Kinetics Short

16-1
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chapter 16
Kinetics: Rates and Mechanisms
of Chemical Reactions
16-2
Kinetics: Rates and Mechanisms of Chemical Reactions
16.1 Factors That Influence Reaction Rates
16.2 Expressing the Reaction Rate
16.3 The Rate Law and Its Components
16.4 Integrated Rate Laws: Concentration Changes over Time
16.7 Reaction Mechanisms: Steps in the Overall Reaction
16.8 Catalysis: Speeding Up a Chemical Reaction
16.5 The Effect of Temperature on Reaction Rate
16.6 Explaining the Effects of Concentration and Temperature
16-3
Figure 16.1
Reaction rate: the central focus of chemical kinetics
16-4
Figure 16.2 The wide range of reaction rates.
16-5
Factors That Influence Reaction Rate
Under a specific set of conditions, every reaction has its own
characteristic rate, which depends upon the chemical nature of
the reactants.
Four factors can be controlled during the reaction:
1. Concentration - molecules must collide to react;
Rate collision frequency concentration
2. Physical state - molecules must mix to collide;
3. Temperature - molecules must collide with enough energy to react;
Rate collision energy temperature
4. The use of a catalyst.
16-6
Figure 16.3 The effect of surface area on reaction rate.
16-7
Figure 16.4 Collision energy and reaction rate.
16-8
Expressing the Reaction Rate
reaction rate - changes in the concentrations of reactants or
products per unit time
reactant concentrations decrease while product concentrations
increase
rate of reaction = -
for A B
change in concentration of A
change in time
= -
conc A
2
-conc A
1

t
2
-t
1

(conc A)
-
t
16-9
Table 16.1 Concentration of O
3
at Various Time in its
Reaction with C
2
H
4
at 303K
C
2
H
4
(g) + O
3
(g) C
2
H
4
O(g) + O
2
(g)
Time (s)
Concentration of O
3
(mol/L)
0.0
20.0
30.0
40.0
50.0
60.0
10.0
3.20x10
-5

2.42x10
-5

1.95x10
-5

1.63x10
-5

1.40x10
-5

1.23x10
-5

1.10x10
-5

(conc A)
-
t
The rate over the entire 60.0 s (or average rate) is the
total change in concentration divided by the change in time.
16-10
Figure 16.5
The concentrations of O
3
vs. time during its reaction with C
2
H
4

C
2
H
4
(g) + O
3
(g) C
2
H
4
O(g) + O
2
(g)
-
[C
2
H
4
]
t
rate =
-
[O
3
]
t
=
The slope of a line tangent
to the curve at a particular point
gives the instantaneous rate
at that time.

To avoid complications with
the reverse reaction we often
measure the initial rate.
16-11
Figure 16.6 Plots of [C
2
H
4
] and [O
2
] vs. time.
Tools of the
Laboratory
The equation coefficients are identical so the curve shapes are also identical.
16-12
In general, for the reaction
aA + bB cC + dD
rate =
1
a
- = -
[A]
t
1
b
[B]
t
1
c
[C]
t
= +
1
d
[D]
t
= +
The numerical value of the rate depends upon the substance that
serves as the reference. The rest is relative to the balanced
chemical equation.
16-13
Sample Problem 16.1
PLAN:
SOLUTION:
Expressing Rate in Terms of Changes in
Concentration with Time
PROBLEM: Because it has a nonpolluting product (water vapor), hydrogen
gas is used for fuel aboard the space shuttle and may be used
by Earth-bound engines in the near future.
2H
2
(g) + O
2
(g) 2H
2
O(g)
(a) Express the rate in terms of changes in [H
2
], [O
2
], and [H
2
O] with time.
(b) When [O
2
] is decreasing at 0.23 mol/L*s, at what rate is [H
2
O]
increasing?
Choose [O
2
] as a point of reference since its coefficient is 1. For every
molecule of O
2
which disappears, 2 molecules of H
2
disappear and 2
molecules of H
2
O appear, so [O
2
] is disappearing at half the rate of
change of H
2
and H
2
O.
-
1
2
[H
2
]
t
= -
[O
2
]
t
= +
[H
2
O]
t
1
2
0.23mol/L*s = +
[H
2
O]
t
1
2
; = 0.46mol/L*s
[H
2
O]
t
rate =
(a)
[O
2
]
t
- = - (b)
16-14
The rate law expresses the rate as a function of
reactant concentrations, product concentrations and
temperature.
Only considering the reactants:
Rate = k [A]
m
[B]
n
k or rate constant, is specific for a given reaction at a
given temperature.
k does change with temperature.
m and n are reaction orders and defined how the rate
is affected by reactant concentration.
KEY POINT rate, reaction orders, and rate
constant are found by experiment.
THE RATE LAW AND ITS COMPONENTS
16-15
Sample Problem 16.2
SOLUTION:
Determining Reaction Order from Rate Laws
PROBLEM: For each of the following reactions, determine the reaction order
with respect to each reactant and the overall order from the
given rate law.
(a) 2NO(g) + O
2
(g) 2NO
2
(g); rate = k[NO]
2
[O
2
]
(b) CH
3
CHO(g) CH
4
(g) + CO(g); rate = k[CH
3
CHO]
3/2

(c) H
2
O
2
(aq) + 3I
-
(aq) + 2H
+
(aq) I
3
-
(aq) + 2H
2
O(l); rate = k[H
2
O
2
][I
-
]
PLAN: Look at the rate law and not the coefficients of the chemical reaction.
(a) The reaction is 2nd order in NO, 1st order in O
2
, and 3rd order overall.
(b) The reaction is 3/2 order in CH
3
CHO and 3/2 order overall.
(c) The reaction is 1st order in H
2
O
2
, 1st order in I
-
and zero order in H
+
,
while being 2nd order overall.
16-16
Table 16.2 Initial Rates for a Series of Experiments in the
Reaction Between O
2
and NO
Experiment
Initial Reactant
Concentrations (mol/L)
Initial Rate
(mol/L*s)
1
2
3
4
5
O
2
NO
1.10x10
-2
1.30x10
-2
3.21x10
-3

1.10x10
-2
3.90x10
-2
28.8x10
-3

2.20x10
-2

1.10x10
-2

3.30x10
-2

1.30x10
-2

2.60x10
-2

1.30x10
-2

6.40x10
-3

12.8x10
-3

9.60x10
-3

2NO(g) + O
2
(g) 2NO
2
(g)
16-17
Determining Reaction Orders
Using initial rates -
Run a series of experiments, each of which starts with a different
set of reactant concentrations, and from each obtain an initial rate.
See Table 16.2 for data on the reaction
O
2
(g) + 2NO(g) 2NO
2
(g) rate = k [O
2
]
m
[NO]
n

Compare 2 experiments in which the concentration of one reactant
varies and the concentration of the other reactant(s) remains constant.
k [O
2
]
2
m
[NO]
2
n

k [O
2
]
1
m
[NO]
1
n

=
rate
2

rate
1

=
[O
2
]
2
m

[O
2
]
1
m

=
6.40x10
-3
mol/L*s
3.21x10
-3
mol/L*s
[O
2
]
2

[O
2
]
1

m
=
1.10x10
-2
mol/L
2.20x10
-2
mol/L
m
; 2 = 2
m
m = 1
Do a similar calculation for the other reactant(s).
16-18
Sample Problem 16.3
PLAN:
SOLUTION:
Determining Reaction Order from Initial Rate Data
PROBLEM: Many gaseous reactions occur in a car engine and exhaust
system. One of these is
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
rate = k[NO
2
]
m
[CO]
n

Use the following data to determine the individual and overall reaction orders.
Experiment Initial Rate(mol/L*s) Initial [NO
2
] (mol/L) Initial [CO] (mol/L)
1
2
3
0.0050
0.080
0.0050
0.10
0.10
0.40
0.10
0.10
0.20
Solve for each reactant using the general rate law using the
method described previously.
rate = k [NO
2
]
m
[CO]
n

First, choose two experiments in which [CO] remains
constant and the [NO
2
] varies.
16-19
Sample Problem 16.3 Determining Reaction Order from Initial Rate Data
continued
0.080
0.0050
rate 2
rate 1
[NO
2
]

2

[NO
2
]

1
m
=
k [NO
2
]
m
2
[CO]
n
2

k [NO
2
]
m
1
[CO]
n
1
=
0.40
0.10
=
m
; 16 = 4
m
and m = 2
k [NO
2
]
m
3
[CO]
n
3

k [NO
2
]
m
1
[CO]
n
1
[CO]

3

[CO]

1
n
=
rate 3
rate 1
=
0.0050
0.0050
=
0.20
0.10
n
; 1 = 2
n
and n = 0
The reaction is
2nd order in NO
2
.
The reaction is
zero order in CO.
rate = k [NO
2
]
2
[CO]
0
= k [NO
2
]
2

16-20
Reaction orders
Reaction orders cannot be deduced from the
balanced equation.
Reaction orders must be determined from rate
data.
Reaction orders are usually positive integers or
zero, but they can also be fractional or
negative
16-21
NOW WE CONSIDER THE TIME FACTOR.
HOW LONG WILL IT TAKE FOR X
MOLES/L OF A TO BE USED UP?
WHAT IS THE CONCENTRATION OF A
AFTER Y MINUTES OF REACTION?
INTEGRATED RATE LAWS: CONCENTRATION CHANGES
OVER TIME
16-22
Integrated Rate Laws
rate = -
[A]
t
= k [A]
rate = -
[A]
t
= k [A]
0

rate = -
[A]
t
= k [A]
2

first order rate equation
second order rate equation
zero order rate equation
ln
[A]
0
[A]
t
= - kt ln [A]
0
= -kt + ln [A]
t

1
[A]
t

1
[A]
0

- = kt
1
[A]
t

1
[A]
0

+ = kt
[A]
t
- [A]
0
= - kt
16-23
Table 16.3 Units of the Rate Constant k for Several Overall
Reaction Orders
Overall Reaction Order Units of k (t in seconds)
0 mol/L*s (or mol L
-1
s
-1
)
1 1/s (or s
-1
)
2 L/mol*s (or L mol
-1
s
-1
)
3 L
2
/ mol
2
*s (or L
2
mol
-2
s
-1
)
16-24
Sample Problem 16.4
PLAN:
SOLUTION:
Determining Reaction Concentration at a Given Time
PROBLEM: At 1000
0
C, cyclobutane (C
4
H
8
) decomposes in a first-order
reaction, with the very high rate constant of 87s
-1
, to two
molecules of ethylene (C
2
H
4
).
(a) If the initial C
4
H
8
concentration is 2.00M, what is the
concentration after 0.010 s?
(b) What fraction of C
4
H
8
has decomposed in this time?
Find the [C
4
H
8
] at time, t, using the integrated rate law for a 1st order
reaction. Once that value is found, divide the amount decomposed by
the initial concentration.
; ln
2.00
[C
4
H
8
]
= (87s
-1
)(0.010s)
[C
4
H
8
] = 0.83mol/L
ln
[C
4
H
8
]
0

[C
4
H
8
]
t

= kt
(a)
(b) [C
4
H
8
]
0
- [C
4
H
8
]
t
[C
4
H
8
]
0
=
2.00M - 0.87M
2.00M
= 0.58
16-25
Figure 16.7 Integrated rate laws and reaction order
ln[A]
t
= -kt + ln[A]
0

1/[A]
t
= kt + 1/[A]
0

[A]
t
= -kt + [A]
0

16-26
Figure 16.8
Graphical determination of the reaction order for the
decomposition of N
2
O
5
.
16-27
Figure 16.9 A plot of [N
2
O
5
] vs. time for three half-lives.
t
1/2
=
for a first-order process
ln 2
k
0.693
k
=
During each half life, the concentrations is halved.
16-28
Sample Problem 16.5
PLAN:
SOLUTION:
Determining the Half-Life of a First-Order Reaction
PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its
60
0
bond angles allow poor orbital overlap, its bonds are weak.
As a result, it is thermally unstable and rearranges to propene at
1000
0
C via the following first-order reaction:
CH
2
H
2
C CH
2
(g)

H
3
C CH CH
2
(g)
The rate constant is 9.2s
-1
, (a) What is the half-life of the reaction? (b) How
long does it take for the concentration of cyclopropane to reach one-quarter of
the initial value?
Use the half-life equation, t
1/2
=
0.693
k
, to find the half-life.
One-quarter of the initial value means two half-lives have passed.
t
1/2
= 0.693/9.2s
-1
= 0.075s (a) 2 t
1/2
= 2(0.075s) = 0.150s (b)
16-29
Table 16.4 An Overview of Zero-Order, First-Order, and
Simple Second-Order Reactions
Zero Order First Order Second Order
Plot for straight line
Slope, y-intercept
Half-life
Rate law
rate = k
rate = k [A] rate = k [A]
2

Units for k
mol/L*s
1/s L/mol*s
Integrated rate law in
straight-line form
[A]
t
=
k t + [A]
0

ln[A]
t
=
-k t + ln[A]
0

1/[A]
t
=
k t + 1/[A]
0

[A]
t
vs. t
ln[A]
t
vs. t 1/[A]
t
= t
k, [A]
0

-k, ln[A]
0

k, 1/[A]
0

[A]
0
/2k ln 2/k 1/k [A]
0

16-30
Figure 16.10 Dependence of the rate constant on temperature
16-31
The Arrhenius Equation
The Effect of Temperature on Reaction Rate
ln k = ln A - E
a
/RT
ln
k
2

k
1

=
E
a

RT
-
1
T
2

1
T
1

-
where k is the kinetic rate constant at T
E
a
is the activation energy
R is the energy gas constant
T is the Kelvin temperature
A is the collision frequency factor
16-32
Figure 16.11 Graphical determination of the activation energy
ln k = -E
a
/R (1/T) + ln A
16-33
Sample Problem 16.6
PLAN:
SOLUTION:
Determining the Energy of Activation
PROBLEM: The decomposition of hydrogen iodide,
2HI(g) H
2
(g) + I
2
(g)
has rate constants of 9.51x10
-9
L/mol*s at 500. K and 1.10x10
-5
L/mol*s at 600. K. Find E
a
.
Use the modification of the Arrhenius equation to find E
a
.
ln
k
2

k
1

=
E
a

-
R
1
T
2

1
T
1

-
E
a
= - R ln
k
2

k
1

1
T
2

1
T
1

-
-1
1
600K
1
500K
-
ln
1.10x10
-5
L/mol*s
9..51x10
-9
L/mol*s
E
a
= - (8.314J/mol*K)
E
a
= 1.76x10
5
J/mol = 176 kJ/mol
16-34
Figure 16.12
Information sequence to determine the kinetic parameters of a reaction.
Series of plots
of concentra-
tion vs. time
Initial
rates
Reaction
orders
Rate constant
(k) and actual
rate law
Integrated
rate law
(half-life,
t
1/2
)
Rate constant
and reaction
order
Activation
energy, E
a

Plots of
concentration
vs. time
Find k at
varied T
Determine slope
of tangent at t
0
for
each plot
Compare initial
rates when [A]
changes and [B] is
held constant and
vice versa
Substitute initial rates,
orders, and concentrations
into general rate law:
rate = k [A]
m
[B]
n

Use direct, ln or
inverse plot to
find order
Rearrange to
linear form and
graph
Find k at
varied T
16-35

16-36
Figure 16.13
The dependence of possible collisions on the product
of reactant concentrations.
A
A
B
B
A
A
B
B
A
4 collisions
Add another
molecule of A
6 collisions
Add another
molecule of B
A
A
B
B
A B
16-37
Table 16.5 The Effect of E
a
and T on the Fraction (f) of Collisions
with Sufficient Energy to Allow Reaction
E
a
(kJ/mol) f (at T = 298 K)
50 1.70x10
-9

75 7.03x10
-14

100 2.90x10
-18

T f (at E
a
= 50 kJ/mol)
25
0
C(298K) 1.70x10
-9

35
0
C(308K) 3.29x10
-9

45
0
C(318K) 6.12x10
-9

Notice the fraction nearly doubles for a 10C increase.
Doubling the fraction doubles the rate constant, which
doubles the reaction rate
16-38
Figure 16.14
The effect of temperature on the distribution of collision energies
16-39
Figure 16.15 Energy-level diagram for a reaction
REACTANTS
PRODUCTS
ACTIVATED STATE
C
o
l
l
i
s
i
o
n

E
n
e
r
g
y

C
o
l
l
i
s
i
o
n

E
n
e
r
g
y

E
a (forward)

E
a (reverse)

The forward reaction is exothermic because the
reactants have more energy than the products.
16-40
Figure 16.16
An energy-level diagram of the fraction of collisions
exceeding E
a
.
The larger the Ea the smaller the k and the slower the reaction.
16-41
Figure 16.17
The importance of molecular orientation to an effective collision.
NO + NO
3
2 NO
2

A is the frequency factor
A = pZ where
Z is the collision frequency
p is the orientation probability factor
16-42
Figure 16.18
Nature of the transition state in the reaction between CH
3
Br and OH
-
.
CH
3
Br + OH
-
CH
3
OH + Br
-

transition state or activated complex
16-43
Figure 16.19 Reaction energy diagram for the reaction of CH
3
Br and OH
-
.
16-44
Figure 16.20
Reaction energy diagrams and possible transition states.
16-45
Reaction progress
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y
Sample Problem 16.7
SOLUTION:
Drawing Reaction Energy Diagrams and
Transition States
PROBLEM: A key reaction in the upper atmosphere is
O
3
(g) + O(g) 2O
2
(g)
The E
a(fwd)
is 19 kJ, and the H
rxn
for the reaction is -392 kJ. Draw a
reaction energy diagram for this reaction, postulate a transition state, and
calculate E
a(rev)
.
PLAN: Consider the relationships among the reactants, products and
transition state. The reactants are at a higher energy level than the
products and the transition state is slightly higher than the
reactants.
O
3
+O
2O
2
E
a
= 19kJ
H
rxn
= -392kJ
E
a(rev)
= (392 + 19)kJ =
411kJ
transition state
16-46
Most of the reactions occur through a reaction
mechanism, a sequence of single reaction steps
that sum to the overall reaction.
Reaction intermediates do not appear in the
overall balanced equation. They are molecules
with normal bonds and are sometimes stable
enough to isolated.
REACTION MECHANISMS
16-47
Table 16.6 Rate Laws for General Elementary Steps
Elementary Step Molecularity Rate Law
A product
2A product
A + B product
2A + B product
Unimolecular
Bimolecular
Bimolecular
Termolecular
Rate = k [A]
Rate = k [A]
2

Rate = k [A][B]
Rate = k [A]
2
[B]
REACTION MECHANISMS
Elementary steps each describes a single molecular event.
16-48
Sample Problem 16.8
PLAN:
SOLUTION:
Determining Molecularity and Rate Laws for
Elementary Steps
PROBLEM: The following two reactions are proposed as elementary steps in
the mechanism of an overall reaction:
(1) NO
2
Cl(g) NO
2
(g) + Cl

(g)
(2) NO
2
Cl(g) + Cl

(g) NO
2
(g) + Cl
2
(g)
(a) Write the overall balanced equation.
(b) Determine the molecularity of each step.
(a) The overall equation is the sum of the steps.
(b) The molecularity is the sum of the reactant particles in the step.
2NO
2
Cl(g) 2NO
2
(g) + Cl
2
(g)
(c) Write the rate law for each step.
rate
2
= k
2
[NO
2
Cl][Cl]
(1) NO
2
Cl(g) NO
2
(g) + Cl

(g)
(2) NO
2
Cl(g) + Cl

(g) NO
2
(g) + Cl
2
(g)
(a)
Step(1) is unimolecular.
Step(2) is bimolecular.
(b)
rate
1
= k
1
[NO
2
Cl] (c)
16-49
The Rate-Determining Step of a Reaction Mechanism
The overall rate of a reaction is related to the rate of the
slowest, or rate-determining step.
Correlating the Mechanism with the Rate Law
The elementary steps must add up to the overall equation.
The elementary steps must be physically reasonable.
The mechanism must correlated with the rate law.
16-50
Figure 16.21
Reaction energy diagram for the two-step reaction of NO
2
and F
2
.
16-51
If the rate-limiting step in a mechanism is not
the initial step, it acts as a bottleneck later in
the reaction sequence.
The product of the fast initial step accumulates
and starts reverting to reactant, while waiting
for the slow step to remove it. (equilibrium)
Mechanism with a fast initial step
16-52
Lets consider the oxidation of nitric oxide.
2NO
(g)
+ O
2(g)
2NO
2(g)

NO
(g)
+ O
2(g)
NO
3(g) fast, reversible

NO
3(g)
+ NO
(g)
2NO
2(g) slow, rate determining

An overall rate law can include only
reactants (and products).
16-53
Thus to test the validity of a mechanism with a
fast initial, reversible step:
1. Write rate laws for both directions of the fast step and for
the slow step.
2. Show the slow steps rate law is equivalent to the overall
rate law, by expressing intermediate in terms of reactant:
set the forward rate law of the fast, step equal to the
reverse rate law, and solve for intermediate.
1. Substitute the expression for [intermediate] into the rate law
for the slow step to obtain the overall rate law.

Make sure you do 16.72 and 16.73
16-54
CATALYSTS
Each catalyst has its own specific way of functioning.
In general a catalyst lowers the energy of activation.
Lowering the E
a
increases the rate constant, k, and
thereby increases the rate of the reaction
A catalyst increases the rate of the forward AND the
reverse reactions.
A catalyzed reaction yields the products more quickly,
but does not yield more product than the uncatalyzed
reaction.
A catalyst lowers E
a
by providing a different mechanism,
for the reaction through a new, lower energy pathway.
16-55
Figure 16.22
Reaction energy diagram of a catalyzed and an uncatalyzed process.
16-56
Figure 16.23
Mechanism for the catalyzed hydrolysis of an organic ester.
H
+
+
R C
O
O
R'
R C
O
O
R'
H
fast
R C
O
O
R'
H
R C
O
O
R'
H
R C
O
O
R'
H
resonance hybrid
resonance forms
R C
O
O
R'
H
H
O H R C
O
O
R'
H
H
O H
slow, rate-
determining
step
R C
O
OH
R'
H
+
O H
all fast
16-57
16-58
Figure 16.24 The metal-catalyzed hydrogenation of ethylene
H
2
C CH
2
(g) + H
2
(g) H
3
C CH
3
(g)
16-59
Figure 16.24
16-60
Figure B16.4
The widely separated amino acid groups that form an active site.
16-61
Figure B16.5
Two models of enzyme action

Kinetics Short

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