2.

2 LESSON: INTEGRATED RATE LAW Name:

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2.2 LESSON
Integrated Rate Law
AP CHEMISTRY LEARNING OBJECTIVES
• Topic 5.3 [TRA-3.C]: Identify the rate law expression of a chemical reaction using data that show how the concentrations of reaction species change
over time.

0 Order Reaction Integrated Rate Law

Describes the relationship
Consider the zero-order reaction: A → products. between the concentration of
• Write the rate law for this zero-order reaction. rate = k[A]0 the reactant and time.
• As the concentration of A decreases, the rate (or slope) is constant.
A graph in which the slope is constant is a straight line. Therefore the

[A]
rate = slope = –k (it’s negative because A is a reactant getting used up).
• Sketch the concentration vs. time graph on the right (let y = [A] and x = t). m = –k
• Write the equation of the graph in slope-intercept form (y = mx + b) or
point-slope form (y – y0= m(x – x0)). This is the Integrated Rate Law for zero-order reactions.
y = mx + b → [A]t = –k·t + [A]0
y – y0= m(x – x0) → [A]t – [A]0 = –k·t
Here, [A]0 is the initial concentration and [A]t is the concentration at time t for a zero time
Note: Integrated Rate Laws
order reaction.
The AP Equation Sheet gives
the Integrated Rate Laws in
1st Order Reaction point-slope form.

Consider the first-order reaction: A → products.

[A]
• Write the rate law for this first-order reaction. rate = k[A]1
• As the concentration of A decreases, the rate (or slope) decreases.
As the rate gets slower, the slope gets smaller, so we get a curve.
• Sketch the concentration vs. time graph:
• Unlike the zero-order reaction, the concentration vs. time graph is not very useful
because … it’s not a straight line, so it’s not useful for analysis.

For the first-order reaction, we get a linear relationship when we graph ln [A] vs. time with the time
slope m = –k.
• Write the equation of the graph in slope-intercept form or point-slope form.
ln [A]

This is the Integrated Rate Law for first-order reactions.

y = mx + b → ln[A]t = –k·t + ln[A]0
y – y0= m(x – x0) → ln[A]t – ln[A]0 = –k·t m = –k
Again, [A]0 is the initial concentration, and [A]t is the concentration at
time t for a first order reaction.
• The half-life (t1/2) is the time it takes for a reactant to reach half its original concentration.
1 time
Solve for t1/2 using the first-order integrated rate law if [A] = [A]0 and t = t1/2.
2
ln([A]0/2) – ln[A]0 = –k·t½
Multiply both sides by –1: ln[A]0 – ln([A]0/2) = k·t½ Note: Half-Life Formula
Combine the ln: ln2 = k·t½ Only the half-life formula for a
first-order reaction is
Solve for t½: t½ = ln 2 / k = 0.693/k
provided on the AP Equation
Note that the half-life of a first-order reaction does not depend on the concentration. This Sheet.
is a key indicator that a reaction is first-order.
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2.2 LESSON: INTEGRATED RATE LAW Name:

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2nd Order Reaction

Consider the second-order reaction: A → products.

[A]
• Write the rate law for this second-order reaction. rate = k[A]2
• As the concentration of A decreases, the rate (or slope) decreases.
As the rate gets slower, the slope gets smaller, so we get a curve.
• Sketch the concentration vs. time graph:
• Unlike the zero-order reaction, the concentration vs. time graph is not very useful
because … it’s not a straight line, so it’s not useful for analysis.

time
For the second-order reaction, we get a linear relationship when we graph 1/[A] vs. time with the
slope m = +k.

1/[A]
• Write the equation of the graph in slope-intercept form or point-slope form.
This is the Integrated Rate Law for second-order reactions.
1 1 m = +k
y = mx + b → [A]t = +k·t + [A]0
1 1
y – y0= m(x – x0) → [A]t – [A]0 = +k·t
1
• Solve for t1/2 using the second-order integrated rate law if [A] = [A]0 and t = t1/2.
2 time
How is this different from the half-life of a first-order reaction?
1 1 2 1 1 1 Note: Integrated Rate Law
[A]0/2 – [A]0 = +k·t1/2 → [A]0 – [A]0 = k·t1/2 → [A] = k·t1/2 → t1/2 = k·[A]
0 0 While we can derive the
Integrated Rate Law for any
This equation is NOT on the AP Equation Sheet, and you will not be asked to calculate a
order reaction, only zero-,
second-order half-life. However, it’s interesting to see how the second-order half-life IS First-, and second-order will
dependent on the concentration. ONLY first-order reactions have a concentration- be tested.
independent half-life.

Summary
Order 0 ORDER 1ST ORDER 2ND ORDER
∆[A] ∆[A] ∆[A]
Rate Law rate = – ∆t = k[A]0 rate = – ∆t = k[A]1 rate = – ∆t = k[A]2
[A]

[A]

[A]

m = –k
[A] vs. Time

time time time

1 1
Integrated Rate Law [A]t – [A]0 = – k·t ln [A]t – ln [A]0 = – k·t
[A]t – [A]0 = + k·t
Straight Line Plot [A] vs. time ln [A] vs. time 1/[A] vs. time
Slope –k –k +k
[A]

ln [A]

1/[A]

m = –k m = –k
Straight Line Graph
m = +k

time time time

–1
Units of k mol/L·s s L/mol·s
[A]0 ln 2 1
Half Life t1/2 = 2k t1/2 = k t1/2 = k[A]
0
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2.2 LESSON: INTEGRATED RATE LAW Name:

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Practice Problem
Data for the decomposition of N2O5 in a particular solvent at 45C t (s) [N2O5]t ln[N2O5] t 1/[N2O5] t
are shown. 3.07 2.08 0.732 0.481
a. Plot [N2O5], ln[N2O5], and 1/[N2O5] versus time graphs.
b. Write the rate law and integrated rate law for this reaction. 8.77 1.67 0.513 0.599
The reaction is first-order because the ln[A] vs t graph is
14.45 1.36 0.307 0.735
linear. rate = k[N2O5]1 ln[N2O5]t – ln[N2O5]0 = –k · t
31.28 0.72 –0.329 1.39
c. What is the value of the rate constant, k?
We can use t = 3.07 s and t = 31.28 s.
∆ln[N2O5] (–0.329 – 0.732)
k = –slope = – ∆t = – (31.28 s – 3.07 s) = 0.0376 s–1
d. What is [N2O5] at:
• t = 0 min • t = 10 s
Use t = 31.28 ln[N2O5]10 – ln[N2O5]0 = –k · t
ln [N2O5]0 = ln [N2O5]t + k · t ln[N2O5]10 – 0.847 = –(0.0376 s–1)(10 s)
ln [N2O5]0 = (–0.329) + (0.0376)(31.28) = 0.847 ln [N2O5]10 = 0.471
[N2O5]0 = e0.847 = 2.33 M [N2O5]10 = e0.471 = 1.60 M

Derivation of Integrated Rate Law

0 ORDER 1ST ORDER 2ND ORDER
d[A] d[A] d[A]
Start with the Rate Law: rate = – dt = k[A]0 = k rate = – dt = k[A]1 rate = – dt = k[A]2

Multiply both sides by –dt: d[A] = – k·dt d[A] = – k·[A]·dt d[A] = – k·[A]2·dt
1 1
Move [A] to the left:
[A] ·d[A] = – k·dt [A]2 ·d[A] = – k·dt
[A]t t [A]t [A]t
Integrate both sides: t t

d[A] = – 
k·dt  1 ·d[A] = – k·dt  1 2·d[A] = – k·dt
(Limits of d[A]: [A]0→[A]t
 [A]   [A] 
limits of dt: 0 → t) [A]0 0 0 0
[A]0 [A]0

[A]t – [A]0 = –k (t – 0) ln [A]t – ln [A]0 = – k(t – 0) – 1  – – 1  = – k(t – 0)

 [A]t  [A]0
1 1
Simplify: [A]t – [A]0 = –k·t ln [A]t – ln [A]0 = –k·t
[A]t – [A]0 = +k·t