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12 views92 pagesChemical Kinetics of Engineering Science including rates of reactions, nature of reactants, concentrations of reactants, collision theory, transition state theory, reaction mechanisms, catalysts

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Chemical Kinetics of Engineering Science including rates of reactions, nature of reactants, concentrations of reactants, collision theory, transition state theory, reaction mechanisms, catalysts

© All Rights Reserved

12 views

Chemical Kinetics of Engineering Science including rates of reactions, nature of reactants, concentrations of reactants, collision theory, transition state theory, reaction mechanisms, catalysts

© All Rights Reserved

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You are on page 1of 92

Chapter Goals

1. The Rate of a Reaction

Factors That Affect Reaction Rates

2. Nature of the Reactants

3. Concentrations of the Reactants: The

Rate-Law Expression

4. Concentration Versus Time: The

Integrated Rate Equation

5. Collision Theory of Reaction Rates

2

Chapter Goals

6. Transition State Theory

7. Reaction Mechanisms and the Rate-Law

Expression

8. Temperature: The Arrhenius Equation

9. Catalysts

Kinetics is the study of rates of chemical

reactions and the mechanisms by which

they occur.

The reaction rate is the increase in

concentration of a product per unit time or

decrease in concentration of a reactant per

unit time.

A reaction mechanism is the series of

molecular steps by which a reaction occurs.

4

Consider the hypothetical reaction,

aA(g) + bB(g) cC(g) + dD(g)

equimolar amounts of reactants, A and B,

will be consumed while products, C and D,

will be formed as indicated in this graph:

Note that the reaction does not go entirely to completion.

The [A] and [B] > 0 plus the [C] and [D] < 1.

Mathematically, the rate of a reaction can

be written as:

- A - B

+ C + D

Rate =

or

a t

b t

c t

d t

The rate of a simple one-step reaction is directly

proportional to the concentration of the reacting substance.

Rate A or Rate = k A

[A] is the concentration of A in molarity or moles/L.

k is the specific rate constant.

k is an important quantity in this chapter.

8

rate of reaction is doubled.

time required for the reaction to reach equilibrium would

be:

A. The same as the initial time.

B. Twice the initial time.

C. Half the initial time.

initial rate of reaction is cut in half.

9

If more than one reactant molecule appears

in the equation for a one-step reaction, we

can experimentally determine that the

reaction rate is proportional to the molar

concentration of the reactant raised to the

power of the number of molecules involved in

the reaction.

2 X g Y g + Z g

Rate X or Rate = k X

2

2

10

experimentally.

The rate law cannot be determined from the

balanced chemical equation.

This is a trap for new students of kinetics.

chemical reactions are not one-step reactions.

1. rate laws

2. rate equations

3. rate expressions

11

The order of a reaction can be expressed in

terms of either:

1 each reactant in the reaction or

2 the overall reaction.

Order for the overall reaction is the sum of the orders

for each reactant in the reaction.

For example:

2 N 2 O 5 g 4 NO 2 g + O 2 g

Rate = k N 2 O 5

and first order overall.

12

A second example is:

Rate = k[ CH 3 3 CBr ]

This reaction is first order in CH 3 3 CBr,

zero order in OH - , and first order overall.

13

A final example of the order of a reaction is:

2 NO + O 2 NO

g

2 g

Rate = k[NO] O

2 g

first order in O , and third order overall

2

DETERMINED EXPERIMENTALLY

14

Given the following one step reaction and its rate-law expression.

Remember, the rate expression would have to be experimentally

determined.

2 A g B g C g

Rate = k A

If the [A] is doubled the rate of the reaction will increase

by a factor of 4. 22 = 4

If the [A] is halved the rate of the reaction will decrease

by a factor of 4. (1/2)2 = 1/4

15

Rates

1.

2.

3.

4.

influence the rate of a reaction:

The nature of the reactants.

The concentration of the reactants.

The temperature of the reaction.

The presence of a catalyst.

We will look at each factor individually.

16

Nature of Reactants

This is a very broad category that encompasses the

different reacting properties of substances.

For example sodium reacts with water explosively at

room temperature to liberate hydrogen and form

sodium hydroxide.

2 Na s 2 H 2 O 2 NaOH aq H 2 g

This is a violent and rapid reaction.

The H 2 ignites and burns.

17

Nature of Reactants

Calcium reacts with water only slowly at

room temperature to liberate hydrogen

and form calcium hydroxide.

Ca s 2 H 2 O Ca OH 2 aq H 2 g

This is a rather slow reaction.

18

Nature of Reactants

The reaction of magnesium with water at

room temperature is so slow that that the

evolution of hydrogen is not perceptible to

the human eye.

Mg s H 2 O No reaction

19

Nature of Reactants

However, Mg reacts with steam rapidly to

liberate H2 and form magnesium oxide.

100 o C

Mg s H 2 O ( g ) MgO s H 2 g

The differences in the rate of these three

reactions can be attributed to the changing

nature of the reactants.

20

Concentrations of Reactants:

The

Rate-Law

Expression

Example 16-1: The following rate data were obtained at

25oC for the following reaction. What are the rate-law

expression and the specific rate-constant for this reaction?

2 A(g) + B(g) 3 C(g)

Experiment

Number

1

2

3

Initial [A]

(M)

0.10

0.20

0.10

Initial [B]

(M)

0.10

0.30

0.20

Initial rate of

formation of

C (M/s)

2.0 x 10-4

4.0 x 10-4

2.0 x 10-421

Concentrations of Reactants:

The Rate-Law Expression

The rate law must be of the form :

Rate = k A B

x

the [A] is constant and that the [B] increases by 2.

Notice that the initial rate remains constant.

2 1 y 0

x

0

x

Rate = k A B or Rate = k[A]

Thus, we can can ignore B.

y

22

Concentrations of Reactants:

TheNext,

Rate-Law

Expression

compare experiment

s 1 and 2.

Notice that the [A] increases by 2

and the rate increases by 2.

2 x 1

This reaction is 1st order with respect

to A and 1st order overall.

What is the value and units of k

for this reaction?

You do it!

23

Concentrations of Reactants:

The Rate-Law Expression

We can find the value of k from the rate law.

Rate

k=

A

Using the values of Rate and [A] from experiment 1

-4 M

2.0 x 10 s

-3 1

k=

2.0 x 10 s

0.10 M

Thus the rate law can be written as

Rate = 2.0 x 10

-3 1

[A]

24

Concentrations of Reactants:

The Rate-Law Expression

Example 16-2: The following data were obtained

Initial rate

for the following reaction at 25oC.Initial

What are the

of

[A] Initial

[B]specific

[C] rateformation

rate-law Initial

expression

and the

constant

Experimen

for

t the reaction?

(M)

(M)

(M)

of D (M/s)

2 A(g) + B(g) + 2 C(g) 3 D(g) + 2 E(g)

1

0.20

0.10

0.10

2.0 x 10-4

2

0.20

0.30

0.20

6.0 x 10-4

0.20

0.10

0.30

2.0 x 10-4

0.60

0.30

0.40

1.8 x 10-3

25

Concentrations of Reactants:

The Rate-Law Expression

Compare experiments 1 and 3.

3 1 z 0

x

y

z

x

y

Rate = k A B C or Rate = k A B

z

26

Concentrations of Reactants:

The Rate-Law Expression

Next, compare experiments 1 and 2.

The A remains constant.

The B increases by 3 and the rate increases by 3.

3 3 y 1

x

1

x

Rate = k A B or Rate = k A B

y

27

Concentrations of Reactants:

The Rate-Law Expression

Next, compare experiments 2 and 4.

The B remains constant.

The A increases by 3 and the rate increases by 3.

3 3 x 1

1

1

Rate = k A B or Rate = k A B

x

st

st

nd

28

Concentrations of Reactants:

The Rate-Law Expression

Finally, determine the value and units of k.

Can use the data from experiment 1, 2, 3, or 4.

4 M

Rate

2.0 10 s

k=

A B 0.20 M 0.10 M

1.0 10

2 1

Ms

Rate = 1.0 10

2 1

M s A B

29

Concentrations of Reactants:

The Rate-Law Expression

between compounds A and B that is first order

with respect to A, first order with respect to B,

and second order overall. From the information

Initial Rate

Initial [A]

Initial [B]

given below, fill in the blanks.

Experiment

(M/s)

(M)

(M)

You

do it!

-3

1

4.0 x 10

0.20

0.050

2

1.6 x 10-2

0.050

3.2 x 10-2

0.40

?

30

Concentrations of Reactants:

The Rate-Law Expression

Rate = k A B

From experiment 1 we can determine the value of k.

3 M

Rate

4.0 10 s

k=

A B 0.20 M 0.050 M

0.40 1 M s

Thus the Rate 0.40 1 M s A B

31

Concentrations of Reactants:

The Rate-Law Expression

Use the value of k and data from experiment 2

Rate

[A]

k[B]

2

1.6 10 Ms

[A]

1 -1

0.40 M s 0.050 M

[A] 0.80 M

-1

32

Concentrations of Reactants:

The Rate-Law Expression

Similarly, from experiment 3 we can determine

R

[B]

k[A]

2

3.2 10 Ms

[B]

1 -1

0.40 M s 0.40 M

[B] 0.20 M

-1

33

Integrated Rate Equation

concentration for chemical and nuclear

reactions.

From the integrated rate equation we can predict the

amount of product that is produced in a given

amount of time.

equation for first order reactions.

These reactions are 1st order in the reactant and 1st

order overall.

34

Integrated Rate Equation

reactant and 1st order overall is:

a A products

This is a common reaction type for many

chemical reactions and all simple radioactive

decays.

Two examples of this type are:

2 N2O5(g) 2 N2O4(g) + O2(g)

238

U 234Th + 4He

35

Integrated Rate Equation

The integrated rate equation for first order reactions is:

A 0

ln

akt

A

where:

[A]0= mol/L of A at time t=0.

t = time elapsed since beginning of

reaction.

a = stoichiometric coefficient of A in balanced overall equation.

36

Integrated Rate Equation

Solve the first order integrated rate equation for t.

1 A 0

t

ln

a k A

Define the half-life, t1/2, of a reactant as the time

required for half of the reactant to be consumed,

or the time at which [A]=1/2[A]0.

37

Integrated Rate Equation

At time t = t1/2, the expression becomes:

t 1/2

t 1/2

t 1/2

A 0

ln

ak

1/2 A 0

1

ln 2

ak

0.693

ak

38

Integrated Rate Equation

Example 16-4: Cyclopropane, an

anesthetic, decomposes to propene

according to the following equation.

CH2

H2C

CH2

(g)

H3C

CH

CH2

(g)

k = 9.2 s-1 at 10000C. Calculate the half life of

cyclopropane at 10000C.

t1/2

0.693 0.693

0

.

075

s

-1

k

9 .2 s

39

Integrated Rate Equation

How much of a 3.0 g sample of

cyclopropane remains after 0.50 seconds?

The integrated rate laws can be used for any

unit that represents moles or concentration.

In this example we will use grams rather than

mol/L.

40

Integrated Rate Equation

A

ln

a k t k t for this reaction

A

We must use the laws of logarithms.

0

ln A ln A k t

0

ln 3.0 - ln A 9.2 s

-1

0.50 s

1.10 ln A 4.6

A e 0.03 g or 1% remains

-3.5

41

Integrated Rate Equation

following first order reaction is 688 hours

at 10000C. Calculate the specific rate

constant, k, at 10000C and the amount of

a 3.0 g sample of CS2 that remains after

48 hours.

CS2(g) CS(g) + S(g)

You do it!

42

Integrated Rate Equation

For this reaction a 1.

0.693

t1/2

k

0.693

k

t1/2

0.693

-1

k

0.00101 hr

688 hr

43

Integrated Rate Equation

A ln A 0 k t ln A ln A k t

ln

k t ln A ln0 A k t

A A

-1

ln(3.0) - ln A (0.00101

ln(3.0)

00101hr

hr )(

)(48

48 hr)

hr)

1.10 - ln A 0.048

ln A -(0.048 - 1.10) 1.052

0

-1

A e

1.052

44

Integrated Rate Equation

to a particular reactant and second order

overall, the rate equation is:

1

1

akt

A A 0

Where:

[A]0= mol/L of A at time t=0.

beginning of reaction.

a = stoichiometric coefficient of A in balanced overall equation.

45

Integrated Rate Equation

If we solve for t1/2:

t1/2

a k A 0

reaction depends on the initial

concentration of A.

46

Integrated Rate Equation

Example 16-7: Acetaldehyde, CH3CHO, undergoes gas

phase thermal decomposition to methane and carbon

monoxide.

CH 3CHO g CH 4 g + CO g

The rate-law expression is Rate = k[CH3CHO]2,

and k = 2.0 x 10-2 L/(mol.hr) at 527oC. (a) What

is the half-life of CH3CHO if 0.10 mole is

injected into a 1.0 L vessel at 527oC?

47

Integrated Rate Equation

t1/2

k A 0

2.0 10

1

2

hr

-1

0.10 M

5.0 10 hr

48

Integrated Rate Equation

(b) How many moles of CH3CHO remain after

200 hours?

11

1

1

1

14 M

k t A

1

14 M

A A 0

1 A 10.071 M

. M

A 010

mol

1

1

1

10 M 4.0 M

A

0

.

071

mol

L

49

Integrated Rate Equation

(c) What percent of the CH3CHO remains

after 200 hours?

0.071 mol

% unreacted =

100%

0.10 mol

71% unreacted and 29% reacted

50

Integrated Rate Equation

What is the half-life of CH3CHO if 0.10

mole is injected into a 10.0 L vessel at

527oC?

Note that the vessel size is increased by a

factor of 10 which decreases the

concentration by a factor of 10!

You do it!

51

Integrated Rate Equation

t1/2

k A 0

2.0 10

1

1

-1

M hr 0.010 M

5.0 10 hr

note the time has increased by 10

over Example 16 - 7:

52

Enrichment - Derivation of

Integrated Rate Equations

rate equation.

A 0

ln

akt

A t

53

Enrichment - Derivation of

Integrated Rate Equations

second order in reactant A and second order

overall.

The rate equation is:

d A

2

k A

adt

54

Enrichment - Derivation of

Integrated Rate Equations

on the left and the t terms on the right.

d A

k

d

t

2

a A

55

Enrichment - Derivation of

Integrated Rate Equations

rate equation.

1

1

akt

A A 0

56

Enrichment - Derivation of

Integrated Rate Equations

d A

k

adt

57

Enrichment - Derivation of

Integrated Rate Equations

Which rearranges to:

d A a k d t

58

Enrichment - Derivation of

Integrated Rate Equations

equation.

A A 0 -a k t

or

A A 0 - a k t

59

Determine Reaction Order

Plots of the integrated rate equations can help us

determine the order of a reaction.

If the first-order integrated rate equation is

rearranged.

This law of logarithms, ln (x/y) = ln x - ln y, was applied

to the first-order integrated rate-equation.

ln A 0 ln A a k t

or

ln A a k t ln A 0

60

Determine Reaction Order

The equation for a straight line is:

y mx b

Compare this equation to the rearranged first

order rate-law.

61

to Determine Reaction Order

y mx b

ln A a k t ln A 0

m can be identified with ak and is the slope of the line.

x can be identified with t and plotted on the x-axis.

b can be identified with ln[A]0 and is the y-intercept.

62

Determine Reaction Order

the thermal decomposition of ethyl bromide are

given in the table below. Use the following graphs

of the data to determine the rate of the reaction

and the value of the rate constant.

C 2 H 5 Br g C 2 H 4 g HBr g at 700K

63

Determine Reaction Order

Time

(min)

[C2H5Br]

0

1.00

1

0.82

2

0.67

3

0.55

4

0.45

5

0.37

1/[C2H5Br]

1.0

1.2

1.5

1.8

2.2

2.7

64

to

Determine

Reaction

Order

We will make three different graphs of the

data.

1 Plot the [C2H5Br] (y-axis) vs. time (x-axis)

with respect to [C2H5Br].

If the plot is linear then the reaction is first order

with respect to [C2H5Br].

If the plot is linear then the reaction is second

order with respect to [C2H5Br].

65

to

Determine

Reaction

Order

Plot of [C H Br] versus time.

2

Is it linear or not?

66

to Determine Reaction Order

Plot of ln [C2H5Br] versus time.

Is it linear or not?

67

to Determine Reaction Order

Plot of 1/[C2H5Br] versus time.

Is it linear or not?

68

to Determine Reaction Order

Note that the only graph which is linear is the plot of ln[C 2H5Br] vs.

time.

Next, we will determine the value of the rate constant from the slope

of the line on the graph of ln[C 2H5Br] vs. time.

y 2 - y1 0.80 (0.20)

slope

x 2 - x1

4 1 min

0.60

-1

slope

0.20 min

3 min

69

Determine Reaction Order

From the equation for a first order reaction we

know that the slope = -a k.

In this reaction a = 1.

slope -0.20 -k

Thus the rate constant k 0.20 min .

-1

70

to Determine Reaction Order

The integrated rate equation for a reaction that is

second order in reactant A and second order

overall.

1

1

akt

A A 0

1

1

akt

A

A 0

71

to Determine Reaction Order

y mx b

second order1rate-law expression.

1

akt

A 0

m can be identified with a k and is the slope of the line.

x can be identified with t and plotted on the x-axis

b can be identified with 1/[A]0 and is the y-intercept.

72

to Determine Reaction Order

nitrogen dioxide are given in the table

below. Use the graphs to determine the

rate of the reaction and the value of the

rate constant

2 NO 2 g 2 NO g O 2 g at 500K

73

to Determine Reaction Order

Time

(min)

[NO2]

0

1.0

1

0.53

2

0.36

3

0.27

4

0.22

5

0.18

ln [NO2]

0.0

-0.63

-1.0

-1.3

-1.5

-1.7

1/[NO2]

1.0

1.9

2.8

3.7

4.6

5.5

74

to Determine Reaction Order

1.

of the data.

Plot [NO2] (y-axis) vs. time (x-axis).

respect to NO2.

2.

3.

respect to NO2.

with respect to NO2.

75

to Determine Reaction Order

Plot of [NO2] versus time.

Is it linear or not?

76

to Determine Reaction Order

Plot of ln [NO2] versus time.

Is it linear or not?

77

to Determine Reaction Order

Plot of 1/[NO2] versus time.

Is it linear or not?

78

to Determine Reaction Order

the plot of 1/[NO2] vs. time.

Thus this is a second order reaction with

respect to [NO2].

Next, we will determine the value of the

rate constant from the slope of the line on

the graph of 1/[NO2] vs. time.

79

to Determine Reaction Order

1

y 2 - y1 5.50 (1.90)

slope

x 2 - x1

5 1 min

3.60 1 M

slope

0.90 1 M min

4 min

From the equation for a second order reaction we

know that the slope = a k

In this reaction a = 2.

slope 0.90 2 k

Thus the rate constant k 0.45 M

min

-1

80

Collision Theory of

Reaction Rates

reaction to occur the atoms, molecules

or ions must:

1. Collide.

2. Collide with enough energy to break and

form bonds.

3. Collide with the proper orientation for a

reaction to occur.

81

Collision Theory of

Reaction Rates

One method to increase the number of collisions and

the energy necessary to break and reform bonds is to

heat the molecules.

As an example, look at the reaction of methane and

oxygen:

We must start the reaction with a match.

This provides the initial energy necessary to break the

first few bonds.

Afterwards the reaction is self-sustaining.

82

Collision Theory of

Reaction Rates

that is necessary for this reaction.

X2(g) + Y2(g) 2 XY(g)

X

X

Y Y

X X

Y Y

Y

83

Collision Theory of

Reaction Rates

Y

+

84

Transition state theory postulates that reactants

form a high energy intermediate, the transition

state, which then falls apart into the products.

For a reaction to occur, the reactants must

acquire sufficient energy to form the transition

state.

This energy is called the activation energy or Ea.

energy

85

Boulder

Eactivation

Epot=mgh2

Epot = mgh

h2

Height

Cross section

of mountain

h

h1

Epot=mgh1

86

Representation of a chemical reaction.

Eactivation - a kinetic quantity

Potential

Energy

E H

a thermodynamic

quantity

X2 + Y2

2 XY

Reaction Coordinate

87

88

The relationship between the activation

energy for forward and reverse reactions

is

Forward reaction = Ea

Reverse reaction = Ea + E

difference = E

89

The distribution of molecules possessing

different energies at a given temperature is

represented in this figure.

90

Temperature:

The Arrhenius Equation

relationship among (1) the temperature

(T), (2) the activation energy (Ea), and (3)

the specific rate constant (k).

k = Ae

or

Ea

RT

Ea

ln k = ln A RT

91

Catalysts

Catalysts change reaction rates by providing an

alternative reaction pathway with a different

activation energy.

92

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