Section 12.

3
Determining the Form of the Rate Law
Method of Initial Rates
 Example: NH4+ + NO2-  N2 + 2H2O
Rate = k [NH4+]x[NO2-]y
Experiment [NH4+]o [NO2-] o Initial Rate
1 0.1 0.005 1.35x10-7
2 0.1 0.01 2.70x10-7
3 0.2 0.01 5.40x10-7

Rate1 = k (0.1)x(0.005)y Rate2 = k (0.1)x(0.01)y

Rate3 = k (0.2)x(0.01)y
To determine x, select two experiments where [NO2-] is constant
To determine y, select two experiments where [NH4+] is constant
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Section 12.3
Determining the Form of the Rate Law
Experiment [NH4+]o [NO2-] o Initial Rate
1 0.1 0.005 1.35x10-7
2 0.1 0.01 2.70x10-7
3 0.2 0.01 5.40x10-7

Rate1 = k (0.1)x(0.005)y Rate2 = k (0.1)x(0.01)y

Rate3 = k (0.2)x(0.01)y
Rate2/Rate1= k (0.1)x(0.01)y / k (0.1)x(0.005)y = (2)y
= 2.70x10-7 / 1.35x10-7 = 2  y=1

Rate3/Rate2= k (0.2)x(0.01)y / k (0.1)x(0.01)y = (2)x

= 5.40x10-7 / 2.70x10-7 = 2  x=1
∴ Rate = k [NH4+]1[NO2-]1 overall reaction is 1+1=2 (2nd order reaction)
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Section 12.3
Determining the Form of the Rate Law
Experiment [NH4+]o [NO2-] o Initial Rate
1 0.1 0.005 1.35x10-7
2 0.1 0.01 2.70x10-7
3 0.2 0.01 5.40x10-7

∴ Rate = k [NH4+]1[NO2-]1 overall reaction is 1+1=2 (2nd order reaction)

Determination of K: pick any experiment, e,g experiment 1
Rate1 = k (0.1)1(0.005)1 = 1.35x10-7  k=2.7x10-4 L/mol.s

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Section 12.3
Determining the Form of the Rate Law
Integrated Rate Law
 Shows how the concentrations of species in the reaction
depend on time. -d[A]/dt =k[A]
Example: A  products -d[A] = k[A] dt
x -d[A]/[A] = k dt
-d[A]/dt = Rate = k[A]
- (1/[A]).d[A]= k dt
ln[A]t = -kt + ln[A]o

x Differential rate law Integrated rate law Half-life K unit

1, 1st order Rate = -d[A]/dt = k[A]1 ln[A] t = -kt + ln[A]o t1/2=ln2/k 1/s
2, 2nd order Rate = -d[A]/dt = k[A]2 1/[A] t = +kt + 1/[A]o t1/2=1/k[A]o L/mol.s
0, 0th order Rate = -d[A]/dt = k[A]0 = k [A] t = -kt + [A]o t1/2=[A]o/2k mol/L.s

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Section 12.4
The Integrated Rate Law

First-Order
 Rate = k[A]
 Integrated:
ln[A] = –kt + ln[A]o

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A
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Section 12.4
The Integrated Rate Law
Example: For 2N2O5 4NO2 + O2 Rate=k[N2O2]x verify the rate
law is 1st order in N2O5 (x=1)
Since a plot of ln[N2O5] vs time gives a straight line 1st order

From plot: slope = -k and intercept = ln[N2O5]o

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Section 12.4
The Integrated Rate Law
Slope=(- 5.075 - -2.303)/400-0= -6.93x10-3  k=+6.93x10-3 s-1
Calculate [N2O5] at 150 s: ln[A] = -kt + ln[A]o

ln[N O ]=-6.93x10 -3 (150) + (-2.303) [N O ]= 0.0353 M

 2 5 2 5
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Section 12.4
The Integrated Rate Law

Half-life of First-Order Reactions

 Time required for a reactant to reach half its original
concentration
 Half–Life:
0.693
t1 =
2 k
k = rate constant, 0.693 = ln2
 Half–life for 1st order reactions does not depend on the
concentration of reactants.

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Section 12.4
The Integrated Rate Law

Example: A first order reaction is 35% complete at the end of 55

minutes. What is the value of k? Calculate half-life

Answer: 35% complete means remaining 65%, so if initial

concentration was 1 M, concentration after 55 min is 0.65 M:
ln(0.65) = –k(55) + ln(1)

k = 7.8 x 10-3 min-1

Half-life for first-order reactions is t1/2=ln2/k =0.693/(7.8 x 10-3)

= 88.8 min
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Section 12.4
The Integrated Rate Law

Second-Order
 Rate = k[A]2
 Integrated:
1 1
= kt +
A  A 0

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A
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Section 12.4
The Integrated Rate Law
Example: 2C4H6C8H12 is this a 1st or 2nd order reaction?
[C4H6] (M) t (s) What is the value of k?
0.01 0
0.00625 1000
0.00476 1800
0.00370 2800
….. …..
0.00208 6200

Answer: To verify 1st order reaction, we need to plot

ln[C4H6] vs time, and to verify 2nd order reaction, we
need to plot 1/[C4H6] vs time.

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Section 12.4
The Integrated Rate Law
So we add two columns to the given data
[C4H6] (M) t (s) ln[[C4H6]] 1/[C4H6]
0.01 0 -4.605 100
0.00625 1000 -5.075 160
0.00476 1800 -5.348 210
0.00370 2800 -5.599 270
….. ….. ….. …..
0.00208 6200 -6.175 481

Then we plot ln[[C4H6]] vs time and 1/[C4H6] vs time and

the results are shown in the next slide:

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Section 12.4
The Integrated Rate Law

Plot of ln[C4H6] vs Time and Plot of 1/[C4H6] vs Time

So the
reaction is
2nd order
Section 12.4
The Integrated Rate Law
Value of k for 2nd order reaction = slope of graph
[C4H6] (M) t (s) ln[[C4H6]] 1/[C4H6]
0.01 0 -4.605 100
0.00625 1000 -5.075 160
0.00476 1800 -5.348 210
0.00370 2800 -5.599 270
….. ….. ….. …..
0.00208 6200 -6.175 481

Slope = Δy/Δx = (481-100)/(6200-0)= 6.14x10-2 L/mol.s

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Section 12.4
The Integrated Rate Law

Second-Order
 Half–Life:
1
t1 =
2 k  A 0
k = rate constant
[A]o = initial concentration of A

 Half–life gets longer as the reaction progresses and the

concentration of reactants decrease.
 Each successive half–life is double the preceding one.
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Section 12.4
The Integrated Rate Law
Calculate the value of half-life for this reaction.
[C4H6] (M) t (s) ln[[C4H6]] 1/[C4H6]
0.01 0 -4.605 100
0.00625 1000 -5.075 160
0.00476 1800 -5.348 210
0.00370 2800 -5.599 270
….. ….. ….. …..
0.00208 6200 -6.175 481

t1/2= 1/K[C4H6]o= 1/ (6.14x10-2)(0.01) = 1.13x103 s

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Section 12.4
The Integrated Rate Law

Zero-Order
 Rate = k[A]0 = k
 Integrated:
[A] = –kt + [A]o

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A

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Section 12.4
The Integrated Rate Law

Zero-Order
 Half–Life:
 A 0
t1 =
2 2k

k = rate constant
[A]o = initial concentration of A

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Section 12.4
The Integrated Rate Law

Summary of the Rate Laws

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Section 12.4
The Integrated Rate Law

EXERCISE!

Consider the reaction aA  Products.

[A]0 = 5.0 M and k = 1.0 × 10–2 L/mol.s. Calculate [A] after 30.0
seconds have passed.

Answer=2.0 M
Note: check units of k given in the question

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