CHAPTER 9

CHEMICAL KINETICS

CONCEPT MAP

Chemical Kinetics

is the study of
can be
explained
using the Activation
concept energy
of
Reaction rates

Collision
are affected by
theory

Reactant Is a variable in
concentration Temperature Arrhenius equation

Is used in expressing the

Reaction time
can be
(or process of reaction)
Rate law Integrated rate
transformed law relates
into

reflects Reactant concentration

Molecularity Order of reaction

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LEARNING COMPETENCIES
1. Describe how various factors influence the rate of a reaction
2. Write the mathematical relationship between the rate of a reaction, rate constant,
and concentration of the reactants
3. Differentiate zero, first-, and second-order reactions
4. Write the rate law for first-order reaction
5. Discuss the effect of reactant concentration on the half-time of a first-order reaction
6. Explain the effect of temperature on the rate of a
7. Explain reactions qualitatively in terms of molecular collisions
8. Explain activation energy and how a catalyst affects the reaction rate
9. Cite and differentiate the types of catalysts
10. Determine the effect of various factors on the rate of a reaction

REACTION RATES
Rates of reactions can be determined by monitoring the change in concentration
of either reactants or products as a function of time t.
[A] = concentration of reactant A
 For the reaction A and B there are two ways of measuring rate:
(1) the speed at which the reactants disappear
(2) the speed at which the products appear
 Reactions are reversible, so as products accumulate, they can begin to turn back
into reactants.
 Early on the rate will depend on only the amount of reactants present. We want
to measure the reactants as soon as they are mixed.
 The most useful (and general) way of measuring the rate of the reaction is in
terms of change in concentration per unit time…
Rate = ∆[A]/∆t limits to D[A]/Dt
Most Common Units… Rate = M/s
Where Molarity (M) = moles/Liter

Chemical Kinetics
Thermodynamics – does a reaction take place?
Kinetics – how fast does a reaction proceed?
Reaction rate is the change in the concentration of a reactant or a product with time
(M/s).
A B

Δ[A] = change in concentration of A overtime period Δt

Δ[B] = change in concentration of B overtime period Δt

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Because [A] decreases with time, Δ[A] is negative.

Factors that Affect the Reaction Rate Constant

1. Temperature: At higher temperatures, reactant molecules have more kinetic energy,

move faster, and collide more often and with greater energy
 Collision Theory: When two chemicals react, their molecules have to collide with
each other with sufficient energy for the reaction to take place.
 Kinetic Theory: Increasing temperature means the molecules move faster.
2. Concentrations of reactants
 As the concentration of reactants increases, so does the likelihood that reactant
molecules will collide.
3. Catalysts
 Speed up reactions by lowering activation energy
4. Surface area of a solid reactant
 Bread and Butter theory: more area for reactants to be in contact
5. Pressure of gaseous reactants or products
 Increased number of collisions

FACTORS THAT AFFECT REACTION RATE CONSTANT

Temperature
 Generally, as temperature increases, so does the reaction rate. This is because k
is temperature dependent.
Concentration Affects Reaction Rate Constant
Here’s another way of looking at reaction rates…
2N2O5(g)  4NO2(g) + O2(g)

 Notice that for every 1 mole of O2 that appears, 4 x as many moles of NO2 will
also appear. In the meantime, twice as many moles of N2O5 will be disappearing
as moles of O2 forming.
 Changes in concentrations of the reactants and/or products is inversely
proportional to their stoichiometric proportions.
 This means that the rate of the reaction could be written like this…

* (Notice the negative sign on the rate of [N2O5] reminds us that it is disappearing.)
•In general, for a reaction that looks like this… aA + bBà cC + Dd

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Concentration and Rate
Each reaction has its own equation that gives its rate as a function of reactant
concentrations. This is called its Rate Law
To determine the rate law we measure the rate at different starting
concentrations.

Rate Laws
 Rate laws are always determined experimentally.
 Reaction order is always defined in terms of reactant (not product) concentrations.
 The order of a reactant is not related to the stoichiometric coefficient of the reactant
in the balanced chemical equation.

Rate Law
 In general, rates of reactions increase as concentrations increase since there are
more collisions occurring between reactants.
 The overall concentration dependence of reaction rate is given in a rate law or rate
expression.
 Here’s what a general rate law for a reaction will look like…

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 𝑅𝑎𝑡𝑒 = 𝑘 [𝐴]𝑚 [𝐵]𝑛
Where:
 [A] & [B] represent the reactants.
 The exponents m and n are called “reaction orders”.
 The proportionality constant k is called the rate constant.
 The overall reaction order is the sum of the reaction orders:
𝑚 + 𝑛
Order of Reactions
 A reaction is zero order in a reactant if the change in concentration of that
reactant produces no effect.
 A reaction is 1st order if doubling the concentration causes the rate to double.
 A reaction is 2nd order if doubling the concentration causes a quadruple increase
in rate.
 3rd order…doubling concentration leads to 23 (or 8 times) the rate.
*Note -- The rate constant, k, does not depend on concentration!
 Once we have determined the rate law and the rate constant, we can use them
to calculate initial reaction rates under any set of initial concentrations.

Activation Energy
 There is a minimum amount of energy required for a reaction: the activation
energy, Ea.
 Just as a ball cannot get over a hill if it does not roll up the hill with enough
energy, a reaction cannot occur unless the molecules possess sufficient energy
to get over the activation energy barrier.
 Molecules must possess a minimum amount of energy to react. Why?
– In order to form products, bonds must be broken in the reactants. Bond
breakage requires energy.
– Molecules moving too slowly, with too little kinetic energy, don’t react when
they collide.

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• Activation energy, Ea, is the minimum energy required to initiate a chemical reaction.
− Ea will vary with the reaction.
Arrhenius Equation
Svante Arrhenius developed a mathematical relationship between k and Ea:

Where A is the frequency factor, a number that represents the likelihood that collisions
would occur with the proper orientation for reaction.

Catalyst
A catalyst is a substance that increases the rate of a chemical reaction without itself
being consumed.

Catalysts increase the rate of a reaction by decreasing the activation energy of the
reaction.
Catalysts change the mechanism by which the process occurs.

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 HIGLIGHTS/SUMMARY

Factors that Affect Reaction Rates

chemical kinetics – area of chemistry dealing with speeds/rates of reactions rates of
reactions affected by four factors concentrations of reactants temperature at which
reaction occurs presence of a catalyst surface area of solid or liquid reactants and/or
catalysts

Reaction Rates
reaction rate – speed of a chemical reaction
average rate=change #moles Bchange in time=Δmoles BΔt if A→B(14.S.1)
Δmoles B=moles B at final time−moles B at initial time(14.S.2)
average rate=−Δmoles AΔt if A→B(14.S.3)

Rates in Terms of Concentrations

rate calculated in units of M/s brackets around a substance indicate the concentration
instantaneous rate – rate at a particular time
instantaneous rate obtained from the straight line tangent that touches the curve at a
specific point slopes give instantaneous rates instantaneous rate also referred to as the
rate

Reaction Rates and Stoichiometry

for the irreversible reaction aA+bB→cC+dD
rate=−1aΔ[A]Δt=−1bΔ[B]Δt=1cΔ[C]Δt=1dΔ[D]Δt(14.S.4)

Concentration and Rate

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equation used only if C and D only substances formed
Rate = k[A][B]
Rate law – expression that shows that rate depends on concentrations of reactants
k = rate constant
14.3.1 Reaction Order

Rate = k[reactant 1]m[reactant 2]n

m, n are called reaction orders
m+n, overall reaction order
reaction orders do not have to correspond with coefficients in balanced equation
values of reaction order determined experimentally
reaction order can be fractional or negative

Units of Rates Constants

units of rate constant depend on overall reaction order of rate law
for reaction of second order overall
units of rate = (units of rate constant)(units of concentration)2
units of rate constant = M-1s-1

Using Initial Rates to Determine Rate Laws

zero order – no change in rate when concentration changed
first order – change in concentration gives proportional changes in rate
second order – change in concentration changes rate by the square of the concentration
change, such as 22 or 32, etc…
rate constant does not depend on concentration

The Change of Concentration with Time

rate laws can be converted into equations that give concentrations of reactants or
products

First-Order Reactions
rate=−Δ[A]Δt=k[A]
and in integral form:
ln[A]t−ln[A]0=−kt
or

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ln[A]t[A]0=−kt
ln[A]t=−kt+ln[A]0
corresponds to a straight line with y=mx+b
equations used to determine:
concentration of reactant remaining at any time
time required for given fraction of sample to react
time required for reactant concentration to reach a certain level

Half-Life
half-life of first order reaction
t12=−ln12k=0.693k
half-life – time required for concentration of reactant to drop to one-half of initial value
t1/2 of first order independent of initial concentrations
half-life same at any given time of reaction
in first order reaction – concentrations of reactant decreases by ½ in each series of
regularly spaced time intervals

Second-Order Reactions
rate depends on reactant concentration raised to second power or concentrations of two
different reactants each raised to first power
Rate=k[A]2(14.S.10)
1[A]t=kt+1[A]0(14.S.11)
half life=t12=1k[A]0(14.S.12)
half life dependent on initial concentration of reactant

Temperature and Rate

rate constant must increase with increasing temperature, thus increasing the rate of
reaction

The Collision Model

collision model – molecules must collide to react
greater frequency of collisions the greater the reaction rate
for most reactions only a small fraction of collisions leads to a reaction

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Activation Energy
Svante August Arrhenius
Molecules must have a minimum amount of energy to react
Energy comes from kinetic energy of collisions
Kinetic energy used to break bonds
Activation energy, Ea – minimum energy required to initiate a chemical reaction
Activated complex or transition state – atoms at the top of the energy barrier
Rate depends on temperature and Ea
Lower Ea means faster reaction
Reactions occur when collisions between molecules occur with enough energy and
proper orientation

The Arrhenius Equation

reaction rate data:
the Arrhenius Equation:
k=Ae−EaRT
k = rate constant, Ea = activation energy, R = gas constant (8.314 J/(mol K)), T =
absolute temperature, A = frequency factor
A relates to frequency of collisions, favorable orientations
lnk=−EaRT+lnA
the lnk vs. 1/t graph (also known as an Arrhenius plot) has a slope –Ea/R and the y-
intercept lnA
for two temperatures:
lnk1k2=EaR
used to calculate rate constant, k1 and T1

Reaction Mechanisms
reaction mechanism – process by which a reaction occurs

Elementary Steps
elementary steps – each step in a reaction
molecularity – if only one molecule involved in step
unimolecular – if only one molecule involved in step
bimolecular – elementary step involving collision of two reactant molecules
termolecular – elementary step involving simultaneous collision of three molecules

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elementary steps in multi-step mechanism must always add to give chemical equation of
overall process
intermediate – product formed in one step and consumed in a later step

Rate Laws of Elementary Steps

if reaction is known to be an elementary step then the rate law is known
rate of unimolecular step is first order (Rate = k[A])
rate of bimolecular steps is second order (Rate = k[A][B])
first order in [A] and [B]
if double [A] than number of collisions of A and B will double

Rate Laws of Multi-step Mechanisms

rate-determining step – slowest elementary step
determines rate law of overall reaction
Mechanisms with an Initial First Step
intermediates usually unstable, low and unknown concentrations
whenever a fast step precedes a slow one, solve for concentration of intermediate by
assuming that equilibrium is established in fast step

Catalysis
catalyst – substance that changes speed of chemical reaction without undergoing a
permanent chemical change

Homogeneous Catalysis
homogeneous catalyst – catalyst that is present in same phase as reacting molecule
catalysts alter Ea or A generally catalysts lowers overall Ea for chemical reaction
catalysts provides a different mechanism for reaction

Heterogeneous Catalysis
exists in different phase from reactants
initial step in heterogeneous catalyst is adsorption
adsorption – binding of molecules to surface
adsorption occurs because ions/atoms at surface of solid extremely reactive

Enzymes

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biological catalysts large protein molecules with molecular weights 10,000 – 1 million
amu
catalase – enzyme in blood and liver that decomposes hydrogen peroxide into water and
oxygen
substrates – substances that undergo reaction at the active site
lock-and-key model – substrate molecules bind specifically to the active site
enzyme-substrate complex – combination of enzyme and substrate
binding between enzyme and substrate involves intermolecular forces (dipole-dipole,
hydrogen bonding, and London dispersion forces)
product from reaction leaves enzyme allowing for another substrate to enter enzyme
enzyme inhibitors – molecules that bind strongly to enzymes
turnover number – number of catalyzed reactions occurring at a particular active site
large turnover numbers = low activation energies

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Chapter Assessment
1. For the reaction A + 3B à 2C, how does the rate of disappearance of B compare to
the rate of production
of C?
a. the rate of disappearance of B is 1/2 the rate of appearance of C
b. the rate of disappearance of B is 3/2 the rate of appearance of C
c. the rate of disappearance of B is 2/3 the rate of appearance of C
d. the rate of disappearance of B is 1/3 the rate of appearance of C
2. For the reaction 2A + 3B → 4C + 5D, the rate of the reaction in terms of ΔA would be
written as:
a. –ΔA/Δt. d. +1/2 ΔA/Δt.
b. –1/2 ΔA/Δt. e. –2 ΔA/Δt.
c. +ΔA/Δt.
3. For the reaction 2A + 3B → 4C + 5D, the rate of the reaction in terms of ΔB would be
written as
a. –ΔB/Δt d. +1/3 ΔB/Δt
b. +ΔB/Δt e. –3 ΔB/Δt
c. –1/3 ΔB/Δt
4. For the reaction 2A + 3B → 4C + 5D, the rate of the reaction in terms of ΔC would be
written as
a. +ΔC/Δt d. d. –4 ΔC/Δt
b. +4 ΔC/Δt e. –1/4 ΔC/Δt
c. +1/4 ΔC/Δt
5. In the combustion of methane, CH4(g) + 2 O2(g) → CO2(g) + 2 H2O (g), which reactant
has the greatest rate of disappearance?

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a. CH4 b. O2
c. CO2 d. H2O
e. CH4 and O2 have the same rate of disappearance.
The look of concentration/time graphs

6. Which of the following is not a possible graph of concentration versus time for a
reactant?

7. Assuming that each of the following graphs has the same concentration and time
axes, which has the greatest initial rate of disappearance of reactant?

8. The following graph shows the kinetics curves for the reaction of oxygen with
hydrogen to form water:
O2(g) + 2H2(g) → 2H2O(g). Which curve is hydrogen?
a. the dashed curve

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b. the gray curve
c. the black curve
d. either the gray or the black curve
e. Any of these curves could be hydrogen

9. A scientist conducts an experiment to determine the rate of the following reaction:

N2(g) + O2(g) → 2NO(g)
If the initial concentration of N2 was 0.500 M and the concentration of N2 was 0.450 M
after 0.100 s, what is the rate of the reaction?
a. 0.500 M/s b. 1.00 M/s c. 5.00 M/s d. 10.0 M/s e. 0.250 M/s
10. A scientist conducts an experiment to determine the rate of NO formation in the
reaction:
N2(g) + O2(g) → 2NO(g)
If the initial concentration of N2 was 0.500 M and the concentration of N2 was 0.450 M
after 0.100 s, what is the rate of NO formation?
a. 0.500 M/s d. 10.0 M/s
b. 1.00 M/s e. 0.250 M/s
c. 5.00 M/s
11. If the rate of appearance of O2 in the reaction:
2O3(g) → 3O2(g) is 0.250 M/s over the first 5.50 s, how much oxygen will form during
this time?
a. 1.38 M d. 0.25 M
b. 4.13 M e. 0.46 M
c. 0.69 M
12. HI dissociates to form I2 and H2:
2HI(g) → H2(g) + I2(g) If the concentration of HI changes at a rate of –0.45 M/s, what is
the rate of appearance of I2(g)?
a. 0.90 M/s d. 1.00 M/s
b. 0.45 M/s e. 0.13 M/s
c. 0.23 M/s
13. If the rate of formation of ammonia is 0.345 M/s, what is the rate of disappearance of
N2?
N2 (g) + 3 H2 (g)  2 NH3 (g)
a. 0.173 M/s d. 245 M/s
b. 0.345 M/s e. 0.518 M/s
c. 0.690 M/s

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14. If the rate of formation of ammonia is 0.345 M/s, what is the rate of disappearance of
H2?
N2(g) + 3H2(g) → 2NH3(g)
a. 0.173 M/s d. 245 M/s
b. 0.345 M/s e. 0.518 M/s
c. 0.522 M/s
15. For the reaction 2A + B + 2C à D + 2E, the rate law is: rate =k[A]2[B]1[C]1
Which of the following statements is false:
a. the reaction is second order in [A] b. the reaction is first order in [B]
c. the reaction is second order in [C] d. the reaction is 4th order overall
16. For the reaction 1A + 2B + 1C à 2D + 1E, the rate law is: rate =k [B]2[C]1
Which of the following statements is false:
a. the reaction is first order in [A] b. the reaction is second order in [B]
c. the reaction is first order in [C] d. the reaction is third order overall
17. For the rate law Rate = k[A]1/2[B], the partial order with respect to A is __________,
the partial order with respect to B is __________, and the total order is __________.
a. 1/2; 0; ½ b. 1/2; 1; 1
c. 1/2; 1; 3/2 d. 1/2
e. The orders cannot be determined without a chemical reaction.
18. For the rate law Rate = k[A][B]3/2, the order with respect to A is __________, the
order with respect to B is __________, and the overall reaction order is __________.
a. 0; 3/2; 3/2 b. 1; 3/2 ; 1
c. 1; 3/2 ; 5/2 d. 1; 3/2; 7/2
e. The orders cannot be determined without a chemical reaction.
19. The reaction A + 2B → C is first order in B and A. The overall order of the reaction is
__________
a. first. d. zero.
b. second. e. fourth.
c. third.
20. The reaction CHCl3(g) + Cl2(g) → CCl4(g) + HCl(g) has the following rate law: Rate =
k[CHCl3][Cl2]. If the concentration of CHCl3 is increased by a factor of five while the
concentration of Cl2 is kept the same, the rate will
a. double. d. increase by a factor of five.
b. triple. e. decrease by a factor of one-fifth.
c. stay the same.

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Key to correction
1. B 11. A
2. B 12. C
3. C 13. A
4. C 14. C
5. B 15. C
6. C 16. A
7. A 17. C
8. C 18. C
9. A 19. B
10. B 20. D

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References
Lecture notes edited by John Reif from PPT lectures by:
•Chung (Peter) Chieh, University of Waterloo
•Hana El-Samad, UCSB
•John D. Bookstaver, St. Charles Community College
•Dan Reid, Champaign CHS
Brady, EB. (1990). General Chemistry – Principles and Structure (p. 852). New York:
John Wiley & Sons.
Masterson, WL., Hurley, CN., & Neth, EJ. (2012). Chemistry: Principles and Reactions
(p. 744). California, USA: Brooks/Cole, Cengage Learning.
Padolina, MCD., Sabularse, VC., & Marquez LA. (1995). Chemistry for the 21st Century
(p. 340). Makati, Philippines: Diwa Scholastic Press, Inc.
Silberberg, MS. (2007). Chemistry – The Molecular Nature of Matter and Change
(International Edition, p. 1088). New York: McGraw-Hill Co., Inc.

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