Chemistry: Kinetics

[Chemistry] laboratory work was my first challenge.... I still carry the

scars of my first discovery - that test tubes are fragile.
London 1941
Edward Teller

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Chandra Park
Chemistry
chandrapark0517@gmail.com
1 Reaction Rates
chemical kinetics: area of chemistry concerned with the speed, or rate at which the chemical reactions
occurs

reactions rate: change in concentration of a reactant or a product with time (M/s)

A (reactants) −−→ B (products)

∆[A] ∆[B]
rate = − or rate =
∆t ∆t

• units in kinetics are very important; It is best practice to use mol · L−1 instead of M
• reactants and products from the same reaction may have different rates
• Species for reaction rates must be reported
unique rate (υ): reaction rate that can be reported without specifying the species

1 ∆[J]
υ=
νJ ∆t
νJ = stoichiometric number; positive for product and negative for reactant
spectrophotometry: measure the absorption of light to monitor concentration

Beer-Lambert law:
I0
log = ϵ[J]L
I
(I0 and I are the incident and transmitted intensities, ϵ is molar absorption constant, and L is path length)

Alternate form:
A = ϵ[J]L

2 The Rate Laws

Reverse reaction such that B → A would introduce error in measurement. However, in earlier stages this
complication can be disregarded.

F2 (g) + Cl2 (g) −−→ 2 FClO2 (g)

According to experimentational data, the rate is directly proportional to both F2 and Cl. Therefore, it
can be summarized as

rate ∝ [F2 ][ClO2 ]

rate = k[F2 ][ClO2 ]
k = rate constant, affected only by a change in temperature
The rate law is generally defined as
aA + bB −−→ cC + dD
rate = k[A]x [B]y
x and y are not related to a and b and must be experimentally determined.

reaction order = sum of the powers to which all reactant concentrations appearing in the rate law are
raised

final units: M · s−1 (gas phase: cm−3 )

orders do not have to be integers

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If x = 0, the reaction is zero order in A. Therefore, the rate of this reaction is independent of the
concentration of A.

2.1 Experimental Determination of Rate Laws

isolation method: all components in a reaction in a large excess with the exception of one(monitored
species and is the species that will be present in the concentration vs. time plot)
for the reaction A + B− > P , rate = kr [A][B]2 and [B] ≫ [A],

rate = kr,eff [A], where kr,eff = kr [B]20

pseudo first-order reaction

A pseudo second-order is formed when [A] ≫ [B] as [A] is now incorporated into the kr,eff leaving only
[B]2

3 Reactant Concentration and Time

3.1 First-Order Reactions
∆[A]
− = k[A]
∆t
The units can be determined through the following two steps

∆[A] 1
k=−
[A] ∆t

M 1
= = s−1
Ms s
[A]t
ln = −kt
[A]0
The equation can be rewritten as
ln [A]t = −kt + ln [A]0
y = mx + b
Therefore, a graph of ln [A]t to t gives a straight line of -k

** All nuclear decay processes are first-order reactions.

3.1.1 Half-Life
half-life: the time required for the concentration of a reactant to decrease to half of its initial concentration
The rate law for the first-order reaction can be rearranged as

1 ∆[A]0
t=
k [A]t

[A]t = [A]0 /2
1 [A]0
t 12 = ln
k [A]0 /2
1 0.693
t 12 = ln 2 =
k k
half-life of a first-order reaction is independent of the initial concentration of the reactant.

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3.2 Second-Order Reactions
rate M/s
k= 2 = M 2 = 1/M · s
[A]
1 1
= + kt
[A]t [A]0
half-life in second-order reactions are uncommon, but can be written as:
1
t 12 =
k[A]0

**Half-life of a second-order reaction is inversely proportional to the initial reactant concentration. Half-
life should be shorter in the early stage of the reaction when more reactant molecules are present to collide.

In a second-order reaction , the decay is slower than in a first-order reaction. → many pollutants tend
to be second-order, they decay much slower

3.3 Zero-Order Reaction

rate = k
[A]t = −kt + [A]0
[A]0
t 12 =
2k
**many of the known zero-order reactions take place on a metal surface **enzyme catalysis decomposition
of N20 to nitrogen and oxygen in the presence of Pt: once all the binding sites on Pt are occupied, the
rate becomes constant regardless of of the amount of N2 O

4 Activation Energy and Temperature Dependence of Rate Con-

stants
With very few exceptions, reaction rates increase with increasing temperature.
• As T increases, both desired and undesired reactions occur faster.

4.1 The Collision Theory of Chemistry Kinetics

collision theory: reactions occur as a result of collisions between reacting molecules
activation energy (Ea ): minimum energy required to initiate a chemical reaction

Not all collisions leads to reactions; If every binary collision led to a product, then most reactions would
be complete almost instantly.

The colliding molecules must have a total kinetic energy equal or greater than the activation energy (Ea )

activated complex (transition state): species temporarily formed by the reactant molecules as as result
of the collision before they form the product

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Because more high-energy molecules are present at the higher temperature, the rate of product formation
is also greater at the higher temperature.

reaction profile: represents the potential energy of the reactants throughout the progress of the reaction

• collision frequency between two molecules A and B is proportional to both concentration of A and
B.
• The Maxwell-Boltzmann distribution can be used to calculate the fraction of molecules that exceed
a certain kinetic energy at a certain temperature.
Ea
Ni ∝ e− RT
Ea
ν ∝ [A][B]e− RT

4.2 The Arrhenius Equation

k = Ae−Ea /RT

A = collision frequency (frequency factor)

Rate constant is directly proportional to A

higher activation energy → stronger dependence of T
lower activation energy → smaller dependence of T
The rate constant decreases with increasing activation energy and increases with increasing temperature

ln k = ln Ae−Ea /RT
Ea
ln k = lnA −
RT
  
−Ea 1
ln k = − + ln A
R T
y = mx + b
Calculate the activation energy or to find the rate constant at another temperature if the activation
energy is known.

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Ea 1 1
ln k1 − ln k2 = −
R T2 T1
 
k1 Ea T1 − T2
ln =
k2 R T1 T2
For simple reactions (reactions between atoms), it is possible to equate the frequency factor (A) in the
Arrhenius equations with the frequency of collision between the reacting species.

For more complex reactions, ”orientation factor” must also be considered.

k = ρAe−Ea /RT
Pre-exponential factor:
 1/2
8kT
A=σ NA
πµ

µ : reduced mass
mA mB
µ=
mA + mB

5 Reaction Mechanisms
Overall balanced chemical equation does not tell us about how a reaction actually takes place; merely
the sum of several elementary steps
elementary steps(reactions): series of simple reactions that represent the progress of the overall reaction
at the molecular level.
reaction mechanism: sequence of elementary steps that leads to product formation

5.1 Rate Laws and Elementary Steps

In an elementary reaction, reaction for each reactant is equal to its stoichiometric coefficient in the chem-
ical equation.

molecularity: number of molecules coming together to react in an elementary reaction

kinetic information (rate law) can only support a proposed mechanism; it can never confirm it.

intermediate: species that is formed in one elementary step and is destroyed in a subsequent step
calculate the net rate of formation of the intermediate and solve for the concentration of the intermediate

rate-determining step (RDS): the slowest step in the sequence of steps leading to product formation

side-stepping: different elementary step is preferred (that leads to the same product) as it is faster than
the slow step

consecutive reactions: intermediate that subsequently decays into the product; commonly seen in nuclear
decay and biochemical processes

approximations are useful for consecutive reactions

• pre-equilibrium: intermediate is in rapid equilibrium with its reactants

the decay of the intermediate must be slow enough that the intermediate can be approximated
to reach equilibrium with its reactants

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 • steady-state approximation: concentration of all intermediates remain constant and small through-
out the reaction
as the concentration remains constant, the net rate formation of intermediate = 0
it may be wise to also approximate that some rate laws are much more significant than others
and negate those that aren’t as significant
Lindemann mechanism

6 Catalysis
6.1 Heterogeneous Catalysis
6.2 Homogeneous Catalysis
6.3 Enzyme Catalysis