14.

4 The Change of Concentration with Time

First Order Reactions:
• First-order reaction is one whose rate depends on the concentration of
a single reactant raised to the first power.
• Reaction type A  Products, rate law may be first order:

[ A]
Rate  k[ A]
t
An equation that relates [A]0 at the start of the reaction, to its
concentration at any other time t, [A]t:

[ A]t
ln[ A]t  ln[ A]0  kt or ln  kt or ln[ A]t  kt  ln[ A]0
[ A]0
Exercise: The decomposition of a certain
insecticide in water follows first-order
kinetics w/ a rate constant of 1.45 yr-1 at
12oC. A quantity of this insecticide was
washed into a lake on June 1st, leading to a
concentration of 5.0 x 10-7 g/cm3. Assume
that the average temperature of the lake is
12oC. (a) What is the conc. of the
insecticide on June 1st of the following year?
(b) How long will it take for the conc. of the
insecticide to drop to 3.0 x 10-7 g/cm3?
(a) ln[ A]t  kt  ln[ A]0

  
ln[in sec ticide]t 1 yr  1.45 yr  1 1.00 yr   ln 5.0 x 10 7 
ln[in sec ticide]t 1 yr  1.45   14.51  15.96
ln[in sec ticide]t 1 yr e  15.96 1.2 x 10 7 g / cm 3
Note: Conc. Units for [A]t and [A]o must be the same

(b)
ln[A]t  kt  ln[A]0
ln(3.0 x10 7 )  (1.45 yr  1 )(t )  ln(5.0 x10 7 )
t  [ln(3.0 x10 7 )  ln(5.0 x10 7 )] / 1.45 yr  1
t  ( 15.02  14.51) / 1.45 yr  1 0.35 yr
• The previous equation can be used to verify whether a reaction is
first order and determine its rate constant. This equation has the
form of y = mx +b.

For a first-order reaction, the graph of ln[A]t versus time gives a

straight line with slope of –k and y-intercept of ln[A]0. A reaction that
is not first order will not yield a straight line.

ln[ A]t  kt  ln[ A]0

y = mx +
b
 Second-Order Reactions
• A second-order reaction
is one whose rate
depends on the reactant
concentration raised to
the second power or on
the concentrations of two
different reactants, each
raised to the first power.

Type: A  products [ A]
Rate  k [ A] 2
or A + B  t
products.

1 1
As an equation it becomes: kt 
[ A]t [ A]0
• The previous equation also the form of a straight
line (y = mx+b). If the reaction is second order, a
plot of 1/[A]t versus t will yield a straight line with
slope equal to k and and a y-intercept equal to
1/[A]0.

• One way to distinguish between first- and

second-order rate laws is to graph both ln[A] t
and 1/[A]t against t. If the ln[A]t plot is linear, the
reaction is first order; if the 1/[A] t plot is linear, the
reaction is second order.
Example NO2(g)  NO(g) + ½ O2(g) at 300o C
Determining Reaction order from the Integrated rate law

Time (s) [NO2] (M) ln[NO2] 1/[NO2]

0.0 0.01000 -4.610 100

50.0 0.00787 -4.845 127
100.0 0.00649 -5.038 154
200.0 0.00481 -5.337 208
300.0 0.00380 -5.573 263
 Half-Life
• The half–life of a reaction, t1/2, is the time
required for the concentration of a
reactant to drop to one half its initial value, Half Life 1st Order Rxn
[A]t1/2 = ½ [A]0.
1
• Notice that the half-life of a first-order ln  
2 0.693
reaction is unaffacted by the initial conc. t1    
of the reactant. 2 k k
• In a first-order reaction, the conc. of the
reactant decreases by ½ in each series of
regularly spaced time intervals, namely,
t1/2. Half Life 2nd Order Rxn
1
• Half-life of second-order reaction is t1 
2 k [ A] 0
• Note: This half-life depends on initial
concentration of reactant.
Order or First Second
Rxn
Differential rate law Rate = k[A] = -ΔA / Δt Rate = k[A]2 = -ΔA / Δt

Integrated rate law ln [A]t = -kt + ln [A]0 1 / [A]t = kt + 1/[A]0

Or ln ([A]0/[A]t) = +kt
Half Life T1/2 = 0.693 / k T1/2 = 1 / k [A]0

Straight line plot ln [A] vs. time 1 / [A] vs. time

Slope = -k k
 14.5 Temperature and Rate
• The rates of most
chemical reactions
increase as the
temperature increases.

• Faster rates at higher

temperatures are due to
an increase in the rate
constant with increasing
temperature.

Methyl isonitrile as a function of tempertaure

 The Collision Model
• The Collision model, based on kinetic
molecular theory, accounts for both the
effects of concentration and temperature
at the molecular level. The greater the
number of collisions per second, the
greater the reaction rate. Increasing
concentration or temperature allows more
collisions to occur and increases the rate.
 The Orientation Factor
• In most reactions, molecules must be oriented in certain ways
during collisons in order for a reaction to occur. Molecules not
oriented appropriately will lead to too few collisions and very little
reaction.
 Activation Energy
• In order to react, colliding molecules must have a total
kinetic energy equal to or greater than some minimum
value. The minimum energy required to initiate a
chemical reaction is called the activation energy, Ea.
The value of Ea varies from reaction to reaction.

• The barrier in the diagrams represents the energy

necessary to force the molecule through the relatively
unstable intermediate state to the final product. The
energy difference between that of the starting molecule
and the highest energy along the reaction pathway is the
Ea, or activation energy.

• The particular arrangement of atoms at the top of the

barrier is called the activated complex, or transition
state.
 Activation energy continued.

The reaction to the right is exothermic and has a lower energy than when the
Reaction started. The energy change for the reaction has no effect on the
Rate of the reaction. Generally, the lower the Ea, the faster the reaction.
Notice, the reverse reaction (right to left) is endothermic and the activation
Energy is the sum of the Ea and ΔE.
•
Arrhenius Equation
Arrhenius found that most
reaction-rate data obeyed an
equation based on three factors:
(a) fraction of molecules
possesing an energy Ea or
 E a / RT
greater, (b) the number of
collisions occuring per second,
and (c) the fraction of collisions
k  Ae
that have the appropriate
orientation. Arrhenius Eqn

• k is rate constant
• Ea is activation energy Reaction rates decrease as Ea increases.
• R is gas constant (8.314J/mol-K)
• T is absolute temperature

• Frequency factor, A, is constant

Note: no calcs with Arrhenius eqn
as temperature is varied.
need to be completed.
Rank from slowest to fastest, highest activation energy is the slowest reaction
 Determining the Activation Energy
• We can evalute Ea in a non k1 Ea  1 1
ln    
graphical way if we know the k2 R  T2 T1 
rate constant of a reaction at
two or more temperatures.

• Graphically, activation energy

can be determined by
measuring k at a series of Ea
temps, graphing lnk versus ln k   ln A
1/T, and then calculating Ea RT
from slope of resultant line.
 14.6 Reaction Mechanisms
• The process by which a reaction occurs is called the reaction
mechanism.

Elementary Steps
Reactions take place when molecules collide. An event where
molecules react form a product in a single step are called
elementary steps or processes.

Molecularity of step is defined as the number of molecules that

participate as reactants in the elementary step.

If a single molecule is involved  rxn is unimolecular

If two molecules are involved  rxn is bimolecular
If three molecules are involved  rxn is termolecular
 Multistep Mechanisms
• The net change represented by a balanced equation occurs by a
multistep mechanism, which is made up of a series of elementary
steps.

Example rxn is: NO2(g) + CO(g)  NO(g) + CO2(g)

This rxn proceeds in two elementary steps, both of which are

bimolecular
NO2(g) + NO2(g)  NO3(g) + NO(g)
NO3(g) + CO(g)  NO2(g) + CO2(g)

The elementary steps in a multistep mechanism must always add to

give the chemical equation of the overall process.
2NO2(g) + NO3(g) + CO(g)  + NO2(g) + NO3(g) + NO(g) + CO2(g)

Note: when you sum the above eqn the overall eqn at the top of this
slide is formed. NO3(g) is an intermediate  formed and then
consumed.
 Conversion of ozone into O2 proceeds by a 2 -step
mechanism

O3 (g) --> O2(g) + O (g)

O3 (g) + O(g) --> 2 O2 (g)

1. Describe the molecularity of each

elementary reaction in the mechanism.
2. Write the eqn for the overall rxn
3. Identify the intermediates.
 Rate Laws for Elementary Steps
A rate law can be determined from its mechanism.

If we know that a reaction is an elementary step, then we

know its rate law. Rate law of any elementary step is
based directly on its molecularity.

Rate of unimolecular process is 1st order:

A  products Rate = k[A]

Rate of bimolecular process is 2nd order:

A + B  products Rate = k[A][B]

If the following rxn occurs in a single elementary rxn,
predict the rate law:

H2 (g) + Br2 (g) --> 2 HBr (g)

• Rate = k [H2][Br2]
 Rate-Determining Step for a
Multistep Mechanism
• The overall rate of a rxn cannot exceed
the rate of the slowest elementary step of
the mechanism. This step is called the
rate-determining step.
The decomposition of N2O (nitrous oxide) is believed to
occur by a two step mechanism:

N2O (g) --> N2 (g) + O (g) (slow)

N2O (g) + O(g) --> N2(g) + O2(g) fast

(a)Write the eqn for the overall rxn.

(b) Write the rate law for the overall rxn.
Ozone reacts with nitrogen dioxide to produce dinitrogen pentoxide and
oxygen:

O3 (g) + 2 NO2(g)  N2O5 (g) + O2(g)

The reaction is believed to occur in two steps:

O3(g) + NO2(g)  NO3(g) + O2(g)

NO3(g) + NO2(g)  N2O5 (g)

The experimental rate law is rate = k [O3][NO2]. What

can you say about the relative rates of the two steps of
the mechanism?
Solution

Because the rate law conforms to

the molecularity of the first step, the
first step must be the rate
determining step. The second step
must be much faster than the first
one.
 Notes on Mechanisms
• Do not include a catalyst in overall
reaction
• Catalysts are not intermediates
• Intermediates can be included in the rate
law for the slow step.
 14.7

Important classes in catalysis include acid

base catalysis, surface catalysis, and
enzyme catalysis.
a. In acid-base catalysis, a reactant either
gains or loses a proton; this changes the
rate of the reaction.
b. b. In surface catalysis, either a new
reaction intermediate is formed, or the
probability of successful collisions is
modified.
c. c. Some enzymes accelerate reactions by
binding to the reactants in a way that
lowers the activation energy. Other
enzymes react with reactant species to
form a new reaction intermediate