Reaction Rate & Rate Laws

Fe in salt water
 Chemical Kinetics

Not about spontaneity of a reaction

Thermodynamics described spontaneity of a reaction.
C (s, diamond)  C (s, graphite)
DGof = -2.9 kJ mol-1
This is a spontaneous reaction.

You’d better check your

diamonds for damage.
 Chemical Kinetics

H2 (g) + O2 (g)  2 H2O (g)

H2 (g) + Cl2 (g)  2 HCl (g)
3 H2 (g) + N2 (g)  2 NH3 (g)

These reactions are spontaneous. But we can

mix them at 25 oC, and they can coexist
indefinitely.
 Factors Affecting
Chemical Kinetics

Chemical Kinetics – concerned with the rates

or speeds of reactions and the factors that
affect these rates.
concentrations

temperature

catalyst
surface area of reactants
 Demo: Balanced Equation

2 MnO4- (aq) + 5 H2C2O4 (aq) + 6 H+ (aq)

2 Mn2+ (aq) + 10 CO2 (g) + 8 H2O (l)

What happens to reactants and products

during the reaction?
 Rates of Appearance
(disappearance)
Average Rate of App. = change in moles Mn2+
change in time

= D (moles of Mn2+)
Dt
Average Rate of Dis. = - change in moles MnO4-
change in time
= - D (moles of MnO4-)
Dt
 In Terms of Concentration

Average Rate of App. = D [Mn2+]

Dt

Average Rate of Dis. = - D [MnO4-]

Dt
Units  molarity/time
(generally M/s this represents a rate, molarity
changing during a particular amount of time)
Average Rate of Reaction?
Inst. Rate of Reaction?
 Femtochemistry
•The study of chemical reactions on a very
short time scale
 Stoichiometry/
Rates of Reactions?
2 MnO4- (aq) + 5 H2C2O4 (aq) + 6 H+ (aq)

2 Mn2+ (aq) + 10 CO2 (g) + 8 H2O (l)

Compare the rate of disappearance of MnO4- with

the rate of appearance of Mn2+.

Rate = (1/2) - D [MnO4-] = (1/2) D[Mn2+]

Dt Dt
 Stoichiometry/
Rates of Reactions?
2 MnO4- (aq) + 5 H2C2O4 (aq) + 6 H+ (aq)

2 Mn2+ (aq) + 10 CO2 (g) + 8 H2O (l)

Compare the rate of disappearance of MnO4- with

the rate of appearance of CO2.

Rate = (1/2) - D [MnO4-] = (1/10) D[CO2]

Dt
Dt
Reaction Rates: The Affect of
Concentration and Time

Lecture 13
02/10/03
 Stoichiometry/
Rates of Reactions?
aA + bB  cC + dD

-1/a D[A] = -1/b D[B] = 1/c D[C] = 1/d D[D]

Dt Dt Dt Dt

Unique average rate

How does the concentration
of the reactant affect the
rate of reaction?
 Rate Law

An expression written to show how the rate of a

chemical reaction is dependant on the
concentrations of the reactants.
(Based on the initial concentrations of reactants.)

NH4+ (aq) + NO2- (aq)  N2 (g) + 2 H2O (l)

Rate = k [NH4+]m[NO2-]n
where k is the rate constant
and m and n represent the reaction orders
Assigning Reaction Orders
 Reaction Orders

First order – As the concentration doubles,

the rate of reaction doubles

Second order – As the concentration

doubles, the rate of reaction increases by a
factor of four.

Zero order – As the concentration

doubles, the rate of reaction is unaffected
The following data were collected for the rate
of disappearance of NO in the reaction

2 NO (g) + O2 (g)  2 NO2 (g)

Experiment [NO] (M) [O2] (M) Initial Rate

(M/s)
1 0.0126 0.0125 1.41 x 10-2
2 0.0252 0.0250 1.13 x 10-1
3 0.0252 0.0125 5.64 x 10-2
a) What is the rate law?
b) What are the units of the rate constant
c) What is the average value of the rate constant calculated
from three data sets?
 Overall Reaction Order

Rate = k [NO]2[O2]

Second order in NO
First order in O2
Third order overall

Overall order is the sum of order of all species

involved
 Pressure / Concentration

Pressure may be used for substances that are

gases because:

PV = nRT
P = (n/V)RT
Concentration is moles per liter (n/V)
This shows that P and n/v are directly
proportional for a gas.
 [Concentration] vs. Time

Rate Laws describe the kinetics of a reaction

at a specific temperature while the
concentrations of the reactants are specified.

What happens as time progresses?

Can we relate concentrations
with time?
 Integrated Rate Law

First Order Reaction of the type

A  products
Rate = D[A] or Rate = k[A]
Dt
Or we can use the following to relate time and
concentration
ln[A]t = -kt + ln[A]o
The Mathematics
 Half-life
The time required for the concentration of the
reactant to drop to ½ the original value.
ln[A]t = -kt + ln[A]o

kt(½) = ln [A]t = ln ½ [A]o = ln ½

[A]o [A]o

t(½) = 0.693
k
 Example Problem

The first order rate constant for the decomposition of

N2O5 in this reaction,
N2O5  2 NO2 + ½ O2
at 70 oC is 6.82 x 10-3 s-1. Suppose we start
with 0.0300 mol of N2O5 in a volume of 2.5 L.

a) What concentration of N2O5 remain after 2.5 min?

b) How much time will it take to drop to 0.002 M?
c) What is the half-life for N2O5 at 70 oC?
d) How long does it take for N2O5 to reach 12.5% of its
original value?
 Integrated Rate Law

Second Order Reaction of the type

A  products
Rate = D[A] or Rate = k[A]2
Dt
Or we can use the following to relate time and
concentration
1 = kt + 1_
[A]t [A]o
 Half-life
Second order
1 = kt + 1_
[A]t [A]o

kt = _1_ - _1_
[A]t [A]o

t(½) = _1_
k[A]o
 Example Problem

2 I (g)  I2 (g)
This is a second order reaction in I (g). The
rate constant at 23 oC is 7.0 x 109 M-1s-1.

a) If the initial concentration of I is 0.086 M,

calculate the concentration after 2.0 min.
b) Calculate the half-life of the reaction if the initial
concentration of I is 0.60 M.
c) How long does it take for 75% of the I to be
consumed in the reaction?
Graphing to Identify the Reaction
Order
How do we know whether a reaction is first or
second order?
y = mx + b

1st order 2nd order

ln[A]t = -kt + ln[A]o 1 = kt + 1_
[A]t [A]o
1 st Order Graph
2 nd Order Graph
Comparing 1 st & 2 nd Order
 What affects Rxn Rate?

Cyalume light sticks

Chemiluminescence – chemical reaction
produces light

How does temperature affect rate?

Rate = k [reactants]m

Temperature increases, therefore

the rate increases because k is increased
 Relationship Between k and T

• Arrhenius equation
ln k = ln A – Ea
RT

ln k = – Ea + ln A
RT
Relationship Between k and T

• The larger the Ea, the

more sensitive the
reaction is (k) to
changes in temperature
 2 nd Method to Calculate Ea

• You can calculate Ea if you know the values

of k (the rate constant) at 2 different
temperatures
ln k1 = -Ea + ln A ln k2 = -Ea + ln A
RT1 RT2

ln k1 = Ea ( 1 - 1 )
k2 R T2 T1
 Example problem

• The rate constants of some reactions double

with every 10 degree rise in temperature
(K). Assume that a reaction takes place at
295 K and 305 K. What must the activation
energy be for the rate constant to double as
described?
 Calculating k at Different T

• The rate constant for a second-order reaction is

2.8 x 10-4 Lmol-1s-1 at 35.0 oC. What is the value
of the rate constant at 50.0 oC if the energy of
activation is 90 kJ mol-1?
 Rate is dependent on
Collision Model energy of molecules

• Assertions
1. Collisions between
molecules must occur.
2. Some collisions occur at
speeds that are too low; no
reaction occurs Emin
3. Some collisions are at
speeds high enough to
smash particles
 Factors Affecting the Rate of Reaction

Reaction is dependent on # of collisions/second

Concentration Temperature Frequency of Collisions
Rate of collision
= scNA2[A][B]
s = cross-section
c = mean speed

concentration and temperature - the rate is

increased due to # of collisions increasing
Factors Affecting the Rate of Reaction

Dependency on Energy
(Fraction of collisions
with sufficient energy)
Boltzmann distribution

e-Emin/RT
 Factors Affecting the Rate of Reaction

1. Energy dependence
2. Frequency of collision dependence
Rate of Rxn = (frequency of collision) x (fraction with Esuff)

Rate of Rxn = (scNA2[A][B]) x (e-Emin/RT)

A
Rate of Rxn = k = (scNA2) x (e-Emin/RT)
[A][B] ln k = ln (scNA2) - Emin/RT
ln k = ln A – Ea
RT
 Molecular Orientation; 3rd Factor
(aka Steric Factor)

• Molecules must collide in a certain way

otherwise the reaction will not occur
 Activation Energy

• Ea – minimum amount of energy necessary

to initiate a chemical reaction
A + B  A-B-C-D  C + D

DE?
Potential Energy Surface

H2 + Brl  HBr + Hl
 Reaction Mechanisms
• The existence of Ea indicates that for a chemical
reaction to occur it is not as simple as:
Reactants  Products

Reactants  Intermediate  Products

(transition state)
Reactions may take place in more than one step
Overall Reaction 2 O3 (g)  3 O2 (g)
Reaction
1) O (g)  O (g) + O (g) Mechanism
Elementary 3 2
Reactions 2) O3 (g) + O (g)  O2 (g)
 Reaction Mechanisms
Proposed process by which a reaction occurs.

NO2 (g) + CO (g)  NO (g) + CO2 (g)

How do we know if this reaction has a

reaction mechanism?
Write a rate law.
Compare it with experimental results.
 Reaction Mechanisms

NO2 (g) + CO (g)  NO (g) + CO2 (g)

Predicted Rate Law

Rate = k [NO2]m [CO]n

Actual Rate Law

Rate = k [NO2]2
 NO2 (g) + CO (g)  NO (g) + CO2 (g)

1) NO2 (g) + NO2 (g)  NO3 (g) + NO (g)

Slow reaction; rate determining step
2) NO3 (g) + CO (g)  NO2 (g) + CO2 (g)
Reaction
Intermediate Rate = k [NO2]2
Rules for writing mechanisms
a) Elementary steps must add up to the overall reaction.
b) Elementary steps must be physically reasonable.
c) The mechanism must correlate with the rate law.
 Molecularity

• Referring to the number of molecules of

reactants involved in an elementary step

unimolecular
bimolecular
termolecular – not a likely reaction step.
This would require three molecules
colliding with one another simultaneously
 What if Slow Step is 2nd? And
reversible?
1) NO (g) + O2 (g)  NO3 (g)
2) NO3 (g) + NO (g)  2 NO2 (g)

What is the rate law?

 Chain Reactions
Chain terminating step Propogating step

Chain initiating step

Radical

Chain branching step

 K and k

A + B C + D rate = k [A] [B]

C + D  A + B rate = k’ [C] [D]

k’ [C] [D] = k [A] [B]

The faster the forward

[C] [D] = k = K
reaction, the larger the K.
[A] [B] k’ (Products are favored over
reactants.)
 Catalysis

• Homogeneous
• Heterogeneous
– Surface area
• Enzymes
– Lock and key model
 Homogeneous Catalysis
Same phase for catalyst and reactants
Heterogeneous Catalysis
Enzymes