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Reaction Rates

Section 14.1

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

2

Basic Concepts

Section 14.2

reactants and the p

products as the reaction

proceeds?

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

concentration per unit time.

3

Expression of Rate

Section 14.2

change

h in

i time

i

Rate = Δ[CH3OH]

Δt Brackets represent

the concentration in

Molarity;

Δ indicates change

1

4

Reaction Rates

Section 14.2

Rate = Δ[CH3OH]

Δt

The negative sign indicates a

rate of disappearance.

5

Relationships Between Rates

Section 14.2

= = =

Δt Δt Δt Δt

− − + +

negative negative positive positive

6

Example

Section 14.2

was measured for the

following reaction and the following data were collected:

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

interval between each measurement.

2

7

Rate Comparisons

Section 14.2

• Average rate

of time on a curve; it does not tell you specifically

what happens between these two points

• Instantaneous rate

time; it tells you what is happening at that point, but

not what is happening before or after

8

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)

9

Instantaneous Rate

Section 14.2

curve touches the

1.75

curve only at one

point. The slope of

M)

1 50

1.50

[H + ] (M

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)

3

10

Example Question

Section 14.2

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.

11

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)

12

Stoichiometry and Rates

Section 14.2

= = =

Δt Δt Δt Δt

requires one mole of each reactant to form

one mole of each product.

4

13

Stoichiometry and Rates

Section 14.2

of NH3(g) are formed.

moles of NH3(g) are formed.

of H2(g) are required.

14

Stoichiometric Relationships

Section 14.2

aA + bB → cC + dD

= = =

a Δt b Δt c Δt d Δt

15

Example

Section 14.2

= =

1 Δt 3 Δt 2 Δt

Δ[H2] 3 Δ[NH3]

=

Δt 2 Δt

5

16

Example

Section 14.2

to the following equation:

instant in a reaction vessel is 4.2 x 10-7 M/s, what

is the rate of appearance of

a) NO2

b) O2

17

Solution

Section 14.2

= =

2 Δt 4 Δt Δt

• For NO2, = = 2

Δt 2 Δt Δt

1 Δ[N2O5] Δ[O2]

• For O2, =

2 Δt Δt

18

Concentration and Rates

Section 14.3

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

6

19

Rate Laws

Section 14.3

Rate = k[reactants]

doubled, what happens to the rate?

• If the concentration of the reactants is

quadrupled, what happens to the rate?

20

Rate Laws

Section 14.3

experimentally.

order in that reactant

– If the exponent is 2, we say that the reaction is

second order in that reactant

concentration?

21

Example

Section 14.3

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

reaction varies with reactant concentration in

the following manner:

7

22

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

23

Example Questions

Section 14.3

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?

24

Example

Section 14.3

disappearance of NO in the reaction:

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

8

25

Example Questions

Section 14.3

QUESTIONS:

• What are the units of the rate constant?

• What is the value of the rate constant?

26

First Order Reactions

Section 14.4

A → products

Rate = k[A]

y = mx + b

m = slope of the line

b = intercept = ln[A]0

27

Example

Section 14.4

at 215 °C.

0 502

2,000 335

5,000 180

8,000 95.5

12,000 41.7

15,000 22.4

9

28

Graph 1

Section 14.4

600

500

NC), mmHg

400

The graph of pressure

Pressure (CH3N

200

produce a straight line.

100

0

0 2000 4000 6000 8000 10000 12000 14000 16000

Time, sec

29

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

30

Example

Section 14.4

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

10

31

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)

32

Half-life

Section 14.4

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

33

Derivation

Section 14.4

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

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

½ [A]0

ln = - kt½

[A]0

11

34

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

35

Solution to Example

Section 14.4

rate constant from the slope of the line.

• Therefore,, the half-life can be determined

using the derived equation:

t½ = 0.693

k

36

Example Problem

Section 14.4

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?

12

37

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

1

b = intercept =

[A]0

38

Graphical Analysis

Section 14.4

39

Nuclear Chemistry

Section 21.1

– Stress test ((thallium-201))

– Reaction mechanisms (hydrogen-2)

– Dating historical artifacts (carbon-14)

– Generate electricity

13

40

Complete Atomic Symbols

Section 2.3

mass number

X

atomic number

5 protons

For example,

11

5 B 5 electrons

boron-11

41

Isotopes

Section 2.3

of neutrons, and therefore, the mass

1 2 3

1H 1H 1H

1 electron 1 electron 1 electron

0 neutrons 1 neutron 2 neutrons

42

Definitions

Section 21.1

• Nuclide

– A nucleus with a specified number of

protons and neutrons

• Radionuclides

– Nuclei that are radioactive

• Radioisotopes

– Atoms containing radionuclides

14

43

Types of Radioactive Decay

Section 21.1

44

Radioactive Decay

Section 21.1

Radioactive decay –

238 234

92U → 90Th + 24He

NOTE:

238 = 234 + 4 92 = 90 + 2

45

Example

Section 21.1

the following fission or fusion reactions:

235

92U + 01n → 160

62

Sm + 72

30

Zn + ___ 01n

239

94Pu + 01n → 144

58

Ce + _____ + 2 01n

15

46

Example Calculation

Section 14.4

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?

47

Reaction Mechanisms

Section 14.6

steps, called the reaction mechanism.

simply tell us what reactants are used, what

products are formed, and the stoichiometry.

– They do not give us information on the reaction

mechanism.

the reaction mechanism.

48

Example

Section 14.6

Rate = k[NO2]2

Proposed Mechanism:

NO2(g) + NO2(g) → NO3(g) + NO(g)

NO3(g) + CO(g) → NO2(g) + CO2(g)

elementary step.

16

49

Molecularity

Section 14.6

by its molecularity.

must collide to produce the reaction indicated

by that step.

– bimolecular: a reaction involving two molecules

– termolecular: a reaction involving three molecules

50

Intermediates

Section 14.6

are bimolecular.

NO2(g) 2( ) → NO3(g)

2( ) + NO2(g) 3( ) + NO(g)

( )

NO3(g) + CO(g) → NO2(g) + CO2(g)

during the reaction sequence

51

Reaction Mechanisms

Section 14.6

elementary steps that must satisfy two

requirements:

overall balanced equation for the reaction.

– The mechanism must agree with the experimentally

determined rate law.

criteria are met

17

52

First Criteria

Section 14.6

NO3(g) + CO(g) → NO2(g) + CO2(g)

overall reaction given earlier.

53

Second Criteria

Section 14.6

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.

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

54

Collision Model

Section 14.5

collide

occur, the collision must be

successful

produce the reaction

– The relative orientation must allow formation of any

new bonds necessary to produce the products

18

55

Energetics of a Reaction

Section 14.5

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.

56

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)

57

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.

19

58

Catalysis Example

Section 14.7

destruction of the ozone layer. They form

chlorine atoms in the atmosphere.

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.

59

E-Instruction Question

B increases with time.

time

C stays the same throughout the reaction

60

E-Instruction Question

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

20

61

E-Instruction Question

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

62

E-Instruction Question

which of the following statements is true?

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.

63

E-Instruction Question

what will be the effect on the rate oif the

concentration of A is doubled and the

concentration of B is tripled?

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.

21

64

E-Instruction Question

time can be characterized as

A a curve.

B a straight line with a negative slope.

C a straight line with a positive slope.

65

E-Instruction Question

initial reactant remains?

A 6.25

B 12.5

C 25

D 50

66

E-Instruction Question

intermediate.

Cl + O3 → ClO + O2

O + ClO → Cl + O2

A ClO

B Cl

C O3

22

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