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Chapter 13
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Chemical Kinetics
A B
[A] [A] = change in concentration of A over
rate = -
t time period t
[B] [B] = change in concentration of B over
rate =
t time period t
13.1
A B
time
[A]
rate = -
t
[B]
rate =
t
13.1
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
time
393 nm Detector
light
[Br2] Absorption
13.1
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
slope of
tangent
slope of
tangent slope of
tangent
13.1
2H2O2 (aq) 2H2O (l) + O2 (g)
PV = nRT
n
P= RT = [O2]RT
V
1
[O2] = P
RT
[O2] 1 P
rate = =
t RT t
2A B
1 [A] [B]
rate = - rate =
2 t t
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]x[ClO2]y
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)
13.3
2N2O5 4NO2 (g) + O2 (g)
13.3
The reaction 2A B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it take for A
to decrease from 0.88 M to 0.14 M ?
[A]0 = 0.88 M
ln[A] = ln[A]0 - kt
[A] = 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 s-2 -1
13.3
First-Order Reactions
[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 5.7 x 10 s
-4 -1
# of
half-lives [A] = [A]0/n
1 2
2 4
3 8
4 16
13.3
Second-Order Reactions
[A]
A product rate = - rate = k [A]2
t
1
t½ =
k[A]0
13.3
Zero-Order Reactions
[A]
A product rate = - rate = k [A]0 = k
t
rate [A]
k= = M/s - =k
[A] 0
t
[A]0
t½ =
2k
13.3
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k
13.3
A+ B AB++ C+D
Exothermic Reaction Endothermic Reaction
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
13.4
Ea 1
lnk = - + lnA
R T
13.4
13.4
Reaction Mechanisms
Elementary step: NO + NO N 2 O2
+ 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 2 O2
+ 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 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
Chemistry In Action: Femtochemistry
• •
CH2 CH2 CH2 CH2 CH2 CH2
2 CH2 CH2
CH2 CH2 CH2 CH2 CH2 CH2
2 CH2 CH2
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) 2NH 3 (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
[P]
rate =
t
rate = k [ES]
13.6