Beruflich Dokumente
Kultur Dokumente
2.5
[H O ], M
4 1600.0 0.73000 0.25000 0.0006300
2
2
5 2000.0 0.54000 0.19000 0.0004800
6 2400.0 0.39000 0.15000 0.0003800 1
for a reaction: A + B ! C + D
Rate = k[A]m[B]n
Reaction Order & Rate Change with Concentration Reaction Order & Rate Change with Concentration
consider the reaction: A ! B+C consider the reaction: A ! B + C
the reaction is 2nd order in NO use the Integrated Rate Law to answer these questions
1st Order Overall Reactions:
Integrated Rate Law example:
[A]t 2 H2O2 (aq) ! 2 H2O (l) + O2 (g)
ln = kt
[A]0 The decomposition of hydrogen peroxide is a 1st
order reaction with k = 7.30 x 104 s1.
ln [A]t ln[A]0 = kt
If [H2O2]0 = 2.32 M, determine [H2O2] after 1200
ln [A]t = kt + ln[A]0 seconds of reaction.
ln 2 =
t! = 0.693
k k
At what time after the start of the reaction the sample
of H2O2 decomposed? note: for a 1st order reaction, t! is constant
t! is dependent on k but not on [A]0
Half-Life of a 1st Order Reaction Half-Life of a 1st Order Reaction
plot of 1/[A] vs. t will give a straight line plot of [A] vs. t will give a straight line
example:
Consider the following 2nd order reaction:
2A ! B
For this reaction, k = 0.0250 M1s1. If [A]0 = 1.10 M,
what will be the [B] after 45.0 seconds?
A B A B A B
favorable
+ ! ! +
A B A B A B orientation:
unfavorable orientation:
A A + B B ! no reaction
unfavorable
orientation:
consider the species in the middle of this reaction: Reaction Profile
track how energy changes as the reaction progresses
A B A B A B
from reactant ! transition state ! products
+ ! ! +
A B A B A B
Catalysts
example: A catalyst is a substance that increases the rate of a
chemical reaction without being consumed by it.
Consider a reaction with Ea = 35.7 kJ/mol.
Determine the factor by which the rate of a reaction
increases as temperature is increased from 50C to a catalyst provides an
alternate path from reactant
75C.
to product
path with lower Ea
frequently multiple step path
a catalyst participates in one
step of the mechanism, and is
regenerated in a later step
Reaction Profile for a Catalyzed Reaction: Catalysts
Elementary Processes
Reaction Mechanisms
individual steps in reaction mechanism
a collection of elementary steps that describe the rate law can be written by inspection;
path from reactants to products in a chemical orders equivalent to stoichiometric coefficients
reaction identified by their molecularity
for a mechanism to be plausible, it must meet 2 may be unimolecular, bimolecular, termolecular
criteria: may be fast, reversible (equilibrium) steps
match the overall or net chemical reaction Rateforward = Ratereverse
after steps are added together may be slow
produce a rate law that is consistent with rate determining step (RDS)
the experimentally determined rate law largest Ea
** determines the overall rate of reaction
Raterxn = RateRDS
proposed mechanism for the depletion of ozone (O3) by Cl:
Reaction Intermediates & Catalysts in Mechanisms
step 1: Cl (g) + O3 (g) ! ClO (g) + O2 (g)
step 2: ClO (g) + O (g) ! Cl (g) + O2 (g)
reaction intermediates and catalysts are both
species that may be involved in a mechanism but overall rxn: O3 (g) + O (g) ! 2 O2 (g)
not appear in the overall chemical equation or its
rate law ClO is a reaction
intermediate b/c it is
reaction intermediate generated in one step, then formed in step 1 and
consumed in step 2
consumed in a later step
Cl is a catalyst
catalyst consumed in one step, then regenerated (homogeneous) b/c it
in a later step is consumed in step 1
and regenerated in
step 2
The experimentally determined rate law is: Ozone reacts with nitrogen dioxide to produce
oxygen and dinitrogen pentoxide by the following
Rate = k[H2][ICl] proposed mechanism:
Is this a plausible mechanism? step 1: O3 (g) + NO2 (g) ! NO3 (g) + O2 (g) (slow)
step 1: H2 (g) + ICl (g) ! HI (g) + HCl (g) (RDS) step 2: NO2 (g) + NO3 (g) ! N2O5 (g) (fast)
step 2: HI (g) + ICl (g) ! I2 (g) + HCl (g) (fast)
Determine the overall reaction & rate law consistent
overall rxn: H2 (g) + 2 ICl (g) ! I2 (g) + 2 HCl (g) with this mechanism.
rate law from mechanism: Raterxn = RateRDS
Rate = k[H2][ICl]
Yes this is a plausible mechanism.
example:
example:
Consider the following proposed mechanism for the
Ozone reacts with nitrogen dioxide to produce
reaction between F2 and N2O4:
oxygen and dinitrogen pentoxide by the following Ea, kJ/mol
proposed mechanism: step 1: N2O4 (g) 2 NO2 (g) 59
step 1: O3 (g) + NO2 (g) ! NO3 (g) + O2 (g) (RDS) step 2: NO2 (g) + F2 (g) ! F (g) + FNO2 (g) 83
step 2: NO2 (g) + NO3 (g) ! N2O5 (g) (fast) step 3: F (g) + NO2 (g) ! FNO2 (g) 9
overall rxn: O3 (g) + 2 NO2 (g) ! O2 (g) + N2O5 (g)
example: example:
Consider the following proposed mechanism for the
For the proposed mechanism for the reaction
reaction between F2 and N2O4:
Ea, kJ/mol between F2 and N2O4, consider both the Ea values
step 1: N2O4 (g) 2 NO2 (g) 59 and H values for steps 1 3, and the overall
reaction to sketch the reaction profile.
step 2: NO2 (g) + F2 (g) ! F (g) + FNO2 (g) 83
step 3: F (g) + NO2 (g) ! FNO2 (g) 9 Ea, kJ/mol H, kJ