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Reaction Rates
Section 14.1

• Chemical kinetics is the area of chemistry


concerned with the speed, or the rate, at
which a reaction occurs.

– milk spoiling
Concentration
– iron rusting
Temperature
• What controls the rate? Presence of a
Catalyst
Physical State

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Basic Concepts
Section 14.2

CH3OH(aq) + HCl(aq) → CH3Cl(aq) + H2O(l)

What happens to the concentration of the


reactants and the p
products as the reaction
proceeds?

− Concentration of CH3OH(aq) and HCl(aq) decreases


− Concentration of CH3Cl(aq) and H2O(l) increases

The reaction rate is defines as the change in


concentration per unit time.

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Expression of Rate
Section 14.2

CH3OH(aq) + HCl(aq) → CH3Cl(aq) + H2O(l)

Rate = change in concentration


change
h in
i time
i

Rate = Δ[CH3OH]

Δt Brackets represent
the concentration in
Molarity;
Δ indicates change

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Reaction Rates
Section 14.2

CH3OH(aq) + HCl(aq) → CH3Cl(aq) + H2O(l)

Rate = Δ[CH3OH]

Δt
The negative sign indicates a
rate of disappearance.

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Relationships Between Rates
Section 14.2

CH3OH(aq) + HCl(aq) → CH3Cl(aq) + H2O(l)

Δ[CH3OH] Δ[HCl] Δ[CH3Cl] Δ[H2O]


= = =
Δt Δt Δt Δt

− − + +
negative negative positive positive

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Example
Section 14.2

The rate of disappearance of H+


was measured for the
following reaction and the following data were collected:

CH3OH(aq) + HCl(aq) → CH3Cl(aq) + H2O(l)

Time, min
Ti i [H+],
] M
0.0 1.85
79.0 1.67
158.0 1.52
316.0 1.30
632.0 1.00

Calculate the average rate of reaction for the time


interval between each measurement.

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Rate Comparisons
Section 14.2

• Average rate

– The average rate is determined between two points


of time on a curve; it does not tell you specifically
what happens between these two points

• Instantaneous rate

– The instantaneous rate is determined at a point in


time; it tells you what is happening at that point, but
not what is happening before or after

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Average Rate
Section 14.2

2.00
This line intersects the
1.75 curve at two points.
The slope gives the
[H + ] (M )

1 50
1.50
average rate over an
1.25 interval of time.
Δy
1.00
Δx
0.75 Δy
m=
Δx
0 100 200 300 400 500 600 700
Time (min)

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Instantaneous Rate
Section 14.2

2.00 The tangent to the


curve touches the
1.75
curve only at one
point. The slope of
M)

1 50
1.50
[H + ] (M

this line gives the


1.25 Δy instantaneous rate at
that point in time.
1.00
Δx
0.75
0 100 200 300 400 500 600 700
Time (min)

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Example Question
Section 14.2

Using the graph provided, determine the


instantaneous rate at t = 100 minutes and t = 500
minutes.

PROCESS:
- Draw a tangent line to the curve at each point.
- Select two points on the tangent line and determine
their (x,y) coordinates.
- Calculate the slope of the line.

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Solution
Section 14.2

2.00

1.75
[H + ] (M )

1 50
1.50

1.25

1.00

0.75
0 100 200 300 400 500 600 700
Time (min)

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Stoichiometry and Rates
Section 14.2

CH3OH(aq) + HCl(aq) → CH3Cl(aq) + H2O(l)

Δ[CH3OH] Δ[HCl] Δ[CH3Cl] Δ[H2O]


= = =
Δt Δt Δt Δt

This relationship is true because the reaction


requires one mole of each reactant to form
one mole of each product.

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Stoichiometry and Rates
Section 14.2

N2(g) + 3 H2(g) → 2 NH3(g)

- For every 1 mole of N2(g) that is used, 2 moles


of NH3(g) are formed.

- For every 3 moles of H2(g) that are used, 2


moles of NH3(g) are formed.

- For every 1 mole of N2(g) that is used, 3 moles


of H2(g) are required.

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Stoichiometric Relationships
Section 14.2

For a general reaction,

aA + bB → cC + dD

1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]


= = =
a Δt b Δt c Δt d Δt

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Example
Section 14.2

N2(g) + 3 H2(g) → 2 NH3(g)

1 Δ[N2] 1 Δ[H2] 1 Δ[NH3]


= =
1 Δt 3 Δt 2 Δt

Δ[H2] 3 Δ[NH3]
=
Δt 2 Δt

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Example
Section 14.2

The decomposition of N2O5 proceeds according


to the following equation:

2 N2O5(g) → 4 NO2(g) + O2(g)

If the rate of decomposition of N2O5 at a particular


instant in a reaction vessel is 4.2 x 10-7 M/s, what
is the rate of appearance of
a) NO2
b) O2

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Solution
Section 14.2

2 N2O5(g) → 4 NO2(g) + O2(g)

1 Δ[N2O5] 1 Δ[NO2] Δ[O2]


= =
2 Δt 4 Δt Δt

Δ[NO2] 4 Δ[N2O5] Δ[N2O5]


• For NO2, = = 2
Δt 2 Δt Δt

1 Δ[N2O5] Δ[O2]
• For O2, =
2 Δt Δt

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Concentration and Rates
Section 14.3

• Rates are dependent on the concentration of


the reactants
• Rates are studied in experiments in which the
concentrations are varied and the rates are
measured
• For any reaction, we can write a rate law which
expresses the dependence of rate on the
concentration of the reactants

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Rate Laws
Section 14.3

The form for a rate law is

Rate = k[reactants]

k = rate constant, determined experimentally

• If the concentration of the reactants is


doubled, what happens to the rate?
• If the concentration of the reactants is
quadrupled, what happens to the rate?

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Rate Laws
Section 14.3

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

• The values of m and n must be determined


experimentally.

– If the exponent is 1, we say that the reaction is first


order in that reactant
– If the exponent is 2, we say that the reaction is
second order in that reactant

• How does the rate change with


concentration?

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Example
Section 14.3

Consider the reaction of peroxydisulfate ion,


[S2O8]2-, with iodide ion, I−, in aqueous solution:

S2O82-(aq) + 3 I−(aq) → 2 SO42-(aq) + I3 −(aq)

At a particular temperature, the rate of this


reaction varies with reactant concentration in
the following manner:

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Example Data
Section 14.3

Δ[S2O82-]
Exp [S2O82-] [I−]
Δt
1 0 038
0.038 0 060
0.060 1 4 x 10-55
1.4

2 0.076 0.060 2.8 x 10-5

3 0.076 0.030 1.4 x 10-5

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Example Questions
Section 14.3

• Write the rate law for the rate of


disappearance of S2O82- .
• What is the value of the rate constant for
the disappearance of S2O822-? (don
(don’tt forget
units!)
• What is the rate of disappearance of S2O82-
when [S2O82-] = 0.025 M and [I−] = 0.100 M?
• What is the rate of appearance of SO42-
when [S2O82-] = 0.025 M and [I−] = 0.050 M?

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Example
Section 14.3

The following data were collected for the rate of


disappearance of NO in the reaction:

2 NO(g) + O2(g) → 2 NO2(g)

Exp [NO] [O2] Rate


1 0.0126 0.0125 1.41 x 10-2
2 0.0252 0.0250 1.13 x 10-1
3 0.0252 0.0125 5.64 x 10-2

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Example Questions
Section 14.3

QUESTIONS:

• What is the rate law for the reaction?


• What are the units of the rate constant?
• What is the value of the rate constant?

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First Order Reactions
Section 14.4

A → products
Rate = k[A]

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

y = mx + b

plot ln[A]t on the y-axis and time on the x-axis


m = slope of the line
b = intercept = ln[A]0

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Example
Section 14.4

Data for the gas-phase rearrangement of CH3NC


at 215 °C.

Time, sec Pressure (CH3NC), torr


0 502
2,000 335
5,000 180
8,000 95.5
12,000 41.7
15,000 22.4

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Graph 1
Section 14.4

600

500
NC), mmHg

400
The graph of pressure
Pressure (CH3N

300 versus time does not


200
produce a straight line.

100

0
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, sec

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Graph 2
Section 14.4

6.50
6.00
ln (P ressu re (C H 3 N C ))

5.50
slope = -k
5.00
4.50
4.00
3.50 intercept = ln[A]0
3.00
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, sec

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Example
Section 14.4

Based on the previous graph, determine the


first-order rate constant and the half-life for the
reaction.

PROCESS:
- To determine the rate constant, must calculate the
slope
- To determine the half-life for the reaction, need
more background information

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Graph 2
Section 14.4

6.50
6.00
ln (P ressu re (C H 3 N C ))

5.50
5.00 ((0,6.22)
, )
4.50
4.00
3.50
3.00
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, sec
(15,000, 3.11)

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Half-life
Section 14.4

Half-life is defined as the time required for the


concentration of a reactant substance to
decrease to half of its initial value

If t1/2 = 12 seconds….

t=0 t = 12 t = 24 t = 36 t = 48 t = 60

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Derivation
Section 14.4

Since [A]0 is equal to the initial concentration,


½[A]0 is equal to the concentration at the half-life.

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

ln ½ [A]0 = - kt½ + ln [A]0

ln ½ [A]0 - ln[A]0 = -kt½

½ [A]0
ln = - kt½
[A]0

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Derivation Continued
Section 14.4

½ [A]0
ln = - kt½
[A]0

1
- ln = kt½ The half-life for a
2
first-order reaction
is NOT dependent
0.693 = kt½
on concentration.
t½ = 0.693
k

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Solution to Example
Section 14.4

• Previously, we determined the value of the


rate constant from the slope of the line.
• Therefore,, the half-life can be determined
using the derived equation:

t½ = 0.693
k

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Example Problem
Section 14.4

The first-order rate constant for the


decomposition of a certain antibiotic in
water at 20 °C is 1.65 yr-1. If a 6.0 x 10-3 M
solution
l ti off the
th antibiotic
tibi ti is
i stored
t d att 20
°C, what will its concentration be after 3
months?

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Second Order Reactions
Section 14.4

A → products
Rate = k[A]2
1 1
= ktt +
[A]t [A]0
1
Plot on the y-axis and time on the x-axis
[A]t

m = slope of the line = k


1
b = intercept =
[A]0

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Graphical Analysis
Section 14.4

NO2(g) → NO(g) + ½ O2(g)

The reaction is second order in NO2(g).

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Nuclear Chemistry
Section 21.1

• Nuclear reactions are commonly used for:

– Cancer therapy (cobalt-60)


– Stress test ((thallium-201))
– Reaction mechanisms (hydrogen-2)
– Dating historical artifacts (carbon-14)
– Generate electricity

• Critical content for general science knowledge

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Complete Atomic Symbols
Section 2.3

mass number
X
atomic number

5 protons
For example,
11
5 B 5 electrons

Also written as 6 neutrons


boron-11

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Isotopes
Section 2.3

Atoms of an element which vary in the number


of neutrons, and therefore, the mass

1 2 3
1H 1H 1H

1 proton 1 proton 1 proton


1 electron 1 electron 1 electron
0 neutrons 1 neutron 2 neutrons

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Definitions
Section 21.1

• Nuclide
– A nucleus with a specified number of
protons and neutrons

• Radionuclides
– Nuclei that are radioactive

• Radioisotopes
– Atoms containing radionuclides

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Types of Radioactive Decay
Section 21.1

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Radioactive Decay
Section 21.1

Radioactive decay –

a nucleus spontaneously decomposes

238 234
92U → 90Th + 24He

NOTE:
238 = 234 + 4 92 = 90 + 2

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Example
Section 21.1

Complete and balance the nuclear equations for


the following fission or fusion reactions:

235
92U + 01n → 160
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Sm + 72
30
Zn + ___ 01n

239
94Pu + 01n → 144
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Ce + _____ + 2 01n

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Example Calculation
Section 14.4

The radioactive isotope 32P decays by first-


order kinetics and has a half-life of 14.3
days How long does it take for 95
days. 95.0%
0% of a
sample of 32P to decay?

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Reaction Mechanisms
Section 14.6

• Most chemical reactions occur by a series of


steps, called the reaction mechanism.

– The reactions that we have discussed to date


simply tell us what reactants are used, what
products are formed, and the stoichiometry.
– They do not give us information on the reaction
mechanism.

• Chemical kinetics aids in the determination of


the reaction mechanism.

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Example
Section 14.6

NO2(g) + CO(g) → NO(g) + CO2(g)

Rate = k[NO2]2

Proposed Mechanism:
NO2(g) + NO2(g) → NO3(g) + NO(g)
NO3(g) + CO(g) → NO2(g) + CO2(g)

Each reaction is called an


elementary step.

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Molecularity
Section 14.6

• The rate of an elementary step is determined


by its molecularity.

• The molecularity is the number of species that


must collide to produce the reaction indicated
by that step.

– unimolecular: a reaction involving one molecule


– bimolecular: a reaction involving two molecules
– termolecular: a reaction involving three molecules

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Intermediates
Section 14.6

Both of these reactions


are bimolecular.

NO2(g) 2( ) → NO3(g)
2( ) + NO2(g) 3( ) + NO(g)
( )
NO3(g) + CO(g) → NO2(g) + CO2(g)

An intermediate is formed and consumed


during the reaction sequence

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Reaction Mechanisms
Section 14.6

• Reaction mechanisms are a series of


elementary steps that must satisfy two
requirements:

– The sum of the elementary steps must give the


overall balanced equation for the reaction.
– The mechanism must agree with the experimentally
determined rate law.

• Check each mechanism to determine if the


criteria are met

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First Criteria
Section 14.6

NO2(g) + NO2(g) → NO3(g) + NO(g)


NO3(g) + CO(g) → NO2(g) + CO2(g)

NO2(g) + CO(g) → NO(g) + CO2(g)

This reaction is the same as the


overall reaction given earlier.

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Second Criteria
Section 14.6

• Multistep reactions often have one step that is


much slower than all of the others. This step
is called the rate-determining step.
• The rate of the reaction is dependent on the
rate-determining
t d t i i step.
t
• The rate law is based on the molecularity of
the rate-determining step.

NO2(g) + NO2(g) → NO3(g) + NO(g) slow step


NO3(g) + CO(g) → NO2(g) + CO2(g) fast step

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Collision Model
Section 14.5

• For a reaction to occur, molecules must


collide

• For a reaction to occur


occur, the collision must be
successful

– The collisions must involve enough energy to


produce the reaction
– The relative orientation must allow formation of any
new bonds necessary to produce the products

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Energetics of a Reaction
Section 14.5

transition • Reaction is exothermic,


state
ΔH is less than zero
• The energy that must be
overcome for the
activation
energy reaction to occur is
called the activation
energy, Ea.
• The top of the energy
barrier is called the
activated complex or the
transition state.

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The Arrhenius Equation
Section 14.5

Ea
• An increase in
RT the Ea results in
k = Ae
a decrease in k
A = frequency factor • An increase in T
results in an
increase in k

-Ea 1
ln k = + ln(A)
R T
linear equation with a slope of –Ea/R
and a y-intercept of ln(A)

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Catalysis
Section 14.7

• A catalyst is a substance
that speeds up a reaction
without begin consumed
itself.
• Lowers the activation
energy of the reaction by
providing an alternative
pathway.
• Does not affect the ΔH.
• Can be a homogeneous
catalyst or a heterogeneous
catalyst.

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Catalysis Example
Section 14.7

Freons, such as CCl2F2, contribute to the


destruction of the ozone layer. They form
chlorine atoms in the atmosphere.

CCl2F2(g) → CClF2(g) + Cl(g)

The chlorine atoms catalyze the


decomposition of ozone.
Chlorine is used
to initiate the Cl(g) + O3(g) → ClO(g) + O2(g)
reaction and is
regenerated in O(g) + ClO(g) → Cl(g) + O2(g)
the last step.

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E-Instruction Question

The rate of disappearance of a reactant

A decreases with time.


B increases with time.
time
C stays the same throughout the reaction

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E-Instruction Question

If the [NO2] decreases from 0.0100 to 0.0065 M in


100 s, the rate of disappearance of NO2 for this
period is _____ M/s.

A 0.35
B 7.0 x 10-3
C 3.5 x 10-3
D 1.8 x 10-3
E 3.5 x 10-5

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61
E-Instruction Question

Based on the following reaction, the rate at


which ammonia is formed is _____ that of the
rate that nitrogen is used.

N2 + 3 H2 → 2 NH3

A the same
B two times
C half
D three times

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E-Instruction Question

Based on the following rate law, rate = k[A]2[B],


which of the following statements is true?

A The reaction is first order in A, second


order
d ini B,
B andd third
thi d order
d overall.ll
B The reaction is second order in A, first
order in B, and second order overall.
C The reaction is second order in A, first
order in B, and third order overall.
D The reaction is first order in A, second
order in B, and second order overall.

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E-Instruction Question

Based on the following rate law, rate = k[A]2[B],


what will be the effect on the rate oif the
concentration of A is doubled and the
concentration of B is tripled?

A The rate will increase by a factor of 18.


B The rate will increase by a factor of 12.
C The rate will increase by a factor of 6.
D The rate will increase by a factor of 4.

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64
E-Instruction Question

For a first order reaction, the plot of ln[A] versus


time can be characterized as

A a curve.
B a straight line with a negative slope.
C a straight line with a positive slope.

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E-Instruction Question

After three half-lives, what percentage of the


initial reactant remains?

A 6.25
B 12.5
C 25
D 50

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E-Instruction Question

In the reaction mechanism below, ____ is the


intermediate.

Cl + O3 → ClO + O2
O + ClO → Cl + O2

A ClO
B Cl
C O3

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