Brdy 6ed Ch14 ChemicalKinetics

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Chapter 14:
Chemical Kinetics
Chemistry: The Molecular Nature

of Matter, 6E
Jespersen/Brady/Hyslop
Speeds at Which Reactions Occur
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Kinetics:
Study of factors that govern
How rapidly reactions occur and

How reactants change into products
Rate of Reaction:
Speed with which reaction occurs
How quickly reactants disappear and products
form
Chemistry: The Molecular Nature of Matter, 6E
Important Questions in Kinetics
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Practical value!!
Chemical /pharmaceutical manufacturers
Is it practical to make drug?
Made on manageable time scale?
Can we adjust conditions to improve rate and
yield?
Mechanism of Reaction
Series of individual steps leading to overall

observed reaction
How do reactants change into products?
Detailed sequence of events
Factors that Affect Reaction Rates
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1. Chemical nature of reactants

What elements, compounds, salts are
involved?
What bonds must be formed, broken?
What are fundamental differences in
chemical reactivity?

2. Ability of reactants to come in contact
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If two or more reactants must meet in order to react

Gas or solution phase facilitates this
Reactants mix and collide with each other easily
Homogeneous reaction
All reactants in same phase
Occurs rapidly
Heterogeneous reaction
Reactants in different phases
Reactants meet only at interface between phases
Surface area determines reaction rate
area, rate
area, rate
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3. Concentrations of reactants
Rates of both homogeneous and
heterogeneous reactions affected by [X]
Collision rate between A and B if we [A] or
[B].
Often (but not always)
Reaction rate as [X]
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4. Temperature
Rates are often very sensitive to T
Cooking sugar
Raising T usually makes reaction faster for

two reasons:
a. Faster molecules collide more often and
collisions have more E
b. Most reactions, even exothermic reactions,
require E to get going
Crude Rule of Thumb:

Rate doubles if T by 10 C (10 K)
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5. Presence of Catalysts
Catalysts
Substances that rates of chemical and

biochemical reactions without being used up
Rate-accelerating agents
Speed up rate dramatically
Rate enhancements of 106 not uncommon
Chemicals that participate in mechanism but are

regenerated at the end
Ex. Enzymes
Measuring Rate of Reaction
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Rate = ratio with time unit in denominator

10 dollars
Ex. Rate of pay =
hr
Rate of Chemical Reaction
in [X] of particular species per unit time.
[ reactant ]
reaction rate=
time
Always with respect to (WRT) given reactant or

product
[reactants] w/ time
[products] w/ time
Rate of Reaction with Respect to

Given Species X
[ X ]
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Rate WRT X =
[ X ]t [ X ]t
2
t 2 t 1
Concentration in M
Time in s
mol/L mol M
Units on rate:
=
=
s
Ls
s
Ex.
[product] by 0.50 mol/L per second rate =

0.50 M/s
[reactant] by 0.20 mol/L per second rate =
0.20 M/s
10
Rate of Reaction
Always +
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Whether something is or in [X].
Reactants
Need sign to make rate +

Reactant consumed
[ reactant ]
Rate =
So [X] =
t
Products
Produced as reaction goes along

So [X] = +
[ product ]
Rate =
Thus Rate = +
t
11
Rates and Coefficients
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Relative rates at which reactants are

consumed and products are formed
Related by coefficients in balanced chemical
equation.
Know rate with respect to one product or reactant
Can use equation to determine rates WRT all other
products and reactants.
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (g)
Rate of Reaction
=
[C 3 H 8 ]
t
1 [O2 ] 1 [ CO 2 ] 1 [ H 2 O ]
=
=
=
5 t
3
t
4
t
12
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C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (g)

O2 reacts 5 times as fast as C3H8
Rate=
[O 2 ]
t
=5
[C 3 H 8 ]
t
CO2 forms 3 times faster than C3H8

consumed
Rate=
[ CO2 ]
t
=3
[C 3 H 8 ]
t
H2O forms 4/5 as fast as O2 consumed

[ H 2 O ]
t
4 [O 2 ]
=
5 t
13
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In general
A + B C + D
1 A
1 B 1 C 1 D
Rate=
=
=
=
t
t t t
Which one do I measure?

Doesn't matter. All interrelated.
Often determined by which one is easily
measured
14
Your Turn!
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In the reaction 2CO(g) + O2(g) 2CO2(g), the

rate of the reaction of CO is measured to be
2.0 M/s. 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
15
Change of Reaction Rate with Time
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Generally reaction rate changes during

reaction
i.e. Not constant
Often initially fast when lots of reactant present
Slower at end when reactant depleted
Why?
Rate depends on [reactants]
Reactants being used up, so [reactant] is
[A] vs. time is curve
A is reactant [A] is w/ time
16
Measuring Rates
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Can measure rate using change in

concentration of any substance in reaction
Ex. 2A 3B
Rates based on each substance are related to

one another by the stoichiometric coefficients
of reaction
[ B]
3 [ A]
=
time
2 time
Measured in three ways:
Instantaneous rate
Average rate
Initial rate
17
Instantaneous Reaction Rates

Instantaneous rate
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Slope of tangent to curve at any specific time
Initial rate
Determined at initial time
18
Average Rate of Reaction
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Slope of line connecting starting and ending

coordinates for specified time frame
[ Product ]
=rate
time
19
Concentration vs. Time Curve for HI

Decomposition at 508C
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Rate at any time t = negative slope (or tangent

line) of curve at that point
y rise
Rate=slope=
=
x run
20
Table 14.1 Data at 508 C

2 HI(g) H2(g) + I2(g)
0.100
0.0716
0.0558
0.0457
0.0387
0.0336
0.0296
0.0265
Initial rate
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[HI] (mol/L) Time (s)
rate between first two data

points
0
50
(0 . 07160 .100 ) M
100 rate=
(500 )s
150
(0 . 0284 M )
=
200
50 s
250
=5 .68104 M / s
300
350
21
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y rise
Rate=slope= =
x run
(0 . 0440 . 068) M
=
(15050) s
0 .024 M
=
=2 . 4104 M / s
100 s
22
Rate at 300 s
[HI] (mol/L) Time (s)
0
50
100
150
200
250
300
350
Rate = tangent of curve

at 300 s
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0.100
0.0716
0.0558
0.0457
0.0387
0.0336
0.0296
0.0265
2 HI(g) H2(g) + I2(g)
( 0. 02650 . 0296) M
Rate=
(350300 )s
0 . 0031 M
=
50 s
=6 . 20105 M /s
23
Your Turn!
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A reaction was of NO2 decomposition was studied.

The concentration of NO2 was found to be 0.0258M
at 5 minutes and at 10 minutes the concentration
was 0.0097M. What is the average rate of the
reaction between 5 min and 10 min?
A. 310 M/min
B. 3.2 x 10-3 M/min
C. 2.7 x 10-3 M/min
D. 7.1 x 10-3 M/min
( 0.0258M
0.0097M )
10 min 5 min
= 3.2 x 10 3M / min
24
Concentration and Rate
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Rate Laws
A + B C + D
Homogeneous reaction
Rate = k[A]m[B]n
Rate Law or Rate expression

m and n = exponents found experimentally
No necessary connection between stoichiometric
coefficients (, ) and rate exponents (m, n)
Usually small integers
Sometimes simple fractions (, ) or zero
25
Rate Laws
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Rate = k[A]m[B]n
k = Rate Constant
Dependence of rate on concentration goes as

some power (m) of concentration [A]
All other factors (T, solvent) are included in k
Specific rate constant
k depends on T
Must specify T at which you obtained k.
[ A]
Rate=
= k[A]m[B]n
t
26
Learning Check
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The rate law for the reaction 2A +B3C is

rate= 0.045M-1s-1 [A][B]
If the concentration of A is 0.2M and that of
B is 0.3M, what will be the reaction rate?
rate=0.045 M-1 s-1 [0.2][0.3]
rate=0.0027 M/s 0.003 M/s
27
Rate Laws
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Rate = k[A]m[B]n
Exponents tell Order of Reaction with

respect to (WRT) each reactant
Order of Reaction
m=1
m=2
m=3
m=0
[A]0 =
[A]1 1st order WRT reactant

[A]2 2nd order WRT reactant
[A]3 3rd order WRT reactant
[A]0 0th order WRT reactant
1 means A doesn't affect rate
Overall order of reaction = sum of orders

(m and n) of each reactant in rate law
28
Example 1
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5 Br + BrO3 + 6H+ 3Br2 + 3H2O
BrO 3 ]
x
y
+ z
=k [ BrO 3 ] [ Br ] [ H ]
x=1 y=1
z=2
1st order WRT BrO3
1st order WRT Br

2nd order WRT H+
Overall order = 1 + 1 + 2 = 4
rate=k [
1
BrO3 ] [
+ 2
Br ] [ H ]
29
Example 2
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Sometimes n and m are coincidentally the

same as stoichiometric coefficients
2 HI (g) H2 (g) + I2 (g)
[ HI ]
2
rate=
=k [ HI ]
t
2nd order WRT HI

2nd order overall
30
Your Turn!
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The following rate law has been observed:

Rate = k[H2SeO][I-]3[H+]2. The rate with
respect to I- and the overall reaction rate is:
A. 6, 2
B. 2, 3
C. 1, 6
D. 3, 6
31
Calculating k from Rate Law
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If we know rate and concentrations, can use

rate law to calculate k
Ex. 2 at 508 C
Rate= 2.5 x 104 M/s
[HI] = 0.0558 M
[ HI ]
2
rate=
=k [ HI ]
t
4
rate 2. 510 M /s
1 1
k=
=
=0
.
08029
M
s
[ HI ]2 (0 . 0558 M )2
32
How To Determine Exponents in Rate Law
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Experiments
Method of Initial Rates
If reaction is sufficiently slow
or have very fast technique
Can measure [A] vs. time at very beginning

of reaction
before it curves up very much, then
[ A] 1[ A ]0
initial rate=
t 1t 0
Set up series of experiments, where initial
concentrations vary
33
Ex 1. Method of Initial Rates
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3A + 2 B products
Rate = k[A]m[B]n
Expt. # [A]0, M
1
2
3
0.10
0.20
0.20
[B]0, M
Initial Rate, M/s
0.10
0.10
0.20
1.2 104
4.8 104
4.8 104
Convenient to set up experiments so
[X] of one species is doubled or tripled

while [X] of all other species are held constant
Tells us effect of [varied species] on initial rate

34
Reaction Order and Rate

If reaction is 1st order WRT given species X,
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Doubling [X]1 21
Rate doubles
If reaction is 2nd order WRT X,

Doubling [X]2 22
Rate quadruples
If reaction is 0th order WRT X,

Doubling [X]0 20
Rate doesn't change
If reaction is nth order WRT X

Doubling [X]n 2n
35
Back to our Example

Expt. # [A]0, M
[B]0, M
Initial Rate, M/s
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1
0.10
0.10
1.2 104
2
0.20
0.10
4.8 104
3
0.20
0.20
4.8 104
Comparing 1 and 2
4
Rate 2 4. 810
Doubling [A]
=
=4
4
Rate 1 1 . 210
Quadruples rate
Reaction 2nd order in A
[A]2
m
n
m
n
m
k
A
B
[
]
[
]
k
[
0
.
20
]
[
0
.
10
]
[
0
.
20
]
Rate 2
2
2
m
4=
=
=
=
=2
Rate 1 k [ A ]m [ B ]n k [ 0. 10 ]m [ 0 .10 ]n [ 0 . 10 ] m
1
1
2m = 4 or
m=2
36
Back to our Example

Expt. # [A]0, M
[B]0, M
Initial Rate, M/s
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1
0.10
0.10
1.2 104
2
0.20
0.10
4.8 104
3
0.20
0.20
4.8 104
Comparing 2 and 3
4
Rate 3 4. 810
Doubling [B]
=
=1
4
Rate 2 4. 810
Rate does not change
Reaction 0th order in B
[B]0
m
n
m
n
n
k
A
B
[
]
[
]
k
[
0.
20
]
[
0
.
20
]
[
0
.
20
]
Rate 3
3
3
n
1=
=
=
=
=2
Rate 2 k [ A ]m [ B ]n k [ 0 . 20 ] m [ 0. 10 ] n [ 0 .10 ]n
2
2
2n = 1 or
n=0
37
Ex. 1 Method of Initial Rates

[B]0, M
Initial Rate, M/s
0.10
0.20
0.10
0.10
1.2 104
4.8 104
0.20
0.20
4.8 104
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Expt. # [A]0, M
1
2
3
Conclusion: rate = k[A]2

Can use data from any experiment to determine k
Lets choose experiment 1
k=
rate
[ A]
1 . 210
M/s
( 0. 10 M )
=1 . 210
1 1
38
Ex. 2. Method of Initial Rates
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2 SO2 + O2 2 SO3
Rate = k[SO2]m[O2]n
Expt [SO2], [O2], Initial Rate of SO3

#
M
M
formation, Ms1
1
0.25 0.30
2.5 103
2
3
4
0.50
0.30
1.0 102
0.75
0.60
4.5 102
0.50
0.90
3.0 102
39
Ex. 2
Compare 1 and 2
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[SO2] doubles, [O2] constant,

Rate quadruples, 22
2
Rate 2 1 .010
=
=4
3
Rate 1 2 . 510
k[
Rate 2
4=
=
Rate 1 k [
m
SO 2 2
m
SO 2 1
n
O2 2
n
O2 1
] [ ]
] [ ]
k [ 0 . 50 ] [ 0. 30 ]
k [ 0 . 25 ] [ 0 .30 ]
[ 0. 50 ]
m
=
=2
m
[ 0. 25 ]
2m = 4
or
m=2
40
Ex. 2
Compare 2 and 4
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[O2] triples, [SO2] constant

Rate triples, 31
2
Rate 4 3 . 010
=
=3
Rate 2 1 . 0102
k[
Rate 4
3=
=
Rate 2 k [
m
SO 2 4
m
SO 2 2
n
O2 4
n
O2 2
] [ ]
] [ ]
k [ 0. 50 ] [ 0 . 90 ]
k [ 0. 50 ] [ 0 . 30 ]
[ 0. 90 ]
n
=
=3
n
[ 0. 30 ]
3n = 3
or
n=1
41
Ex. 2
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Rate = k[SO2]2[O2]1
1st order WRT O2
2nd order WRT SO2

3rd order overall
Can use any experiment to find k
2
rate
3. 010 M / s
2 1
k=
=
=0 . 13 M s
2
1
2
[ SO 2 ] [O 2 ] ( 0 . 50 M ) ( 0. 90 M )
42
Ex. 3. Method of Initial Rates
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BrO3 + 5 Br + 6H+ 3Br2 + 3H2O
Rate =
Expt
#
[ BrO 3 ]
[BrO3],
mol/L
0.10
m
n
+ p
=k [ BrO 3 ] [ Br ] [ H ]
[Br], [H+],
mol/L mol/L
Initial Rate,
mol/(Ls)
0.10
0.10
8.0 104
0.20
0.10
0.10
1.6 103
0.20
0.20
0.10
3.2 103
0.10
0.10
0.20
3.2 103
43
Ex. 3 Compare 1 and 2

m
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Rate 2 1 .610 M / s k (0 . 20 M ) (0. 10 M ) (0 .10 M )

=
=
4
Rate 1 8 .010 M / s k (0. 10 M )m (0 . 10 M )n (0. 10 M ) p
0 . 20 M
2 . 0=
0 . 10 M
=( 2 . 0 )m
m=1
Compare 2 and 3
Rate 3 3 . 210 M / s k (0 . 20 M ) ( 0. 20 M ) (0 . 10 M )
=
=
3
Rate 2 1 .610 M / s k (0. 20 M )m (0 .10 M ) n (0 .10 M ) p
0 . 20 M
2 . 0=
0 . 10 M
=(2 . 0)n
n=1
44
Ex. 3 Compare 1 and 4

m
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Rate 4 3 . 210 M /s k ( 0. 10 M ) (0 . 10 M ) (0 . 20 M )
=
=
Rate 1 8 . 0104 M /s k (0 .10 M ) m(0 . 10 M )n (0. 10 M ) p
0 . 20 M
4 . 0=
0. 10 M
=( 2 .0 ) p
p=2
First order in [BrO3] and [Br]
Second order in [H+]

Overall order = m + n + p = 1 + 1 + 2 = 4
Rate Law is: Rate = k[BrO3][Br][H+]2
45
Your Turn!
A. 2, 0
B. 3,1
C. 2, 1
D. 1, 1
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Using the following experimental data, determine the

order with respect to NO and O2 .
Exp [NO] [O2] Initial Rate of NO2
t # , M , M formation, Ms1
1
0.12 0.25
1.5 103
2
0.24 0.25
6.0 103
3
0.50 0.50
5.2 102
46
Your Turn! - Solution
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0.24M
R 2 6.0 x 10 M s
=
=
3
1
x
R1 1.5 x 10 M s
0.12M
x = 2
3
0.50M
R 3 5.2 x 10 M s
=
=
3
1
2
R1 1.5 x 10 M s
0.12M
y =1
2
0.25M
y
0.25M
y
0.50M
y
0.25M
47
Concentration and Time
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Rate law tells us how speed of reaction varies

with [X]'s.
Sometimes want to know
[reactants] and [products] at given time during
reaction
How long for [reactants] to drop below some
minimum optimal value
Need dependence of Rate on Time
48
Concentration vs. Time for 1st Order

Reactions
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[ A ]
Rate =
=k [ A ]
t
Corresponding to reactions
A products
Integrating we get
ln
[ A ]0
[ A ]t
=kt
Rearranging gives
ln [ A ]t =kt + ln [ A ]0
Equation of line
y = mx + b
49
Plot ln[A]t (y axis) vs. t (x axis)
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ln [ A ]t =kt + ln [ A ]0
Slope = k
Yields straight line

Indicative of 1st
order kinetics
slope = k
intercept = ln[A]0
If we don't know
already
50
First Order Kinetics Graph
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Plot of [A] vs. time gives an exponential decay

kt
[ A] t =[ A ]o e
51
Concentration vs. Time for 2nd Order

Reactions
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[ B ]
Rate =k [ B ] =
t
2
Corresponding to reactions
2B products
Integrating we get
Rearranging gives
Equation of line
1
1
=kt
[ B ]t [ B ] 0
1
1
=kt +
[ B ]t
[ B ]0
y = mx + b
52
Plot 1/[B]t (y axis) vs. t (x axis)
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1
1
=kt +
[ B ]t
[ B ]0
indicative of 2nd
order kinetics
slope = + k
intercept = 1/[B]0
Graph of [B] vs. time

is still function,
which curves up
Not an exponential
Slope
= +k
53
How to Determine Reaction Order

Using Graphs
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Make 2 plots
1.ln [A] vs. time
2.1/[A] vs. time
If ln [A] is linear and 1/[A] is curved, then
reaction is 1st order WRT [A]
If 1/[A] plot is linear and ln [A] is curved,
then reaction is 2nd order WRT [A]
If both horizontal lines, then 0th order WRT
[A]
54
Ex 4. SO2Cl2 SO2 + Cl2

ln[SO2Cl2]
1/[SO2Cl2] (L/mol)
0.1000
-2.3026
10.000
0.0876
-2.4350
11.416
0.0768
-2.5666
13.021
0.0673
-2.6986
14.859
0.0590
-2.8302
16.949
0.0517
-2.9623
19.342
0.0453
-3.0944
22.075
0.0397
-3.2264
25.189
800
0.0348
-3.3581
28.736
900
0.0305
-3.4900
32.787
1000
0.0267
-3.6231
37.453
1100
0.0234
-3.7550
42.735
0
100
200
300
400
500
600
700
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Time, min [SO2Cl2], M
55
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Ex 4. SO2Cl2 SO2 + Cl2
Clearly reaction is 1st order in SO2Cl2.

56
Ex. 2 HI (g) H2 (g) + I2 (g)

[HI]
(mol/L)
ln[HI]
0.1000
-2.3026
10.000
0.0716
-2.6367
13.9665
0.0558
-2.8860
17.9211
0.0457
-3.0857
21.8818
0.0387
-3.2519
25.840
0.0336
-3.3932
29.7619
300
0.0296
-3.5200
33.7838
350
0.0265
-3.6306
37.7358
0
50
100
150
200
250
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Time
(s)
1/[HI]
(L/mol)
57
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Ex. 5 HI (g) H2 (g) + I2 (g)
Clearly reaction is 2nd order in HI.

58
Your Turn!
Zeroth Order Plot
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A plot for a zeroth order

reaction is shown. What
is the proper label for
the y-axis in the plot ?
200
400
600
800
A. Concentration
B. ln of Concentration
C. 1/Concentration
D. 1/ ln Concentration
1000 1200
time (min)
59
Half-lives for 1st Order Reactions
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Half-life = t
First Order Reactions
1
[ A]t = [ A] 0
2
Set
Substituting into
Gives
ln 1
ln
[ A ]0
2[
A]0
[ A ]0
[ A ]t
=kt
=kt 1
Canceling gives ln 2 = kt
ln 2 0 . 693
t1 =
=
Rearranging gives
k1
k1
2
60
Half-life for 1st Order Reactions
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Observe:
1. t is independent of [A]o
For given reaction (and T)

Takes same time for concentration to fall from
2 M to 1 M as from
5.0 10-3 M to 2.5 10-3 M
1. k1 has units (time)-1, so t has units (time)
t called half-life
Time for of sample to decay
61
Half-life for 1st Order Reactions
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Does this mean that all of sample is gone

in two half-lives (2 x t)?
No!
In 1st t, it goes to [A]o
In 2nd t, it goes to ([A]o) = [A]o

In 3rd t, it goes to ([A]o) = [A]o
In nth t, it goes to [A]o/2n
Existence of [X] independent half-life is

property of exponential function
Property of 1st order kinetics
62
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Half-Life Graph
63
Ex. Using Half-Life

I is used as a metabolic tracer in hospitals.
It has a half-life, t = 8.07 days. How long
before the activity falls to 1% of the initial
value?
131
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kt
N = N oe
N
t ln 2
ln
=kt=
No
1
2
( )
N
1
1 ln
( 8. 07 days ) ln
No
100
2
t =
=
=53. 6 days
ln 2
ln 2
64
Learning Check
( )
A0
ln
=kt
A
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The radioactive
decay of a new
atom occurs so that
after 21 days, the
original amount is
reduced to 33%.
What is the rate
constant for the
reaction in s-1?
100
ln(
)=k ( 21da )
33
k = 0.0528 da-1
k = 6.1110-7 s-1
65
Learning Check
( )
( )
ln
ln
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The half-life of I-132 is 2.295h. What percentage

remains after 24 hours?
ln 2
ln( 2) 1
0.302 h1 = k
=t 2 k =
k
2 . 295 h
Ao
=kt
Ao
A
=0 . 302 h 24 h=7 . 248

kt
A=A o e
7. 248
=Ao e
A = .0711 % Ao
66
Your Turn!
A.
B.
C.
D.
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Which order has a half-life that is independent

of the original amount?
Zero
First
Second
None depend on the original quantity
67
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Half-lives of Second Order

Reactions
How long before [A] = [A]o?
1
t1 =
k[ A ]0
2
t, depends on [A]o
t, not useful quantity for 2nd order reaction
68
Learning Check
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The rate constant for the second order reaction

2AB is 5.310-5 M-1s-1. What is the original
amount present if, after 2 hours, there is 0.35M
available?
1
1
=kt
[ A ] [ A 0]
1
1
5 .310 5
=
7200 s
[ 0. 35 ] [ A 0 ] M s
A0=0.40 M
69
Your Turn!
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Plutomium-239 has a
half life of 24,100 yrs.
How many years will it
take for 1.0 grams of
Pu-239 to decay to
0.025 g ?
A. 9.6 x 105 yrs
B. 2.4 x 105 yrs
C. 1.3 x 105 yrs
D. 4.8 x 105 yrs
The number of half-lifes if given by:

1.00 g
n
0.025 g =
2
= 40
n
2
n log 2 = log 40
n = 5.32
5.32 x 24,100 yrs = 1.3 x 105 yrs
70
Theories about Reaction Rates
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Reaction rate depends on [reactants] and T

Collision Theory
Based on Kinetic Molecular Theory
Accounts for both effects on molecular level
Central Idea
Molecules must collide to react
Greater number of collision/sec = greater reaction
rate
71
Theories about Reaction Rates
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Collision Theory
As [reactants]
number of Collisions
Reaction rate
As T
Molecular speed
Molecules collide with more force (energy)
Reaction rate
72
Collision Theory
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Rate of reaction proportional to number of effective

collisions/sec among reactant molecules
Effective collision
1 that gives rise to product
Ex. At Room Temperature and Pressure

H2 and I2 molecules undergoing 1010 collisions/sec
Yet reaction takes a long time
Not all collisions lead to reaction
Only very small % of all collisions lead to net
change
73
1. Molecular Orientation
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Molecules must be oriented in a certain way during

collisions for reaction to occur
Ex. NO2Cl + Cl NO2 + Cl2
Cl must come in pointing directly at another Cl atom
for Cl2 to form
74
1. Molecular Orientation
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Wrong Orientation
Correct Orientation
75
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2. Temperature Greatly Affects Rates
Over moderate T range, Ea unchanged

As T,
More molecules have Ea

So more molecules undergo reaction
Reaction rate as T
76
3. Activation Energy, Ea
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Molecules must possess certain amount of kinetic

energy (KE) in order to react
Activation Energy, Ea
Minimum KE needed for reaction to occur
Get energy from collision with other molecules

Upon collision, KE converted to potential energy (PE),
used to stretch, bend, and break bonds leading to
chemical reaction
If molecules move too slowly, too little KE, they just
bounce off each other
Without this minimum amount, reaction will not occur
even when correctly oriented
Major reason all collisions do not lead to reaction
77
Transition State Theory
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Used to explain details of reactions

What happens when reactant molecules collide
Potential Energy Diagram
To visualize what actually happens during
successful collision
Relationship between Ea and developing Total
PE
78
Activation energy (Ea)

= hill or barrier
between reactants
and products
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Potential Energy
heat of reaction (H)

= difference in PE between
products and reactants
Hreaction = Hproducts Hreactants
Products
Reaction Coordinate (progress of reaction)

79
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Potential Energy

(Exothermic)
Exothermic reaction
Products lower PE
than reactants
Exothermic
Reaction
H =
Products
Reaction Coordinate (progress of reaction)

80
Exothermic Reaction
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Hreaction < 0 ()
in PE of system
Appears as in KE
So T system
Reaction gives off heat

Cant say anything about Ea from size of H
Ea could be high and reaction slow even if Hrxn
large and negative
Ea could be low and reaction rapid
81
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(Endothermic)
Endothermic
Reaction
H = +
Hreaction = Hproducts Hreactants

82
Endothermic Reaction
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Hreaction > 0 (+)

in PE
Appears as in KE
So T system
Have to add E to get reaction to go

Ea Hrxn as Ea includes Hrxn
If Hrxn large and +
Ea must be high
Reaction very slow
83
Transition State or Activated Complex
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Arrangement of atoms at top of activation

barrier
Brief moment during successful collision when
bond to be broken is partially broken and
bond to be formed is partially formed
Ex.
H3C
H3C
H3C
Transition State (TS)

84
Ex. NO2Cl + Cl NO2 + Cl2
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As NO2Cl and Cl come

together
Start to form ClCl bond
Start to break NCl bond
Requires E, as must
bring 2 things together
In TS
NCl bond broken
ClCl bond formed
After TS
ClCl bond forms
NCl breaks
Releases E as products
more stable
85
Your Turn!
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U Energy
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Examine the potential energy diagram. Which

is the Slowest (Rate Determining) Step?
A. Step 1
Has greatest Ea
B. Step 2
C. Cant tell from the given information
1
2
Reaction Progress
Measuring Activation Energy
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Generally we find k as T
Usually magnitude of effect as T
Arrhenius Equation
Equation expressing T dependence of k
k = Ae
E a / RT
A = Frequency factorhas same units as k

R = gas constant in energy units
= 8.314 Jmol1K1
Ea = Activation Energyhas units of J/mol
T = Temperature in K
87
How To Calculate Activation Energy
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Method 1. Graphically
Take natural logarithm of both sides
Rearranging
( )( )
ln k =ln A
Equation for a line

y = b + mx
Ea
R
T
Arrhenius Plot
Plot ln k (y axis) vs. 1/T (x axis)
88
Ex. 2N2O5(g) 4NO2(g) + O2(g)

1/T (K1)
k (s1)
ln k
293
3.41 103
2.00 105
10.82
303
3.30 103
7.30 105
9.53
313
3.19 103
2.70 104
8.22
50
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T (C) T (K)
323
3.09 103
9.10 104
7.00
60
333
3.00 103
2.90 103
5.84
20
30
40
89
Arrhenius Plot
-6
ln k
-7
-8
-9
-10
2 N2O5 (g) 4 NO2 (g) + O2 (g)
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-5

slope = Ea/R
intercept = A
-11
3.0E-03 3.1E-03 3.2E-03 3.3E-03 3.4E-03 3.5E-03
1/T (1/K)
90
How To Determine Ea w/ Arrhenius Plot
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Pick 2 points on line
(3.030 103, 6.20)

(3.375 103, 10.4)
Point 1
Point 2
slope=
( ln k )
( )
1
(10 . 4(6 . 20 ) )
3
(3 . 3753 . 030 )10 K
4 . 20
=
K
4
3 . 4510
4
slope=1 . 2210 K =
Ea
R
91
Determine Ea from Arrhenius Plot
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E a =slopeR
Ea = (1.22 105 K) * 8.314 Jmol1K1

Ea = 1.01 105 J/mol
92
Working With Arrhenius Equation

k (M/s)
0.000886
0.000894
0.000908
0.000918
?
T C
25
50
100
150
75
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Given the following

data, predict k at
75C using the
graphical approach
Ea 1
ln k = +lnA
R T
T, K
298
348
398
448
348
ln (k) = -36.025/T 6.908
ln (k) = 36.025/(348) 6.908 = 7.01152

7 . 012
k =e
=9 . 0110
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Working with Arrhenius Equation
94
Method 2. van't Hoff Equation
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Sometimes a graph is not needed

Only have 2 k s at 2 Ts
Here use van't Hoff Equation

Derived from Arrhenius equation
ln
( )
k2
k1
E a
R
1
1
T 2 T1
95
Using van't Hoff Equation
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Ex. CH4 + 2 S2 CS2 + 2 H2S

k (L/mols)
1.1 = k1
T (C)
550
T (K)
823 = T1
6.4 = k2
625
898 = T2
E a
6.4
1
1
ln
=
1. 1
8 .3145 J / Kmol 898 K 823 K
( )
Ea =
(
) (
)
)
6.4
(8 . 314 J / Kmol ln
1. 1
1
1
898 K 823
=1 . 410 5 J / mol
96
Learning Check
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Given that k at 25C is 4.6110-1 M/s and that

at 50C it is 4.6410-1 M/s, what is the
activation energy for the reaction?
k 2 E a 1
1
ln( )=
k1
R T2 T1
1
4 . 6410 M/s
E a
1
1
ln(
)=
1
4 . 6110 M/s 8. 314J/ ( molK ) 323K 298K
Ea = 208 J/mol
Your Turn!
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A reaction has an activation energy of 40 kJ/mol.

What happens to the rate if you increase the
temperature from 70 oC to 80 0C?
A. Rate increases approximately 1.5 times
B. Rate increases approximately 5000 times
C. Rate does not increase
D. Rate increases approximately 3 times
98
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Your Turn! - Solution

Rate is proportional to the rate constant
k2
=
k1
e
e
40000 J
J
8.314
x(80 + 273)K
mol K
40000 J
8.314 J x(70 + 273)K
mol K
= 1.49
99
Collision Theory and Reaction Mechanisms

Sometimes rate law has simple form
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N2O5 NO2 + NO3

Rate =
d [ N 2 O5 ]
dt
=k 1 [ N 2 O 5 ]
NO2 + NO3 N2O5

Rate =
d [ NO 2 ]
dt
=k 2 [ NO 2 ][ NO 3 ]
But others are complex
H2 + Br2 2 HBr
Rate =
d [ H 2]
dt
k [ H 2 ][ Br 2 ]
k ' [ HBr ]
1+
[ Br 2 ]
100
Why?
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Some reactions occur in a single step, as

written
NO2 bumps into NO3
Bond forms
Others involve a sequence of steps

Reaction Mechanism
Entire sequence of steps
Elementary Process
Each individual step in sequence (mechanism)

Single step that occurs as written
101
What makes an elementary step

elementary?
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Exponents in rate law for elementary process

are equal to coefficients of reactants in
balanced chemical equation for that
elementary process
Rate laws for elementary processes are
directly related to stoichiometry
Number of molecules that participate in
elementary process defines molecularity of
step
102
Unimolecular Process
Only one molecule as reactant
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H3CNC H3CCN
Rate = k[CH3NC]
1st order overall
As number of molecules , number that rearrange

in given time interval 's proportionally
103
Bimolecular Process
Elementary step with 2 reactants
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NO (g) + O3 (g) NO2 (g) + O2 (g)

Rate = k[NO][O3]
2nd order overall
From collision theory:
If [A] doubles, number of collisions between A and

B will double
If [B] doubles, number of collisions between A and
B will double
Thus, process is 1st order in A, 1st order in B, and
2nd order overall
104
Termolecular Process
Elementary reaction with 3 molecules
Why?
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Very rare
Very low probability that 3 molecules will collide

simultaneously
3rd order overall
105
Summary of Elementary Processes

Rate Law
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Molecularity Elementary Step

Unimolecular
A products
Rate = k[A]
Bimolecular
Bimolecular
Termolecular
A + A products
A + B products
A + A + A products
Rate = k[A]2
Rate = k[A][B]
Rate = k[A]3
Termolecular
A + A + B products
Rate = k[A]2[B]
Termolecular
A + B + C products
Rate = k[A][B][C]
Significance of elementary steps:

If we know that reaction is elementary step
Then we know its rate law
106
Multi-Step Mechanisms
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Contains 2 or more steps to yield net reaction

Elementary processes in multi-step mechanism
must always add up to give chemical
equation of overall process
Any mechanism we propose must be
consistent with experimentally observed
rate law
107
Multi-Step Mechanisms
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Ex. Net reaction is:

NO2(g) + CO(g) NO(g) + CO2(g)
Proposed mechanism is:
NO2(g) + NO2(g) NO3(g) + NO(g)
NO3(g) + CO(g)
1
NO2(g) + CO2(g)
2NO2(g) + NO3(g) + CO(g) NO2(g) + NO3(g) + NO(g) + CO2(g)
or
NO2(g) + CO(g) NO(g) + CO2(g)
108
Intermediates
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Species which are formed in one step and used

up in subsequent steps
Species which are neither reactant nor product
in overall reaction
NO3 in this reaction
Product in one step
Reactant in later step
Mechanisms may involve one or more

intermediates
109
How Observed Rate Law Relates to

Mechanism
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Can we deduce mechanism based on rate

law?
Complicated problem
Sometimes we can make simplifying
assumptions
Most important: concept of Rate-determining
or Rate-limiting step
Slowest step in mechanism
110
How Observed Rate Law Relates to

Mechanism
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If process follows sequence of steps, slow

step determines rate.
Think of an assembly line
Fast earlier steps may cause intermediates to pile
up
Fast later steps may have to wait for slower initial
steps
Rate-determining step governs rate law

for overall reaction
Can only measure up to rate determining step
too fast to see
111
Mechanism Examples
(aq)
+ Cl (aq)
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(CH3)3CC l(aq) + OH (aq) (CH3)3COH

chlorotrimethylmethane
trimethylmethanol
Observed rate = k[(CH3)3CCl]

If reaction was elementary
Rate would depend on both reactants
Frequency of collisions depends on both
concentrations
Mechanism is more complex than single step
What is mechanism?
Evidence that it is a two step process
112
Mechanisms with Slow Initial Step
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Step 1: (CH3)3CCl(aq) (CH3)3C+(aq) + Cl(aq)
(slow)
Step 2: (CH3)3C+(aq) + OH(aq) (CH3)3COH(aq) (fast)

Two steps
Go at different rates
Each step in multiple step mechanism is elementary
process, so
Has its own rate constant
Has its own rate law
Hence only for each step can we write rate law
directly
113
Mechanisms with Slow Initial Step
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For above reaction

Observed rate law says that step 1 is very slow
compared to step 2
i.e. Carbonium ion is formed very slowly
Once it forms, it reacts immediately
Thus, rate determining step of overall

reaction is controlled by this slow step
Rate-determining step (RDS)
In this case, RDS = step 1
Overall rate = k1[(CH3)3CCl]
Consistent with observed rate
114
Mechanisms with Fast Initial Step
O3
O
( g)
( g)
kf
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1st step involves fast, reversible reaction

Ex. Decomposition of Ozone (No catalysts)
Net reaction: 2 O3 (g) 3 O2 (g)
2
k [O3]
Observed Rate =
[ O2 ]
Proposed mechanism:
O2
(g )
+ O
(g )
(fast)
kr
+ O3
(g )
k2
2 O2
(g )
(slow)
115
Your Turn!
B [O3]*
C. [O]*
D. [O4]*
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What is the activated complex in the reaction

3O2 (g) 2O3(g) ? The * indicates the
species is in a high energy (activated) state.
A. [O2]*
The activated complex is formed during the

slow, rate determining step.
116
Consistent with Observed Rate Law?
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Rate of formation of O2 = Rate of rxn 2

= k2[O][O3]
But O is intermediate
Need rate law in terms of reactants and
products
and possibly catalysts
Rate (forward) = kf[O3]

Rate (reverse) = kr[O2][O]
When step 1 comes to equilibrium
Rate (forward) = Rate (reverse)
kf[O3] = kr[O2][O]
117
Consistent with Observed Rate

Law?
Solving this for intermediate O gives:
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[O ]=
k f [ O3 ]
k r [O 2 ]
Substitution into rate law for step 2 gives:

2
Observed Rate =
Rate of RXN 2 = k2[O][O3] =

where
k obs =
k2k f
kr
k [O3]
[ O2 ]
k 2 k f [O 3 ]
k r [O 2 ]
This is observed rate law

Yes, mechanism consistent
118
?????
Questions
?????
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1. How do you determine if a proposed

mechanism is consistent with the observed
rate law?
2. What do you do if the first step is rate
determining?
3. What if the first step is a fast equilibrium and
the second step is slow?
119
Learning Check
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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?

First step is slow so RDS
rate=k[H2O2][I]
120
Learning Check
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The reaction: A + 3 B 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 Step 2=k2[C][B]
Rate = kobs[A][B]2
Rate forward = kf[A][B]

Rate reverse = kr[C]
kf[A][B] = kr[C]
[C]= kf[A][B]/kr
121
Catalyst
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Substance that changes rate of chemical

reaction without itself being used up
Speeds up reaction, but not consumed by
reaction
Appears in mechanism, but not in overall
reaction
Does not undergo permanent chemical change
Regenerated at end of reaction mechanism
May appear in rate law
May be heterogeneous or homogeneous
122
How Does A Catalyst Work?
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By providing
alternate
mechanism
One with lower Ea
Because Ea lower,
more reactants and
collisions have
minimum KE, so
reaction proceeds
faster
123
Homogeneous Catalyst
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Same phase as reactants

Consider : S (g) + O2 (g) + H2O (g) H2SO4 (g)
S (g) + O2 (g) SO2 (g)
NO2 (g) + SO2 (g) NO (g) + SO3 (g) Catalytic pathway
SO3 (g) + H2O (g) H2SO4 (g)
NO (g) + O2 (g) NO2 (g)
Regeneration of catalyst
Net: S (g) + O2 (g) + H2O (g) H2SO4 (g)

NO2 (g)
What is Catalyst?
Reactant (used up) in early step
Product (regenerated) in later step
NO and SO2
WhichJespersen/Brady/Hyslop
are Intermediates?
124
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Heterogeneous Catalyst
Exists in separate phase from reactants
Usually a solid
Many industrial catalysts are heterogeneous
Reaction takes place on solid catalyst
Ex. 3 H2 (g) + N2 (g) 2 NH3 (g)
125
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Heterogeneous Catalyst
H2 & N2
approach
Fe
catalyst
H2 & N 2
bind to Fe
& bonds
break
NH
bonds
forming
NH
bonds
forming
NH3
formation
complete
NH3
dissociates
126
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Other Examples of Heterogeneous

Catalysts
Catalytic converters in cars to remove
CO, NO, N2O, and unburned hydrocarbons
Enzymes
Proteins that catalyze reactions in living
systems.
Insulin, digestive enzymes, nitrogenase, etc.
127
?????
Question
?????
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What is the difference between a catalyst and

an intermediate?
128

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