11.

R E A C T I O N R AT E

C H E M I S T RY U N I T SK027

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OBJECTIVES:
1. Write the integrated rate laws for zero order, 1st order and 2nd order reaction 2. Define half-life. 3. Draw the respective graphs for the different order reactions. 4. Solve quantitative problems.

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Integrated Rate Laws

o The integrated rate law is an equation that

describes the concentration of a reactant as a function of time. It can use to determine rate constant, half life and concentration of reactant at specific time

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Integrated Rate Equation

For reaction, A product (a) For Zero-order reaction
Rate = k[A]o Rate = d[A] dt d[A] = k The differential rate equation;

dt

The integrated rate equation;

[A]o [A]t = kt

[A]o = initial concentration of A [A]t = concentration of A at time t k = rate constant t = time t S K 0 2 7 C H E M I S T RY

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Integrated Rate Equation

o Half life(t1/2) of a zero order reaction o Half life (t1/2) is defined as the length of time required
for the concentration of a reactant to decrease to half of its initial value. [A]o [A]t = kt Since, Substituting t = t1/2 , Thus, [A]t =

[A]o [A]o = kt1/2 2

[A] o 2

t1/2

[A]o = 2k
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Characteristic graphs for zero order reaction

Rate = k[A]o Rate

[A] [A]o [A]t = kt [A]t = [A]o kt y = C + mx t

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[A]o [A] Gradient = k

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Integrated Rate Equation

For reaction, A product (b) For first-order reaction Rate = d[A] Rate = k[A]1

dt
The differential rate equation;

d[A] dt

= k[A]

The integrated rate law;

ln[A]o ln[A]t = kt

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Integrated Rate Equation

Half life(t1/2) of a first-order reaction Since,

[A]o = kt ln [A]t
[A]t = [A]o

Substituting t = t1/2 ,

[A]o ln = kt1/2 [A]o 2

t1/2 ln 2 = k

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Characteristic graphs for first-order reaction

Rate = k [A] rate ln[A]o ln[A] t = kt ln[A]o ln[A]

[A] [A] ln[A]o [A]

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Graph of half life(t1/2) for first-order reaction

[A] [A]o

t1/2

ln 2 = k

t1/2 is independent of initial concentration [A]o/2 [A]o/4 t1 t2 time

t1 = t2

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Exercise: The reaction 2A B is first order in A with a rate constant of 2.8 x 10-2 s-1 at 800oC. How long will it take for A to decrease from 0.88 M to 0.14 M ? Solution:

[A]o ln = kt [A] t

[A]0 = 0.88 M [A]t = 0.14 M t = 66 s

ln(0.88 0.14) t= 2.8102

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Exercise: 2. For the first order decomposition of H2O2(aq) given that k = 3.66 x 10-3 s-1 and [H2O2 ]o = 0.882 M, determine; (105.26 s) a) the time at which [H2O2] = 0.600 M b) the [H2O2 ] after 225 s. ([H2O2] = 0.387 M) 3. The decomposition of ethane, C2H6 to methyl radicals is a 1st order reaction with a rate constant of 5.36 x 10-4 s-1 at 700o C. C2H6(g) 2CH3(g) Calculate the half life of the reaction in minutes. (t1/2 = 21.5 min)
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Exercise: The decomposition of nitrogen pentoxide is as below; N2O5(g) 2 NO2(g) + O2(g)

time, t/min [N2O5] x 10-4 M 0 176 10 124 20 93 30 71 40 53 50 39 60 29

The decomposition is first order reaction. a)Plot a linear graph to prove it. b)From the plot determine rate constant, k
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Solution:
time, t/min 0 10 124 20 93 30 71 40 53 50 39 60 29 -5.84 [N2O5] x 10-4 M 176 ln[N2O5] -4.04

-4.39 -4.68
t (s)

-4.95 -5.24 -5.55

0 -1 0 -2 ln [N2O5] -3 -4 -5 -6 -7 y = -0.0296x - 4.0686 20 40 60 80

Plot ln [N2O5] vs t gives a linear plot & -ve gradient as the linear equation for The integrated rate law for first order rxn is ln[N2O5]t = ln [N2O5]o-kt From the plot gradient = k = 0.0296 s-1

ln [N2O5] vs t

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Exercise: The following results were obtained from an experimental investigation on dissociation of dinitrogen pentokside at 45oC N2O5(g) 2 NO2(g) + O2(g)
time, t/min [N2O5] x 10-4 M 0 176 10 124 20 93 30 71 40 53 50 39 60 29

Plot graph of [N2O5] vs time, determine i) The order of the reaction ii) the rate constant k

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Solution:
180 160

1st t1/2 = 20 min (176 x 10-4 M 88 x 10-4 M) 2nd t1/2 = 20 min (88 x 10-4 M 44 x 10-4 M) t1/2 for the reaction is a constant and does not depend on the initial [N2O5] Thus, the above reaction is first order k=

[N2O5] x 10-4 M

140 120 100 80 60 40 20 10 20 30

ln 2 = 0.035 min 1 20

40

50

60

70

80

t (min)

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Integrated Rate Equation

For reaction, A product (b) For second-order reaction
d[A] Rate = dt

Rate = k[A]2

d[A] = k[A]2 The differential rate equation; dt

The integrated rate law;
1 1 = kt [A]t [A]o

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Integrated Rate Equation

Half life(t1/2) of a second-order reaction Since,

1 1 = kt [A]t [A]o
[A]t =

Substituting t = t1/2 ,

1 1 = kt1/2 [A]o 2 [A]o

t1/2 1 = [A]o k
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[A]o 2

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Characteristic graphs for second-order reaction 1 1 Rate = k [A]2 = kt [A]t [A]o

1/[A] 1/[A]o [A] t 1/[A] 1/[A]o [A] rate

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Graph of half life(t1/2) for second-order reaction

[A]o

t1/2

1 = [A]o k

t1/2 is dependent on initial concentration [A]o/2 [A]o/4 t2 = 2t1

t1

t2

time

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Exercise: Iodine atoms combine to form molecular iodine in the gaseous phase, I(g) + I(g) I2(g) This reaction follows second order and has a high rate constant 7.0 x 109 M-1s-1 If the initial concentration of iodine was 0.086 M, i) calculate its concentration after 2 min. ii) calculate the half life of the reaction if the initial concentration of iodine is 0.06 M and 0.42 M respectively.
[I] = 1.190 x 10-12 M , 3.4 x 10-10 s 2.4 x 10-9s
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Exercise:
1) The decomposition of HI is second order, at 500oC, the halflife of HI is 2.11 min when the initial HI concentration is 0.10 M. What will be the half-life (in minutes) when the initial HI concentration is 0.010 M? (21 min) The rate constant for the first-order decomposition of N2O5(g) at 100oC is 1.46 10-1s-1. a) If the initial concentration of N2O5 in a reaction vessel is 4.5 10-3 mol/L, what will the concentration be 20.0 s after the decomposition begins? (2.4 10-4 M) b) What is the half-life (in s) of N2O5 at 100oC? (4.75 s) c) If the initial concentration of N2O5 is 4.50 10-3 M, what will be the concentration be after three half-lives? (5.62 10-4 M) S K 0 2 7 C H E M I S T RY

2)

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Summary
Integrated Rate Law [A]o-[A]t = kt Linear Plot [A]t vs t ln[A]t vs t 1/[A]t vs t

Order 0 1 2

Rate Law rate = k rate = k [A] rate = k [A]2

Half-Life t = [A]0 2k

t = ln2 ln[A]o - ln[A]t = kt k 1 1 1 = kt t = k[A]0 [A]t [A]o

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Problem-solving Tip 1. Which equation to use: o The rate-law expression relates rate and conc. o The integrated rate equation relates time and conc. 2. To know the Order of reaction o Order is stated o Rate law expression is given o Unit of rate constant, k. order 0 M time-1 order 1 time-1 order 2 M-1 time-1
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