Interpreting Rate Laws

Rate = k [A]m[B]n
ƒ If m = 1, rxn. is 1st order in A

If [A] doubles, then rate goes up by factor

of __
ƒ If m = 2, rxn. is 2nd order in A.

Doubling
g [A] increases rate byy ________
ƒ If m = 0, rxn. is zero order.

If [A] doubles, rate ________

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Reaction Rate Constants

Zero order reaction:

First order reaction:

Second order reaction:

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Derivation of the Second Order Integrated Rate Law

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Concentration / Time Relations

What is the concentration of
reactant as function of time?

Consider FIRST ORDER REACTIONS

The rate law is

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Concentration / Time Relations
Integrating -(∆ [R] / ∆ time) = k [R], we get

[R] / [R]0 = fraction remaining after time t has elapsed.

This is the integrated first-order rate law.

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Integrated Rate Laws

For the general reaction R → P, if [R]0 is the starting

concentration of R and [R]t is the concentration at time t,

Integrated
Reaction order in Rate Equation
Rate Law
R:
−Δ[R] ⎛ [R] ⎞
First Order = k[R] ln⎜ t ⎟ = −kt
Δt ⎝ [R]0 ⎠
Δ[R]
−Δ[R] 1 1
Second Order = k[R]2 − = kt
Δt [R]t [R]0
−Δ[R]
Zero Order = k[R]0 = k [R]0 − [R]t = kt
Δt

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Concentration / Time Relations
Sucrose decomposes to simpler sugars like glucose
Rate of disappearance of sucrose = k [sucrose]

If k = 0.21 hr-1
and [sucrose] = 0.010 M

How long to drop 90%

(to 00.0010
0010 M)?

Glucose

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Rate of disappearance of sucrose = k [sucrose].

k = 0.21 hr-1. If initial [sucrose] = 0.010 M, how
long to drop 90% or to 0.0010 M?

Use the first order integrated rate law

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 The reaction below is second order.
kk=30
30 L/mol•min.
L/mol min. If Initial [HI] =0.3
0.3 mol/L,
what will the [HI] be in 5 minutes?
2HI(g) ---> H2(g) + I2(g)

A. 0.29 mol/L
B 0.17
B. 0 17 mol/L
l/L
C. 0.032 mol/L
D. 0.0065 mol/L

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Using the Integrated Rate Law

The integrated rate law suggests a way to tell the order

based on experiment.
2 N2O5(g) ---
--->
> 4 NO2(g) + O2(g)

Time (min) [N2O5]0 (M) ln [N2O5]0

0 1.00 0
1 0.705 -0.35
2 0.497 -0.70
5 0.173 -1.75

Rate = k [N2O5]
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Using the Integrated Rate Law
2 N2O5(g) ---> 4 NO2(g) + O2(g)
Rate = k [N2O5]
[N 2 O5 ] v s . t i m e
l n [N 2 O5 ] v s . t i m e
1
0

0
-2
0 5
t i me 0 5
t i me

Data of conc. vs. Plot of ln [N2O5] vs.

time plot do not fit time is a straight
straight line. line!
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Using the Integrated Rate Law

l n [N2 O5 ] v s . t i m e
0 Plot of ln [N2O5] vs. time
is a straight line!
Eqn. for straight line:
y = mx + b

-2
0 t i me 5

All 1st order reactions have straight line on a plot of

ln [R] vs. time
(All 2nd order reactions give straight line on a plot of
1/[R] vs. time)
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Summary of Rate Laws

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Half-Life of Reaction

HALF-LIFE is
the time it
takes for 1/2
a sample is
disappear.
For 1st order
reactions,
the concept
of HALF-LIFE
is especially
useful.

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 Half-Life

ƒ Reaction is 1st
order
decomposition of
H2O2.

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Half-Life

ƒ Reaction after 1
half-life.
ƒ 1/2 of the
reactant has
been consumed
and 1/2
remains.

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 Half-Life

ƒ After 2 half
half-lives
lives
1/4 of the
reactant
remains.

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Half-Life

ƒ A 3 half
half-lives
lives
1/8 of the
reactant
remains.

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 Half-Life

ƒ After 4 half
half-lives
lives
1/16 of the
reactant
remains.

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Half-Life

Sugar is fermented in a 1st order process (using an

enzyme as a catalyst).
catalyst)
sugar + enzyme --> products
Rate of disappearance of sugar = k[sugar]

k = 3.3 x 10-4 sec-1

What is the half-life of this reaction?

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 Half-Life

Rate = k[sugar] and k = 3.3 x 10-4 sec-1. What is the half-

life of this reaction?
S l ti
Solution
[R] / [R]0 = fraction remaining
when t = t1/2 then fraction remaining = _________

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Half-Life

If rate = k[sugar] and k = 3.3 x 10-4 sec-1 and the

half-life is 35 min. Starting with 5.00 g sugar, how
much h iis lleft
ft after
ft 2 h
hr and
d 20 min
i (140 min)?
i )?
Solution
2 hr and 20 min = 4 half-lives

Half-life Time Elapsed Mass Left

1st 35 min 2.50 g
2nd 70 1.25 g
3rd 105 0.625 g
4th 140 0.313 g
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 Half-Life

Radioactive decay is a first order process.

Tritium ---> beta + helium

3H ---> beta + 3He

Carbon-14 decay:
14C ---> beta + 14N

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Half-Lives of Radioactive Elements

Rate of decay of radioactive isotopes given in
terms of half-life.

238U --> 234Th + He 4.5 x 109 yr

14C --> 14N + beta 5730 y
131I --> 131Xe + beta 8.05 d

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