Ch13 Reaction Rates

Chapter 13
Kinetics: The Study of Rates of

Reaction
Brady and Senese

5th Edition
1
Index
13.1 Five factors affect reaction rates
13.2 Rates of reaction are measured by monitoring change in
concentration over time
13.3 Rate laws give reaction rate as a function of reactant
concentrations
13.4 Integrated rate laws give concentration as a function of time
13.5 Reaction rate theories explain experimental rate laws in terms
of molecular collisions
13.6 Activation energies are measured by fitting experimental data
to the Arrhenius equation
13.7 Experimental rate laws can be used to support or reject
proposed mechanisms for a reaction
13.8 Catalysts change reaction rates by providing alternative paths
between reactants and products
Introduction
Rate of reaction - the relationship between changes
in concentration and time: the “speed” of a
reaction
13.1 Five factors affect reaction rates 3

Factors Affecting Reaction Rate
1. Chemical nature
• Bond strengths
• General reactivity
2. Ability to establish contact with one another
• Physical state
• Surface area for liquids, solids, and heterogeneous
mixtures
• Amount of mixing
• Particle shape/size

Factors Affecting Reaction Rate (Cont.)
3. Concentration of reactants
 Molarity for solutions
 Pressure effects for gases
 Volume effects for gases
4. Temperature
5. Catalysts

Your Turn!
Which of the following would speed a reaction?
A. Stirring it
B. Dissolving the reactants in water, if ionic
C. Adding a catalyst
D. Grinding any solids
E. All of these

Measuring Rates
• Can be measured using any substance in the reaction
• Units: M s-1
• Measured in three ways:
 Instantaneous rate (text uses this unless specified)
 Average rate
 Initial rate
13.2 Rates of reaction are measured by monitoring change in concentration over time 7
Instantaneous Reaction Rates
• Instantaneous rate - the slope of the tangent to the curve at
any specific time
• Initial rate is determined at the initial time
NO2 Appearance
0.035
0.030
0.025
0.020
[NO2]
0.015
0.010
0.005
0.000
-0.005
0 200 400 600 800
Time (s)
Instantaneous Rates Changes with Time
• As reactants are
consumed, reaction slows
• The process of
Slope = -0.01 M/100 s
determining rates is
rate = 1 × 10-4 M s-1
important for
reproducibility
Δ[Reactant ]
Average Reaction Rates  rate
Δtime
Average rate of reaction - the slope of the line
connecting the starting and ending coordinates for
a specified time frame
NO2 Appearance
0.035
0.030
0.025
0.020
[NO2]
0.015
0.010
0.005
0.000
-0.005
0 100 200 300 400 500 600 700 800
Time (s)
Your Turn!
What is the average rate 0.4
of disappearance of B
between 10 and 40 s? 0.3
Concentration of B (M)
A. -0.006 M s-1 0.2
B. +0.006 M s-1
0.1
C. -0.002 M s-1
D. +0.002 M s-1 0.0
E. Can’t tell form the 10 20 30 40
information Time Elapsed in Reaction Progress (s)
Rates and Stoichiometry
• Rates based on each substance are related to one
another by the stoichiometric coefficients of the
reaction
• Examine the reaction: aA + bB → dD
 The stoichiometric relationship between substances A
and B is given as
a mole A : b mole B
 RateA × (b/a) = RateB
mol A b mol B mol B
 
L s a mol A Ls
Learning Check
• In the reaction: 2A + 3B → 5D We measured
the rate of disappearance of substance A to be
3.5 × 10-5 M s-1. What is the rate of appearance
of D?
8.75 × 10-5 M s-1
• In the reaction 3A + 2B → C, we measured the

rate of B. How does the rate of C relate?
rateC = 1/2 rateB
Your Turn!
In the reaction 2CO(g) + O2(g) → 2CO2(g), the rate
of the reaction of CO is measured to be 2.0 M s-1.
What would be the rate of the reaction of O2?
A. The same
B. Twice as great
C. Half as large
D. You cannot tell from the given information
The Rate Law Depends on the Concentrations
Used
• rate = k[reactant]order
• k is a reaction rate constant, a measure of time
efficiency
• High values of k mean high efficiency
• k must be determined experimentally
• Each experiment has its own rate law
• Rate law must be determined experimentally
13.3 Rate laws give reaction rate as a function of reactant concentrations 15

Learning Check
The rate law for the reaction 2A + B → 3C is
rate = 0.045 M-1 s-1 [A][B]
if the concentration of A is 0.2 M and that of B is
0.3 M, what will be the reaction rate?
rate = 0.045 M-1 s-1 (0.2 M)(0.3 M)

rate = 0.0027 M s-1

Determining the Rate Law
• Run reaction under the same conditions, varying
only the concentrations of reactants
• A ratio of rate laws for each experiment allows us
to determine the orders of each reactant
• The rate law is unique to temperature and
concentration conditions
• The rate law cannot be predicted from the
chemical equation, but must be determined
experimentally

Orders
• Indicate the degree of resistance to reaction - a high order
suggests a reactant that is slow to react
• Are indicated for each reactant
• The overall reaction order is the sum of individual reactant
orders
• May be negative, fractional or integers, but in this course
we will usually encounter positive integers
• Must be determined from experimental data
• The units for k depends on the order of the reaction
 zero order mol L-1 s-1 M s-1
 1st order s-1 s-1
 2nd order L mol-1 s-1 M-1 s-1

Use Rate Laws to Determine Orders
2NO(g) + O2(g) → 2NO2(g)
• Select 2 rate laws that vary
exp [NO] [O2] RNO2 M s-1
in concentration for only
1 0.015 0.015 0.048
one of the substances
2 0.030 0.015 0.192
• Next choose 2 rate laws
3 0.015 0.030 0.096
where the unknown
changes 0.048 M s-1 k[0.015 M ]x [0.015 M ]y

• Since we know the 0.192 M s -1
k[0.030 M ]x [0.015 M ]y
exponent on the other, at
this stage it doesn’t matter 0.096 M s-1 k[0.015 M ]x [0.030 M ]y
-1

if it changes 0.048 M s k[0.015 M ]x [0.015 M ]y
x=2 y=1 rate = k[NO]2[O2]
Determining the Value of k
At this stage, we can exp [NO] [O2] RNO2 M s-1
solve for k. Use any rate
1 0.015 0.015 0.048
law and substitute the
2 0.030 0.015 0.192
now known orders.
3 0.015 0.030 0.096
rate = k[NO]2[O2]
0.048 M s-1 = k[0.015 M]2[0.015 M]
1.4 × 104 M-2 s-1 = k

Determine the Rate Law from Given Data
0.0002 M s-1 k[0.01]a [0.02]b [0.15]c
[A] [B] [C] Rate M s-1 -1

0.0004 M s k[0.02]a [0.02]b [0.15]c
0.01 0.02 0.15 0.0002
0.02 0.02 0.15 0.0004
0.0002 M s-1 k[0.01]a [0.02]b [0.15]c

0.01 0.01 0.15 0.0001 0.0001 M s-1 k[0.01]a [0.01]b [0.15]c
0.01 0.02 0.30 0.0002

0.0002 M s-1 k[0.01]a [0.02]b [0.15]c

0.0002 M s-1 k[0.01]a [0.02]b [0.3]c
a=1 b=1 c=0
rate = k[A][B]

Your Turn
For the following data, determine the order of NO2 in the
reaction at 25 °C
2NO2(g) + F2(g) → 2NO2F(g):
Exp. [NO2] [F2] Rate NO2 disappearance (M s-1)
1 0.001 0.005 2 × 10-4
2 0.002 0.005 4 × 10-4
3 0.006 0.002 4.8 × 10-4
A. 0
B. 1
C. 2
D. 3
E. Not enough information given
Your Turn
Chlorine dioxide, ClO2, is a reddish-yellow gas that is soluble in
water. In basic solution it gives ClO3- and ClO2- ions.
2ClO2(aq) + 2OH-(aq) → 6ClO3- (aq) + ClO2- (aq) + H2O(l)
The rate law is Rate = k[ClO2]2[OH-], what is the value of the rate
constant given that when [ClO2] = 0.060 M, [OH-] = 0.030 M, the
reaction rate is 0.0248 M s-1.
A. 0.02 M-1 s-1
B. 0.02 M s-1
C. 0.02 s-1
D. None of these
2.3 × 102 M-2 s-1

Rate Law Overview
• Rate laws relate the rate of the reaction to the
reactant concentrations used for a given set of
conditions
• Because the value of k varies with temperature, so
will the rate law

Integrated Rate Laws
• Integrated rate laws tell us how the reactant
concentration varies with time during the
course of a reaction.
• Derived from one-reactant systems and a plot of
the relationships of [reactant] and time
 zero order: linear plot [reactant ] vs. time
 first order: linear plot ln [reactant] vs. time
 second order: linear plot 1/[reactant] vs. time
13.4 Integrated rate laws give concentration as a function of time 25

Learning Check
Determine the order of the reactant graphically
2N2 O5 (g ) → 4NO2 (g ) + O2 (g ) 0 order plot

Time (s) [N2O5] [NO2 ] [O2 ] 1st order plot
0 0.0200 0.0000 0.0000 2nd order plot
100 0.0169 0.0063 0.0016
200 0.0142 0.0115 0.0029
300 0.0120 0.0160 0.0040
400 0.0101 0.0197 0.0049
500 0.0086 0.0229 0.0057
600 0.0072 0.0256 0.0064
700 0.0061 0.0278 0.0070
Zero-Order Reactions
• Rate=k
• Plot of [reactant ] vs. time will be linear
• The equation of the line will be [A]=[A0]-kt
 A= amount remaining after elapsed time, t.
 Ao=original amount
• Diffusion controlled - usually are fast reactions in
viscous media
• Rate is independent of concentrations of reactants, but
the reaction still requires reactants

Learning Check
The rate law for the reaction of A→B is zero order

in A and has a rate constant of 0.02 M/s. If the
reaction starts with 1.50 M A, how much is
present 15 seconds after the reaction begins?
•[A]=[A0]-kt
•[A]=1.2M

Learning Check
The rate law for the reaction of A→2B is zero
order in A and has a rate constant of 0.12 M/s. If
the reaction starts with 1.50 M A, after what time
will the concentration of A be 0.90M?
•[A]=[A0]-kt
•t=5 s

Your Turn!
Which of the following is the correct set of units for
the rate constant for a zero order reaction?
A. M/s
B. M-1/s
C. M-2/s
D. Can’t tell from the given data

Your Turn!
What was the starting quantity if 2.5 M remain after
5 hr. k=2.3×10-5 M/s
A. Ao=2.9 M
B. Ao=2.5 M
C. Ao=2.1 M
D. None of these

First Order Reactions
• Rate = k[A]1
• Typically these reactions are decomposition type,
or radioactive decay
• If the rate law is specified as d[A]/dt = k[A] or
Integrating the equation gives us:
 A0
ln  kt
 At

Learning Check
The radioactive decay
 A0
of a new atom occurs so ln  kt
that after 21 days, the
 At
original amount is 100
reduced to 33%. What ln  k (21 day)
33
is the rate constant for
the reaction in s-1? k = 0.0528 day-1
k = 6.11×10-7 s-1

Half-Life of First Order Reaction
• In monitoring decay
processes, a half-life
(t1/2) is often
recorded, in lieu of k
• t1/2 is the time needed
for exactly half of the
substance to decay.
At this time,
[A]t = [A]0/2

How Does t1/2 Relate to k for a First Order
Reaction?
 A0 At t1/2, [A]0/2 = [A]

ln  kt
 At
 A0
ln  kt 1
1
2
 A0 2
ln 2
ln 2  kt1/2  t1/ 2
k
Learning Check
The half-life of I-132 is 2.295 h. What percentage
remains after 24 hours?
ln 2 0.302 h-1 = k
 t1
k 2
 A0 A = 0.0711%
ln  kt
 At

Your Turn!
What is the half-life of a new element, Barclium-146,
if, after 2.2 h, 1.3% remains?
A. 2.0 h
B. 0.35 h
C. 0.51 h
D. None of these

Second Order Reaction
• Are of several types:
Rate = k[A]2
Rate = k[A]1[B]1
Rate = k[A]2[B]0
etc…
• The integrated equation is of the form
1 1
  kt
[A]t [A]0
Learning Check
The rate constant for the
second order reaction 1 1
  kt
2A → B [A] t [A] 0
is 5.3×10-5 M-1s-1. What 1 1 5.3  105
   7200 s
is the original amount 0.35  A0 M s
present if, after 2 hours,
there is 0.35 M [A]0 = 0.40 M
available?

Second Order Half-Life
• Depends on the amount present at the start of the
time period
• What is the relationship between k and t1/2 for this
reaction type?
1 1
  kt1/2
0.5  A 0  A0
1
 t1/2
k  A0

Learning Check
The rate constant for a 1

 t1/2
second order reaction is k  A0
4.5 × 10-4 M-1 s-1. What
is the half-life if we start 1
 t1/2
with a reactant
concentration of 5.0 M?
 4.5  10-4 M -1 s-1  5 M 
t1/2 = 440 s
= 7.4 min

Your Turn!
Which order has a half-life that is independent of the
original amount?
A. Zero
B. First
C. Second
D. None depend on the original quantity

Your Turn!
A 0.10 M solution of moxium, a new antidepressant
is bottled. The drug decays to fortium, a toxic
chemical as a second order process. The rate
constant is 2.3 × 10-3 M-1 h-1. What quantity of
moxium is present after 90. days?
A. 0.098 M
B. 5.5 × 10-5 M
C. 0.067 M
D. None of the above

Collision Theory of Reactions
For a reaction to occur, three conditions must be met:
1. Reactant particles must collide
2. Collision energy must be enough to break bonds/initiate
3. Particles must be oriented so that the new bonds can form
13.5 Reaction rate theories explain experimental rate laws in terms of molecular 44
collisions
Potential Energy Diagrams
• Demonstrate the energy needs and products as a
reaction proceeds
• Tell us whether a reaction is exothermic or
endothermic
• Tell us if a reaction occurs in one step or several
steps
• Show us which step is the slowest
collisions
Potential Energy Diagrams
collisions
Features of Potential Energy Diagrams
Activation Energies
Activated
Potential Energy
Complexes
Product
Energy
Enthalpy of
Reaction
Reactant Energy
Reaction Coordinate
(progress of reaction)
collisions
Your Turn!
Examine the potential energy diagram.
Which is the slowest (rate determining) step?
A. Step 1
Has greatest Ea
B. Step 2
C. Can’t tell from the given information
Step 2
Potential Energy
Step 1
Reaction Coordinate (progress of reaction)

collisions
Temperature Effects
Changes in temperature affect the rate constant, k,
according to the Arrhenius equation:
 p is the steric factor
 Z is the frequency of collisions.
 Ea is the activation energy
 R is the Ideal Gas Constant (8.314 J/mol K)
 T is the temperature (K)
 A is the frequency factor
k  pZe- Ea / RT k  Ae - Ea / RT
13.6 Activation energies are measured by fitting experimental data to the Arrhenius 49
equation
Working with the Arrhenius Equation
Linear Form: To determine the Ea and A value
 Ea 1 
ln k  ln A    
 R T
Ratio form: Can be used when A isn’t known.
 k2   Ea  1 1
ln     
 k1  R  T2 T1 
equation
Learning Check
Given that k at 25 °C is 4.61 × 10-1 M s-1 and that at 50 °C
it is 4.64 × 10-1 M s-1, what is the activation energy for the
reaction?
 4.64 101 M s-1   Ea  1 1 

ln   
 4.61 101 M s-1  8.314 J mol1 K 1  323 K 298 K 
 
208 J mol-1 = Ea
 k2   Ea  1 1
ln     
 k1  R  T2 T1 
equation
Working with the Arrhenius Equation
k (M s-1) T°C
Given the following
0.000886 25
data, predict k at 75 °C
0.000894 50
using the graphical
approach 0.000918 150
0.000908 100
graph
Ea 1
ln k     ln A
R T
ln k = -0.0278/T - 0.1917
k = 8.25 × 10-1
equation
Your Turn!
In the reaction 2N2O5(g)  4NO2(g) + O2(g) the
following temperature and rate constant information
is obtained. What is the activation energy of the
reaction?
A. 108 kJ
T (K) k (s-1)
B. -108 kJ
338 4.87 × 10-3
C. 1004 kJ
328 1.50 × 10-3
D. -1004 kJ
318 4.98 × 10-4
E. None of these
equation
Reaction Mechanisms
• Tell what happens on the molecular level, and in
what order
• Tell us which steps in a reaction are fast and
slow
• The rate determining step is the slowest step of
the reaction that accounts for most of the
reaction time
• Elementary steps sum to the overall reaction
13.7 Experimental rate laws can be used to support or reject proposed mechanisms for a 54
reaction
Elementary Steps
Elementary Reactions Molecularity Rate Law

A → Products Unimolecular Rate = k[A]
A + A → Products Bimolecular Rate = k[A]2
A + B → Products Rate = k[A][B]
A + A + B → Products Termolecular Rate = k[A]2[B]
3A → Products Rate = k[A]3
A + B + C → Products Rate = k[A][B][C]
reaction
Intermediates and Catalysts
• Because catalysts interact with the reactant, they
will appear in the mechanism
• Catalysts are consumed in an early step and are
regenerated in a subsequent step
• Intermediates are temporary products
• Intermediates are formed in an early step and
consumed in a later step
reaction
Learning Check
The reaction mechanism that has been proposed for
the decomposition of H2O2 is
1. H2O2 + I- → H2O + IO- (slow)
2. H2O2 + IO- → H2O + O2 + I- (fast)
• Which is the rate determining step? step 1
• Are there any intermediates? IO-
reaction
Rate Laws and Mechanisms
• The majority of the reaction time is taken by the
rate determining step
• Substances that react in this step have the
greatest effect on the reaction rate
• The observed rate law usually matches the rate
law based on the rate determining step where the
order of each reactant is its stoichiometric
coefficient
reaction
Learning Check
The reaction mechanism that has been proposed for
the decomposition of H2O2 is
1. H2O2 + I- → H2O + IO- (slow)
2. H2O2 + IO- → H2O + O2 + I- (fast)
What is the expected rate law?
rate = k[H2O2][I-]
reaction
Learning Check
The reaction: A + 3B → D + F was studied and the
following mechanism was finally determined
1. A+B→C (fast)
2. C+B→D+E (slow)
3. E+B→F (very fast)
What is the expected rate law?
rate = k[C][B]
reaction
Catalysts
• Speed a reaction, but are not
consumed by the reaction
• May appear in the rate law
• Lower the Ea for the reaction.
• May be heterogeneous or
homogeneous
13.8 Catalysts change reaction rates by providing alternative paths between reactants and 61
products
Catalytic Actions
• May serve to weaken bonds through induction
• May serve to change polarity through
amphipathic/surfactant effects
• May reduce geometric orientation effects
• Heterogeneous catalyst - reactant and product
exist in different states.
• Homogeneous catalyst - reactants and catalyst
exist in the same physical state
products
Heterogeneous Catalysts
products
Solutions slides- graphs to
accompany previous slides
Ch 13 Brady & Senese, 5th
64
return to problem
[Reactant] vs. time
Zero Order Plot
0.025
0.02
[N2O5] M
0.015
0.01
0.005
0
0 200 400 600 800
time(s)
Solutions 65
return to problem
Ln [Reactant] vs time
First Order Plot
-3
-3.5 0 200 400 600 800
ln[N2O5]
-4
-4.5
-5
-5.5
Time(s)
Solutions 66
return to problem
Inverse [Reactant ] vs time
Second Order Plot

Inverse Concentration
200
150
N2O5 1/M
100
50
0
0 200 400 600 800
Time (s)
Solutions 67
return to the problem
Arrhenius Plot
0.0035
0.003
ln(k)
0.0025
ln(k) = -0.0278/T - 0.1917
0.002
-7.04 -7.03 -7.02 -7.01 -7 -6.99
Inverse T (1/K)
Solutions 68

Ch13 Reaction Rates

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Ch13 Reaction Rates

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Chapter 13

Kinetics: The Study of Rates of

Brady and Senese

13.1 Five factors affect reaction rates 3

13.1 Five factors affect reaction rates 4

13.1 Five factors affect reaction rates 5

13.1 Five factors affect reaction rates 6

• In the reaction 3A + 2B → C, we measured the

rateC = 1/2 rateB

13.3 Rate laws give reaction rate as a function of reactant concentrations 15

rate = 0.045 M-1 s-1 (0.2 M)(0.3 M)

13.3 Rate laws give reaction rate as a function of reactant concentrations 16

13.3 Rate laws give reaction rate as a function of reactant concentrations 17

13.3 Rate laws give reaction rate as a function of reactant concentrations 18

0.048 M s-1 = k[0.015 M]2[0.015 M]

1.4 × 104 M-2 s-1 = k

13.3 Rate laws give reaction rate as a function of reactant concentrations 20

0.01 0.02 0.30 0.0002

13.3 Rate laws give reaction rate as a function of reactant concentrations 21

13.3 Rate laws give reaction rate as a function of reactant concentrations 23

13.3 Rate laws give reaction rate as a function of reactant concentrations 24

13.4 Integrated rate laws give concentration as a function of time 25

2N2 O5 (g ) → 4NO2 (g ) + O2 (g ) 0 order plot

13.4 Integrated rate laws give concentration as a function of time 27

The rate law for the reaction of A→B is zero order

13.4 Integrated rate laws give concentration as a function of time 28

13.4 Integrated rate laws give concentration as a function of time 29

13.4 Integrated rate laws give concentration as a function of time 30

13.4 Integrated rate laws give concentration as a function of time 31

13.4 Integrated rate laws give concentration as a function of time 32

13.4 Integrated rate laws give concentration as a function of time 33

13.4 Integrated rate laws give concentration as a function of time 34

 A0 At t1/2, [A]0/2 = [A]

13.4 Integrated rate laws give concentration as a function of time 36

13.4 Integrated rate laws give concentration as a function of time 37

13.4 Integrated rate laws give concentration as a function of time 39

13.4 Integrated rate laws give concentration as a function of time 40

The rate constant for a 1

13.4 Integrated rate laws give concentration as a function of time 41

13.4 Integrated rate laws give concentration as a function of time 42

13.4 Integrated rate laws give concentration as a function of time 43

Reaction Coordinate (progress of reaction)

Ratio form: Can be used when A isn’t known.

 4.64 101 M s-1   Ea  1 1 

Elementary Reactions Molecularity Rate Law

Ch 13 Brady & Senese, 5th

Zero Order Plot

First Order Plot

Second Order Plot

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