Kinetics

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Chemistry, The Central Science, 11th edition

Theodore L. Brown; H. Eugene LeMay, Jr.;


Bruce E. Bursten; Catherine J. Murphy

Chapter 14
Chemical Kinetics
Ahmad Aqel Ifseisi
Assistant Professor of Analytical Chemistry
College of Science, Department of Chemistry
King Saud University
P.O. Box 2455 Riyadh 11451 Saudi Arabia
Building: 05, Office: 1A7 & AA53
Tel. 014674198, Fax: 014675992
Web site: http://fac.ksu.edu.sa/aifseisi
E-mail: ahmad3qel@yahoo.com
aifseisi@ksu.edu.sa
In chemical kinetics we study the speeds or
rates of reactions.

Besides information about the speed at which


reactions occur, kinetics also sheds light on the
reaction mechanism (exactly how the reaction
occurs).

Speed is a type of rate. A rate is a change over time. Speed is the rate defined as a
change in distance over time. In chemical reaction we're analyzing a change in
concentration over time so we don't use the term speed but speed is a type of rate.
14.1
Factors that Affect Reaction
Rates
Factors that Affect Reaction Rates
Because reactions involve the breaking and forming of bonds, the speeds of
reactions depend on the nature of the reactants themselves. Four factors allow us
to change the rates at which particular reactions occur:

Physical state of the reactants


• In order to react, molecules must come in contact with each other.
• The more homogeneous the mixture of reactants, the faster the molecules can
react.
Concentration of reactants
• As the concentration of reactants increases, so does the likelihood that
reactant molecules will collide.
Temperature
• At higher temperatures, reactant molecules have more kinetic energy, move
faster, and collide more often and with greater energy.
Presence of a catalyst
• Catalysts speed up reactions by changing the mechanism of the reaction.
• Catalysts are not consumed during the course of the reaction.
On a molecular level, reaction rates depend on the
frequency of collisions between molecules. The greater
the frequency of collisions, the greater is the rate of reaction.

For a collision to lead to a reaction, however, it must occur


with sufficient energy to stretch bonds to a critical length
and with suitable orientation for new bonds to form in the
proper locations.
14.2
Reaction Rates
Reaction Rates
The speed of an event is defined as the change that occurs in a given interval of
time: Whenever we talk about speed, we necessarily bring in the notion of time.

Progress of a hypothetical
reaction A B

The speed of a chemical reaction - its reaction rate - is the change in the
concentration of reactants or products per unit of time. Thus, the units for reaction
rate are usually molarity per second (M/s) – that is the change in concentration
(measured in molarity) divided by a time interval (seconds).
A B

By convention, rates are always expressed as positive quantities. Because [A] is


decreasing with time, Δ [A] is a negative.
Sample Exercise 14.1 Calculating an Average Rate of Reaction

From the data given in the caption of Figure, calculate the average rate at which A
disappears over the time interval from 20 s to 40 s.

Solution
Change of Rate with Time

In this reaction, the concentration


of butyl chloride, C4H9Cl, was
measured at various times.

The concentration of C4H9Cl


decreases with the time.
The average rate of the reaction
over each interval is the change
in concentration divided by the
change in time.
Note that the average rate
decreases as the reaction
proceeds. This is because as the
reaction goes forward, there are
fewer collisions between reactant
molecules.
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• In this reaction, the ratio of


C4H9Cl to C4H9OH is 1:1.
• Thus, the rate of disappearance
of C4H9Cl is the same as the
rate of appearance of C4H9OH.

-[C4H9Cl] [C4H9OH]
Rate = =
t t

It is typical for rates to decrease as a reaction proceeds, because the


concentration of reactants decreases.
Instantaneous Rate
Instantaneous rate is the rate at a particular moment in the reaction.
The instantaneous rate is determined from the slope (or tangent) of this curve at
the point of interest.

e.g., to determine the instantaneous rate at


600 s, we draw the tangent to the curve at
this time, then construct horizontal and
vertical lines to form the right triangle. The
slope is the ratio of the height of the vertical
side to the length of the horizontal side:

- The term “rate” means “instantaneous rate”, unless indicated otherwise.


- The instantaneous rate at t = 0 is called the initial rate of the reaction.
Sample Exercise 14.2 Calculating an Instantaneous Rate of Reaction
Using the Figure, calculate the instantaneous rate of disappearance of C4H9Cl at t = 0 (the initial
rate).

Solution
The slope of this straight line equals the change in
the vertical axis divided by the corresponding
change in the horizontal axis (that is, change in
molarity over change in time). The straight line falls
from [C4H9Cl] = 0.100 M to 0.060 M in the time
change from 0 s to 210 s. Thus, the initial rate is

Practice Exercise
Using the Figure to determine the instantaneous rate
of disappearance of C4H9Cl at t = 300 s.
Answer: 1.1 × 10–4 M/s
Reaction Rates and Stoichiometry

-[C4H9Cl] =
[C4H9OH]
Rate =
t t
the ratio of C4H9Cl to C4H9OH is 1:1.

• What if the ratio is not 1:1?


H2(g) + I2(g)  2 HI(g)
Only 1/2 HI is made for each H2 used.
• To generalize, for the reaction

Reactants (decrease) Products (increase)


Sample Exercise 14.3 Relating Rates at Which Products Appear and
Reactants Disappear
(a) How is the rate at which ozone disappears related to the rate at which oxygen appears in the
reaction 2 O3(g) → 3 O2(g)?
(b) If the rate at which O2 appears, Δ[O2]/ Δt, is 6.0 × 10–5 M/s at a particular instant, at what
rate is O3 disappearing at this same time, –Δ[O3]/Δ t?

Solution

(a)

(b)
14.3
The rate Law: the Effect of
Concentration on rate
If we compare Experiments 1 & 2, we see that when [NH4+] doubles
while [NO2−] hold constant, the initial rate doubles.
Likewise, when we compare. experiments 5 & 6, we see that when
[NO2−] doubles while [NH4+] hold constant, the initial rate doubles.
If [NH4+] is increased by a factor 4 with [NO2−] left unchanged
(Experiments 1 & 3), the rate changes by a factor of 4, and so forth.
This means
Rate  [NH4+]
Rate  [NO2−]
Therefore,
Rate  [NH4+] [NO2−]
which, when written as an equation, becomes

Rate = k [NH4 +] −
[NO2 ]
This equation is called the rate law, and k is the rate
constant.
- A rate law shows the relationship between the reaction rate and the
concentrations of reactants.
- The exponents tell the order of the reaction with respect to each reactant.
- Since the rate law is

Rate = k [NH4+] [NO2−]


the reaction is
First-order in [NH4+] and
First-order in [NO2−]

Rate = k [NH4+] [NO2−]


- The overall reaction order can be found by adding the exponents on the
reactants in the rate law.
- This reaction is second-order overall.
For a general reaction,

The rate law generally has the form

The constant k in the rate law is called rate constant. k has a specific value
for each reaction. The value of k is determined experimentally. The
magnitude of k changes with temperature and therefore determines how
temperature affects rate.

The exponents m and n are typically small whole numbers (usually 0, 1, or


2). We will consider these exponents more closely very shortly.

A rate law shows the relationship between the reaction rate and the
concentrations of reactants.
For gas-phase reactants use PA instead of [A].
The rate laws for most reactions have the general form

The exponents m and n in a rate law are called reaction orders.

The overall reaction order is the sum of the orders with respect to each
reactant in the rate law.

For the first order reactions in a reactant [A], changes in the concentration of
that reactant will produce proportional changes in the rate. Thus, doubling or
tripling the reactant concentration, doubles or triples the rate, and so forth.

If the rate law is second order in a particular reactant [A]2, then doubling the
concentration of that substance causes the reaction rate to quadruple ([2]2 = 4),
whereas tripling the concentration causes the rate to increase ninefold ([3]2 = 9),
and so forth.

If a reaction is zero order in a particular reactant [A]0, changing its concentration


will have no effect on rate, any concentration raised to the power zero equals 1
(catalytic reaction).
The following are some additional examples of rate laws:

Although the exponents in a rate law are sometimes the same as the
coefficients in the balanced equation, this is not necessarily the case.

The values of these exponents must be determined experimentally. In


most rate laws, reaction orders are 0, 1, or 2.

However, we also occasionally encounter rate laws in which the reaction


order is fractional or even negative.
Units of Rate Constants
The units of the rate constant depend on the overall reaction order of the rate law.

For the first order reactions

For the second order reactions

For the zero order reactions


Units of rate = (unit of rate constant) (units of concentration)0
Unit of rate constant = units of rate = M/s
Using Initial Rates to Determine Rate Laws

The rate law for any chemical reaction must be determined


experimentally; it cannot be predicted by merely looking at
the chemical equation.

In working with rate laws, it is important to realize that the rate


of a reaction depends on concentration, but the rate constant
does not.

The rate constant (and hence the reaction rate) is affected by


temperature and by the presence of a catalyst.
Sample Exercise 14.6 Determining a Rate Law from Initial Rate Data
The initial rate of a reaction A + B → C was measured for several different starting concentrations of A and B,
and the results are as follows:

Using these data, determine (a) the rate law for the reaction, (b) the rate constant, (c) the rate of the reaction
when [A] = 0.050 M and [B] = 0.100 M.

Solution
(a)
Solution (continued)
Because 2m = 4, we conclude that

(b) Using the rate law and the data from


experiment 1, we have

(c) Using the rate law from part (a) and


the rate constant from part (b), we have

Because [B] is not part of the rate law, it is irrelevant to the rate, if there is at least some B present to
react with A.
14.4
The Change of Concentration
with Time
The rate laws that we have examined so far enable us to
calculate the rate of a reaction from the rate constant and
reactant concentrations.

These rate laws can also be converted into equations that


show the relationship between the concentrations of the
reactants or products and time.
Integrated Rate Laws (first-order process only)
Consider a simple 1st order reaction: A  B

Differential form:

How much A is left after time, t ? Integrate:

Integrated form:
The integrated form of first order rate law:

[A]0 is the initial concentration of A (t = 0).


[A]t is the concentration of A at some time, t, during the course of the reaction.

Manipulating this equation produces…

… which is in the form y = mx + b


ln [A]t
If a reaction is first-order, a plot of
-k
ln [A]0
ln [A]t vs. t
t
will yield a straight line with a slope of -k.
ln [A]o will be the intercept.

So, use graphs to determine reaction order.


Consider the process in which methyl isonitrile is converted to acetonitrile.

CH3NC CH3CN
How do we know this is a first order reaction?

Does
rate=k[CH3NC]
for all time intervals?

The transformation of methyl isonitrile (CH3NC) to


acetonitrile (CH3CN) is a first-order reaction. Both are These data were collected for this reaction
isomers, molecules that have the same atoms arranged at 198.9°C
differently. This reaction called isomerization reaction.
(a) Variation in the
partial pressure of
CH3NC with time during
the reaction. A plot of
natural logarithm of
CH3NC pressure as a
function of time. Straight
line confirms that the
rate law is first order.

When ln P is plotted as a function of t, a straight line results,


and hence;
- The process is first-order.
- k is the negative slope: 5.1  10-5 s-1.
Sample Exercise 14.7 Using the Integrated First-Order Rate Law
The decomposition of a certain insecticide in water follows first-order kinetics with a rate constant of
1.45 yr–1 at 12 oC. A quantity of this insecticide is washed into a lake on June 1, leading to a
concentration of 5.0 × 10–7 g/cm3. Assume that the average temperature of the lake is 12 oC. (a) What
is the concentration of the insecticide on June 1 of the following year? (b) How long will it take for the
concentration of the insecticide to decrease to 3.0 × 10–7 g/cm3?

Solution
(a)

Note that the concentration units for [A]t and [A]0 must be the same.

(b)
Half-Life (first-order process only)
Half-life is defined as the time required for one-half of a reactant to react.
Because [A] at t1/2 is one-half of the original [A]0,
[A]t = 0.5 [A]0

The change in concentration over time


for the first-order rearrangement of
CH3NC at 198.9 oC. The first half-life
is shown at 13,600 s (that is 3.78 h).
At this time isonitril concentration has
decreased to one-half of one half, or
one-fourth the original concentration.

In a first-order reaction, the


concentration of the reactant
decreases by ½ in each of a series of
regularly spaced time intervals,
namely, t1/2. Isonitrile shows two successive half-lifes of the
isomerization reaction.
For a first-order process, set [A]t = 0.5 [A]0 in integrated rate equation:

NOTE: For a first-order process, the half-life does not depend on [A]0.
Sample Exercise 14.9 Determining the Half-Life of a First-Order Reaction
The reaction of C4H9Cl with water is a first-order
reaction. The Figure shows how the concentration
of C4H9Cl changes with time at a particular
temperature. (a) From that graph, estimate the half-
life for this reaction. (b) Use the half-life from (a)
to calculate the rate constant.

Solution
(a) From the graph, we see that the initial value of
[C4H9Cl] is 0.100 M. The half-life for this first-
order reaction is the time required for [C4H9Cl] to
decrease to 0.050 M, which we can read off the
graph. This point occurs at approximately 340 s.
(b) Solving Equation for k, we have
Order
zero first second (equal conc.)
Overall reaction A B A B 2A B
Definition of rate - Δ[A] / Δt - Δ[A] / Δt - Δ[A] / 2 Δt
Rate law Rate = k Rate = k [A] k [A]2
k unit M s-1 s-1 M-1s-1
Integrated rate law [A] = -k t + [A]0 ln[A] = -k t + ln[A]0 1/[A] = k t + 1/[A]0
Plot needed to give a [A] vs. t ln[A] vs. t 1 / [A] vs. t
straight line
Relationship of k to -k -k k
slope of straight line
Half-life [A]0 / 2 k ln 2 / k 1 / 2 k [A]0

Note:
Zero, second, third (equal and different concentrations)… etc. orders are not included.
14.5
Temperature and Rate
The rates of most chemical reactions increase as the temperature rises.
This due to an increase in the rate constant with increasing temperature;
(k is temperature dependent).

Temperature affects the rate of the


The figure shows the rate constant for this reaction as a chemiluminescence reaction in Cyalume light
function of temperature. The k and hence the rate of sticks. The light stick in hot water glows more
the reaction, increases rapidly with temperature, brightly than the one in cold water. At higher
approximately doubling for each 10 oC rise. temperature the reaction is faster.
The Collision Model
- In a chemical reaction, bonds are broken and new bonds are formed.

- Molecules can only react if they collide with each other (molecules must
collide to react). The greater the number of collisions, the greater is the
reaction rate.

- Furthermore, molecules must collide with the correct orientation and with
enough energy to cause bond breakage and formation.

- As the concentration of reactant molecules increases, the number of


collisions increases, leading to an increase in reaction rate.

- Increasing the temperature increases molecular speed. Then collide


more forcefully (with more energy) and more frequently, increasing reaction
rates.
Activation Energy
- There is a minimum amount of energy required for reaction:
the activation energy, Ea.
- The value of Ea varies from reaction to reaction.

- Just as a ball cannot get over a hill if it does not roll up the hill with
enough energy, a reaction cannot occur unless the molecules possess
sufficient energy to get over the activation energy barrier.
Reaction Coordinate Diagrams
It is helpful to visualize energy changes throughout a process on a reaction
coordinate diagram like this one for the rearrangement of methyl isonitrile.

The energy change for the


reaction, ΔE, has no effect
on the rate of the reaction.
The rate depends on the
magnitude of Ea; generally,
the lower Ea is the faster
the reaction.

The activation barrier for the


reverse reaction is equal to
the sum of ΔE and Ea for
the forward reaction.
-The diagram shows the energy of the reactants and products (and, therefore, E).
-The high point on the diagram is the transition state.
-The particular arrangement of atoms at the top of the barrier is called the activated
complex or transition state.
-The energy gap between the reactants and the activated complex is the activation
energy barrier.
Maxwell–Boltzmann Distributions
Temperature is defined as a measure of the average kinetic energy of the
molecules in a sample.
- At any temperature there is a
wide distribution of kinetic
energies.
- As the temperature increases,
the curve flattens and broadens.
- Thus at higher temperatures, a
larger population of molecules
(greater fraction of the
molecules) has higher energy
(greater than Ea).
- As a result, the reaction rate
increases.

If the dotted line represents the activation energy, then as the temperature
increases, so does the fraction of molecules that can overcome the activation
energy barrier.
This fraction of molecules can be found through the
expression:

where: R is the gas constant and T is the Kelvin


temperature.
Arrhenius Equation
Svante Arrhenius noted that for most reactions, the increase in rate with
increasing temperature is nonlinear. Arrhenius developed a mathematical
relationship between k and Ea:

where k is the rate constant, Ea is the activation energy, R is the gas constant
(8.314 J/mol-K), and T is the absolute temperature, A is the frequency factor,
a number that represents the likelihood that collisions would occur with the
proper orientation. A is constant or nearly so as temperature is varied.

As the magnitude of Ea increases, k decreases because the fraction of


molecules that possess the required energy is smaller. Thus, reaction
rates decrease as Ea increases.
Taking the natural logarithm of both sides, the equation becomes:

Therefore, if k is determined experimentally


at several temperatures, Ea can be calculated
from the slope of a plot of ln k vs. 1/T.
Sample Exercise 14.10 Relating Energy Profiles to Activation Energies
and Speed of Reaction
Consider a series of reactions having the following energy profiles:

Rank the reactions from slowest to fastest assuming that they have nearly the same frequency
factors.

Solution
The lower the activation energy, the faster the reaction. The value of ΔE does not affect the rate.
Hence the order is (2) < (3) < (1).

Practice Exercise
Imagine that these reactions are reversed. Rank these reverse reactions from slowest to fastest.
Answer: (2) < (1) < (3) because Ea values are 40, 25, and 15 kJ/mol, respectively
We can evaluate Ea in a non-graphical way if we know the rate constant of a
reaction at two or more temperatures.

Suppose that at two different temperatures, T1 and T2, a reaction has rate
constants k1 and k2. For each condition, we have:
Sample Exercise 14.11 Determining the Energy of Activation
The following table shows the rate constants for the rearrangement of methyl isonitrile at various temperatures :

(a) From these data, calculate the activation energy for the reaction. (b) What is the value of the rate constant at
430.0 K?

Solution
(a)

Graphical determination of
activation energy. The natural
A graph of ln k versus 1/T
logarithm of the k for the
results in a straight line.
rearrangement of isonitrile is
plotted as a function of 1/T. The
linear relationship is predicted by
Arrhenius equation giving a slope
equal to -Ea/R.
Solution (continued)

(b)

Practice Exercise
Using the data in the above Sample Exercise, calculate the rate constant for the rearrangement of methyl
isonitrile at 280 oC.
Answer: 2.2 × 10–2 s–1
Q & A
The rate of a chemical reaction
is affected by:

a. the concentration of the reactants


b. the temperature of the reaction
c. the presence of a catalyst
d. all of the above
As a chemical reaction
proceeds, the rate of the
reaction tends to:
a. increase
b. decrease
c. remain constant
d. oscillate
The time needed for half of the
reactant to be consumed is
called the __________ of the
reaction.
a. midpoint
b. equivalence point
c. half-rate
d. half-life
The half-life of a first-order
reaction is equal to _________,
where k is the rate constant.

a. 0.693/k
b. 0.693k
c. k/2
d. 2k
The minimum energy a collision
between molecules must have
to produce the products is
called the __________ energy.
a. initiation
b. internal
c. external
d. activation
The rate-determining step is the
__________ step in a reaction
mechanism.

a. first
b. last
c. fastest
d. slowest
Which expression correctly states
the rate of reaction?
N2(g) + 3 H2(g) 2 NH3(g)
What is the rate law for the
reaction? A + 2 B products

• Rate = k[A][B]2 [A] [B] Initial Rate M/s

• Rate = k[A][B] 0.10 0.10 1.0 x 10–4


• Rate = k[A]2[B]
0.10 0.20 1.0 x 10–4
• Rate = k[A]
• Rate = k[B] 0.20 0.20 2.0 x 10–4
What is the rate law for the
reaction? 2 A + B products

• Rate = k[A][B]2 [A] [B] Initial Rate M/s

• Rate = k[A][B] 0.10 0.10 1.0 x 10–4


• Rate = k[A]2[B]
0.10 0.20 4.0 x 10–4
• Rate = k[A]2[B]4
• Rate = k[B] 0.20 0.20 8.0 x 10–4
What are the units of the rate
constant for a reaction with a
rate law of:
Rate = k [A][B]
• Ms
• M2 s
• M–1 s–1
• M–1 s–2
• M–2 s–1
If t1/2 = 500 s for a first-order
reaction, how long will it take for the
concentration of a reactant to
decrease to 1/8 of its original value?
• 2 x 500 = 1000 s
• 3 x 500 = 1500 s
• 4 x 500 = 2000 s
• 5 x 500 = 2500 s
• 8 x 500 = 4000 s
For the reaction pictured in the
Figure to calculate the average rate
of appearance of B over the time
interval from 0 to 40 s.

Answer:
1.8 × 10–2 M/s
The decomposition of N2O5 proceeds
according to the following equation:
2 N2O5(g) → 4 NO2(g) + O2(g)
If the rate of decomposition of N2O5 at a
particular instant in a reaction vessel is
4.2 × 10–7 M/s, what is the rate of
appearance of (a) NO2, (b) O2?
Answer: (a) 8.4 × 10–7 M/s,
(b) 2.1 × 10–7 M/s
The following data were measured for the reaction of
nitric oxide with hydrogen:

(a) Determine the rate law for this reaction. (b)


Calculate the rate constant. (c) Calculate the rate when
[NO] = 0.050 M and [H2] = 0.150 M

Answers: (a) rate = k[NO]2[H2];


(b) k = 1.2 M–2 s–1; (c) rate = 4.5 × 10–4 M/s
The decomposition of dimethyl ether,
(CH3)2O, at 510 oC is a first-order
process with a rate constant of
6.8 × 10–4 s–1:

If the initial pressure of (CH3)2O is 135


torr, what is its pressure after 1420 s?

Answer: 51 torr
(a) Calculate t1/2 for the decomposition of
the insecticide described in Sample
Exercise 14.7. (b) How long does it take
for the concentration of the insecticide to
reach one-quarter of the initial value?

Answer: (a) 0.478 yr = 1.51 × 107 s;


(b) it takes two half-lives, 2(0.478 yr) =
0.956 yr

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