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[B]/t = 2(-[A]/t)
C < 0
C > 0
The rate is positive by convention, but C is (-)
for the reactants and (+) for the products
Rate = -[A]/t
or
Rate = [B]/t
Example:
For the reaction N2 + 3H2 2NH3, the rate of
formation of NH3 is 1.4 M/min. Calculate the
rate of disappearance of H2 and the reaction
rate.
[NH 3 ]
mol NH 3
M
= 1.4
1.4
t
L min
min
mol NH 3 3 mol H 2
mol H 2
1.4
= 2.1
L min 2 mol NH 3
L min
Rate =
1 [NH 3 ] 1
mol NH 3
mol NH 3
= 1.4
= 0.70
2 t
2
L min
L min
Rate =
1 [A]
1 [B] 1 [C] 1 [D]
=
=
=
a t
b t
c t
d t
Rate =
Reactant concentration
(C) versus time (t)
C
(C - C )
= 2 1
t
( t 2 - t1 )
= slope (a )
C1
a
b
C
C2
Rate = slope (b )
t1
t2
Instantaneous
rate at time t
Slope of c
Slope of d
aA + bB + Products
k is a
constant
(slope
of line)
Slope of b
b
a
Slope of a
d [N2O5]
Rate = k[A]m[B]n
Rate =
k[A]m[B]n
Rate
[N2O5]
Examples:
CH3Br + OH- CH3OH + Br-
Examples:
2O3 3O2
2SO2 + O2 SO3
2NH3 N2 + 3H2
Example:
For the reaction 2NO + 2H2 N2 + 2H2O, the
rate increases by a factor of nine when the
concentration of NO is tripled while the
concentration of H2 is kept constant. What is the
order of the reaction with respect to NO?
Rate law Rate = k[NO]m[H2]n
9Rate = k(3[NO])m[H2]n = 3mk[NO]m[H2]n
9Rate = 3mRate
9 = 3m m = 2 2nd order in NO
1
2
3
1.1
1.3
3.2
2
3
2.0
1.1
1.3
3.0
5.8
17.0
Rate = k[O2]m[NO]n
#1
3.210-3 = k(1.110-2)m (1.310-2)n
Divide eq.2 by eq.1
#2
5.810-3 = k (2.010-2)m (1.310-2)n and eq.3 by eq.1 :
-3
-2
m
-2
n
#3
17.010 = k (1.110 ) (3.010 )
1
m
5 .8
k 2 .0 m 1 .3 n
5 .8 2 .0
m
=
=
1 .8 = 1 .8
3 .2
k 1 .1 m 1 .3 n
3 .2 1 .1
n
1
2
Relative Conc.
O2
1.1/1.1=1.0
1.8
2.0/1.1=1.8
Exp
#
1
3
O2
1.0
1.0
Relative Rate
NO
1.0
1.0
Relative Conc.
NO
1.3/1.3=1.0
2.3
3.0/1.3=2.3
3.2/3.2=1.0
5.8/3.2=1.8
1.81
Relative Rate
3.2/3.2=1.0
17.0/3.2=5.3
2.32
Rate = k[O2][NO]2
Exp
#
Alternative method:
Initial Conc. 10-2 (mol/L)
O2
NO
Rateo = k[A]om[B]on
Exp.#
aA + bB Products
17 . 0 k 1 .1 m 3 .0 n
17 . 0 3 .0
=
=
5 .3 = 2 .3 m
3 .2
k 1 .1 m 1 .3 n
3 .2
1 .3
Rate
3.2 10 3 mol/L s
=
2
[O 2 ][NO]
1.1 10 2 mol/L 1.3 10 2 mol/L
k = 1.7 10 3 L2 /mol 2 s
Rate = -[A]/t
Rate = k
and
Rate = -[A]/t
Rate = -[A]/t
-[A]/t =
k[A]2
1/[HI] = 1/[HI]o + kt
1/[HI] 1/[HI]o = kt
t = (1/[HI] 1/[HI]o)/k
1
1
0.035mol/L 0.050mol/L
t=
= 3.6 1021s = 1.1 1014 yr
2.4 1021 L/mol s
[A] = [A]o kt
y = b + mx
If a plot of [A]
versus time gives
a straight line, the
reaction is zeroorder in A
ln[A] = ln[A]o kt
y = b + mx
If a plot of
ln[A] versus time
gives a straight
line, the reaction is
1st order in A
1/[A] = 1/[A]o + kt
y = b + mx
If a plot of
1/[A] versus time
gives a straight
line, the reaction is
2nd order in A
Calculate
ln[N2O5] and
1/[N2O5]
Reaction Half-Life
(10.0, -4.39)
(50.0, -5.55)
k = -slope
k = -y/x
A plot of
[N2O5] versus t is
not a straight line
reaction is not
zero-order
A plot of
ln[N2O5] versus t
gives a straight
line reaction is
1st order
[-5.55 - (-4.39)]
(50.0 10.0)
k = 0.029
min-1
[A]o = [A]oe-kt
ln() = -kt
ln(2) = kt
t = ln(2)/k = 0.693/k
t is independent of the initial concentration [A]o
During the course of the reaction, t remains the
same, so it always takes the same time to half [A]
t1/2
[A]o = [A]o kt
kt = [A]o [A]o
kt = [A]o
t = [A]o/2k
t is directly proportional to [A]o
ln
k = Ae-Ea/RT
lnk = lnA (Ea/R)(1/T)
T k Rate
y = b + mx
Ea is the minimum energy the molecules must
have in order to react (Ea can be determined by
measuring k at different T from the slope of a plot
of lnk versus 1/T)
k 1 1
Ea = R ln 2
k1 T2 T1
Ea = 8.314
Z = Zo[A][B]
k1 = 2.610-10 s-1
k2 = 6.710-4 s-1
J 6.7 10-4 s 1 1
1
ln
-10 1
mol K 2.6 10 s 773 K 573 K
1 1
T2 T1
k2
E
= a
k1
R
k = Ae-Ea/RT
The equation is the same as the Arrhenius equation
A contains the steric factor, p, and part of the
collision frequency, Zo (Zo depends weakly on T)
2N2O5 4NO2 + O2
(overall reaction)
unimolecular
2. Rate2 = k2[NO2][NO3]
bimolecular
3. Rate3 = k3[NO][NO3]
bimolecular
A Int
[Slow]
[Fast]
k2
Int B
[Fast]
[Slow]
+ AB
Rate = k1[A] Rate = k2[Int]
[Int] can not be in the rate law (intermediate) and
must be expressed through the concentrations of
the reactants (or products) in the overall reaction
If the first reaction is fast and reversible, it
quickly reaches equilibrium and the rate of
formation of the intermediate is equal to the rate
of its consumption (steady state approximation)
The steady state approximation allows the
calculation of [Int]
k1
1
1. NO + Br2
NOBr2
k
[Fast, revers.]
2. NOBr2 + NO 2NOBr
[Slow, RDS]
-1
k2
k1
1. NO + Br2 NOBr2
k-1
k2
2. NOBr2 + NO 2NOBr
16.7 Catalysis
Catalyst a substance that increases the
reaction rate without being consumed in it
In general catalysts increase the rate by lowering
the activation energy (Ea) of the reaction
Catalysts provide a
different mechanism
for the reaction
Catalysts speedup
both the forward and
reverse reactions
Catalysts dont
change the Hr
2H2O2(aq)
Br2(aq)
2H2O(l) + O2(g)
[Slow, RDS]
[NOBr2] = (k1/k-1)[NO][Br2]
[Fast, revers.]