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Chapter 13
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Chemical Kinetics
A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
13.1
A B
time
D[A]
rate = -
Dt
D[B]
rate =
Dt
13.1
Reactants & Products over Time
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
time
393 nm Detector
light
D[Br2] a DAbsorption
13.1
Br2 (aq) + HCOOH (aq) 2Br– (aq) + 2H+ (aq) + CO2 (g)
slope of
tangent
slope of
tangent slope of
tangent
13.1
Reaction Rates and Stoichiometry
2A B
1 D[A] D[B]
rate = – rate =
2 Dt Dt
aA + bB cC + dD
13.1
Write the rate expression for the following reaction:
13.1
The Rate Law
The rate law expresses the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants
raised to some powers.
aA + bB cC + dD
Rate = k [A]x[B]y
13.2
F2 (g) + 2ClO2 (g) 2FClO2 (g)
rate = k [F2][ClO2] 1
13.2
Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S2O82– (aq) + 3I– (aq) 2SO42– (aq) + I3– (aq)
Initial Rate
Experiment [S2O82 – ] [I – ]
(M/s) rate = k [S2O82–]x[I–]y
1 0.08 0.034 2.2 x 10–4 y=1
2 0.08 0.017 1.1 x 10–4 x=1
3 0.16 0.017 2.2 x 10–4 rate = k [S2O82–][I–]
13.3
2N2O5 4NO2 (g) + O2 (g)
[A]0 = 0.88 M
ln[A]t = ln[A]0 – kt
[A]t = 0.14 M
kt = ln[A]0 – ln[A]
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10–2 s–1
13.3
Half-Life of First-Order Reactions
The half-life, t½, is the time required for the concentration of a
reactant to decrease to half of its initial concentration.
[A]0
ln
[A]0/2 ln2 0.693
t½ = = =
k k k
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10–4 s–1?
t½ = ln2 = 0.693
= 1200 s = 20 minutes
k –4
5.7 x 10 s –1
1
t½ =
k[A]0
13.3
Half-Lives of Second-Order Reactions
The data give a straight line when plotting 1/[A] vs. time,
characteristic of a second-order reaction.
Zero-Order Reactions
D[A]
A product rate = - rate = k [A]0 = k
Dt
rate D[A]
k= = M/s – =k
[A] 0 Dt
[A]0
t½ =
2k
13.3
Half-Lives of a Zero-Order Reaction
Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k
13.3
Comparison of Graphs for H2O2 Decomposition
The reaction is
second order
with rate law
Rate = k[H2O2]2
From www.sparknotes.com
+
A+B AB+ C+D
Exothermic Reaction Endothermic Reaction
13.4
Activation Energy
Temperature Dependence of the Rate Constant
k = A • exp( -Ea / RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor
Ea 1
lnk = - + lnA
R T
Y-Intercept = lnA
Slope = –Ea/R
13.4
Importance of Orientation
13.4
K + CH3I KI + •CH3
Reaction Mechanisms
The overall progress of a chemical reaction can be represented
at the molecular level by a series of simple elementary steps
or elementary reactions.
Elementary step: NO + NO N 2O 2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
13.5
2NO (g) + O2 (g) 2NO2 (g)
13.5
Intermediates are species that appear in a reaction
mechanism but not in the overall balanced equation.
An intermediate is always formed in an early elementary step
and consumed in a later elementary step.
Elementary step: NO + NO N 2O 2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
13.5
The experimental rate law for the reaction between NO2
and CO to produce NO and CO2 is rate = k[NO2]2. The
reaction is believed to occur via two steps:
Step 1: NO2 + NO2 NO + NO3
Step 2: NO3 + CO NO2 + CO2
What is the equation for the overall reaction?
NO2+ CO NO + CO2
What is the intermediate?
NO3
What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 so
step 1 must be slower than step 2
13.5
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
k = A • exp( -Ea / RT ) Ea k
Uncatalyzed Catalyzed
• Acid catalysis
• Base catalysis
13.6
Haber Process
Fe/Al2O3/K2O
N2 (g) + 3H2 (g) 2NH3 (g)
catalyst
13.6
Ostwald Process
Pt catalyst
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)
Hot Pt wire
Pt-Rh catalysts used over NH3 solution
in Ostwald process 13.6
Catalytic Converters
catalytic
CO + Unburned Hydrocarbons + O2 converter CO2 + H2O
catalytic
2NO + 2NO2 converter 2N2 + 3O2
13.6
Enzyme Catalysis
13.6
enzyme
uncatalyzed catalyzed
D[P]
rate =
Dt
rate = k [ES]
13.6