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1 [ A] 1 [ B]
; rate is a
=
a t b t
positive quantity.
Rates can be determined by measuring the change in the concentration of a reactant or product
with time. Possible methods are pressure measurements for gases using a manometer or
pressure gauge, volume measurement for gases using a gas syringe, color changes using a
colorimeter or spectrophotometer, heat changes using a thermometer, mass changes using a
balance, pH changes using a pH meter, titrations, etc.
Collision Theory
Activation energy is the minimum energy required for reactants to react in order to
convert into products (via a transition state or activated complex).
Transition state is an unstable arrangement in which the bonds are in the process of
being broken and formed and presents the maximum point on a potential energy
diagram; it can not be isolated.
Increase in concentration: Greater number of particles per unit volume per time means
greater frequency of collisions and faster rate.
Increasing the surface area of solids reactants: This increases the number of particles
that can collide, i.e., increases the frequency of successful collisions.
A catalyst does not change the position of equilibrium; rather it increases the
rate of both the forward and reverse reactions to the same extent; does not
change H of a reaction.
For the reaction: A + B + C products, rate =k[A]m[B]n[C]p, where m, n, and p are the
orders of the reaction with respect to each reactant A, B, C. The overall order = (m + n + p).
CHAPTER 6 KINETICS
(IB TOPICS 6 AND 16) SUMMARY
Orders of reaction are obtained experimentally, not from Stoichiometry; however any
mechanism must be consistent with overall Stoichiometry of the reaction.
Rate constant, k, is the constant in the rate expression. It is temperature dependent. Units
of rate constant depend on the rate expression; units of zero order rate constant, ko = units
of rate = mol dm3 s1. Units of 1st order rate constant, k1 = s1. Units of 2nd order rate
constant, k2 = dm3 mol1 s1; units of 3rd order rate constant, k3 = dm6 mol2 s1 (units must
not be memorized, but easily derived from the appropriate rate expression).
The rate expression, determined only experimentally, need not be a simple one, i.e., it
need not contain whole numbers, or positive numbers for that matter although this is often
the case.
In general, given the rate as a function of concentration, reaction order can be determined
as follows:
If only one reactant is involved, since rate = k [conc.]n, find the ratio of the rates at two
different concentrations and apply the relation:
n
rate2 [conc 2 ]
=
; n is the reaction order.
rate1 [conc1 ]
Find the ratio of the rates when [B] is constant but [A] changes. Using the equation above,
find the order with respect to A.
Repeat the process when [A] is constant but [B] changes to determine the order with respect
to B.
Orders of reaction
o
Zero-order reaction is when the rate of a reaction is independent of the
concentration of a reactant: rate=k [A]0 = k. Graph of [A] vs time is a straight line, with
a negative slope = rate. [A]t = [A]0 kt.
o
First-order reaction is where the rate doubles when concentration doubles: rate =k
[A]1. Graph of [A] against time is an exponential curve; graph of ln [A] vs. t is a
straight line with a negative slope where slope = k the rate constant. Half-life of a first
order reaction is a constant; t1/2=0.693/k. Integrated form of first order equation:
ln
ln [A]t = kt + ln [A]0 OR ln [A]0 ln[A]t = kt OR
[ A]0
= kt
[ A]t
;
[A]t = [A]0e-kt (the last two equations are given in the Data Book).
o
irst-order reaction is where the rate doubles when concentration doubles: rate =k
[A]1. Graph of [A] against time is an exponential curve; graph of ln [A] vs. t is a
straight line with a negative slope where slope = k the rate constant. Half-life of a first
order reaction is a constant; t1/2=0.693/k. Integrated form of first order equation: ln [A]t
ln
= kt + ln [A]0 OR ln [A]0 ln[A]t = kt OR
equations are given in the Data Book).
[ A]0
= kt
[ A]t
; [A]t = [A]0e-kt (the last two
o
If the rate quadruples when concentration doubles: rate = k [A]2. Graph of 1/[A]
against time is a straight line for a second order reaction with a positive slope = k.
IBID Press 2007
CHAPTER 6 KINETICS
(IB TOPICS 6 AND 16) SUMMARY
o
For a third-order reaction, if rate = k[A]3, then as [A] doubles, rate increases 8
times.
o
Rate increases with temperature when concentrations are constant, k increases
rapidly with T and is temperature dependent, producing a straight line graph of ln k vs
1/T with a negative slope. Slope of the line = - Ea/R. Thus Ea can be determined; T
must be in Kelvin, not C.
o
RT
booklet): k = A e
:
ln k = ln A
o
Ea 1
R T
OR
log10 k = log10 A
Ea 1
where: A, the
2.303 R T
Arrhenius constant is the collision factor that represents the frequency of successful
collisions with the favourable geometry, R is the Ideal Gas Constant (= 8.314 J mol-1 K1
), Ea is the activation energy (the minimum energy required for a reaction to occur),
and T must be in Kelvin scale.
o
Intermediates are species produced in earlier steps that are consumed in later
steps.
o
Transition state is an unstable arrangement in which the bonds are in the process
of being broken and formed and presents the maximum point on a potential energy
diagram; it can not be isolated.
o
o
Stoichiometry of an equation gives no information about the rate expression or
about the mechanism of a reaction. However any mechanism must be consistent with
overall Stoichiometry, rate expression, etc. For a 3rd order reaction, the first step
(containing a maximum of two particles) cannot be the slow, rate determining step.
A Unimolecular step
A Bimolecular step