12/3/12

CHEMICAL REACTIONS

1.  Will the reaction occur?

2.  How far will the reaction proceed?
LECTURE 11: CHEMICAL KINETICS 3.  How fast will the reaction occur?

CHEMICAL REACTIONS
KINETICS

C(s, diamond) C(s, graphite) •  Studies the rate at which a chemical process occurs.
•  Besides information about the speed at which reactions
ΔG°rxn = -2.87 kJ/mole occur, kinetics also sheds light on the reaction
mechanism (exactly how the reaction occurs).

Is the reaction favorable?

1
 12/3/12

OUTLINE : KINETICS Factors That Influence Reaction Rate

Reaction Rates How we measure rates.

Under a specific set of conditions, every reaction has its own
Rate Laws How the rate depends on amounts of reactants. characteristic rate, which depends upon the chemical nature of
the reactants.
Integrated Rate Laws How to calculate amount left or time to reach a given amount.
Four factors can be controlled during the reaction:
Half-life How long it takes to react 50% of reactants. 1.  Concentration - molecules must collide to react
2.  Physical state - molecules must mix to collide
Arrhenius Equation How rate constant changes with Temperature.
3.  Temperature - molecules must collide with enough energy to react
Mechanisms Link between rate and molecular scale processes. 4.  The use of a catalyst

REACTION RATES
FACTORS THAT AFFECT REACTION RATES

•  Concentration of Reactants
–  As the concentration of reactants increases, so does the likelihood that reactant
molecules will collide.
•  Temperature
–  At higher temperatures, reactant molecules have more kinetic energy, move
faster, and collide more often and with greater energy.
•  Catalysts
–  Speed up the reaction by changing Rates of reactions can be determined by monitoring the change
mechanism. in concentration of either reactants or products as a function of
time. Δ[A] vs Δt

2
 12/3/12

REACTION RATES REACTION RATES

C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
Average Rate, M/s
[C4H9Cl] M The average rate of the
reaction over each interval is
In this reaction, the the change in concentration
concentration of butyl divided by the change in
chloride, C4H9Cl, was time:
measured at various times, t.

REACTION RATES REACTION RATES

C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
•  A plot of concentration vs. time for
•  Note that the average rate this reaction yields a curve like
decreases as the reaction this.
proceeds. •  The slope of a line tangent to the
•  This is because as the reaction curve at any point is the
goes forward, there are fewer instantaneous rate at that time.
collisions between reactant
molecules.

3
 12/3/12

REACTION RATES REACTION RATES AND STOICHIOMETRY

C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
•  The reaction slows down with time •  In this reaction, the ratio of C4H9Cl
because the concentration of the to C4H9OH is 1:1.
reactants decreases. •  Thus, the rate of disappearance
of C4H9Cl is the same as the rate
of appearance of C4H9OH.

-Δ[C4H9Cl] Δ[C4H9OH]
Rate = =
Δt Δt

REACTION RATES AND STOICHIOMETRY REACTION RATES AND STOICHIOMETRY

•  What if the ratio is not 1:1? •  To generalize, for the reaction

H2(g) + I2(g) ⎯⎯→ 2HI(g) aA + bB cC + dD

•  Only 1/2 HI is made for each H2 used.

Reactants (decrease) Products (increase)

4
 12/3/12

Sample Problem Expressing Rate in Terms of Changes in Expressing Rate in Terms of Changes in
Concentration with Time Concentration with Time
PROBLEM: Because it has a nonpolluting product (water vapor), hydrogen PROBLEM: Because it has a nonpolluting product (water vapor), hydrogen
gas is used for fuel aboard the space shuttle and in prototype gas is used for fuel aboard the space shuttle and in prototype
cars with Earth-bound engines: cars with Earth-bound engines:

2H2(g) + O2(g) 2H2O(g) 2H2(g) + O2(g) 2H2O(g)

(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with time. SOLUTION:
1 Δ[H2] Δ[O2] 1 Δ[H2O]
(a) rate = - =- =+
(b) When [O2] is decreasing at 0.23 mol/L•s, at what rate is [H2O] 2 Δt Δt 2 Δt
increasing?

PLAN: Choose [O2] as a point of reference since its coefficient is 1. For every
molecule of O2 which disappears, 2 molecules of H2 disappear and 2
Δ[O2] Δ[H2O] Δ[H2O]
molecules of H2O appear, so [O2] is disappearing at half the rate of (b) - = - 0.23 mol/L•s =+ 1 ; = 0.46 mol/L•s
change of H2 and H2O. Δt 2 Δt Δt

CONCENTRATION AND RATES CONCENTRATION AND RATE

Each reaction has its own equation that gives its rate as
a function of reactant concentrations.

⇒ this is called its Rate Law

To determine the rate law we measure the rate at different
starting concentrations.
Compare Experiments 1 and 2:
when [NH4+] doubles, the initial rate doubles.

5
 12/3/12

CONCENTRATION AND RATE CONCENTRATION AND RATES

This equation is called the rate law, and k is the

Likewise, compare Experiments 5 and 6:
when [NO2-] doubles, the initial rate doubles. rate constant.

RATE LAWS RATE LAWS

•  A rate law shows the relationship between the reaction rate and the •  Exponents tell the order of the reaction with respect to each
concentrations of reactants. reactant.
–  For gas-phase reactants use PA instead of [A].
•  This reaction is
•  k is a constant that has a specific value for each reaction. First-order in [NH4+]
•  The value of k is determined experimentally. First-order in [NO2−]
•  The overall reaction order can be found by adding the
exponents on the reactants in the rate law.
“Constant” is relative here- •  This reaction is second-order overall.
k is unique for each rxn
k changes with T

6
 12/3/12

Sample Problem 16.2 Determining Reaction Order from Rate Laws

PROBLEM: For each of the following reactions, use the given rate law to
determine the reaction order with respect to each reactant and
the overall order:
(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

(b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2

(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); rate = k[H2O2][I-]

Determining Reaction Orders Sample Problem 16.3 Determining Reaction Orders from Initial Rate Data
Using initial rates - PROBLEM: Many gaseous reactions occur in a car engine and exhaust
Run a series of experiments, each of which starts with a different set systems. One of these is
of reactant concentrations, and from each obtain an initial rate. NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO ]m[CO]n
2
See Table 16.2 for data on the reaction Use the following data to determine the individual and overall reaction orders:
O2(g) + 2NO(g) 2NO2(g) rate = k [O2]m[NO]n
Experiment Initial Rate (mol/L•s) Initial [NO2] (mol/L) Initial [CO] (mol/L)
Compare 2 experiments in which the concentration of one reactant 1 0.0050 0.10 0.10
varies and the concentration of the other reactant(s) remains constant. 2 0.080 0.40 0.10
rate2 3 0.0050 0.10 0.20
k [O2]2m[NO]2n [O2]2m [O2]2 m
= = [O ] m =
rate1 k [O2]1 [NO]1
m n 2 1 [O2]1 PLAN: Solve for the order with respect to each reactant using the general
rate law using the method described previously.
6.40 x 10-3 mol/L•s 2.20 x 10-2 mol/L m
= ; 2 = 2m m=1 SOLUTION: rate = k [NO2]m[CO]n
3.21 x 10-3 mol/L•s 1.10 x 10-2 mol/L
First, choose two experiments in which [CO] remains
Do similar calculations for the other reactant(s). constant and the [NO2] varies.

7
 12/3/12

Sample Problem 16.3 Determining Reaction Order from Initial Rate Data SAMPLE PROBLEM:
continued
The initial rate of a reaction A + B → C was measured for several different starting
concentrations of A and B, and the results are as follows:

rate 2 k [NO2]m2[CO]n2 [NO2] 2 m
= = The reaction is Expt. No [A], M [B], M Initial Rate,
rate 1 k [NO2]m1 [CO]n1 [NO2] 1
2nd order in NO2. M/s
0.080 0.40 m
= 16 = 4.0m and m = 2.0 1 0.100 0.100 4.0 x 10-5
0.0050 0.10
n 2 0.100 0.200 4.0 x 10-5
rate 3 k [NO2]23[CO]n3 [CO] 3 The reaction is
= = 3 0.200 0.100 16.0 x 10-5
rate 1 k [NO2]21 [CO]n1 [CO] 1 zero order in CO.
0.0050 0.20 n
= 1 = 2.0n and n = 0 Using the data, determine a) rate law for the reaction, b) the rate constant
0.0050 0.10 c) rate of the reaction when [A] = 0.50M and [B] = 0.100M
rate = k [NO2]2[CO]0 = k [NO2]2
The reaction is second order overall.

RATE LAWS

Consider a simple zero order rxn: A → B

dA 0
rate = k [A] = k [A] = k
in differenti al form -
dt
How much A is left after time t? Integrate :
d [A] = − kdt

[A] = [A]0 − kt

8
 12/3/12

RATE LAWS INTEGRATED RATE LAWS

Consider a simple 1st order rxn: A → B

The integrated form of first order rate law:
Differential form:

How much A is left after time t? Integrate:

Can be rearranged to give:

[A]0 is the initial concentration of A (t = 0).

[A]t is the concentration of A at some time, t, during the
course of the reaction.

INTEGRATED RATE LAWS FIRST ORDER PROCESSES

Manipulating this equation produces…

If a reaction is first-order, a plot of ln [A]t vs. t will yield a
straight line with a slope of -k.

So, use graphs to determine reaction order.

…which is in the form y = mx + b

9
 12/3/12

SAMPLE PROBLEM FIRST ORDER PROCESSES

Consider the process in which

Methyl methanoate is hydrolyzed when dissolved in
methyl isonitrile is converted to
excess hydrochloric acid at 298 K. The ester’s acetonitrile.
concentration was 0.01 mol/li at the start of the
reaction, but 8.09 x 10-3 after 21 min. What is the value CH3NC CH3CN
of the first order rate constant k1?
How do we know this is a
first order reaction?
What is the concentration of methyl methanoate after 30
minutes?

FIRST ORDER PROCESSES FIRST ORDER PROCESSES

CH3NC CH3CN

This data was collected for

this reaction at 198.9°C.

Does
rate=k[CH3NC]
for all time intervals? •  When ln P is plotted as a function of time, a straight line
results.
–  The process is first-order.
–  k is the negative slope: 5.1 × 10-5 s-1.

10
 12/3/12

SECOND ORDER PROCESSES SECOND ORDER PROCESSES

Similarly, integrating the rate law for a process that is

second-order in reactant A:
So if a process is second-order in A, a plot of 1/[A] vs. t
will yield a straight line with a slope of k.

Rearrange, integrate:

First order:
also in the form y = mx + b
If a reaction is first-order, a plot of ln [A]t vs. t will yield a straight line
with a slope of -k.

SAMPLE PROBLEM SAMPLE PROBLEM

The dimerization of methyl viologen, an active ingredient Consider a second order reaction which consumes 15%
in weed killers is second order with respect to methyl of the initial material after 12 min and 23 s. If the initial
viologen, MV. Calculate the value of the rate constant, k concentration was 0.001 mol/L calculate the rate
if the initial concentration of MV was 0.001 mol/L and the constant k.
concentration dropped to 4 x 10-4 mol/L after 0.02 s.

11
 12/3/12

DETERMINING ORDER OF REACTION DETERMINING ORDER OF REACTION

The decomposition of NO2 at 300°C is described by the equation Graphing ln [NO2] vs. t yields:

NO2 (g) NO (g) + 1/2 O2 (g) •  The plot is not a straight line, so
and yields these data: the process is not first-order in [A].

Time (s) [NO2], M Time (s) [NO2], M ln [NO2]

0.0 0.01000 0.0 0.01000 -4.610
50.0 0.00787 50.0 0.00787 -4.845 Does not fit:

100.0 0.00649 100.0 0.00649 -5.038

200.0 0.00481 200.0 0.00481 -5.337
300.0 0.00380 300.0 0.00380 -5.573

SECOND ORDER PROCESSES SECOND ORDER PROCESSES

A graph of 1/[NO2] vs. t gives this

The second type of second order reactions is
plot. represented by:
A + B products

•  This is a straight line.

d[ A] d[ B]
Time (s) [NO2], M 1/[NO2] rate = − =− = k [ A ][ B ]
0.0 0.01000 100 Therefore, the process is dt dt
second-order in [NO2].
50.0 0.00787 127
100.0 0.00649 154 1 [ B ][ A ] 0
200.0 0.00481 208 ln = kt
[ B ] 0 − [ A ] 0 [ A ][ B ] o
300.0 0.00380 263

12
 12/3/12

SECOND ORDER PROCESSES SAMPLE PROBLEM: Determining order of reaction

from Rate Law
For some reactions like: For each of the following reactions, use the given rate law to determine the
CH3COCl(aq) + H2O(l) CH3COOH(aq) + HCl(aq) reaction order with respect to each reactant and the overall order:

(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

rate = k' [ CH3COCl ][ H2O ]
but if one reactant is always in excess, amount consumed is (b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2

negligible, thus reaction rate is :

(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); rate = k[H2O2][I-]
rate = k [ CH3COCl ] where k = k' [ H2O ]

also called pseudo first order reaction.

HALF-LIFE
SAMPLE PROBLEM
•  Half-life is defined as the
A 1:1 reaction occurs between A and B, and is second
time required for one-half
order. The initial concentrations of A and B are 0.1 mol/L of a reactant to react.
and 0.2 mol/L, respectively. What is the rate constant, k if •  Because [A] at t1/2 is one-
the concentration of A after 0.5 hr is 0.05 mol/L? half of the original [A],
[A]t = 0.5 [A]0.

13
 12/3/12

HALF LIFE HALF-LIFE SECOND ORDER

For a first-order process, set [A]t=0.5 [A]0 in integrated rate For a second-order process, set
equation: [A]t=0.5 [A]0 in 2nd order equation.

NOTE: For a first-order process,

the half-life does not depend on
[A]0.

SUMMARY OF RATE EQUATIONS:

SAMPLE PROBLEM
Order Differential Form Integrated Form Half-Life Units of the Rate
Constants
The half-life of 60Co
is 10.5 min. If we start with 100g of 0
60Co, how much remains after 42 minutes?
1

2 -

14
 12/3/12

DETERMINATION OF REACTION ORDER Reaction Orders

For the reaction: A →B, the rate law is:
rate = k[A]m
Order (m) Δ[A] by a factor of: Effect on rate
Zero (0) 2, 4, 15, ½, etc. None
2 2X
1st (1)
3 3X
2 4X
2nd (2) 3 9X
½ ¼X

Determining Reaction Orders from Initial Rate Data NH4+(aq) + NO2¯(aq) → N2(g) + 2 H2O(l)
PROBLEM: Many gaseous reactions occur in a car engine and exhaust systems. One of these
is Exp. # [NH4+]o [NO2¯]o Initial Rate (M·s-1)
NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO2]m[CO]n 1 0.100 0.0050 1.35 x 10-7
Use the following data to determine the individual and overall reaction orders: 2 0.100 0.0100 2.70 x 10-7
Experiment Initial Rate (mol/L•s) Initial [NO2] (mol/L) Initial [CO] (mol/L) 3 0.200 0.0100 5.40 x 10-7
1 0.0050 0.10 0.10
2 0.080 0.40 0.10 Determine the rate law and calculate k.
3 0.0050 0.10 0.20

15
 12/3/12

2 NO(g) + Cl2(g) → 2 NOCl(g) BrO3¯(aq) + 5 Br¯(aq) + 6 H+(aq) → Br2(l) + 2 H2O(l)

Exp. # [NO]o [Cl2]o Initial Rate (M·min-1) Exp. # [BrO3¯]o [Br¯]o [H+]o Initial Rate (M·s-1)
1 0.10 0.10 0.18 1 0.10 0.10 0.10 8.0 x 10-4
2 0.10 0.20 0.36 2 0.20 0.10 0.10 1.6 x 10-3
3 0.20 0.20 1.45 3 0.20 0.20 0.10 3.2 x 10-3
4 0.10 0.10 0.20 3.2 x 10-3
Determine the rate law and calculate k. Determine the rate law and calculate k.

SAMPLE PROBLEM: SAMPLE PROBLEM :

Consider the following reaction: hydrogen peroxide decomposes in the
presence of excess cerous ion (Ce+3). The following data were obtained: Consider the data below which relate to the racemization of glucose in
aqueous hydrochloric acid.
Time, s [H2O2], mol/L
Time, s [Glucose], mol/L
2 6.23 Determine the order of 0 0.400
4 4.84 reaction with respect to 600 0.350
6 3.76 hydrogen peroxide. 1200 0.311
8 3.20
1800 0.279
10 2.60
2400 0.254
12 2.16
14 1.85
16 1.49
What is the order of reaction with respect to glucose?
18 1.27
20 1.01

16
 12/3/12

SAMPLE PROBLEM:
Ch 47.5 FIRST LONG EXAM
Consider the following kinetic data for the reaction below at 25oC.
OCl- + I- ⎯→ OI- + Cl-
December 6, 2012 Thursday, 10:30-12:00 C114
[OI-], Mol/L [Cl-], Mol/L Initial rate, mol/L-s
0.0017 0.0017 1.75
0.0030 0.0017 5.45 Using the differential
0.0040 0.0017 9.69 method, determine the order
0.0050 0.0017 15.14 of reaction with respect to
0.0060 0.0017 21.80 OCI-.
0.0070 0.0017 27.67
Coverage: Kinetics, Enzyme Kinetics

REACTION MECHANISM: REACTION MECHANISM:

Reaction is broken into steps with intermediates being formed.
A reaction mechanism is a sequence of molecular events, or reaction steps,
that defines the pathway from reactants to products. “some reactions occur in one step, but most occur in in multiple steps.”

Each step is called an elementary step, and the number of molecules involved
OH-(aq) + CH3Cl(aq) → CH3OH(aq) + Cl-(aq) in each step defines the molecularity of the step.

Molecularity: is the number of reactants.

17
 12/3/12

REACTION MECHANISM: Reaction Mechanisms

The overall progress of a chemical reaction can be represented at the molecular
UNIMOLECULAR REACTIONS: A single reactant is involved. level by a series of simple elementary steps or elementary reactions.

O3* → O2 + O
The sequence of elementary steps that leads to product formation is the reaction
BIMOLECULAR REACTIONS: elementary steps that involves two reactants mechanism.
(most common) NET EQUATION
2NO (g) + O2 (g) 2NO2 (g)
N2O2 is detected during the reaction!
HI + HI → activated complex → H2 + I2

TERMOLECULAR REACTIONS: Three reactants are involved (rare, due to REACTION MECHANISM
probability of orientation and energy both being correct.) 1. Elementary step: NO + NO N2O2
2.+Elementary step: N2O2 + O2 2NO2
O(g) + O2(g) + N2(g) → O3(g) + “energetic” N2(g)
Overall reaction: 2NO + O2 2NO2
13.5

Intermediates are species that appear in a reaction mechanism but not in the
overall balanced equation. The rate-determining step is the slowest step in the sequence of steps
An intermediate is always formed in an early elementary step and consumed in leading to product formation.
a later elementary step.
Elementary step: NO + NO N2O2
The reaction rate and rate law can be determined
+ Elementary step: N2O2 + O2 2NO2 from the stoichiometry (coefficients) of the slowest
Overall reaction: 2NO + O2 2NO2 elementary step in the mechanism

*Know the difference between an elementary

reaction and the net reaction !

13.5

18
 12/3/12

The Raschig process for the preparation of hydrazine (N2H4) The following is only true for individual steps:

The rate law of an elementary step is given by the product of a rate

Overall RXN: 2NH3(g) + NaOCl(aq) → N2H4(aq) + NaCl(aq) + H2O(l)
constant and the conc. of the reactants in the step.
Proposed Mechanism: (Only from experiment)
Step Molecularity rate law
Step 1: NH3(aq) + OCl (aq) → NH2Cl(aq) ‡ + OH-‡ (aq)
-
A → Product(s) uni rate = k[A]
Step 2: NH Cl(aq) ‡ + NH (aq) → N H +‡ + Cl-(aq)
2 3 2 5
A + B → Product(s) bi rate = k[A][B]
Step 3: N2H5+(aq) ‡ + OH-‡ (aq) → N2H4(aq) + H2O(l) bi rate = k[A]2
A + A → Product(s)
“Cancel intermediates and “add steps” to give overall RXN.” 2A + B → Product(s) ter rate = k[A]2[B]
2NH3(g) + OCl-(aq) → N2H4(aq) + Cl-(aq) + H2O(l)

The overall rate law, mechanism, and the total order can’t be predicted from The overall mechanism must match the observed rate law.
the stoichiometry, only by experiment. Usually one STEP is assumed to be the rate determining step.
73 74

Example: Example:
Overall RXN: 2NO2(g) + F2(g) → 2NO2F(g) Overall RXN: 2NO2(g) + F2(g) → 2NO2F(g)

Observed Experimental rate law: rate = k[NO2][F2] Observed Experimental rate law: rate = k[NO2][F2]

Question: Why does this rule out a single step reaction? k1

slow: NO2(g) + F2(g) → NO 2F(g) + F(g)
‡ rate = k[NO2][F2]

Answer: k2
fast: NO2(g) + F(g) ‡ → NO2F(g)
rate law for single step process would be: rate = k[NO2]2[F2]
2NO2(g) + F2(g) → 2NO2F(g)

The rate law is dependent upon the slow step.

“Let’s try to work out a mechanism that matches the
observed rate law.”

75 76

19
 12/3/12

The rate law is dependent upon the slow step.

SAMPLE PROBLEM:
Let’s try making the 2nd reaction slow and the first fast
Overall RXN: 2NO2(g) + F2(g) → 2NO2F(g) The experimental rate law for the reaction between NO2 and CO to
produce NO and CO2 is rate = k[NO2]2. The reaction is believed to
Observed Experimental rate law: rate = k[NO2][F2] occur via two steps:
STEP 1 NO2 + NO2 → NO3 + NO
k1
fast: NO2(g) + F2(g) → NO 2F(g) + F(g)
‡ STEP 2 NO3 + CO → NO2 + CO2
k2 What is the overall reaction?
slow: NO2(g) + F(g) ‡ → NO2F(g) rate = k[NO2][F ‡]
What is/are the intermediate/s?
2NO2(g) + F2(g) → 2NO2F(g) What can you say about the relative rates of reaction 1 and 2?

77

SAMPLE PROBLEM: REACTION MECHANISM and RATE LAWS

The following substitution reaction has a first order rate law: Determine rate law by experiment.
(Co(CN)5(H2O)2- + I- → Co(CN)5I3- + H2O Devise a mechanism.

Predict the rate law for the mechanism

Rate = k[Co(CN)5(H2O) 2-]
If the predicted rate laws do not agree, retry devising a mechanism.
Suggest a mechanism in accord with the rate law.
If predicted and experimental rate laws agree, look for additional supporting
evidence.

20
 12/3/12

SAMPLE PROBLEM
One possible mechanism to
account for this reaction is:
2 NO(g) → N2O2(g)
Nitrogen oxide is reduced by hydrogen
N2O2(g) + H2(g) → N2O(g) + H2O(g)
to give water and nitrogen,
N2O(g) + H2(g) → N2(g) + H2O(g)

2 H2(g) + 2 NO(g) → N2(g) + 2 H2O(g)

A MODEL FOR KINETICS

What is the molecularity of each of the
three steps? Generally reactions occur more rapidly at higher
temperatures than at lower temperatures.

Show that the sum of these elementary

The rate generally doubles for every 10 K rise in
steps is the net reaction. temperature. It’s an exponential increase!

21
 12/3/12

TRANSITION STATE THEORY

•  energy barrier must be overcome

•  reaction energy diagram [humpy diagrams]
•  transition state energy--max of rxn. E diagram
•  activated complex--deformed molecules in their transition
state, formed at the Ets--unstable, can go either way!
•  Activation energy, E*, Ea--energy a reacting molecule must
absorb from its environment in order to react. uncatalyzed catalyzed

COLLISION THEORY

Assumes molecules must collide in

order to react!

EFFECTIVE COLLISIONS ARE hindered by

concentration,
temperature and geometry of reactants and
transition states

22
 12/3/12

THE EFFECT OF TEMPERATURE OF REACTION RATE:

ARRHENIUS EQUATION A is the frequency factor units of
L/(mol • s) & depends on the frequency of
collisions and the fraction of these that have the
correct geometry--# of effective collisions

e-E*/RT is always less than 1 and is the fraction of

molecules having the minimum energy required
for reaction

*Notice in the equation: As "Ea" increases, "k"

gets smaller and thus, the rate would decrease.

Also, notice that as "T" goes up, "k" increases

and so the rate would also increase.

23
 12/3/12

Taking this equation, plot 1/T vs. ln [k],

and get a straight line.

From the straight line, find the slope

and then find the activation energy.

slope = - Ea
R
so ... Ea = - (R) (slope)

Used to calculate

-value of activation energy from temperature

dependence of the rate constant

-rate constant for a given temp - if the E*

[also known as Ea] and A factor are known.

24
 12/3/12

Points to remember!! SAMPLE PROBLEM

The colorless gas dinitrogen tetroxide decomposes to
the brown gas NO2 in a first order reaction with a value
of:
1. Ea is smaller; k is greater; the
reaction is faster.
k = 4.5 x 103/s at 274K.
2. Ea is greater; k is smaller; the If k is 1.00 x 104/s at 283K, what is the energy of
reaction is slower. activation?

SAMPLE PROBLEM
Calculate the activation energy for
the following set of data:

T (°C) k (l/mol- s)
3 1.4 x 10-3
13 2.9 x 10-3
24 6.2 x 10-3
33 1.2 x 10-2

25
 12/3/12

COMPLEX REACTIONS – REVERSIBLE REACTIONS

SAMPLE PROBLEM
2H2 (g) + O2 (g) 2H2O (g)

The gas-phase reaction between methane and diatomic sulfur is given by

the equation:
CH4 (g) + 2S2 (g) à CS2 (g) + 2H2S (g)
At 550° C the rate constant for this reaction is 1.1 M-1 • s-1 and at 625° C
the rate constant is 6.4 M-1 • s-1. Using these values, calculate Ea for
this reaction.

SAMPLE PROBLEM:
THE COLLISION THEORY OF REACTION RATES
For the reaction A + B C + D, various initial rate measurements
were run using A and B only and C and D only. From the data below • Particles must collide.
calculate the equilibrium constant for the reaction:

Rate, (M/s) [A] [B] • Only two particles may collide at one time.
1.081 x 10-5 0.660 1.23
6.577 x 10-5 4.01 1.23
1.312 x 10-4 4.01 2.25 • Proper orientation of colliding molecules so that
Rate, (M/s) [C] [D] atoms can come in contact with each other to
7.805 x 10-7 2.88 0.995 become products.
1.290 x 10-6 2.88 1.65
4.528 x 10-7 1.01 1.65

26
 12/3/12

The collision must occur with enough energy to

overcome the electron/electron repulsion of the
This new collision product is
valence shell electrons of the reacting species
at the peak of the activation
and must have enough energy to transform energy hump and is called
translational energy into vibrational energy in the activated complex or the
order to penetrate into each other so that the transition state. At this
electrons can rearrange and form new bonds. point, the activated complex
can still either fall to
reactants or to products.

With all of these criteria met, the

reaction may proceed in the forward
direction.

Amazing that we have reactions

occurring at all!

27
12/3/12

28
12/3/12

29
12/3/12

30
12/3/12

31
 12/3/12

CATALYSTS Figure 16.19

Reaction energy diagram for a catalyzed and an uncatalyzed process.

Each catalyst has its own specific way of functioning.

In general, a catalyst lowers the energy of activation.
Lowering the Ea increases the rate constant, k, and thereby increases the
rate of the reaction.
A catalyst increases the rate of the forward and reverse reactions.
A catalyzed reaction yields the products more quickly, but does not yield
more product than the uncatalyzed reaction.
A catalyst lowers Ea by providing a different mechanism, for the reaction
through a new, lower energy pathway.

Figure 16.20
Mechanism for the catalyzed hydrolysis of an organic ester. Figure 16.21 The metal-catalyzed hydrogenation of ethylene.

H2C CH2 (g) + H2 (g) H3C CH3 (g)

32