Chemical Kinetics

U N IVERSIT Y OF IN D ON ESIA
Chemical Kinetics
Reaction Rates
Rate of a reaction - how fast the concentration of
a reactant or a product changes per unit time.
Rate = concentration/time
a. increase in the concentration of a product per unit time
b. decrease in the concentration of a reactant per unit time
Units - M/s or mol/(L. s).

a. allows rate to be independent of the scale of the reaction
b. use a minus sign in calculating the rate of disappearance
of a reactant
Reaction Rates
Relative rates of product formation and
reactant consumption depend on the
coefficients in the balanced equation.
Specify the reactant or product when quoting a
rate.
Rate changes as the reaction proceeds.

Specify the time.
Reaction rates decrease as the reaction mixture
runs out of reactants.
Reaction Rates
Plot concentration (y axis) versus time (x axis).
(concentration) and (time) represent vertical and
horizontal sides of a right triangle.
Slope of hypotenuse of triangle is the average rate
during that time period.
Instantaneous rate at time t - the slope of the

tangent to a concentration-versus-time curve at
time t.
Initial rate - the instantaneous rate at the
beginning of a reaction (t = 0).
Reaction Rates
Reaction Rates
Reaction Rates
Reaction Rates
EXAMPLE:
It was found that the rate of formation of N2 (g) in the following reaction
4 NH3 (g)
3 O2 (g)
2 N2 (g)
is 0.52 Ms-1 at a particular point in time.

Determine
the
rate
of
disappearance
6 H2 O (g)
of
NH3.
SOLUTION: Knowing that the rate of appearance is 0.52 , we can use the
stoichiometry of the balanced equation to determine the rate of
disappearance of NH3.
mol N 2 4 mol NH 3
mol NH 3
0.52
= 1.04
Ls
2 mol N2
Ls
This rate should be reported as 1.04 Ms-1 because we are reporting the
rate of disappearance of NH3.
Rate Laws and

Reaction Order
Rate law - states the dependence of the

reaction rate on concentration.
Equation that tells how the rate depends on the
concentration of each reactant.
For the reaction a A + b B products, the rate
law is
Rate = -
[A]
= k[A]m [B ]n
t
k = proportionality constant called the rate constant
Rate Laws and

Reaction Order
Reaction order - determined by the values of

the exponents.
The values of the exponents in the rate law must
be determined by experiment; they cannot be
deduced from the stoichiometry of the reaction.
Values of m and n indicate the reaction order with
respect to A and B.
exponent = 1; first order
exponent = 2; second order
exponent = 3; third order
Rate Laws and

Reaction Order

the exponents.
Overall reaction order = m + n.
Indicates how the change in concentration can
affect the rate.
Unrelated to the coefficients in the balanced
equation.
Rate Laws and

Reaction Order

the exponents.
Usually small positive integers but can be
negative, zero, or even fractions.
exponent = 1; rate depends linearly on the
concentration of the corresponding reactant
exponent = 0; the rate is independent of the
concentration of the corresponding reactant
exponent < 1; the rate decreases as the concentration
of the corresponding reactant increases
Experimental
Determination of a
Rate Law
To determine the reaction order (values of the
exponents in a rate law) - measure the initial
rate of a reaction as a function of different
sets of initial concentrations.
Design pairs of experiments to investigate the

effect of the initial concentration of a single
reactant on the inital rate of change.
If, by doubling the concentration of a reactant, the
rate also doubles, then the reaction is first order
with respect to that reactant.
Experimental
Determination of a
Rate Law

exponents in a rate law) - measure the initial rate
of a reaction as a function of different sets of
initial concentrations.
rate increases by a factor of 22 = 4, the reaction is
second order with respect to that reactant.
rate of the reaction increases by a factor of 23 = 8, the
reaction is third order with respect to that reactant.
Experimental
Determination of a
Rate Law
exponents in a rate law) - measure the initial
rate of a reaction as a function of different
sets of initial concentrations.
Use initial rates to avoid complications from the

reverse reaction.
initial rates measure only the rate of the forward
reaction
only reactants and catalysts appear in the rate law
Rate Laws and

Reaction Order
Experimental
Determination of a
Rate Law
Can determine the value of k from the rate
law.
Value is characteristic of a reaction.

Depends on temperature.
Does not depend on concentration.
Units depend on the number of concentration
terms in the rate law and on the values of the
exponents.
Rate Laws and

Reaction Order
Experimental
Determination of a
Rate Law
EXAMPLE:
The reaction
2 NO (g) + 2 H2 (g) N2 (g) + 2 H2O (g)
is first order in H2 and second order in NO.
1. Write the rate law.
2. What is the overall order of the reaction?
3. How does the reaction rate change if the concentration
of H2 is doubled and the concentration of NO is held
constant?
4. How does the reaction rate change if the concentration
of NO is cut in half and the concentration of H2 is held
constant?
Experimental
Determination of a
Rate Law
SOLUTION:
1. Rate = [H2][NO]2
2. Overall order = 1 + 2 = 3
3. If the concentration of H2 is doubled while the
concentration of NO is held constant, the rate
will double, (2)1 = 2.
4. If the concentation of NO is cut half while the
concentration of H2 is held constant, the rate will
be cut by 1/2, (1/2)2 = 1/4
Integrated Rate Law

for a First-order
Reaction
Integrated Rate law - a concentration-time
equation that allows us to calculate the

concentration of a reactant at any time t or the
fraction of a reactant that remains at any time t.
Can be used to calculate the time required for the
initial concentration of a reactant to drop to any
particular value or to any particular fraction of its
initial concentration.
Integrated Rate Law

for a First-order
Reaction
For the reaction a A products, the integrated

rate law is
Can
rearrange
[A ]t
ln
= kt
[A]0
the
equation
to
give
ln[A]t = kt + ln[A]0
Plot of ln [A] versus time gives a straight line if the

reaction is first order in A.
k = (slope).
Integrated Rate Law

for a First-order
Reaction
Integrated Rate Law

for a First-order
Reaction
EXAMPLE:
When sucrose reacts with water, glucose is formed
according to the reaction:
C12H22O11 + H2O 2 C6H12O6
This reaction follows first order kinetics with respect to the
sucrose.
Calculate the value of k, if it takes 9.70 hours for the
concentration of sucrose to decrease from 0.00375 M to
0.00252 M.
Determine the amount of time required for the reaction to go to
80% completion.
Integrated Rate Law

for a First-order
Reaction
SOLUTION: To calculate the value of k, we simply substitute

the data given into the first-order integrated rate equation.
0.00252
ln
= k(9.70 h);
0.00375
k = 4.10 10
-1
We can now calculate the amount of time required for the

reaction to be 80% complete.
To determine the concentration at this time, we multiply
the initial concentration by 0.80.
0.80 0.00375 = 0.00300
Integrated Rate Law

for a First-order
Reaction
We can now calculate the amount of time required for the reaction to be
80% complete. To determine the concentration at this time, we multiply
the initial concentration by 0.80.
0.80 0.00375 = 0.00300
This value represents the amount of sucrose that has reacted.
The amount of sucrose remaining after the reaction is 80% complete is
0.00375 0.00300 = 0.00075.
We now have the initial concentration and the concentration at time t,
which can be substituted into the first-order integrated rate law, along
with the value of k we calculated in the first part of the problem.
ln
0.00075
2 -1
= (4.10 10 h )t;
0.00375
t = 39.3 h
Integrated Rate Law

for a First-order
Reaction
First Order Reaction
Half-Life of a Firstorder Reaction
Half-life (t1/2) - the time required for the reactant

concentration to drop to one-half of its initial
0.693
value.
t =
1/ 2
For first-order reaction, half-life is a constant.

depends
only
on
the
rate
constant
EXAMPLE:
Determine the half-life for the reaction of sucrose with
water.
SOLUTION: We can calculate the half-life by substituting
the rate constant determined in the previous example into
the equation for the first-order half-life.
t1/ 2
0.693
=
= 16.9 h
4.10 10 2 h -1
Second-order
Reactions
Integrated rate law for a second-order reaction.

1
1
= kt +
A
[ ]t
[A ]0
1
[A ]t
Plot of
versus time gives a straight line if the
reaction is second-order.
slope of line = k; intercept =
1
[A ]0
Second-order
Reactions
Half-life for a second-order reaction

Depends on both the rate constant and the initial
concentration.
t1/ 2 =
1
k[A]0
Second-order
Reactions
EXAMPLE:
The reaction 2 NOBr (g) 2 NO (g) + Br2 (g)
is a second order reaction with respect to NOBr.
The rate constant for this reaction is k = 0.810 M-1s-1
when the reaction is carried out at a temperature of
10o C.
If the initial concentration of NOBr = 7.5 10-3 M, how
much NOBr will be left after a reaction time of 10
minutes?
Determine
the
half-life
of
this
reaction.
Second-order
Reactions
SOLUTION: We can solve for the amount of

NOBr after 10 minutes by substituting the
given data into the integrated rate law for a
second-order reaction.
1
1
= kt +
[A ]t
[A ]0
1
1
-1 -1
= (0.810 M s ) (600 s) +
;
3
NOBr
[
]t
7.5 10 M
1
= 6.19 10 2 M -1;
[NOBr ]t
[NOBr ]t = 1.6 10 3 M
Second-order
Reactions
To determine the half-life for this reaction, we

substitute the intitial concentration of NOBr
and the rate constant for the reaction into the
equation for the half-life of a second-order
reaction.
t1/ 2
t1/ 2 =
1
=
k[A]0
1
= 160 s
-1 1
3
0.810 M s (7.5 10 M)
Second-order
Reactions
Konsep Laju Reaksi
Reaction
Mechanisms
Reaction mechanism - the sequence of

molecular events, or reaction steps, that
defines the pathway from reactants to
products.
Reaction steps - involve the breaking of chemical
bonds and/or the making of new bonds.
Knowing reaction mechanisms allows for better
control of known reactions and predictions of new
reactions.
Reaction
Mechanisms
Elementary step - a single step in a reaction

mechanism.
Description of an individual molecular event
(collisions of individual molecules).
Describe the reaction mechanism.
Reaction
Mechanisms

mechanism.
Classified on the basis of their molecularity.
molecularity - the number of molecules on the reactant side
of the chemical equation
unimolecular reaction - elementary reaction that involves a
single reactant molecule
bimolecular reaction - elementary reaction that results from
energetic collisions between two reactant molecules
termolecular reaction - involve three atoms or molecules;
rare
Reaction
Mechanisms

mechanism.
Reaction intermediate - a species that is formed in
one step of a reaction mechanism and consumed
in a subsequent step.
do not appear in the net equation for the overall
reaction
presence is only noticed in the elementary steps
Elementary
Steps
Unimolecular
Reactions
Bimolecular
Reaction
Bimolecular
Reaction
Bimolecular Reaction
Termolecular
Reaction
Reaction
Mechanisms
Balanced equation for an overall reaction.

Provides no information about how the reaction
occurs.
Describes reaction stoichiometry.
Rate Laws and

Reaction
Mechanisms
Rate law for overall reaction - determined by

experimentation.
Rate law for an elementary reaction - determined from
its molecularity.
Contains the concentration of each reactant raised to an
exponent equal to its coefficient in the chemical equation
for the elementary reaction.
Only applies to elementary reactions, not overall
reactions.
Rate of a unimolecular reaction is first order in the
concentration of the reactant molecule.
Overall reaction order for an elementary reaction is equal
to its molecularity.
Rate Laws and

Reaction
Mechanisms
Experimentally observed rate law for an overall

reaction depends on the reaction mechanism.
Overall reaction occurs in a single elementary step.
experimental rate law = rate law for the elementary step
Overall reaction occurs in two or more steps.

rate-determining step - the slowest step in a reaction
mechanism
limits the rate at which reactants can be converted to products
overall reaction can occur no faster than the speed of the

rate-determining step
Rate Laws and

Reaction
Mechanisms
Two criteria for an acceptable reaction

mechanism.
The elementary steps must sum to give the overall
reaction.
The mechanism must be consistent with the
observed rate law for the overall reaction.
Rate Laws and

Reaction
Mechanisms
Procedure used for establishing a reaction

mechanism.
Determine the overall rate law experimentally.
Devise a series of elementary steps.
Predict the rate law based on the reaction
mechanism.
Rate Laws and

Reaction
Mechanisms
Procedure used for establishing a reaction

mechanism.
If observed and predicted rate laws agree, the
proposed mechanism is a plausible pathway for
the reaction.
Easy to disprove a mechanism; impossible to
"prove" a mechanism.
Rate Laws and

Reaction
Mechanisms
Given the following reaction mechanism:

Z2 2 Z
2 Z + 3 H2O 2 ZH3 + 3/2 O2
2 ZH3 + 5/2 O2 2HZO3 2H2O
a) Determine the overall reaction.
b) Identify the reaction intermediates and
determine the molecularity of each step.
c) Determine the rate law if the second step is
the rate determining step.
Rate Laws and

Reaction
Mechanisms
SOLUTION:
To determine the overall reaction, we simply
cross out the species common on both the
reactant and product sides of the reactions.
Z2 2 Z
1 H2 O
2 Z + 3 H2O 2 ZH3 + 3/2 O2
2 ZH3 + 5/2 O2 2HZO3 + 2H2O
2/2 O2
Rate Laws and

Reaction
Mechanisms
Overall reaction: Z2 + H2O + O2 2HZO3

The reaction intermediates are those species in the
reaction mechanism that are not included in the
overall reaction: Z, ZH3.
The molecularity of the 1st step = 1 (unimolecular)
The molecularity of the 2nd step = 5
The molecularity of the 3rd step = 9/2.
Rate law = k[Z]2[H2O]3
Reaction Rates and

Temperature; The
Arrhenius Equation
Reaction rates tend to double when the

temperature is increased by 10o C.
Collision theory model - a bimolecular
reaction occurs when two properly oriented
reactant molecules come together in a
sufficiently
energetic
collision.
Surface Reaction Hydrogenation
Reaction Rates and

Temperature; The
Arrhenius Equation
For the reaction: A + BC AB + C.

For a single step reaction, a new bond, A-B,
develops at the same time as the old bond, B-C,
breaks.
Nuclei pass through a configuration in which all
three atoms are weakly linked together.
A + B-C A--B--C A-B + C
Reaction Rates and

Temperature; The
Arrhenius Equation

Need energy to overcome repulsions.
comes from kinetic energy of the colliding particles
stored as potential energy in A--B--C.
A--B--C has more potential energy than either the reactants or
products
Reaction Rates and

Temperature; The
Arrhenius Equation

Potential energy barrier that must be surmounted
before reactants can be converted to products.
potential energy profile - plot of potential energy
versus reaction progress.
activation energy, Ea, - the height of the barrier
transition state (or activated complex) -configuration of
atoms at the maximum in the potential energy profile
Reaction Rates and

Temperature; The
Arrhenius Equation

All the energy needed to climb the potential
energy barrier must come from the kinetic energy
of the colliding molecules.
Reaction Rates and

Temperature; The
Arrhenius Equation
Comparison of collision rates and reaction

rates leads to experimental evidence for the
idea of an activation energy barrier.
Only a small fraction of collisions lead to reaction.
very few collisions occur with a kinetic energy as large
as the activation energy
area under the curve to the right of Ea represents the
fraction of the collision with an energy equal to or
greater than the activation energy
fraction,
f =e
Ea / RT
Reaction Rates and

Temperature; The
Arrhenius Equation
Comparison of collision rates and reaction rates

leads to experimental evidence for the idea of an
activation energy barrier.
Distribution of collision energies broadens and shifts
to higher energies with an increase in temperature.
exponential increase in the fraction of collision that lead to
products
Accounts for exponential dependence of reaction

rates on temperature.
Explains why reaction rates are so much lower than
collision rates.
Reaction Rates and

Temperature; The
Arrhenius Equation
Orientation requirement also reduces the

fraction of collisions that lead to products.
Reactants won't react unless the orientation of
the reaction partners is correct for formation of
the transition state.
Steric factor, p, - fraction of collisions having
proper orientation.
Reaction Rates and

Temperature; The
Arrhenius Equation
For a bimolecular collision between A and B.

Collision rate = Z[A][B].
Z is a constant related to collision frequency
Reaction rate < collision rate by a factor of p x f.

Reaction rate = p fZ[A][B]
Reaction rate = k[A][B].

k = pfZ = pZ e Ea / RT
Reaction Rates and

Temperature; The
Arrhenius Equation
Arrhenius equation.
k = Ae
Ea
RT
A = frequency factor = pZ.
Reaction Rates and

Temperature; The
Arrhenius Equation
Using the Arrhenius

Equation
Can determine the activation energy if values

of the rate constant are known at different
temperatures.
Rearrange
the
equation
to
get
Ea 1
ln k =
+ ln A
R T
Plot ln k versus 1/T gives a straight line.

slope = -Ea/R
Using the Arrhenius

Equation
Can estimate the activation energy from rate

constants at just two temperatures using
another form of the equation.
k 2 Ea 1
1

ln =
k1 R T2 T1
Using the Arrhenius

Equation
EXAMPLE:
The activation energy for the reaction
ClO2F (g) ClOF (g) + O (g)
is 186 kJ/mol.
If the value of k is 6.76 10-4 s-1 at 322o C,
what is the value of k at 50o C?
Using the Arrhenius

Equation
SOLUTION: To solve this problem, we simply

substitute the information given into the
Arrhenius equation.
k 2 Ea 1
1
ln =

k1
R T2
T1
k2
1
1.86 10 5 J/mol 1
ln
=
4 -1
6.76 10 s 8.314 J/mol K 323 K 595 K
k2
ln
4 1 = 31.7
6.76 10 s
Using the Arrhenius

Equation
k 2 Ea 1
1

ln =
k1 R T2 T1
k2
1
1.86 10 5 J/mol 1
ln
=
4 -1
6.76 10
s 8.314 J/mol K 323 K 595 K
k2
ln
= 31.7
6.76 10 4 s 1
k2
14
=
1.71
10
;
6.76 10 4 s -1
k 2 = 1.16 10 17 s -1
Catalysis
Catalyst - a substance that increases the rate
of a reaction without being consumed in the
reaction.
Important in chemical industry and in living
organisms.
Chemical industry - favor formation of specific
products and lower reaction temperatures.
Living organisms - enzymes (catalysts) facilitate
specific reactions of crucial biological importance.
Catalysis
Accelerates the rate of a reaction by making a
new and more efficient pathway available for
the conversion of reactants to products.
Speeds up reaction in two ways:
increases the frequency factor A
decreases the activation energy
rate constant is more sensitive to the Ea and a catalyst usually
functions
by
lowering
the
activation
energy
Homogeneous and
Heterogeneous
Catalysts
Homogeneous catalyst - one that exists in the

same phase as the reactants.
Heterogeneous catalyst - exists in a different
phase from the reactants.
Mechanism is complex and not well understood.
Important steps:
adsorption of reactants onto the surface of the catalyst
conversion of reactants to products on the surface
desorption of products from the surface
Homogeneous and
Heterogeneous
Catalysts
Heterogeneous catalyst - exists in a different

phase from the reactants.
Adsorption step:
chemical bonding of reactants to the highly reactive metal
atoms on the surface
breaking or weakening of bonds in the reactants
Industrial
chemical
processes
use
mostly
heterogeneous catalysts due to the ease of separation
of the catalyst from the reaction products.
Used in automobile catalytic converters.
Terima Kasih

Chemical Kinetics

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Chemical Kinetics

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U N IVERSIT Y OF IN D ON ESIA

Units - M/s or mol/(L. s).

Rate changes as the reaction proceeds.

Instantaneous rate at time t - the slope of the

is 0.52 Ms-1 at a particular point in time.

Rate Laws and

Rate law - states the dependence of the

k = proportionality constant called the rate constant

Rate Laws and

Reaction order - determined by the values of

Rate Laws and

Reaction order - determined by the values of

Rate Laws and

Reaction order - determined by the values of

Design pairs of experiments to investigate the

To determine the reaction order (values of the

Use initial rates to avoid complications from the

Rate Laws and

Value is characteristic of a reaction.

Rate Laws and

Integrated Rate Law

equation that allows us to calculate the

Integrated Rate Law

For the reaction a A products, the integrated

Plot of ln [A] versus time gives a straight line if the

Integrated Rate Law

Integrated Rate Law

Integrated Rate Law

SOLUTION: To calculate the value of k, we simply substitute

We can now calculate the amount of time required for the

Integrated Rate Law

Integrated Rate Law

First Order Reaction

Half-Life of a Firstorder Reaction

Half-life (t1/2) - the time required for the reactant

For first-order reaction, half-life is a constant.

Half-Life of a Firstorder Reaction

Half-Life of a Firstorder Reaction

Integrated rate law for a second-order reaction.

slope of line = k; intercept =

Half-life for a second-order reaction

SOLUTION: We can solve for the amount of

To determine the half-life for this reaction, we

Konsep Laju Reaksi

Reaction mechanism - the sequence of

Elementary step - a single step in a reaction

Elementary step - a single step in a reaction

Elementary step - a single step in a reaction

Balanced equation for an overall reaction.

Rate Laws and

Rate law for overall reaction - determined by

Rate Laws and

Experimentally observed rate law for an overall

Overall reaction occurs in two or more steps.

overall reaction can occur no faster than the speed of the

Rate Laws and

Two criteria for an acceptable reaction

Rate Laws and

Procedure used for establishing a reaction

Rate Laws and

Procedure used for establishing a reaction

Rate Laws and

Given the following reaction mechanism:

Rate Laws and