements for combustion. A combustible material,
E oxygen, and heat are necessary for combustion. The heat, a
form of energy, added to the reactants overcomes the energy Arrhenius in 1888. He reasoned that a discrete minimum
M barrier separating reactants and products. The quantity of amount of energy must be supplied to transform molecules
1 energy required to overcome the barrier is known as the ac- from one chemical state into another.
tivation energy, symbolized Ea. It is apparent, from experimental data, that the rate law for
S a reaction only applies for a given temperature; however, the
According to the collision theory, molecular collisions are
T a fundamental requisite for chemical reactions, and concen- temperature function does not appear in the statement.
R trations are important since they affect the collision fre- Nevertheless, the reaction rates usually increase with in-
Y quency. However, while billions of molecular collisions may creasing temperature. Since the concentrations are insigifi-
occur in a reaction vessel, not all of the collisions are effective; cantly affected by temperature change, the temperature-
in others words, every collision does riot lead to products, sensitive factor in the rate law must be the specific rate con-
because the energy of collision is insufficient to overcome the stant, k. Arrhenius determined, empirically, that the increase
energy barrier separating reactants and products. For an ef- in reaction rate with increasing temperature obeyed the
fective collision to occur, sufficient translational energy must equation
be converted into internal energies of the parts of a molecule
k=
so that some chemical bonds are broken in the reactants, new
bonds form, and reactants are converted to products. The In this, the Arrhenius equation, k is the specific rate constant
necessity to break bonds during the course of a reaction means from the rate law; the parameter A is called the frequency
that energy is required to activate a reaction even if the net factor; e is the base of the natural logarithm. The term Ea is
process is exothermic. Figure 3 shows the relationship among the activation energy, R is the universal gas constant, and T
the activation energy, net energy change, and the energies of represents the Kelvin temperature. The composite factor,
reactants and products. e-EjRT represents the fraction of molecules that possess
Inasmuch as temperature is a measure of the vigor of mo- energy equal to or greater than the activation energy, Ea.
lecular motion or kinetic energy, it is easy to predict that an Since a conti nous exchange of energy takes place between
increase in the temperature of reactant molecules will increase colliding molecules, some molecules will have a higher kinetic
the number of molecules that have sufficient energy to over- energy than the average and some will have a lower kinetic
come the actiuation energy barrier; consequently the reaction energy. However, the average kinetic energy of molecules is
rate is increased. proportional to the Kelvin temperature (~3T cal mole '1). The
The concept of activation energy was proposed by Svante mathematical expression that describes the molecular speed

662 / Journal of Chemical Education

distribution in a gaseous sample was derived by James C.
Maxwell and Ludwig Boltzmann in 1860. Figure 4 shows how
the distribution of molecular speeds (kinetic energies) varies
in response to changes in the Kelvin temperature.
The temperature dependence of the Maxwell-Boltzmann
distribution curve is valuable in explaining the effect of
temperatures on reaction rates. For example, consider that
in order to react, a molecule must have a threshold energy
equal to the activation energy, Ea. The number of molecules,
corresponding to the area under the distribution curves,
possessing the kinetic energy required to overcome the energy
barrier is very small at 300°K. As the temperature increases
to 700° K, the distribution curve broadens, and there is a
corresponding increase in the number of molecules that satisfy
the kinetic energy criterion for reaction; thus, the reaction rate
increases.

Catalysis
The rate of many reactions may be influenced by the
presence of a substance which itself undergoes no permanent -
Progress of Reaction ---—
»

chemical change during the reaction. Such substances, called Figure 5. Comparison of activation energies for an uncatalyzed and catalyzed
catalysts, are very important in many biological processes and reaction. The catalyst provides a low-energy pathway to overcome the energy s
in most industrial processes as well. Several theories have been barrier.
E
developed to explain the various mechanisms of catalysis;
these have been discussed in an article in this series by D. Kolb C
2 H2(g) + 02(g> 2 H20(g)
(8). The catalyst presumably functions by reducing the acti- 2000°
r
0
vation energy barrier as shown by the dotted line curve in For reactions that are reversible, the concepts of catalysis and N
Figure 5. Since a smaller activation energy is required, a larger activation energy barrier apply to the forward and reverse D
fraction of the molecules can react at a given temperature (Fig. reactions in the same way. In other words, if a catalyst lowers
4), hence the reaction will proceed more rapidly. the energy barrier of the forward reaction, the barrier of the A
Reversible and Irreversible Reactions reverse reaction will be lowered by exactly the same degree. R
Sometimes the amount of reversibility in a reaction is so Y
Many chemical changes seem to go forward until there is small that the changes cannot be determined by any available
some rather definite quantitative relationship between the
concentrations of the reactants and the concentration of the experimental method, but it would be contrary to the concept
of probability to assume that any chemical reaction is abso- S
products. Then the changes seem to stop. At least the con- lutely irreversible. However, when no detectable amount of
centrations of the reactants and products do not change per- C
reversibility is ever observed, it is common practice to classify
ceptibly. The constancy of the concentrations of these sub- the reaction as irreversible. For example, when concentrated
H
stances could be ascribed to either of two causes; viz., the ab- O
sulfuric acid is poured into sugar (C12H22O11), the decompo-
sence of any change whatever, or the presence of two con-
sition of sugar into carbon and water proceeds: 0
current changes which produce the original substances from
the products. The first proposal can be dismissed on the basis h2so4 L
Ci2H220h(S)- 12 C(8) + 11 H20(u
of experimental evidence; the latter proposal, however, is
experimentally sound. Under no conditions currently known will carbon combine
with water to form sugar. Hence the dehydration of sugar is C
Such chemical changes are said to be reversible. For ex-
ample, when elementary nickel is heated to 80° C in the irreversible; that is, the products will not react to re-form the H
presence of excess carbon monoxide, at a pressure of 15 atm, original substance. The following are other examples which E
tetracarbonylnickel(O) is formed: from a practical standpoint, are classified as irreversible re-
M
80°C , __,
actions:
Ni(S) + 4 CO(g) —-— 1
[Ni(CO)4](g)
2Na<S) + 2H20(p -*
2NaOH(aq) + H2(g)
This reaction is reversible, since at a temperature of 200°C and S
a pressure of one atmosphere, the tetracarbonylnickel(O) de- 2KC103(8) -> 2KC1(8) + 302(g) T
composes C7H16(g> + 1102,g>
-* 7 C02(g) + 8H20(g) R
200°C
r ,
+ 4 CO(g» For obvious reasons, reactions in which a gas is formed tend Y
[Ni(CO)4](g) N'<9>
to be irreversible when they are carried out in an open
Generally a reversible reaction is represented by a single vessel.
equation with arrows pointing in opposite directions. Thus,
the reversibility of the previous system can be shown as Literature Cited
(1) Kolb, D., J. CHEM. EDUC., 55,728 (1978).
Ni(S) + 4 CO,g, g---r
200°; atm
[Ni(CO)4],g, (2) Edelson. D„ J. CHEM. EDUC., 52,642 (1975).
Mickey, C. D„ J. CHEM. EDUC., 57,275 (1980).
•
1
(3)
Similarly, the following are also examples of reversible reac- (4)
(5)
Mickey, C. D., J. CHEM. EDUC., 57, 210 (1980).
Perkins. R. S., J. CHEM. EDUC., 51,254 (1974).
tions (6) Hinshelwood, C. N., and Burk, R. E., J. Chem. Soc., 127,1051 (1925).
700° (7) Frost, A. A., and Pearson, R. G., "Kinetics and Mechanism", 2nd.*Ed., John Wiley and
3 Fe(s) + 4 H20(g)-r Fe204(8) + 4 H2(g) Sons, Inc., New York, 1963.
(8) Kolb, D„ J. CHEM. EDUC., 56, 743 (1979).

Volume 57, Number 9, September 1980 / 663