CHEMICAL KINETICS

Chemical kinetics is the area of chemistry concerned with the speeds, or rates, at which a chemical reaction occurs.
Rate of reaction (reaction rate) – the change in the concentration of a reactant or a product with time (M/s)
A → B
rate = - ∆[A]/∆t or rate = ∆[B]/∆t

rate = ∆[pg]/∆t = 1/RT(∆P/∆t)

Factors that Influence Reaction Rate

1. Concentration
2. Physical state
3. Temperature
4. Catalyst

Reaction rates and stoichiometry

aA + bB → cC + dD
rate = -1 ∆[A] = -1 [∆B] = 1 ∆[C] = 1 ∆[D]
a ∆t b ∆t c ∆t d ∆t
Examples:
Write the rate expressions for the following reactions in terms of the disappearance of the reactants and
the appearance of the products.
(a) I-(aq) + OCl-(aq) → Cl-(aq) + OI-(aq)
(b) 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)

Consider the reaction

4PH3(g) → P4(g) + 6H2(g)
Suppose that, at a particular moment during the reaction, molecular hydrogen is being formed at the rate of 0.078
M/s. (a) At what rate is P4 being formed? (b) At what rate is PH3 reacting?

Rate Law expresses the relationship of the rate of a reaction to the rate constant and the concentrations of the
reactants raised to some powers
aA + bB → cC + dD
rate = k[A]x[B]y where: x and y are numbers determined experimentally
k is the rate constant
Examples:
The reaction of nitric oxide with hydrogen at 1280°C is
2NO(g) + 2H2(g) → N2(g) + 2H2O(g)
From the following data collected at this temperature, determine (a) the rate law, (b) the rate constant, and (c) the
rate of the reaction when [NO] = 12x10-3 M and [H2] = 6x10-3M.
Experiment [NO](M) [H2](M) Initial Rate (M/s)
1 5x10-3 2x10-3 1.3x10-5
-3 -3
2 10x10 2x10 5x10-5
-3 -3
3 10x10 4x10 10x10-5

Practice Problem:
The reaction of peroxydisulfate ion (S2O82--) with iodide ion (I-) is
S2O82-- (aq) + 3I—(aq) → 2SO42—(aq) + I3—(aq)
From the following data collected at a cetain temperature, determine the rate law and calculate the rate constant.
Experiment [S2O82--](M) [I--](M) Initial Rate (M/s)
1 0.080 0.034 2.2x10-4
2 0.080 0.017 1.1x10-4
3 0.16 0.017 2.2x10-4

The relation Between Reactant Concentration and Time

First-Order Reactions
A first-order reaction is a reaction whose rate depends on the reactant concentration raised to the first
power.
A → product
rate = - ∆[A]/∆t
rate = k[A]
ln{[A]t/[A]0} = -kt or ln[A]t = -kt + ln[A]0
Reaction Half-life
The half-life, t1/2, the time required for the concentration of a reactant to decrease to half of its initial
concentration.
For the first-order reaction, t1/2 = ln2/k

Examples:
The conversion of cyclopropane to propene in the gas phase is a first-order reaction with a rate constant of 6.7x10-
4 -1
s at 500°C. (a) If the initial concentration of cyclopropane was 0.25M, what is the concentration at 8.8 min. (b)
How long (in minutes) will it take for the concentration of cyclopropane to decrease from 0.25M to 0.15M? (c)
How long (in minutes) will it take to convert 74 percent of the starting material?

The decomposition of ethane (C2H6) to methyl radicals is a first-order reaction with a rate constant of 5.36x10-4 s-1
at 700°C: C2H6(g) → 2CH3(g)
Calculate the half-life of the reaction in minutes.

Practice Problem:
The reaction 2A → B is first order in A with a rate constant of 2.8x10-2 s-1 at 80°C. How long (in seconds) will it take
for A to decrease from 0.88M to 0.14M? What is its half-life?

Second-Order Reactions
A second-order reaction is a reaction whose rate depends on the concentration of one reactant raised to
the second power or on the concentration of two different reactants, each raised to the first power.
A + B → Product (rate = k[A][B])
A → Product (rate = k[A]2)
For this reaction: 1/[A]t = kt + 1/[A]0
t1/2 = 1/k[A]0
Example:
Iodine atoms combine to form molecular iodine in the gas phase I(g) + I(g) → I2(g)
This reaction follows second-order kinetics and has high rate constant 7x109/M∙s at 23°C. (a) If the initial
concentration of I was 0.086M, calculate the concentration after 2min. (b) Calculate the half-life of the reaction if
the initial concentration of I is 0.60M and if it is 0.42M.

Practice Problem:
The reaction 2A → B is second order with a rate constant of 51/M∙min at 24°C. (a) Starting with [A] 0 = 0.0092M,
how long will it take for [A]t = 3.7x10-3M? Calculate the half-life of the reaction.

Zero-Order Reactions
A → product
rate = k
The rate of a zero-order reaction is a constant, independent of reactant concentration.
[A]t = -kt + [A]0
t1/2 = [A]0/2k

Activation Energy (Ea) is the minimum amount of energy required to initiate a chemical reaction
Activated complex (transition state) – a temporary species formed by the reactant molecules as a result of the
collision before they form the product.

Arrhenius equation: ln k = lnA – Ea/RT where Ea is in kJ/mol

R is 8.314 J/mol∙K
T is in K

ln(k1/k2) = Ea/R[(1/T2) – (1/T1)]

ln(k1/k2) = Ea/R[(T1-T2)/T1T2]
Example:
The rate constant of a first-order reaction is 3.46x10-2 s-1 at 298K. What is the rate constant at 350K if the
activation energy for the reaction is 50.2 kJ/mol?

Practice Problem:
The rate constant of a first-order reaction is 4.60x10-4 s-1 at 350°C. If the activation energy is 104 kJ/mol, calculate
the temperature at which its rate constant is 8.80x10-4 s-1.

REACTION MECHANISMS
Elementary steps (elementary reactions) – a series of simple reactions that represent the progress of the overall
reaction at the molecular level.
Reaction mechanism – the sequence of elementary steps that leads to product formation.
Example: Step 1: NO(g) + NO(g) → N2O2(g)
Step 2: N2O2(g) + O2(g) → 2NO2(g)
Overall reaction: 2NO(g) + O2(g) → 2NO2(g)

Intermediates are species that appear in the mechanism of the reaction but not in the overall balanced equation.
Molecularity of a reaction – the number of molecules (of the same or of different kinds) reacting in an elementary
step.
a. Unimolecular reaction – involves only one reacting molecule
b. Bimolecular reaction –involves 2 molecules
c. Termolecular reaction – involves 3 molecules
Rate-determining step – the slowest step in the sequence of steps leading to product formation

Measuring the Formulating Postulating a

rate of a the rate law reasonable reaction
reaction mechanism
Sequence of steps in the study of a reaction

CATALYSIS
Catalyst – a substance that increases the rate of a reaction by lowering the activation energy
Heterogeneous catalysis – the reactants and the catalyst are in different phase
Homogeneous catalysis – the reactants and catalyst are dispersed in a single phase, usually liquid.
Enzyme catalysis: enzymes – biological catalysts