Chapter 20 Notes: Kinetics

Section 20.2: Rates and Rate Laws

 The rate of a reaction is an indication of how many moles of a reactant or product are
reacted or produced over a period of time.
 It is conventional to define rates of reactions as they would be at the very beginning of a
chemical process, where only reactants are present, no products. The rate of a reaction
at this extent ε = 0 is called the rate of initial reaction or the initial reaction rate.
 General: rate = change in amount/change in time.
 Experimentally, what is found is that the initial rate is proportional to the concentration
(that is, molarity) of some or all of the reactants raised to some exponent. Expressing
this concept mathematically, for some general reaction “aA + bB  products”: rate =
k*[A]m*[B]n where k (mol/s or M/s) is the rate constant for the reaction (independent of
the exact concentrations of A and B but dependent on temperature) and m/n are
orders. This is also called a rate law.
Section 20.3: Characteristics of Specific Initial Rate Laws

 The basic equation that relates how the concentration of A varies over time for a first-
order reaction, the integrated form of a first-order rate law (or more simply, the
integrated rate law): ln([A]0/[A]t) = k*t where [A]0 is the initial amount of A at time 0,
[A]t is the amount of A at some time t, and t represents elapsed time. Independent of
the initial amount.
 The half-life of a first-order reaction is the amount of time necessary for half of the
original amount to react: t1/2 = ln(2)/k. Independent of the initial amount.
 Integrated second-order rate law: 1/[A]t – 1/[A]0 = k*t where amounts must be
expressed in concentration units if the rate law is expressed in concentration units.
 For second-order reactions, the half-life t1/2 can be defined as: t1/2 = 1/(k*[A]0). As the
initial amount [A]0 gets larger, the amount of time it takes for half of the reactant to
react gets smaller.
 A reaction following zeroth-order kinetics has a rate law of –d[A]/dt = k*[A]0 = k. That is,
the rate of disappearance of A is a constant, the zeroth-order rate constant.
 The integrated zeroth-order rate law: [A]0 – [A]t = k*t where t represents elapsed time.
 The expression for the half-life for a zeroth-order reaction: t1/2 = [A]0/(2*k). Note that
the half-life depends on the initial amount, as expected. You need to recognize
something else about a zeroth-order reaction: After two half-lives, all of reactant A is
gone and the reaction is finished. (This assumes that the reaction remains zeroth order
at all concentrations and actually goes to completion).
 Probably the most common usage of this tactic is where the order m equals 1, so that
the rate of the reaction follows the approximate expression: rate ≈ k’[A]. Reactions that
are intentionally set up this way are said to be following pseudo first-order kinetics, and
 the constant k’ is the pseudo first-order rate constant. Only under special conditions
(that is, with a high, almost unchanging concentration of the other reactant(s)) will the
reaction show pseudo first-order kinetics. Note too that the pseudo first-order rate
constant k’ has different units than the true rate constant k of the same reaction. The
units on k’ are always 1/s.
Section 20.4: Equilibrium for a Simple Reaction
kf
 Equilibrium constant K for the simple first order reaction A⇌B
kr
is the quotient of the
concentration of the products and the reactants: [B]eq/[A]eq ≡ K where [A]eq and [B]eq are
the expected equilibrium concentrations of A and B.
 For a first-order reaction: K = kf/kr.
Section 20.5: Parallel and Consecutive Reactions

 Consider a system in which the rate laws of both reactions are first-order with respect to
A. The initial rate of disappearance of A (integrated form): [A]t = [A]0*e-(k1+k2)t where the
initial time is set to zero so that the variable t stands for elapsed time.
 The concentrations of B and C over time, assuming integration and that the initial
amounts of B and C are zero at some initial time ([B]t = [C]t = 0 at t = 0): [B]t =
(k1*[A]0/(k1+k2))*(1- e-(k1+k2)t) and [C]t = (k2*[A]0/(k1+k2))*(1- e-(k1+k2)t). Both of these
concentrations depend on negative exponentials, but in these cases the negative
exponential is subtracted from 1. Therefore, as time increases and the negative
exponential gets smaller and smaller, the difference gets larger and larger, and [B] and
[C] increase as the elapsed time increases.
 The ratio of [B]t and [C]t has a very simple expression: (1) [B]t/[C]t = k1/k2. This
expression is valid for any time t, as long as the reverse reactions are negligible.
 At equilibrium (that is, as t  ∞), the concentrations of products and reactant are:
[A]eq=[A]0/(K1+K2+1), [B]eq=(K1*[A]0)/(K1+K2+1), and [C]eq=(K2*[A]0)/(K1+K2+1) where
K1=k1/k-1 and K2=k2/k-2 (see diagram to the right – scheme on pg 713). Consequently, (2)
[B]eq/[C]eq = K1/K2. At the limit of small times, the effects of the reverse reactions are
negligible and equation (1) is applicable. Only in the case of long times, where reverse
reactions have an appreciable effect on concentrations and equilibria are being
established, does equation (2) become applicable. However, there is no reason to
presume that the ratios [B]t/[C]t, the product ratio at some intermediate time, and
[B]eq/[C]eq, the product ratio at “infinite time,” are the same.
 The integrated rates of change of concentration of the three species in the diagram to
the right are: [A]t = [A]0*e-k1t, [B]t = ((k1*[A]0)/(k2-k1))*(e-k1t - e-k2t) and
[C]t=[A]0*[1+((1/(k1-k2))*((k2*e-k1t) – (k1*e-k2t)))] where again, t represents the elapsed
time and [A]0 is the original amount of reactant A in the system. (Remember, we are
assuming that the original amounts of B and C are zero.) If, for example, the second
reaction is much slower than the first reaction (that is, k1 >> k2 ), there is an initial
 buildup of product B and only over long periods of time will product B eventually react
to form the final product C. When k1 << k2, the second reaction is much faster than the
first one and the penultimate product B reacts to the ultimate product C almost as fast
as B itself is formed.
Section 20.6: Temperature Dependence

 Arrhenius equation: k = A*e-EA/RT where k is the rate constant of the reaction, A is the
pre-exponential factor, EA is the activation energy. The natural logarithm of this
equation is: ln(k) = ln(A) + (-EA/R)*(1/T) where ln(k) is like y, ln(A) is like b, (-EA/R) is like
m and (1/T) is like x.
 If we have two sets of conditions: ln(k1/k2) = (-EA/R)*(1/T1 – 1/T2).
 Contributions to the value of A: collision frequency factor and steric factor (steric factor
includes size of collisional cross section and considerations of reactant structure and
geometry).
Section 20.7: Mechanisms and Elementary Processes

 For elementary processes, the rate law is determined directly from the stoichiometry of
the process. Instead of using the term “the order with respect to the reactants,” we
refer to “the molecularity with respect to the individual species” in the elementary
process.
 There is a useful point, however: An overall reaction of consecutive steps can go only as
fast as its slowest step. The elementary process that has the slowest rate is the one that
controls the rate of the overall chemical reaction.
 The elementary process that controls the rate of the overall reaction is called the rate-
determining step (or RDS for short).
 If the RDS is the initial elementary process in a mechanism then the rate law of the
entire reaction is simple: It is just the rate law as dictated by the stoichiometry of the
first elementary process.
 For elementary processes, the rate law can be determined directly from the
stoichiometry of the process. For net balanced chemical reactions, we can’t. However,
we have proposed that we can know the rate of the overall reaction if we know the
rate-determining step.
Section 20.8: The Steady-State Approximation

 If the rate-determining step is the first step in the mechanism, then the rate law for the
overall reaction is simply the rate law from the elementary process.
 The steady-state approximation of reaction mechanisms: A ⇌ B (fast) and B  C (slow).
 If the first step in the above two-step process is in fact in equilibrium, then we can write
an equilibrium constant expression for it: K = [B]/[A] where we are using molar
concentrations as an arbitrary unit of amount.
  If the RDS is the second step, then we can immediately write a rate law for the reaction
as: rate = k’*[A] where k’ = k*K.
 Concentration of the intermediate B: [B] = k1*[A]/(k-1 + k2) = (k1/(k-1 + k2))*[A] (see
diagrams at right to understand subscripting).
 rate = k*[A] where k = k2*(k1/(k-1 + k2)).
Section 20.9: Chain and Oscillating Reactions
Section 20.10: Transition-State Theory

 Draw Figure 20.24 and define terms

 If the reaction considered is in fact an elementary process, then from the ideas in
section 20.7, the rate laws can be written in terms of the stoichiometry of the reaction:
rate = k*[A]*[B] = k_star*[C_star] where looking at the diagram to the right will help
define the terms.
 The elementary process rate constant k: k = (k_star*[C_star])/([A]*[B])
 k = (Kc_star*k_star)/co where co is the standard concentration unit (that is, 1 M or a = 1).
 A unimolecular rate constant like k_star has units of s-1 (that is, seconds in the
denominator), we submit that the rate constant k_star should be proportional to the
transition state’s vibrational frequency ν_star (also units of s-1) that promotes the
formation of products.
 The variable κ, called the transmission coefficient, is defined as the proportionality
constant, yielding k_star = κ*ν_star as our expression for the unimolecular rate constant
for step b. Transmission coefficients are usually assumed to be 1, and k_star is simply
equal to ν_star.
 EA = ΔH_star + RT    or     ΔH_star = EA - RT