CHEMICAL KINETICS Unit 5 / Chapter 13

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RATE OF A REACTION
Rate – change in a measure per unit time
­ Velocity = meters per second
­ APM = actions per minute

Reaction rate – change in the concentration of a reactant or product with time (M/s)

A à B
∆# ∆[&]
rate = − =
∆$ ∆$

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GENERAL RATE EQUATIONS
aA + bB à cC + dD

'∆ * '∆ - '∆ / ' ∆[2]

!"#$ = − =− = =
( ∆+ , ∆+ . ∆+ 0 ∆+

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 4NO2 (g) + O2 (g) à 2N2O5 (g)

At a particular moment during the reaction, O2 is reacting at the rate of 0.024 M/s.
(a) At what rate is N2O5 being formed? (b) At what rate is NO2 reacting?

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BROMINE AND FORMIC ACID EXAMPLE
Time (s) [Br2] (M) Rate (M/s) !"#$
[&'(]
(?)

0.0 0.0120
50.0 0.0101
100.0 0.00846
150.0 0.00710
200.0 0.00596
250.0 0.00500
300.0 0.00420
350.0 0.00353
400.0 0.00296

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BROMINE AND FORMIC ACID EXAMPLE
Time (s) [Br2] (M) Rate (M/s) k (s-1)
Instantaneous Rates of Br2 Consumption
0.0 0.0120 4.20 x10-5 3.50 x10-3 0.014

50.0 0.0101 3.52 x10-5 3.49 x10-3 0.012

100.0 0.00846 2.96 x10-5 3.50 x10-3 0.01
150.0 0.00710 2.49 x10-5 3.51 x10-3
0.008

[Br2] (M)
200.0 0.00596 2.09 x10-5 3.51 x10-3
0.006
250.0 0.00500 1.75 x10-5 3.50 x10-3
0.004
300.0 0.00420 1.48 x10-5 3.52 x10-3
0.002
350.0 0.00353 1.23 x10-5 3.48 x10-3
0
400.0 0.00296 1.04 x10-5 3.51 x10-3 0 100 200 300 400 500
Time (s)

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BROMINE AND FORMIC ACID EXAMPLE
Time (s) [Br2] (M) Rate (M/s) k (s-1) Proportionality btw Conc. and Rate
0.0 0.0120 4.20 x10-5 3.50 x10-3 4.50E-05

4.00E-05
50.0 0.0101 3.52 x10-5 3.49 x10-3
3.50E-05
100.0 0.00846 2.96 x10-5 3.50 x10-3
3.00E-05
150.0 0.00710 2.49 x10-5 3.51 x10-3

Rate (M/s)
2.50E-05
200.0 0.00596 2.09 x10-5 3.51 x10-3 2.00E-05

250.0 0.00500 1.75 x10-5 3.50 x10-3 1.50E-05

300.0 0.00420 1.48 x10-5 3.52 x10-3 1.00E-05

5.00E-06
350.0 0.00353 1.23 x10-5 3.48 x10-3
0.00E+00
400.0 0.00296 1.04 x10-5 3.51 x10-3 0 0.0025 0.005 0.0075 0.01 0.0125 0.015
[Br2] (M)

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RATE LAW
aA + bB (+ …) à cC + dD

Rate = k[A]x[B]y(…)
x, y: orders (ex: “order with respect to A”)
­ 0th, 1st, or 2nd order
­ Overall order of the reaction = x + y (+ …)

k: rate constant
­ Variable units

Must be determined experimentally (cannot be known from chemical equation)

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RATE LAW CONT.
A + B à products
0th Order Reaction
­ Rate = k

1st Order Reaction

­ Rate = k[A]
­ Rate = k[B]

2nd Order Reaction

­ Rate = k[A]2
­ Rate = k[B]2
­ Rate = k[A][B]

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 2NO (g) + 2H2 (g) à N2 (g) + 2H2O (g)

From the following data, determine (a) the rate law, (b) the rate constant, and (c) the rate of the reaction when
[NO] = 12.0 x10-3 M and [H2] = 6.0 x10-3 M

Experiment [NO] (M) [H2] (M) Initial Rate (M/s)

1 5.0 x10-3 2.0 x10-3 1.3 x10-5
2 10.0 x10-3 2.0 x10-3 5.0 x10-5
3 10.0 x10-3 4.0 x10-3 10.0 x10-5

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INTEGRATED RATE LAWS
!∆[$]
(Rate =) = ([)] ----[Magic]----> ln ) = −(- + ln[)]/
∆&

!∆[$]
=( ----[Magic]----> ) = −(- + [)]/
∆&

!∆[$] 0 1 1
= ([)] ----[Magic]----> = (- +
∆& [$] [$]2

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INTEGRATED RATE LAW GRAPHS

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INTEGRATED RATE LAW
GRAPHS SUMMARY
Important points
- Linear plot y-axis
- [A], ln[A], 1/[A]
- Rate constant (k) units
- M/s, 1/s, 1/(Ms)
- Half life equations
- 1st order half life does not depend on conc.

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The conversion of cyclopropane to propene in the gas phase is a first order reaction with a rate constant of
6.7 x10-4 s-1 at 500 oC. (a) If the intial concentration of cyclopropane was 0.25 M, what is the concentration
after 8.8 minutes? (b) How long (in minutes) will it take for the concentration of cyclopropane to decrease from
0.25 M to 0.15 M? ( c) How long (in minutes) will it take to convert 74% of the starting material?

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COLLISION THEORY
In order for a reaction to occur, the reactants must collide, in the correct orientation,
and with enough energy
­ Anything that would influence those factors, would influence the rate of the reaction

Factors that affect reaction rate:

­ Concentration
­ Temperature
­ Catalysts (Enzymes)
­ Surface Area

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TEMPERATURE DEPENDENCE OF K
Arrhenius Equation
&'(
%)*
! = #$

For two different temperatures, or rate constants

-. 1( 3 3
+, =− −
-/ 2 4. 4/

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The rate constant of a first order reaction is 3.46 x10-2 s-1 at 298 K.
What is the rate constant at 350 K if the activation energy for the reaction is 50.2 kJ/mol?

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MECHANISMS
Overall, balanced reaction does not describe HOW a reaction occurs
Mechanisms show step by step how reactants become products
Ex: Overall Rxn: 2A + B à C + D
Step 1: A + B à E
Step 2: A + E à C + D

Each step is an elementary reaction

Chemical E is an intermediate

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ELEMENTARY REACTIONS
Molecularity – number of molecules reacting in an elementary step
­ Unimolecular (A), Bimolecular (A + B), Termolecular (A + B + C)

For an elementary reaction, the coefficients DO relate to the orders of the rate law for that step
­ Ex: A + A à products Rate = k[A]2

The sum of the elementary steps must match the balanced overall reaction
The rate law of the rate-determining step much match the overall rate law

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Example: The gas-phase decomposition of dinitrogen monoxide is believed to occur via two elementary steps
%&
Step 1: !" # → !" + #
%(
Step 2: !" # + # → !" + #"

Experimentally the rate law is found to be Rate = k[N2O]. (a) Write the equation for the overall reaction. (b) Identify the
intermediate. (c) What can you say about the relative rates of steps 1 and 2?

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PRE-EQUILIBRIUM APPROACH
Easy Case: Slow Step First Difficult Case: Slow Step Second
&' &'
!"# + !"# → !"( + !" (slow) !" + !" → !# "# (fast)

&* &*
!"( + )" → !"# + )"# (fast) !# "# + +# → +# " + !# " (slow)

&*
!# " + +# → !# + +# " (fast)

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CATALYSTS
Added to increase the rate of the reaction.
Changes the reaction mechanism
­ The catalyzed mechanism will have a lower activation
energy than the uncatalyzed mechanism

Catalyst is a chemical (or enzyme) that will be consumed and produced during the mechanism
­ Ex: A+FàE
B+EàC+F

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HALF LIVES
Time it takes to consume half the initial concentration

['])
0th Order: !#⁄$ =
*+
,-*
1st Order: !#⁄$ = (Does not depend on initial concentration!)
+
.
2nd Order: !#⁄$ =
+['])

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Example: The decomposition of ethane is a first-order reaction with a rate constant of 5.36 x10-4 s- at 700 oC.
Calculate the half-life of the reaction in minutes.

Example: Iodine atoms combine to form molecular iodine. This reaction follows second-order kinetics and has a rate
constant of 7.0 x109 M-1s-1. Calculate the half-life if the initial concentration is 0.60 M and if it is 0.42 M.

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