Ch13 Reaction Rates
Ch13 Reaction Rates
Ch13 Reaction Rates
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
13.2 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)
13.2 Rates of reaction are measured by monitoring change in concentration over time 8
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
13.2 Rates of reaction are measured by monitoring change in concentration over time 9
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)
13.2 Rates of reaction are measured by monitoring change in concentration over time 10
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)
13.2 Rates of reaction are measured by monitoring change in concentration over time 11
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 Ls
13.2 Rates of reaction are measured by monitoring change in concentration over time 12
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
13.2 Rates of reaction are measured by monitoring change in concentration over time 13
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
13.2 Rates of reaction are measured by monitoring change in concentration over time 14
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
rate = k[NO]2[O2]
rate = k[A][B]
A. 0
B. 1
C. 2
D. 3
E. Not enough information given
13.3 Rate laws give reaction rate as a function of reactant concentrations 22
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
A0
ln kt
At
k = 6.11×10-7 s-1
ln 2
ln 2 kt1/2 t1/ 2
k
13.4 Integrated rate laws give concentration as a function of time 35
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
A0 A = 0.0711%
ln kt
At
1 1
kt
[A]t [A]0
13.4 Integrated rate laws give concentration as a function of time 38
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 5.3 105
7200 s
is the original amount 0.35 A0 M s
present if, after 2 hours,
there is 0.35 M [A]0 = 0.40 M
available?
1 1
kt1/2
0.5 A 0 A0
1
t1/2
k A0
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
13.5 Reaction rate theories explain experimental rate laws in terms of molecular 45
collisions
Potential Energy Diagrams
13.5 Reaction rate theories explain experimental rate laws in terms of molecular 46
collisions
Features of Potential Energy Diagrams
Activation Energies
Activated
Potential Energy
Complexes
Product
Energy
Enthalpy of
Reaction
Reactant Energy
Reaction Coordinate
(progress of reaction)
13.5 Reaction rate theories explain experimental rate laws in terms of molecular 47
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
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
k2 Ea 1 1
ln
k1 R T2 T1
13.6 Activation energies are measured by fitting experimental data to the Arrhenius 50
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?
13.6 Activation energies are measured by fitting experimental data to the Arrhenius 51
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
13.6 Activation energies are measured by fitting experimental data to the Arrhenius 52
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
13.6 Activation energies are measured by fitting experimental data to the Arrhenius 53
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
13.7 Experimental rate laws can be used to support or reject proposed mechanisms for a 55
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
13.7 Experimental rate laws can be used to support or reject proposed mechanisms for a 56
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-
13.7 Experimental rate laws can be used to support or reject proposed mechanisms for a 57
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
13.7 Experimental rate laws can be used to support or reject proposed mechanisms for a 58
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-]
13.7 Experimental rate laws can be used to support or reject proposed mechanisms for a 59
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]
13.7 Experimental rate laws can be used to support or reject proposed mechanisms for a 60
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
13.8 Catalysts change reaction rates by providing alternative paths between reactants and 62
products
Heterogeneous Catalysts
13.8 Catalysts change reaction rates by providing alternative paths between reactants and 63
products
Solutions slides- graphs to
accompany previous slides
64
return to problem
[Reactant] vs. time
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
-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
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