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reaction rates are dependent on concentration; this dependence is given by the rate law
note: there is one class of reaction that we will discuss for which plot of [X] vs. time is linear, and rate is not
dependent on concentration
rates of consumption and formation of reactants and products within a reaction are related by stoichiometry
ex. 4 NH3 (g) + 5 O2 (g) 4 NO (g) + 6 H2O (g)
Calculate the rate of consumption of NH3 if [NH3]0 = 4.000 M, and [NH3] = 2.560 M at t = 25 s.
RateNH3 = |[NH3]| t; RateNH3 = 0.058 Ms 1
for a given reaction the rate law defines the dependence of rate on concentration
consider the generic reaction: A + B C + D
more about k:
dependent on specific reaction and temperature
independent of concentration
units depend on m and n (orders)
How does rate change dependent on order? What is the factor of change?
k[A]21
k[A]1
rate2
rate1
k[A]22
k[A]12
rate2
rate1
k(2x)1
k(x)1
rate2
rate1
21
k(2x)2
k(x)2
rate2
rate1
22
rate2 = (rate1)(4)
rate2
rate1
rate2 = (rate1)(2)
k[A]2-1
k[A]1
-1
rate2
rate1
k(2x)-1
k(x)-1
rate2
rate1
2-1
rate2 = (rate1)(1/2)
rate is multiplied by
2 1 = 1/2
20 = 1
21 = 2
22 = 4
23 = 8
m=
1
0
1
2
3
rate is multiplied by
3 1 = 1/3
30 = 1
31 = 3
32 = 9
33 = 27
rate law
rate = k[A]0
k=
k = rate
units of k
Ms 1
1st
rate = k[A]1
k = rate/[A]
s1
2nd
rate = k[A]2
k = rate/[A]2
M 1s 1
3rd
rate = k[A]3
k = rate/[A]3
M 2s 1
several examples determine the rate law for the following reactions based on experimental data
ex.
expt
1
2
initial rate, Ms 1
4.8 x 10 6
9.6 x 10 6
[N2O5]0, M
0.010
0.020
2 approaches:
by inspection: [N2O5] doubles, rate doubles 1st order with respect to N2O5
set up rate law ratio, plug in data, solve for m
rate2
rate1
k[N2O5]2m
k[N2O5]1m
m = 1;
ex.
k(0.020)m
2 = 2m
k(0.010)m
rate = k[N2O5]
expt
1
2
3
[HgCl2]0, M
0.105
0.105
0.052
[C2O42 ]0, M
0.15
0.30
0.30
compare expts 1 and 2 to determine the order with respect to C2O42 (b/c [HgCl2] held constant)
compare expts 2 and 3 to determine the order with respect to HgCl2 (b/c [C2O42 ] held constant)
m[C
2- n
2O4 ]2
k[HgCl2]2
rate2
=
rate1
k[HgCl2]1m[C2O42-]1n
7.1 x
k[HgCl2]2m[C2O42-]2n
rate2
=
rate3
k[HgCl2]3m[C2O42-]3n
m = 1, n = 2;
10-5
Mmin-1
3.5 x
10-5
Mmin-1
k(0.105)m(0.30)n
k(0.105)m(0.15)n
k(0.105)m(0.30)n
k(0.052)m(0.30)n
rate = k[HgCl2][C2O42 ]2
4 = 2n
2 = 2m
using expt 2:
Determine the rate of this reaction when [HgCl2] = 0.050 M and [C2O42 ] = 0.025 M.
ex.
expt
1
2
3
4
[H2O2]0, M
0.010
0.020
0.010
0.010
[I ]0, M
0.010
0.010
0.020
0.010
[H+]0, M
0.00050
0.00050
0.00050
0.00100
initial rate, Ms 1
1.15 x 10-6
2.30 x 10-6
2.30 x 10-6
1.15 x 10-6
note: in comparing expts 1 and 4, [H2O2] and [I ] are held constant and only [H+] is varied, but the rate does not
change. Therefore, the order with respect to H+ is 0.
ex.
expt
1
2
3
[NO], M
0.0010
0.0010
0.0030
[O2], M
0.0010
0.0040
0.0040
initial rate, Ms 1
7.10
28.4
255.6
[A]t
[A]0
= -kt
OR ln[A]t = k t + ln[A]0
for a 1st order reaction a plot of ln[A] vs time yields a straight line with slope = k, y int. = ln[A]0
ex.
Determine the [H2O2] after1200 s of reaction if the initial concentration of H2O2 is 2.32 M.
answer: 0.967 M
Determine the percent H2O2 that has decomposed after 500 s of reaction.
answer: 30.6 % decomposed
time at which 50% of the reactant has been consumed; time reqd for [reactant] to decrease to 1/2 of its initial value
at t1/2:
t = t1/2
[A]t = 1/2[A]0
substitute these into the integrated rate law
st
note: for a 1 order reaction the half-life is constant; dependent on k but not of [A]0
ex. Consider a first-order reaction A B + C with t1/2 = 200 s.
if [A]0 = 1.0 M:
[A] 1.0 M 0.50 M
[A] 100% 50%
t = 200 s
[A] 0.50 M 0.25 M
[A] 50% 25%
t = 200 s
[A] 0.25 M 0.125 M
[A] 25% 12.5%
t = 200 s
etc.
Total time required for [A] to decrease to 6.25% of its initial value? t = 4t1/2 = 4(200s) = 800 s
ex. Calculate the half-life for the decomposition of H2O2. k = 7.3 x 10 4 s 1
t1/2 = 0.693/k = 0.693/7.3 x 10 4 s 1 = 950 s
rate = k[A]2
kt
[A]0
[A]t
plot of 1/[A] vs. t will yield a straight line; slope = k (units M 1s 1); y int = 1/[A]0
half-life equation
t1/2 =
1
k[A]0
note: for a 2nd order reaction each succesive half-life is 2x as long as the one before it; dependent on [A]0
Consider a first-order reaction A B + C with t1/2 = 200 s.
[A] 1.0 M 0.50 M
[A] 100% 50%
t = 200 s
[A] 0.50 M 0.25 M
[A] 50% 25%
t = 400 s
[A] 0.25 M 0.125 M
[A] 25% 12.5%
t = 800 s
etc.
Total time required for [A] to decrease to 6.25% of its initial value? t = 200 + 400 + 800 + 1600 s = 3000 s
ex.
if [A]0 = 1.0 M:
Zero-order reactions
rate is not dependent on concentration; rate is constant (as long as there is some A present)
once the reaction starts it will continue at the same rate until [A] = 0
plot of [A] vs t will yield a straight line; slope = k (units Ms 1); y int = [A]0
half-life equation:
t1/2 =
[A]0
2k
Order
Rate Law
Rate = k[A]0
Rate = k[A]
Rate = k[A]2
Half-life Equation
Graph
[A]t = kt + [A]0
t1/2 = [A]0/2k
[A] vs t; slope = k
ln[A]t = kt + ln[A]0
t1/2 = 0.693/k
ln[A] vs t; slope = k
1/[A]t = kt + 1/[A]0
t1/2 = 1/k[A]0
1/[A] vs t; slope = k
a few examples:
ex. For a certain reaction k = 0.0217 s 1. Calculate half-life, and determine the time when 5% of the reactant
remains.
t1/2 = 0.693/k
answer: 138 s
ex. For a certain reaction (2A B) the rate law is: rate = k[A]2 and k = 0.0250 M 1s 1. If [A]0 = 1.1 M,
determine [A] at 45.0 s. What is [B] at this time?
use the intergrated rate law for a 2nd order reaction to determine [A]t
answer: 0.493 M
a.
b.
c.
d.
e.
f.
Time, min
[A], M
0.00
1.00
5.00
0.63
10.0
0.46
15.0
0.36
25.0
0.25
Calculate the average rate of reaction of A between 10.0 and 15.0 min. Be sure your units on rate
are correct.
Determine the order of this reaction (by graphing).
From your graph, determine the value of the rate constant (include appropriate units).
What is the rate of reaction when [A] = 0.85 M?
Calculate t1/2 for this reaction.
What percent of reactant A remains after 32.5 min of reaction?
You can find the answer to this problem online on the Handouts page (Answer to Kinetics Practice Problem)
Reactions occurs when molecules collide with appropriate orientation and sufficient energy.
not all molecular collisions result successfully in the formation of product
molecular orientation
consider A2 + B2 2 AB
= B2
= A2
= AB
2 possible orientations:
VS.
transition state or
activated complex
energy of collision
molecular collisions are successful when they occur with enough energy to break bonds
minimum energy required for a reaction to occur = activation energy (Ea) of the reaction
Ea is dependent on the numbers and types of bonds present; units kJ/mol
if Ecollision > Ea product
Ecollision is dependent on temperature; frequency of collision is dependent on concentration and temperature
R = 8.314 J/Kmol
T = temp in K
Ea
RT
ln
k2
k1
Ea
T1
1
T2
examples
ex. 2 N2O5 (g) 4 NO2 (g) + O2 (g) is a 1st order reaction. If [N2O5]0 = 2.68 M, and at 50 C Ea = 88 kJ/mol, and
A = 4.0 x 1013 s 1 determine the rate of reaction at 50C and the value of k at 30C.
3 step process:
1st use the Arrhenius equation to determine k at 50C
answer: 0.19 s 1
answer: 0.51 Ms 1
answer: 0.021 s 1
ex. The half-life of a 1st order reaction triples when temperature decreases from 25C to 0C. Calculate the
activation energy for this reaction.
2 Ts:
Catalysis
A catalyst is a substance that increases the rate of a chemical reaction without being consumed by it.
catalysts can be recovered and used again
catalysts are typically required in only small amounts
catalysts are reaction specific
a catalyst provides an alternate path from reactant to product (alternative mechanism); path with lower Ea
can use the Arrhenius equation to determine the factor of rate change (= kcat/kuncat) if you know Eacat vs. Eauncat
can use the Arrhenius equation to determine the catalyzed reactions Ea if you know factor of rate change (or ks)
i.e
i.e.
catalytic hydrogenation of ethylene: C2H4 (g) + H2 (g) C2H6 (g); catalyzed by SiO2
i.e.
be easily regenerated
Reaction Profiles:
plot of energy vs. reaction coordinate for a chemical reaction
reactants at some initial energy level
energy increases as reactants come together to form reaction intermediate
transition state (intermediate) corresponds to energy maximum in profile (activation barrier of reaction, Ea)
energy decreases as the intermediate goes on to form products at some final energy level
can identify Ea and E for the both the forward and reverse reaction; Ea kinetics vs. E thermodynamics
Reaction Mechanism
molecularity
each step in a mechanism can be described by its molecularity; number of molecules interacting
unimolecular: 1 molecule; i.e A2 2 A
bimolecular: 2 molecules; A2 + B2 2 AB
termolecular and beyond: 3 or more molecules; not very likely
ex. consider the proposed mechanism for the depletion of ozone by chlorine atoms in the stratosphere
step 1:
step 2:
net rxn:
ex. Consider the reaction: 2 ICl (g) + H2 (g) I2 (g) + 2 HCl (g). The experimentally determined rate law is:
rate = k[H2][ICl]. Is the following proposed mechanism plausible?
step 1(SLOW):
H2 + ICl HI + ICl
step 2 (FAST):
HI + ICl HCl + I2
net rxn:
H2 + 2 ICl 2 HCl + I2
The net reaction and rate law from the mechanism suggest that this IS a plausible mechanism.
note: rate law determined experimentally can often provide clues to the reaction mechanism
ex. Consider the data below for the proposed reaction between F2 and N2O4:
Hf data: N2O4 8.8 kJ/mol; NO2 32.3 kJ/mol; 93.5 kJ/mol; FNO2 81.3 kJ/mol
mechanism:
step 1:
N2O4 2 NO2
Ea = 59 kJ/mol
H1 = +55.6 kJ
step 2:
NO2 + F2 F + FNO2
Ea = 83 kJ/mol
H2 = 20 kJ
step 3:
F + NO2 FNO2
Ea = 9 kJ/mol
H3 = 207 kJ
net rxn:
N2O4 + F2 2 FNO2
Hrxn = 171.4 kJ
step 2 is the RDS because it has the largest Ea and will therefore be the slowest
NO2 and F are reaction intermediates
putting this all together construct a reaction profile:
F2 + N2 O4
step 1
step 2
step 3
2 FNO2
reaction coordinate