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CHM096
CHAPTER 2
CHEMICAL
KINETICS
1
TOPICS
2.1 Rate of Chemical Reactions
2.2 Rate Laws
2.3 Integrated Rate Laws
2.4 Collision Theory, Transition State Theory,
Activation Energy and Factors Controlling
Rates of Reactions
2.5 Arrhenius Equation
2.6 Reaction Mechanisms and Rate
Determining Step
2
TOPIC
RATE OF CHEMICAL REACTIONS
3
2.1 RATE OF CHEMICAL REACTIONS
Introduction
Rate = Δ [concentration]
Δ time
Rate = Δ [products] = - Δ [reactants]
Δ time Δ time
5
2.1 RATE OF CHEMICAL REACTIONS
at t = 0 at t = 0
[A] = 8 [X] = 8
[B] = 8 [Y] = 8
[C] = 0 [Z] = 0
at t = 16 at t = 16
[A] = 4 [X] = 7
[B] = 4 [Y] = 7
[C] = 4 [Z] = 1
6
2.1 RATE OF CHEMICAL REACTIONS
Average Rate
• The average rate is the change in measured
concentrations in any particular time period
– linear approximation of a curve
8
2.1 RATE OF CHEMICAL REACTIONS
C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl (aq)
12
2.1 RATE OF CHEMICAL REACTIONS
13
2.1 RATE OF CHEMICAL REACTIONS
Stoichiometry
C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl (aq)
-[C4H9Cl] [C4H9OH]
Rate = t = t
14
2.1 RATE OF CHEMICAL REACTIONS
Stoichiometry
What if the ratio is not 1:1?
16
2.1 RATE OF CHEMICAL REACTIONS
Stoichiometry
aA + b B cC + d D
17
2.1 RATE OF CHEMICAL REACTIONS
Example 1
Write the rate expressions for the following reactions in
terms of the disappearance of the reactants and the
appearance of the products:
18
2.1 RATE OF CHEMICAL REACTIONS
Answer to Example 1
Strategy To express the rate of the reaction in terms of
the change in concentration of a reactant or product with
time, we need to use the proper sign (minus or plus) and
the reciprocal of the stoichiometric coefficient.
Solution
(a) Because each of the stoichiometric coefficients equals
1,
19
2.1 RATE OF CHEMICAL REACTIONS
Example 2
20
2.1 RATE OF CHEMICAL REACTIONS
Answer to Example 2
22
2.1 RATE OF CHEMICAL REACTIONS
Answer to Example 3
23
2.1 RATE OF CHEMICAL REACTIONS
Exercise 1
Because it has a nonpolluting product (water vapor),
hydrogen gas is used for fuel aboard the space shuttle
and may be used by earthbound engines in the near
future.
2H2(g) + O2(g) 2H2O(g)
24
2.1 RATE OF CHEMICAL REACTIONS
Exercise 2
25
2.1 RATE OF CHEMICAL REACTIONS
Exercise 3
26
TOPIC
RATE LAWS
27
2.2 RATE LAWS
28
2.2 RATE LAWS
• The exponent on each reactant in the rate law is
called the order with respect to that reactant
• The sum of the exponents on the reactants is called
the overall order of the reaction
• The rate law for the reaction given:
30
2.2 RATE LAWS
The Order of a Reaction
A reaction has an individual order “with respect
to” or “in” each reactant, and an overall order,
the sum of the individual orders.
Rate = k[A]n
32
2.2 RATE LAWS
Finding the Rate Law: The Initial Rate Method
36
Plots of reactant concentration, [A], vs. time for
first-, second-, and zero-order reactions.
37
Plots of rate vs. reactant concentration, [A],
for first-, second-, and zero-order reactions.
38
2.2 RATE LAWS
Finding the Rate Law: The Initial Rate Method
Determining the Rate Law when there are Multiple
Reactants
• Changing each reactant will effect the overall rate of
the reaction
• By changing the initial concentration of one reactant
at a time, the effect of each reactant’s concentration
on the rate can be determined
• In examining results, we compare differences in rate
for reactions that only differ in the concentration of
one reactant
39
2.2 RATE LAWS
Individual and Overall Reaction Orders
NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)
40
2.2 RATE LAWS
Individual and Overall Reaction Orders
42
2.2 RATE LAWS
Individual and Overall Reaction Orders
Consider the reaction between NO and O2. From the
experiment, the results showed that;-
2 NO (g) + O2 (g) 2 NO2 (g)
Rate = k[NO]2[O2]
The reaction is:
second order with respect to [NO],
first order with respect to [O2],
and third order overall.
43
2.2 RATE LAWS
Individual and Overall Reaction Orders
The decomposition of ammonia on a platinum surface at
856oC is a zero order reaction
NH3 (g) 1/2 N2 + 3/2 H2 (g)
Rate = k[NH3]0 = k
The reaction rate is independent of NH3 concentration
44
2.2 RATE LAWS
Concentration and Rate
One can gain information about the rate of a reaction by
seeing how the rate changes with changes in
concentration (with the temperature held constant).
• The rate law of a reaction is the mathematical
relationship between the rate of the reaction and the
concentrations of the reactants
and homogeneous catalysts as well
• The rate law must be determined experimentally!!
• The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
45
2.2 RATE LAWS
Effect of Concentration and Reaction Rate
Consider, the decomposition of N2O5 to NO2 and O2.
N2O5 2NO2 + ½ O2
[N2O5] Rates (M.min-1)
0.17 0.00080
0.34 0.0014
0.68 0.0028
48
2.2 RATE LAWS
Rate Constant
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
49
2.2 RATE LAWS
Rate Constant
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
rate α [Br2]
rate = k [Br2]
rate
k=
[Br2]
k = rate constant
= 3.50 x 10-3 s-1
Knowing the k allow you to calculate the rate at a particular
concentration. The units of k depends on the rate law or order of
reaction for a particular reaction- next slide will discussed further. 50
2.2 RATE LAWS
The Unit of Rate Constant
Reaction rates have units of mol/L.time when
concentrations are given as moles per liter.
51
2.2 RATE LAWS
Example 4
52
2.2 RATE LAWS
Answer to Example 4
PLAN:
Look at the rate law and not the coefficients of the
chemical reaction.
SOLUTION:
The reaction is 1st order in H2O2, 1st order in I- and zero
order in H+, while being 2nd order overall.
53
2.2 RATE LAWS
Example 5
54
2.2 RATE LAWS
Answer to Example 5
Given: [NO] = 1.00 x 10 −6 M, [O3] = 3.00 x 10−6 M,
Find: k, M−1s−1
55
2.2 RATE LAWS
Example 6
56
2.2 RATE LAWS
Answer to Example 6
57
2.2 RATE LAWS
Example 7
Determine the rate law and rate constant for the reaction
NO2(g) + CO(g) NO(g) + CO2(g)
given the data below
58
2.2 RATE LAWS
Answer to Example 7
59
2.2 RATE LAWS
Answer to Example 7
60
2.2 RATE LAWS
Answer to Example 7
61
2.2 RATE LAWS
Answer to Example 7
62
2.2 RATE LAWS
Origins of Organic Chemistry
Answer to Example 7
Foundations of organic chemistry from mid-1700’s.
63
2.2 RATE LAWS
Origins of Organic Chemistry
Answer to Example 7
Foundations of organic chemistry from mid-1700’s.
64
2.2 RATE LAWS
Origins of Organic Chemistry
Answer to Example 7
Foundations
Substitute theof organic chemistry from mid-1700’s.
Expt. Initial Initial Rate
Initial
concentrations Number [NO2], (M) [CO], (M) (M/s)
Compounds
and rate for obtained from plants, animals hard to isolate, and
any purify.
experiment 1. 0.10 0.10 0.0021
into the rate 2. 0.20 0.10 0.0082
Compounds
law and solvealso decomposed more easily.
3. 0.20 0.20 0.0083
for k
Torben Bergman (1770) 4. first to make
0.40 distinction
0.10between0.033
organic
Rateand k[NO
inorganic
2
]2
chemistry.
for expt 1
It was thought that organic compounds must contain some “vital
k 0.10 they
M were from living sources.
2
M because
force”
0.0021 s
0.0021 Ms 1 1
k 0.21 M s
0.01 M2 65
2.2 RATE LAWS
Origins of Organic Chemistry
Example 8
Foundations
Determine of organic
the chemistry
rate law from
and rate mid-1700’s.
constant for the reaction
NH4+ + NO2− N2 + 2 H2O
Compounds obtained from plants, animals hard to isolate, and
purify. given the data below
66
2.2 RATE LAWS
Origins of Organic Chemistry
Answer to Example 8
67
2.2 RATE LAWS
Origins of Organic Chemistry
Answer to Example 8
68
2.2 RATE LAWS
Origins of Organic Chemistry
Answer to Example 8
Rate = k[NH4+]n[NO2]m
Foundations of organic chemistry from mid-1700’s.
69
2.2 RATE LAWS
Exercise 4
Ammonia decomposes to nitrogen and hydrogen gases
at ToC. The rate of decomposition is first order with
respect to ammonia.
70
2.2 RATE LAWS
Exercise 5
2A A2
71
2.2 RATE LAWS
Exercise 6
Determine
Compounds the
also rate law andmore
decomposed evaluate
easily. the rate constant
from the experimental data.
Torben BergmanInitial
Experiment
(1770) first to make
[CH3Br]
distinction between
Initial [OH-]
organic
Initial Rate
and inorganic chemistry.
(M) (M) (M/s)
1 0.050 0.010 2.4 x 10-3
It was thought that organic compounds must contain some -3“vital
2 because they
force” 0.080 0.020
were from living sources. 7.7 x 10
3 0.080 0.010 3.8 x 10-3
73
2.2 RATE LAWS
Origins of Organic
Exercise 8
Chemistry
Consider the reaction X + Y Z
Foundations of organic chemistry from mid-1700’s.
These data are obtained are 360 K
Compounds obtained from plants, animals hard to isolate, and
Exp
purify. Initial Rate (M/s) [X] [Y]
1 0.147 0.10 0.50
Compounds
2 also decomposed
0.127 more easily. 0.20 0.30
3 4.064 0.40 0.60
Torben 4Bergman (1770)1.016
first to make distinction
0.20 between organic
0.60
and inorganic chemistry.
5 0.508 0.40 0.30
It was thought that organic compounds must contain some “vital
a) Determine thethey
force” because order of from
were the reaction
living sources.
b) Determine the initial rate of disappearance of X when
the concentration of X is 0.30 M and Y is 0.40 M
74
2.2 RATE LAWS
Exercise 9
The rate of reaction between bromate ions and bromide ions in acidic
aqueous solution in terms of changes in concentration of reactants and
products is given below
Rate = - ∆[BrO-3] = -1/5 ∆[Br-] = -1/6∆[H+] = 1/3∆[Br2] = 1/3 ∆[H2O]
∆t ∆t ∆t ∆t ∆t
The data from 4 experiments are listed in table below
76
2.3 INTEGRATED RATE LAWS
Origins of OrganicRelationships:
Concentration-Time Chemistry
Integrated Rate Laws
Foundations of organic chemistry from mid-1700’s.
The rate laws only tell us the rate or concentration at a
given instant
Compounds allowing
obtained from us to find
plants, the hard
animals “How to fast”
isolate,isand
the
purify. proceeding at the moment [reactants] are
reaction
mixed.
Compounds also decomposed more easily.
It is important
Torben to know
Bergman (1770) first “how
to makelong” a reaction
distinction must
between organic
proceed to reach
and inorganic a predetermined concentration of
chemistry.
some reactant of product, or what the reactant and
Itproduct concentrations
was thought will be after
that organic compounds mustsome time
contain has
some “vital
elapsed- therefore
force” because integrated
they were ratesources.
from living laws will employ
77
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Zero Order Reactions
Using calculus
Foundations to integrate
of organic the rate
chemistry from law for a zero-order
mid-1700’s.
process gives us
Compounds obtained from plants, animals hard to isolate, and
purify.
[A]t = −kt + [A]0
Where also decomposed more easily.
Compounds
[A]0 is the initial concentration of A, and
Torben Bergman (1770) first to make distinction between organic
[A]tand inorganic
is the chemistry. of A at some time, t, during the
concentration
course of the reaction.
It was thought that organic compounds must contain some “vital
force” because they were from living sources.
78
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Zero Order Reactions
Foundations of organic chemistry from mid-1700’s.
• Rate = k[A]0 = k
• Compounds
Integrated
purify.
obtained
rate from
law: plants,
[A] = − k
animalst hard
+ [A]to isolate, and
initial
• Graph of [A] vs. time is straight line with slope
= −k andalso
Compounds y–intercept
decomposed = [A]easily.
more initial
79
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Zero Order Reactions
Foundations of organic chemistry from mid-1700’s.
time
80
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Half Life for Zero Order Reactions
Foundations of organic chemistry from mid-1700’s.
• Integrated rate law: [A]t = −kt + [A]0
• Compounds
= [A]t obtained
t ½purify. = ½ [A]from
0
plants, animals hard to isolate, and
½[A]0 = -k
• Compounds alsot ½ + [A]0 more easily.
decomposed
t ½ = [A
• Torben ]/2k
Bergman = [A
(1770)0 firstkto make distinction between organic
]/2
0
and inorganic chemistry.
• ItWhen Ratethat
was thought = M/sec, k = M/sec
organic compounds must contain some “vital
force” because they were from living sources.
81
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Integrated Rate Laws : First-Order Reactions
Foundations of organic chemistry from mid-1700’s.
Using calculus to integrate the rate law for a first-order
process gives us
Compounds obtained from plants, animals hard to isolate, and
purify. [A] t
ln = −k t
[A] 0
Compounds also decomposed more easily.
TorbenWhere
Bergman (1770) first to make distinction between organic
and inorganic chemistry.
[A]0 is the initial concentration of A, and
It was thought that organic compounds must contain some “vital
[A]t force”
is the because
concentration
they wereoffrom
A atliving
some time, t, during the
sources.
course of the reaction.
82
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Integrated Rate Laws : First-Order Reactions
Foundations ofthis
Manipulating organic chemistry
equation from mid-1700’s.
produces…
[A]
Compounds obtained from plants, animals hard to isolate, and
t
purify. ln = −k t
[A]0
Compounds also decomposed more easily.
ln [A]t − ln [A]0 = − kt
Torben Bergman (1770) first to make distinction between organic
and inorganic chemistry.
ln [A]t = − kt + ln [A]0
It was thought that organic compounds must contain some “vital
…which is in thethey
force” because formwere from living sources.
y = mx + b
83
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Integrated Rate Laws : First-Order Reactions
Foundations of organic chemistry from mid-1700’s.
• Rate = k[A]1 = k[A]
Compounds obtained from plants, animals hard to isolate, and
• ln[A] t = −kt + ln[A]0
purify.
• Graph ln[A] vs. time gives straight line with
Compounds also decomposed more easily.
slope = −k and y–intercept = ln[A]0
– used
Torben to determine
Bergman (1770) first tothe rate
make constant
distinction between organic
and inorganic chemistry.
84
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Integrated Rate Laws : First-Order Reactions
Foundations of organic chemistry from mid-1700’s.
ln[A]0
Compounds obtained from plants, animals hard to isolate, and
purify.
time 85
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Half-Life
•Foundations of organic
The half-life, t1/2chemistry from mid-1700’s.
, of a reaction is the time it
takes for the concentration of the reactant
Compounds obtained from plants, animals hard to isolate, and
to
fall to ½ its initial value
purify.
• The half-life of the reaction depends on the
Compounds also decomposed more easily.
order of the reaction
Torben Bergman (1770) first to make distinction between organic
and inorganic chemistry.
86
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Half Life for First- Order
Foundations of organic chemistry from mid-1700’s.
• Integrated rate law : ln[A]t = −kt + ln[A]0
Compounds obtained from plants, animals hard to isolate, and
purify.
• t ½ = [A]t = ½ [A]0
Compounds also decomposed more easily.
• ln ½ [A]0 = −k t½ + ln[A]0
Torben Bergman (1770) first to make distinction between organic
• ln and
½ [A] 0 = −k chemistry.
inorganic t½
[A]0
It was thought that organic compounds must contain some “vital
• t½ force”
= 0.693/ k. The
because half-life
they of aliving
were from first sources.
order reaction is
constant
• When Rate = M/sec, k = s–1
87
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
The Half-Life of a First Order Reaction
is Constant
Foundations of organic chemistry from mid-1700’s.
88
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Rate Data for:
C4H9Cl +ofHorganic
Foundations 2O chemistryC 4H9mid-1700’s.
from OH + HCl
89
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
The Half-Life of a First Order Reaction
is Constant
Foundations of organic chemistry from mid-1700’s.
90
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
The Half-Life of a First Order Reaction
is Constant
Foundations of organic chemistry from mid-1700’s.
91
2.3 INTEGRATED RATE LAWS
Origins of of
The Half-Life Organic Chemistry
a First Order Reaction
is Constant
Foundations of organic chemistry from mid-1700’s.
92
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Second Order Reactions
Foundations of organic chemistry from mid-1700’s.
Using calculus to integrate the rate law for a Second-
order process
Compounds gives
obtained fromusplants, animals hard to isolate, and
purify.
1 1
= ktmore
Compounds also decomposed + easily.
[A]t [A]0
TorbenWhere
Bergman (1770) first to make distinction between organic
and inorganic chemistry.
[A]0 is the initial concentration of A, and
It was thought that organic compounds must contain some “vital
[A]t force”
is the because
concentration
they wereoffrom
A atliving
some time, t, during the
sources.
course of the reaction.
93
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Second Order Reactions
Foundations of organic chemistry from mid-1700’s.
• Rate = k[A] 2
1/[A]t = kobtained
• Compounds t + 1/[A]from
0 plants, animals hard to isolate, and
purify.
• Graph 1/[A] vs. time gives straight line with
slope = kalso
Compounds and y–intercept
decomposed = 1/[A]initial
more easily.
– used to determine the rate constant
Torben Bergman (1770) first to make distinction between organic
and inorganic chemistry.
94
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Second Order Reactions
Foundations of organic chemistry from mid-1700’s.
time 95
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Half Life for Second Order Reactions
Foundations of organic chemistry from mid-1700’s.
• Integrated Law: 1/[A] = kt + 1/[A]0
Compounds obtained from plants, animals hard to isolate, and
purify.
• t ½ = [A]t = ½ [A]0
Compounds also decomposed more easily.
• 1/ ½ [A]0 = k t½ + 1/[A]0
Torben Bergman (1770) first to make distinction between organic
and inorganic chemistry.
• t½ = 1/(k[A0])
It was thought that organic compounds must contain some “vital
force” because they were from living sources.
• When Rate = M/sec, k = M−1s−1
96
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Foundations of organic chemistry from mid-1700’s.
97
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Table 1 Units of the Rate Constant k
Foundations of organic chemistry from mid-1700’s.
Overall Reaction Order Units of k (t in seconds)
Compounds obtained from plants, animals hard to isolate, and
purify.
0 mol/L*s (or mol L-1 s-1)
Compounds also decomposed more easily.
1 1/s (or s-1)
Torben Bergman (1770) first to make distinction between organic
and inorganic chemistry.
2 L/mol*s (or L mol -1 s-1)
It was thought that organic compounds must contain some “vital
force” because they were from2living sources.
3 L / mol2 *s (or L2 mol-2 s-1)
98
2.3 INTEGRATED RATE LAWS
Origins of Organic
Example 9
Chemistry
Determining
Foundations the Half-Life
of organic of a First-Order
chemistry from mid-1700’s. Reaction
Cyclopropane is the smallest cyclic hydrocarbon. It is thermally
Compounds
unstable obtained from
and rearranges plants, at
to propene animals
1000oChard to isolate,
via the andfirst-
following
orderpurify.
reaction:
CH2
Compounds alsoHdecomposed
2C CH2 (g) more easily.
H3C CH CH2 (g)
100
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Example 10
Foundations of organic chemistry from mid-1700’s.
The reaction SO2Cl2(g) SO2(g) + Cl2(g) is first order with a
rate constant of 2.90 x 10 −4 s−1 at a given set of
Compounds obtained from plants, animals hard to isolate, and
conditions.
purify. Find the [SO2Cl2] at 865 s when [SO2Cl2]initial =
0.0225 M
Compounds also decomposed more easily.
Given: [SO2Cl2]init = 0.0225 M, t = 865, k = 2.90 x 10-4 s−1
Torben Bergman
Find: [SO(1770)
2Cl2]
first to make distinction between organic
and inorganic chemistry.
Conceptual Plan:
[SO2Cl2]init, t, k [SO2Cl2]
ItRelationships:
was thought that organic compounds must contain some “vital
force” because they were from living sources.
101
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Answer to Example 10
Foundations of organic chemistry from mid-1700’s.
Compounds
Solution:obtained from plants, animals hard to isolate, and
purify.
102
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Example 11
The reactionof
Foundations 2 R chemistry
Q organic is secondfromorder in Q. If the initial [Q]
mid-1700’s.
= 0.010 M and after 5.0 x 102 seconds the [Q] = 0.0010 M,
Compounds obtainedfind
fromthe rate animals
plants, constant
hard to isolate, and
purify.
103
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Answer to Example 11
Foundations
Given:of[Q]
organic= chemistry
0.010 M, t from
= 5.0 mid-1700’s.
x 102 s, [Q]t = 0.0010 M
init
Find:obtained
Compounds k from plants, animals hard to isolate, and
purify.
Conceptual
[Q]init, t, [Q]t k
Plan:also decomposed more easily.
Compounds
Relationships:
Torben Bergman (1770) first to make distinction between organic
and inorganic chemistry.
Solution:
It was thought that organic compounds must contain some “vital
force” because they were from living sources.
104
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Graphical Determination of the
Rate Law for A Product
Foundations of organic chemistry from mid-1700’s.
• Plots of [A] vs. time, ln[A] vs. time, and 1/[A] vs. time
Compounds obtained fromofplants,
allow determination animals
whether hard to isolate,
a reaction and
is zero,
purify.
first, or second order
Whichever
• Compounds plot
also gives a straight
decomposed line determines the
more easily.
order with respect to [A]
– if linear
Torben is (1770)
Bergman [A] vs.first
time, = k[A]0 between organic
Ratedistinction
to make
–and
if inorganic
linear is chemistry.
ln[A] vs. time, Rate = k[A]1
– if linear is 1/[A] vs. time, Rate = k[A]2
It was thought that organic compounds must contain some “vital
force” because they were from living sources.
105
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Example 12
Complete
Foundations of organicthe Table and
chemistry fromDetermine
mid-1700’s. the
Rate Equation for the Reaction A 2 Product
Compounds obtained from plants, animals hard to isolate, and
purify.
107
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700’s.
108
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700’s.
109
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700’s.
110
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700’s.
Conclusion for the determination of the
rate equation
Compounds obtainedfor
fromtheplants,
reaction A hard to2isolate,
animals Product and
purify.
Because the graph 1/[A] vs. time is linear, the
reaction is second order,
Compounds also decomposed more easily.
Rate k[A]2
k Bergman
Torben slope of(1770) firstto0.10
the line make –1 s –1
Mdistinction between organic
and inorganic chemistry.
111
2.3 INTEGRATED RATE LAWS
Origins of Organic Chemistry
Relationship Between Order and Half-Life
Foundations of organic chemistry from mid-1700’s.
• For a zero order reaction, the half-life is directly
proportional
Compounds to the
obtained initial
from concentration.
plants, animals hard toThe lower
isolate, andthe
initial
purify.concentration of the reactants, the shorter the
half-life
– t1/2 = [A]init
Compounds /2kdecomposed more easily.
also
• For a first order reaction, the half-life is independent of
the concentration.
Torben Bergman (1770) (t first = constant)
1/2 to make distinction between organic
= ln(2)/k chemistry.
t1/2inorganic
–and
• For a second order reaction, the half-life is inversely
It proportional
was thought that to organic
the initial concentration
compounds – increasing
must contain some “vital
the initial
force” concentration
because they were from shortens the half-life
living sources.
– t1/2 = 1/(k[A]init)
112
Exercise 10
113
Exercise 11
114
Exercise 12
Substance A reacts according to a first order rate law
with k = 5.0 x 10-5 s-1
115
Exercise 13
116
Try this- Test 1 Nov-Mac 2012
Origins of Organic Chemistry
The reaction between A2 and B2 at 277oC is 2nd order overall
Foundations of organic2A + B2 from mid-1700’s.
chemistry
2 2A2B
117
2.4 THEORIES OF CHEMICAL KINETICS
118
2.4 THEORIES OF CHEMICAL KINETICS
119
2.4 THEORIES OF CHEMICAL KINETICS
OriginsThe
of Collision
OrganicTheory
Chemistry
• Foundations
Moleculesofor organic
atoms chemistry
or ions from mid-1700’s.
can only react if they collide
Compounds
with eachobtained
other. from plants, animals hard to isolate, and
purify.
• In a chemical reaction,
bonds arealso
Compounds broken and new
decomposed more easily.
bonds are formed.
For aBergman
• Torben collision(1770)
to befirst to make distinction between organic
effective, thechemistry.
and inorganic reacting
molecules must have
It sufficient
was thoughtkinetic energy
that organic to
compounds must contain some “vital
force” because
overcome the they were from living sources.
energy
barrier.
120
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
The Collision Theory
The collision
Foundations theorychemistry
of organic developed
fromfrom kinetic theory to
mid-1700’s.
account for the effects of concentrations and
temperature
Compounds on reaction
obtained rates.
from plants, animals hard to isolate, and
purify.
The reaction
Compounds alsorate is measured
decomposed on effective collision.
more easily.
Any factor that increases the rate of effective collision
will also
Torben increase
Bergman the
(1770) rate
first of the
to make reaction.
distinction between organic
and inorganic chemistry.
The effective collision = (total collision frequency) X
(fraction of
It was thought that organic compounds molecules
must with“vital
contain some
force” because they weresufficient
from living sources.
energy)
121
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
Activation Energy
Foundations of organic chemistry from mid-1700’s.
• The activation energy, Ea is a minimum amount of
energy required to initiate reaction:
Compounds obtained from plants, animals hard to isolate, and
• Molecules
purify. must possess a certain minimum kinetic
energy called the activation energy for a reaction to
occur
Compounds also decomposed more easily.
energy needed to break the bonds of the reacting molecules
reaction
Torben with(1770)
Bergman low activation energy
first to make is easier between
distinction to take place, and
organic
isand
faster
inorganic chemistry.
122
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
The Collision Theory
Furthermore,
Foundations molecules
of organic must
chemistry collide
from with the correct
mid-1700’s.
orientation and with enough energy to cause bond
breakage obtained
Compounds and formation.
from plants, animals hard to isolate, and
purify.
123
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
Activation Energy
Just as a ball
• Foundations cannot
of organic get over
chemistry a hill
from if it does not roll up
mid-1700’s.
the hill with enough energy, a reaction cannot occur
unless theobtained
Compounds molecules
frompossess sufficient
plants, animals energy
hard to isolate,to get
and
purify.
over the activation energy barrier.
124
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
Activation Energy
The activation
• Foundations energy
of organic may be
chemistry shown
from on diagrams called
mid-1700’s.
energy profiles. The energy barrier, Ea is the activation
energy forobtained
Compounds forwardfrom
reaction
plants, animals hard to isolate, and
purify.
E
n E
n
Compounds also
e
r
Ea decomposed more easily.
e products
g r
g Ea
y
y
Torbenreactants
Bergman (1770) first
∆H = -veto make distinction between organic
∆H = +ve
and inorganic chemistry.
products
reactants
It was thought
Progressthat organic compounds must contain
of reaction some “vital
Progress of reaction
force” because they were from living sources.
(a) Energy profile for an (b) Energy profile for an
exothermic reaction endothermic reaction
125
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic
Activation Chemistry
Energy
Activated state Activated state
Foundations
E
of organic chemistry from mid-1700’s.
n E Ea (reversed)
Ea (forward) Ea (reversed) n
e Ea (forward)
r e
Compounds obtained from plants, animals hard to isolate, and
g r
g
ypurify.
reactants
products
y
products
∆H = -ve ∆H = +ve
•AItreversible
was thought thathas
reaction organic compounds
two activation must contain some “vital
energies:-
activation
•Theforce” energythey
because ,Ea (forward) , is the
were from energy
living difference between the
sources.
activated state and the reactants
•The activation energy ,Ea (reverse) is the energy difference between the
activated state and the products.
126
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
The Transition State Theory
The transition
•Foundations state
of organic theory from
chemistry is concerned
mid-1700’s.with what
actually happens during a collision.
This theory
•Compounds explains
obtained fromhow the
plants, energy
animals hardof to
collisions
isolate, andis
used
purify.to form a high-energy activated complex when
reactants particles collide with each other.
•Compounds
There existsalso decomposed
an intermediate more easily.
stage before reactant
molecules change into products.
•Torben
The Bergman (1770)
activated first toormake
complex
and inorganic chemistry.
distinction
transition between
state is a organic
chemical species with partially broken and partially
formed
It was bonds
thought that organic compounds must contain some “vital
– has highest
force” becauseenergy
they and
were extremely unstable
from living – exists at instant
sources.
– has more potential energy than either the reactants or the products
– the bonds in the reactant molecules are in the process of breaking
while the new bonds in the products molecules are start to form. 127
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
The Transition State Theory
Reaction
Foundations of energy diagrams
organic chemistry andmid-1700’s.
from possible transition
states.
Compounds obtained from plants, animals hard to isolate, and
purify.
128
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic
Exercise
Chemistry
The gas phase
Foundations reaction
of organic chemistry from mid-1700’s.
NO (g) + F2 (g) NOF (g) + F (g) has an overall
enthalpy
Compounds change
obtainedoffrom
-60 kJ. Theanimals
plants, activation energy
hard to isolate,the
and
reaction
purify. is 16.3 kJ
a)Compounds
Sketch the alsoenergy profile
decomposed for easily.
more the reaction and label Ea
∆H and draw the activated complex.
b)Torben
WhatBergman
is the activation energy
(1770) first to for reverse
make distinction reaction?
between organic
and inorganic chemistry.
129
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic
Exercise
Chemistry
Based on their
Foundations activation
of organic energies
chemistry and energy changes
from mid-1700’s.
and assuming that all collision factors are the same,
which of theobtained
Compounds following
fromreactions would
plants, animals beto
hard fastest
isolate,and
and
which would be slowest?
purify.
I)Compounds
Ea = 45 kJ/mol ; ∆H = -25
also decomposed kJ/mol
more easily.
I)Torben
Ea =Bergman
35 kJ/mol ; ∆H
(1770) = -15
first kJ/mol
to make distinction between organic
and inorganic chemistry.
I) Ea = 55 kJ/mol ; ∆H = 10 kJ/mol
It was thought that organic compounds must contain some “vital
Whichforce”
of because they were
the reactions from
will be living
fastestsources.
and will be slowest
in reverse direction?
130
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
FACTORS CONTROLLING
RATES
Foundations of organic OF REACTIONS
chemistry from mid-1700’s.
1 CONCENTRATIONS OF REACTANTS
Compounds obtained from plants, animals hard to isolate, and
purify.
2 CHEMICAL NATURE OF REACTANTS
Compounds also decomposed more easily.
3 TEMPERATURE
Torben Bergman (1770) first to make distinction between organic
and4inorganic chemistry.
THE USE OF A CATALYST
It was thought that organic compounds must contain some “vital
force” because they were from living sources.
131
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
FACTORS CONTROLLING
RATES
Foundations of organic OF REACTIONS
chemistry from mid-1700’s.
Concentrations of Reactants
Compounds obtained from plants, animals hard to isolate, and
purify.– As the concentration of reactants
increases, so does the likelihood that
Compoundsreactant
also decomposed morewill
molecules easily.
collide.
132
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
FACTORS CONTROLLING
RATES
Foundations of organic OF REACTIONS
chemistry from mid-1700’s.
The Effect
Compounds of Concentration
obtained onhard
from plants, animals Collision Theory
to isolate, and
purify.
When the concentration increases, the frequency of
Compounds also decomposed more easily.
collision also increases
Torben Bergman (1770) first to make distinction between organic
The more
and particles
inorganic present in the same volume, so
chemistry.
they are more likely to collide more frequently, thus
increase the that
It was thought reactions
organic rate.
compounds must contain some “vital
force” because they were from living sources.
133
2.4 THEORIES OF CHEMICAL KINETICS
FACTORS CONTROLLING
RATES OF REACTIONS
Chemical Nature of Reactants
– In order to react, molecules must come in
contact with each other.
– The more homogeneous the mixture of
reactants, the faster the molecules can
react.
134
2.4 THEORIES OF CHEMICAL KINETICS
FACTORS CONTROLLING
RATES OF REACTIONS
Temperature
– At higher temperatures, reactant
molecules have more kinetic energy,
move faster, and collide more often and
with greater energy.
135
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
FACTORS CONTROLLING
RATES
Foundations of organic OF REACTIONS
chemistry from mid-1700’s.
The Effect
Compounds of Temperature
obtained on Collision
from plants, animals Theory
hard to isolate, and
purify.
When the temperature of the reaction is increased ,
the frequency
Compounds alsoofdecomposed
collision also
moreincreases
easily.
According to the
Torben Bergman kinetic-molecular
(1770) theorybetween
first to make distinction of gases,
organic
increasing the temperature
and inorganic chemistry. increases molecular
speeds.
It was thought that organic compounds must contain some “vital
As molecules move
force” because theyfaster,
were fromthey collide
living more forcefully
sources.
(more energy), and more frequently, increasing
reaction rates. 136
2.4 THEORIES OF CHEMICAL KINETICS
FACTORS CONTROLLING
RATES OF REACTIONS
The Use of A Catalyst
137
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
Effect of Temperature on Reaction Rate:
FoundationsMaxwell-Boltzmann
of organic chemistry fromDistributions
mid-1700’s.
• Temperature is defined as a measure of the average
kinetic energy
Compounds of the
obtained frommolecules in ahard
plants, animals sample.
to isolate, and
purify.
• Some molecules are moving at different speeds, at any
Compounds
given time.also decomposed
Some more easily.
have higher energies, some medium
or some molecules have lower energies.
Torben Bergman (1770) first to make distinction between organic
and inorganic chemistry.
• At any temperature there is a wide distribution of
kinetic energies.- Use Maxwell-Boltzman Distribution
It was thought that organic compounds must contain some “vital
force” because they were from living sources.
138
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
Effect of Temperature on Reaction Rate:
Maxwell-Boltzmann
Foundations of organic chemistry fromDistributions
mid-1700’s.
The area under distribution curve is proportional to total
number of molecules
Compounds obtained from plants, animals hard to isolate, and
purify. Most of molecules have
values somewhere in the
Fraction of molecules
middle
Compounds also decomposed more easily.
It was thought
-50000 that organic compounds must contain some
-25000“vital
force”
8.314 xbecause
293 they were from living sources. 8.314 x 293
f=e f=e
= 1.21 x 10-9 = 3.47 x 10-5
144
2.4 THEORIES OF CHEMICAL KINETICS
Origins of Organic Chemistry
Exercise
Foundations of organic chemistry from mid-1700’s.
The activation energy for isomerization of methyl
isonitrile is 160 kJ/mol. Calculate the fraction of methyl
Compounds obtained from plants, animals hard to isolate, and
isonitrile
purify. molecules that has an energy of 160 kJ at 500 K
IfCompounds
the abovealso
reactions using
decomposed a catalyst
more easily. to speed up the
reaction rate and found that the new activation energy is
lower
Torbenabout three-quarter
Bergman (1770) first tofrom
makethe original
distinction values.
between organic
Determine the ratio
and inorganic of the fraction of molecules
chemistry.
145
TOPIC
2.5 ARRHENIUS EQUATION
146
2.5 ARRHENIUS EQUATION
Svante Arrhenius found that the most reactions the increase in rate
with increasing temperature is nonlinear but exponential.
147
2.5 ARRHENIUS EQUATION
148
2.5 ARRHENIUS EQUATION
K1 = Ae-Ea/RT1 K2 = Ae-Ea/RT2
K2 = Ae-Ea/RT2 K2 = e-Ea/RT2
K1 = Ae-Ea/RT1 K1 = e-Ea/RT1
K2
= e-(Ea/RT2)-(Ea/RT1)
K1
K2
= eEa/R(1/T1)-(1/T2)
K1 151
2.5 ARRHENIUS EQUATION
K = Ae-Ea/RT
Ea 1
ln k = -
R
( T
) + ln A
y = m x + b
Therefore, if k is determined experimentally at several
temperatures, Ea can be calculated from the slope of a
plot of ln k vs. 1T .
152
2.5 ARRHENIUS EQUATION
Example 13
Determine the activation energy and frequency factor
for the reaction O3(g) O2(g) + O(g) given the following
data:
153
2.5 ARRHENIUS EQUATION
Answer to Example 13
154
2.5 ARRHENIUS EQUATION
Answer to Example 13
155
2.5 ARRHENIUS EQUATION
Arrhenius Equation: Two-Point Form
• If you only have two (T,k) data points, the following
forms of the Arrhenius Equation can be used:
K2
= eEa/R(1/T1)-(1/T2)
K1
156
2.5 ARRHENIUS EQUATION
Example 14
157
2.5 ARRHENIUS EQUATION
Answer to Example 14
Relationships:
Solution:
158
Exercise 14
Exp T (K) K
(L/mol.s)
1 288 0.0521
2 298 0.101
3 308 0.142
4 318 0.332
159
Exercise 15
160
Exercise 16
161
TOPIC
REACTION MECHANISMS AND RATE
DETERMINING STEP
162
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
Reaction Mechanisms
The sequence of events that describes the actual
process by which reactants become products is
called the reaction mechanism.
163
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
Multistep Mechanisms
165
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
166
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
Slow Initial Step
169
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
170
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
171
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
• A proposed mechanism is
172
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
173
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
174
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
k1
k−1 [NO] [Br2] = [NOBr2]
175
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
k2k1
Rate = k [NO] [Br2] [NO]
−1
= k [NO]2 [Br2]
176
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
Example 15
177
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
Answer to Example 15
178
Exercise 17
Mechanisms with a slow Initial Step
Proposed mechanism
1. NO2 (g) + F2 (g) NO2F (g) + F (g) (slow, rate determining step)
2. NO2 (g) + F (g) NO2F (g) (fast)
179
Exercise 18
Proposed mechanism
180
End of Chapter 2
Thank You
181