Kinetics
Kinetics
Kinetics
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.
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:
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
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
-[C4H9Cl] [C4H9OH]
Rate = =
t t
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.
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
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.
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 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.
Although the exponents in a rate law are sometimes the same as the
coefficients in the balanced equation, this is not necessarily the case.
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
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.
Differential form:
Integrated form:
The integrated form of first order rate law:
CH3NC CH3CN
How do we know this is a first order reaction?
Does
rate=k[CH3NC]
for all time intervals?
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
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).
- 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.
- 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.
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 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.
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. 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
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:
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?