CHAPTER 13: CHEMICAL

KINETICS

• RATE LAWS

• FIRST ORDER REACTIONS

Reaction Rate: Concentration-Rate Law
Rate Law for Equation with One Reactant:
A  products
Rate = k [A]m

Rate Law for Equation with Two Reactants

A + B  Products
Rate = k[reactant 1]m[reactant 2]n
“k” is the rate law constant; temperature related
“m” and “n” are rate law exponents
Reaction Rate: Concentration-Rate Law
To Deduce IntuitivelyRate Law Exponents:
From data, observe correlation between
change in concentration and rate.

• rate law exponent is zero (zero order) for a

reactant if the change in concentration of that
reactant produces no effect.
• Rate law exponent is one (first order) if
doubling the concentration causes the rate to
double.
 To Deduce, Intuitively, Rate
Law Exponents:

• Rate law exponent is two (second order) if

doubling the concentration results in a 22
increase in rate.
• Note that the rate constant does not depend
on concentration.
Reaction Rate: Concentration
NH4+(aq) + NO2-(aq)  N2(g) + 2H2O(l)
Algebraic Determination of Rate Law
Exponents

• 1. Chose two experiments.

• 2. Compare rates and concentrations
• rate2/rate1 =( [A]2/[A]1)n
 Algebraic Determination of Rate Law
Exponents

• 1. Choose Experiments 1 and 2

• rate2/rate1 =( [A]2/[A]1)n

10.8E-7/5.4E-7 = ( 0.200/0.100)n

2 = (2)n
 Problem 14.22-a, b (9th Edition)
• The reaction 2ClO2 (aq) + 2OH- (aq) ClO3- (aq) +
ClO2- (aq) + H2O (l) was studied with the
following results.
• Exp [ClO2] [OH-] Rate (M/s)
• 1 0.060 0.030 0.0248
• 2 0.020 0.030 0.00276
• 3 0.020 0.090 0.00828
 Problem 14.22-a, b (9th Edition)

• (a) Determine the rate law

• (b) Calculate the value of the rate law

constant
 Problem 13.20: page 604
• Kinetics data was collected for the reaction
given below. Determine the order of the
reaction and the rate constant. T = 290 °C
• ClCO2CCL3 (g)  2COCl2 (g)
• TIME (s) P (mmHg)
0 15.76
181 18.88
513 22.79
1164 27.08
 Rate Laws: General Comments
• Write rate laws for ELEMENTARY
REACTIONS

– Unimolecular
– A B
– Bimolecular
– A + B  Products
 Rate Laws: General Comments
• UNIMOLECULAR REACTIONS

– DECOMPOSITION
– 2N2O5  4NO2 + O2

– REARRANGEMENT
– CH2
–  CH3CH=CH2
– CH2 CH2
Rate Laws: General Comments
• REACTION ORDER

– RATE = [A]1
– RATE = [A]2
– RATE = [A] [B]
– RATE =[A]0
Effect of Concentration: Rate Laws
First-Order Reactions
• rate = k[A]1

lnA t   kt  lnA 0

• A plot of ln[A]t versus t is a straight line with

slope -k and intercept ln[A]0.
The Change of Concentration with Time
Half-Life
 Problem
• ….The decomposition of sulfuryl choride
(SO2Cl2) is a first order process. The rate
constant for the decomposition at 660 K is
4.5E-2s-1. (a) If we begin with an initial
SO2Cl2 pressure of 375 torr, what is this
pressure after 65 seconds.
 Problem
• ln[A]t = -kt +ln [A]0

• 4.5E-2s-1
• [A]t = ?
• [A]0 = 375 torr

• ln (x) = -(4.5E-2s-1)(65 seconds) + (ln 375)

• ln (x) = -2.925 + 5.927 = 3.0019
• inverse/antilog/ex = 20.1 torr
 Reaction Rate & Concentration:
First Order Reactions
• The first-order rate constant for the
decomposition of an antibiotic is 6.82E-3
hour –1. The initial concentration of the
antibiotic is 125 mg. How long will it take
for the antibiotic to decompose to 25.0 mg?
 Effect of Concentration: Rate Laws
First Order Reactions and Half-Life
• Half-life is the time taken for the concentration of
a reactant to drop to half its original value.
• That is, half life, t1/2 is the time taken for [A]0 to
reach ½[A]0.
• Mathematically,
ln 1
t1   2  0.693
2 k k
 First Order Reactions: Half-Life
• The first-order rate constant for the
decomposition of an antibiotic is 6.82E-3
hour–1. Calculate the half-life for this
antibiotic.
Effect of Concentration: Rate Laws
First-Order Reactions
lnA t   kt  lnA 0
 Reaction Rate: Concentration
Second-Order Reactions: rate = k [A] rate = k [A] [B]
• For a second order reaction with just one reactant
1 1
 kt 
At A0

• A plot of 1/[A]t versus t is a straight line with slope k

and intercept 1/[A]0
• For a second order reaction, a plot of ln[A]t vs. t is
not linear.
The Change of Concentration with Time
Second-Order Reactions
The Change of Concentration with Time
Second-Order Reactions
• We can show that the half life
1
t1 
2 k A 0

• A reaction can have rate constant expression of

the form
rate = k[A][B],
i.e., is second order overall, but has first order
dependence on A and B.
Table 13.3
 Problem
• The decomposition of hydrogen iodide
follows the equation
2HI(g)  H2(g) + I2(g). The reaction is second
order and has a rate constant equal to 1.6E-
3 L mole-1s-1 at 700 Celsius degrees. If the
initial concentration of HI in a container is
3.4E-2 M, how many minutes will it take for
the concentration to be reduced to 8.0E-4
M?