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12/12/10 1
Chap 16 - Chemical Kinetics
Integrated Rate Laws: Concentration changes
over time
First, Second, and Zero-Order Reactions
Reaction Order
Reaction Half-Life
The Effect of Temperature on Reaction Rate
Explaining the Effects of Concentration and
Temperature
Collision Theory
Transition State Theory
12/12/10 2
Chap 16 - Chemical Kinetics
Reaction Mechanisms: Steps in the Overall
reaction
Elementary Reactions
The Rate-Determining Step
The Mechanism and the Rate Law
Catalysis: Speeding up a Chemical Reaction
Homogeneous Catalysis
Heterogeneous Catalysis
12/12/10 3
Chemical Kinetics
Chemical Kinetics is the study of:
Chemical Reaction Rates
The changes in Chemical Concentration of
reactants as a function of time
Chemical reactions range from very fast to very slow
Under a given set of conditions each reaction has its
own rate
Factors that influence reaction rate:
Concentration
Physical state (surface area)
Temperature (frequency & energy of particle
collisions
12/12/10 4
Chemical Kinetics
Factors That Influence Reaction Rate
Concentration
Molecule must Collide to React
Reaction rate is proportional to the concentration
of the reactants
Rate ∝ collision frequency ∝ concentration
Physical State
Molecules must Mix to Collide
The more finely divided a solid or liquid reactant:
The greater its surface area per unit volume
The more contact it makes with the other
reactant
The faster the reaction occurs
12/12/10 5
Chemical Kinetics
Temperature
Molecules must collide with enough energy
to react
At a higher temperature, more collisions
occur in a given time
Raising the temperature increases the
reaction rate by increasing the number and
energy of the collisions
Rate ∝ Collision Energy ∝ Temperature
12/12/10 6
Chemical Kinetics
A fundamental question addressed in chemical reactions
is “how fast does the reaction occur?”
Kinetics is the study of the rate of chemical reactions;
rate is a time dependent process
Rate units are concentration over time
Consider the reaction A → B
Reactant concentrations [A] decrease while product
concentrations [B] increase
conc
change in concentration of AΔ(conc A)A 2 - conc A1
Note:
Rate Reaction
of Reaction = -rate is positive, but the = - concentration = - of
change in time t2 - tΔt
A at t2 (A2) is always less than the concentration of 1
12/12/10 7
Chemical Kinetics
Consider the reaction:
A + B → C
Concentrations of both reactants ([A] & [B])
decrease at the same rate
change in concentration
Rate =
change in time
Δ [ A] Δ [ B]
Rate = - = -
Δt Δt
∆ Indicates “Change in”
Brackets [ ] indicate concentration
12/12/10 8
Chemical Kinetics
Reaction - Butyl Chloride (C4H9Cl) and water (H2O)
12/12/10 13
Chemical Kinetics
As reactant concentrations decrease, the reaction
rates decrease with time
Product concentrations increase at the same rate
as the reactants relative to the stoichiometric
ratios
The rate of a reaction depends on the following
variables:
reactant concentration
temperature
presence and concentration of a catalyst
surface area of solids, liquids or catalysts
12/12/10 14
Sample Problems
Write an expression defining equivalent rates for the
loss of NO2 and the formation of NO in the following
reaction with respect to the rate of formation of O2.
Δ [ O2 ] 1 Δ [ NO ] 1 Δ [ NO2 ]
Rate = = = -
Δt 2 Δt 2 Δt
12/12/10 15
Chemical Kinetics –The Rate
Law
The dependence of reaction rate on concentrations is
expressed mathematically by the rate law
The rate law expresses the rate as a function of reactant
concentrations, product concentrations, and temperature
In the following development, only the reactants appear in
the rate law
For a general reaction at a fixed temperature:
aA + bB + … → cC + dD + …
the rate law has the form:
Rate = k[A]m[B]n ...
Note: The Stoichiometric Coefficients – a, b, c – are not
used in the rate equation and are not related to the
reaction order terms – m, n, p, etc.
12/12/10 16
Rate Law
Components of the rate law
aA + bB + …→ products
m n p
Rate = -∆ [A]/∆ t = k[A] [B] [C]
k = rate constant
12/12/10 18
Rate Constant - Units
Units of the Rate Constant k change depending
on the overall Reaction Order
Overall Reaction Order Units of k (t in seconds)
12/12/10 19
The Rate Law
The Rate Law
If the rate does not change even though [A]
doubles, the rate does not depend on the
concentration of A and m = 0.
The Stoichiometric coefficients, a, b, c, etc. in the
general balanced equation are not necessarily
related in any way to the reaction orders m, n,
etc.
The components of the Rate Law – rate, reaction
orders, rate constant – must be determined
experimentally; they cannot be deduced or
inferred from the balanced stoichiometric
equation
12/12/10 20
Rate Law
The Rate Law - Examples
NO(g) + O3(g) → NO2(g) + O(g)
Rate = k[NO]1[O3]1
Reaction is 1st order with respect to NO, m=1
Rate depends on [NO] raised to 1st power
Reaction is 1st order with respect to O3, n=1
The overall reaction is 2nd order, m + n = 1 + 1 =
2
2NO(g) + 2H2(g) → N2(g) + 2H2O(g)
Rate = k[NO]2[H2]1
Reaction is 2nd order in NO and 1st order in H2
Overall reaction is 2 + 1 = 3rd order
Note: [NO] coefficient (2) is not related to the
[NO] reaction order (2)
12/12/10 21
Rate Law
The rate law – Examples
(CH3)3C–Br(l) + H2O(l) → (CH3)C–OH(l) + H+(aq) + Br-(aq)
Rate = k[(CH3)3CBr]1[H2O]0 or
Rate = k[(CH3)3CBr]1
Reaction is first order in 2-bromo-2-methyl propane
Reaction is zero order (n=0) in water [H2O]0
12/12/10 22
Rate Law
The Rate Law
CHCl3(g) + Cl2(g) → CCl4(g) + HCl(g)
Rate = k[CHCL3][Cl2]1/2
The reaction order means that the rate depends
on the square root of the Chlorine (CL2)
concentration
If the initial Cl2 concentration is increased by a
factor of 4, while the initial concentration of
CHCl3 is kept the same, the rate increases by a
factor of 2, the square root of the change in Cl2
12/12/10 23
Rate Law
The Rate Law
12/12/10 24
Rate Law – Reaction Order
Overall reaction order = sum of exponents in
rate equation
Order of Rxn Possible Expression of Rate Law
1 k[A]
2 k[A]2
2 k[A][B]
3 k[A]2[B]
3 k[A][B][C]
12/12/10 25
Practice Problem
What is the reaction order of acetaldehyde and
the overall order in the following reaction
CH3CHO(g) → CH4(g) + CO(g)
Rate = k[CH3CHO]3/2
Ans:
3/2 order in CH3CHO
Overall order: 3/2
12/12/10 26
Practice Problem
Experiments are performed for the reaction
A →B + C
and the rate law has the been determined to be of the form
Rate = k[A]x
Determine the value of the exponent “x” for each of the
following:
a. [A] is tripled and you observe no rate change
Ans: x = 0 k[3A]0
b. [A] is doubled and the rate doubles
Ans: x = 1 k[2A]1
c. [A] is tripled and the rate increases by a factor of 27
Ans: x = 3 k[3A]3
12/12/10 27
Experimental Rate Law
Concentration Exponents (reaction orders) must
be determined experimentally because the
stoichiometric balanced equation with its reaction
coefficients, does not indicate the mechanism of
the reaction
Experimentally, the reaction is run with varying
concentrations of the reactants, while observing
the change in rate over time
The initial rate of reaction is observed, where the
rate is linear with time (instantaneous rate =
average rate); usually just when the reaction
begins
12/12/10 28
Experimental Rate Law
Initial rates of reaction from experiments on the reaction:
O2(g) + 2NO) g) → 2 NO2)g)
Rate = k[O2] m[NO] n
Determine “m” & “n” from experimental data
12/12/10 32
Integration of Rate Equation
First Order Reaction
Δ [ A]
= k [ A]
1
-
Δt
Rearrange Equation
Δ [ A] 1 1
- = kΔt dx = kdt ∫ dx = ln x
[ A] x x
-ln [ A ] = kt + C (at t = 0, C = ln[Ao ])
-ln ( [ A ] t - [ A ] 0 ) = kt
( )
ln [ A ] 0 - [ A ] t = kt
[ A] 0 [ A] 0 kt
ln = kt or log =
[ A] t [ A] t 2.303
12/12/10 33
Integration of Rate Equation
Second Order Reaction
Δ [ A]
= k [ A]
2
-
Δt
Δ [ A] 1 1 xn+1 x-2+1 1
- = kΔt 2 = kdt
dx ∫ n dx = = = -
[ A] 2
x x n +1 -2 + 1 x
1 1
--
[ A ]
= kt + C a t = 0, C =
[ A ] 0
1 1
-- = kt +
[ A] [ A]
t 0
1 1
- = kt
[ A] [ A]
t 0
1
= kt
[ A] t - [ A] 0
12/12/10 34
Integration of Rate Equation
Zero Order Reaction
Δ [ A]
= k [ A]
0
- = k ×1
Δt
Δ [ A]
- = k
At
-Δ [ A ] = kAt
-([ A ] t - [ A ] 0 ) = kt
[ A] t - [ A] 0 = - kt
12/12/10 35
Integrated Rate Law
Integrated Rate Law – Straight Line Plot
For a 1st order reaction
ln[A]0 - ln[A]t = kt
Rearrange into equation for a straight line
ln[A]t = - kt + ln[A]0
y = mx + b (m = slope; b = y - axis intercept)
For a simple 2nd order reaction :
1 1
- = kt
[A]t [A]0
1 1
= kt +
[A]t [A]0
y = mx + b (m = slope; b = y - axis intercept)
For a zero - order reaction :
[A]t - [A]0 = - kt
[A]t = - kt + [A]0
y = mx + b
12/12/10 36
Integrated Rate Law
12/12/10
37
First-Order Concentration vs.
Time Graphs
12/12/10 38
Integrated Rate Law
1st Order Reaction Half-Life
The half-life of a reaction is the time required for the
reactant concentration to reach ½ its initial value
At fixed conditions, the half-life of a 1st order reaction is
a constant, independent of reactant concentration
[A]0
ln = kt
[A]t
Substituting
[A]
ln 1 0 = kt1/ 2
2
[A]0
1 1
- = kt
[ A] 0 [ A] 0
After one half - life, t = t1/ 2 , and [A]t = 1
2 [A]0
1 1 1 1 2 1 1
- - -
[ A] t [ A] 0 1 / 2[ A] 0 [ A] 0 [ A] 0 [ A] 0 [ A] 0
t1/ 2 = = = =
k k k k
1
t1/ 2 =
k [ A] 0
12/12/10 40
Integrated Rate Law – Half-LIfe
Zero Order Reaction Half-Life
[A]t - [A]0 = - kt
12/12/10 41
Practice Problem
A reaction is first order with respect to A. The
first-order rate constant is 2.61 /min. How long
will it take the concentration of A to decrease from
0.100 M to 0.00812 M? What is the half-life of the
reaction? How long will it take for the
concentration
k = 2.61 / min
of A to decrease by 85%?
ln[A]0 - ln[A]t = kt
[A]
ln 0 ln 0.100
ln[A]0 - ln[A]t [A]t 0.00812 ln ( 12.3152709 ) 2.51084
t= = = = =
k k 2.61 / min 2.61 2.61
t = 0.962min
ln2 0.693 0.693
t1/2 = = = = 0.266 min
k k 2.61 / min
[A]
ln 0 ln 0.1
ln[A]0 - ln[A]t [A]t 0.1× 0.15 ln ( 6.66667 ) 1.89712
t= = = = = = 0.727 min
k k 2.61 2.61 2.61
12/12/10 42
Practice Problem
A reaction is second order with respect to B.
The second-order rate constant is 1.5 L/molmin
How long will it take the concentration of B to
decrease from 0.100 M to 0.025 M?
k = 1.5 L / mol • min
1 1
- = kt
[A]t [A]0
1 1
-
[A]t [A]0
t=
k
1 1
-
t = 0.025 mol / L 0.100 mol / L
1.5 L / mol • min
40 - 10
t= = 20min
1.5
12/12/10 43
Temperature Dependence of Reaction
Rate
An increase in Temperature (T) generally
increases the reaction rate
A 10 oC increase in T usually doubles rate
Temperature affects the rate constant (K) of the
rate equation
Temperature effect process is described by
Collision Theory
Can calculate the effect of T on rate of a reaction
using the Arrhenius Equation
12/12/10 44
Effects of Concentration &
Temperature
Two major models explain the observed effects of
Concentration & Temperature on reaction rate
Collision Theory
Views the reaction rate as a result of
particles colliding with a certain frequency
and minimum energy
Transition State Theory
Close-up view of how the energy of a
collision converts reactant to product
12/12/10 45
Collision Theory
Why concentrations are “Multiplied” in the Rate Law
Consider 2 particles of “A” & 2 particles of “B”
Total A-B collisions = 4 (2 x 2)
A1B1 A1B2 A2B1 A2B2
Add additional Particle of “A”
Total A-B collisions = 6 (3 x 2)
A1B1 A1B2 A2B1 A2B2 A3B1 A3B2
It is the product of the number of different particles, not the sum (6
vs 5), that determines the number of collisions (reactions) possible
The number of particles of reactant A (concentration) must be
multiplied by the number of particles of Reactant B to account for
the total number of collisions (reactions) that occur.
12/12/10 46
Collision Theory
Increasing the temperature of a reaction increases the average
speed of particles; thus, the frequency of collision
Most collisions do not result in a “reaction”
Collision Theory assumes that, for a reaction to occur, reactant
molecules must collide with an energy greater than some minimum
value and with proper orientation
Activation Energy (Ea)
The rate constant, k, for a reaction is a function of 3 collision
related factors:
Z, collision frequency
f, fraction of collisions => activation energy
p, fraction of collisions in proper orientation
k = Zpf
12/12/10 47
Collision Theory
At a given temperature, the fraction of molecular
collisions, f, with energy greater than or equal to
the activation energy, Ea, is related to activation
energy by the expression:-E RT
f =e a
12/12/10 48
Arrhenius Equation
Temperature dependence of reaction rate
-Ea/RT
k = Ae
K = rate constant
A = frequency factor (pZ)
Ea = activation energy (J)
R = gas constant (8.314 J/mol•K)
T = temperature (K)
The negative exponential relationship between
temperature (T) and the rate constant k means
that as the temperature increases, the negative
exponent becomes smaller, so the value of k
becomes larger, which means that the rate of the
reaction increases
Higher T ⇒ large k ⇒ increased rate
12/12/10 49
Arrhenius Equation
The activation energy (Ea) can be calculated from
the Arrhenius equation by taking the natural
logarithm of both sides and rearranging the
equation into a “straight line (y=b+mx) form
-Ea / RT
k = Ae
ln k = ln A + ln e ( -Ea / RT
)
Ea 1
ln k = ln A -
R T
y = b + mx
A plot of ln k (y) vs. 1/T (x) gives a straight line whose
slope (m) is -Ea/R and whose y intercept is Ln A (b)
12/12/10 50
Arrhenius Equation
Ea can be determined graphically from a
series of k values at different temperatures
Determine the slope from the plot
Use slope formula = -Ea/R
k2 E 1 1 E T 1 T 1 E T -T
ln =- a - =- a 1× - 2× =- a 1 2
k1 R T2 T1 R T1 T2 T2 T1 R T1T2
k 2 T1T2
Ea = -R × ln ×
k T
1 1 2 - T
12/12/10 51
Practice Problem
Find the Activation Energy (Ea) for the decomposition of
Hydrogen Iodide (HI)
2HI(g) → H2(g) + I2(g)
The rate constants are:
9.51x10-9 L/mols at 500oK
1.10x10-5 L/mols at 600oK
k TT
Ea = -R × ln 2 × 1 2
k 1 T1 - T2
1.10 x 10-5 L / mol • s 500o K × 600o K
Ea = - ( 8.314J / mol • K ) × ln ×
9.51 x 10-9 L / mol • s 500o K - 600o K
( ) (
Ea = - ( 8.314J / mol • K ) × ln 1.156677 x 10 3 × -3.00 x 103 )
(
Ea = - ( 8.314J / mol • K ) ×(7.053307)× -3.00 x 10 3 )
1kJ
Ea = 1.76 x 105 J / mol × 3
2
1 x 10 J
Ea = 1.76x10 kJ / mol
12/12/10 52
Rate – Affects of Temperature
ACTIVATED STATE
Ea(forward)
Collision Energy
Collision Energy
Ea(reverse)
REACTANTS
PRODUCTS
12/12/10 54
Transition-State Theory
Transition-state theory explains the reaction in
terms of the collision of two high energy species –
activated complexes
An activated complex (transition state) is an
unstable grouping of atoms that can break up
to form products.
A simple analogy would be the collision of
three billiard balls on a billiard table.
Suppose two balls are coated with a slightly
stick adhesive.
We’ll take a third ball covered with an
extremely sticky adhesive and collide it with
our joined pair.
12/12/10 55
Transition-State Theory
Transition-state theory (cont’)
At the instant of impact, when all three
spheres are joined, we have an unstable
transition-state complex
The “incoming” billiard ball would likely
stick to one of the joined spheres and
provide sufficient energy to dislodge the
other, resulting in a new “pairing”
If we repeated this scenario several times,
some collisions would be successful and
others (because of either insufficient
energy or improper orientation) would not
be successful.
We could compare the energy we provided
to the billiard balls to the activation
energy, Ea
12/12/10 56
Transition State Theory
Reaction of Methyl Bromide & OH-
Reaction is exothermic – reactants are higher in
energy than products
Forward activation energy Ea(fwd) is less than
reverse Ea(rev)
Difference in activation energies is “Heat of
Reaction”
∆ Hrxn = Ea(fwd) - Ea(rev)
Note the partial
elongated C-O and C-Br
bonds and the trigonal
bipyramidal shape of the
transition state
12/12/10 57
Exothermic Reaction Pathway
Transition State
12/12/10 58
Endothermic Reaction Pathway
12/12/10 59
Reaction Mechanisms
Steps in the overall reaction that detail how
reactants change into products
Reaction Mechanism – set of elementary
reactions that leads to overall chemical equation
Reaction Intermediate – species produced
during a chemical reaction that do not appear in
chemical equation
Elementary Reactions – single molecular event
resulting in a reaction
Molecularity – number of molecules on the
reactant side of elementary reaction
Rate Determining Step (RDS) – slowest step in
the reaction mechanism
This is the reaction used to construct the rate law;
it is not necessarily the overall reaction
12/12/10 60
Reaction Mechanisms
Proposed Overall Reaction
2 NO2(g) + 2 H2(g) → 2 H2O(g) + N2(g)
12/12/10 61
Reaction Mechanisms
Elementary Reactions (Steps) – The individual
steps, which together make up a proposed
reaction mechanism
Each elementary reaction describes a single
molecular event, such as one particle
decomposing or two particles colliding and
combining.
12/12/10 62
Reaction Mechanisms
An elementary step is characterized by its
“Molecularity – the number of reactant
particles involved in the step
2O3(g) → 3O2(g)
Proposed mechanism – 2 steps
1st step – Unimolecular reaction
(decomposition)
O3(g) → O2(g) + O(g)
2nd step – Bimolecular reaction (2 particles
react)
O3(g) + O(g) → O2(g)
12/12/10 63
Rate Law & Reaction
Mechanisms
Rate law for an elementary reaction can be
deduced directly from molecularity of reaction
(w/o experimentation)
An elementary reaction occurs in one step
Its rate must be proportional to the product of the
reactant concentrations
The stoichiometric coefficients are used as the
reaction orders in the rate law for an elementary
step
The above statement holds only for an
elementary reaction
In an overall reaction the reaction orders must be
determined experimentally
12/12/10 64
Rate Law & Reaction
Mechanisms
Steps in determining rate law from reaction
mechanism
Identify the rate determining step (RDS) of the
mechanism
Write out the preliminary rate law from RDS
Remove expressions for intermediates
algebraically
Substitute into preliminary rate law to obtain
final rate law expression
12/12/10 65
Practice Problem
The following two reactions are proposed as elementary
steps in the mechanism of an overall reaction:
(1) NO2Cl(g) NO2(g) + Cl(g)
(2) NO2Cl(g) + Cl(g) NO2(g) + Cl2(g)
(a) Write the overall balanced equation
(b) Determine the molecularity of each step
(c) What are the reaction intermediates
(d) Write the rate law for each step
12/12/10 67
Practice Problem
If a slow step precedes a fast step in a two-step mechanism, do the
substances in the fast step appear in the rate law?
Ans: No, the overall rate law must contain reactants only (no
intermediates) and is determined by the slow step
If the first step in a reaction mechanism is slow, the rate law
for that step is the overall rate law
If a fast step precedes a slow step in a two-step mechanism, how is
the fast step affected?
Ans: If the slow step is not the first one, the faster preceding step
produces intermediates that accumulate before being consumed in
the slow step
How is this effect used to determine the validity of the mechanism?
Ans: Substitution of the intermediates into the rate law for the
slow step will produce the overall rate law.
12/12/10 68
Mechanism with a Slow Initial
Step
Reaction between nitrogen dioxide & chlorine gas
Overall reaction
2NO2(g) + F2(g) → 2NO2F(g)
Experimental Rate Law
Rate = k[NO2][F2] (1st order)
Mechanism
(1) NO2(g) + F2(g) → NO2F(g) + F(g) [slow, rds]
(2) NO2(g) + F(g) → NO2F(g) [fast]
Overall: 2NO2(g) + F2(g) → 2NO2F(g)
Criteria 1: Elementary steps add up to experimental
Criteria 2: Both steps “Bimolecular”
12/12/10 70
Mechanism with a Fast Initial Step
Nitric oxide, NO, is believed to react with chlorine
(Cl2) according to the following mechanism
NO + Cl2 ↔ NOCl2 (Fast, equilibrium)
NOCl2 + NO → 2 NOCl (slow, RDS)
1. What is the overall chemical equation for the
reaction?
2. Identify the reaction intermediates.
3. Propose a viable rateReactant
Intermediate law from
- NOCl 2 the mechanism.
RDS = NOCl 2 + NO → 2NOCl
12/12/10 72
Catalysis – Speeding Up
Reaction
Catalyst:
Causes lower “activation energy”, (Ea)
Lower activation energy is provided by a
change in the reaction mechanism
Makes Rate constant larger
Promotes higher reaction rate
Speeds up forward & reverse reactions
Does not improve yield – just makes it faster
12/12/10 73
Homogeneous Catalysts
Homegeneous Catalysts
Exist in “Solution” with the reactant mixture
All homogenous catalysts are gases, liquids, or
“soluble” solids
Mechanism for the catalyzed hydrolysis of an organic ester.
H+ , the catalyst, is a resonance forms
O fast H O proton supplied by a H O H O
H+ + R C R C strong acid
R C R C
O O +
Step 1: Catalytic H ion H O
O O
R' Step R' bonds to electron rich R C
1 oxygen. R' R'
O
Step 2: Slow, rate R'
determining step. resonance hybrid
Step
H O H O The increased positive
2
R C O H R C O H charge on the Carbon
attracts the partially H+ O
O H O H negative oxygen of the
slow, rate- all fast R C O H
R' determining R' water more strongly, OH
step increasing the fraction of
effective collisions, R'
Steps 3-6
speeding up this rate
determining step
12/12/10 74
Heterogeneous Catalysts
Heterogeneous Catalysts
Speeds up a reaction that occurs in a separate
phase
Ex. A solid interacting with gaseous or liquid
reactants
The solid would have extremely large surface
area for contact
If the rate-determining step occurs on the
surface of the catalyst, many reactions are
zero order, because once the surface area is
covered by the reactant, increasing the
concentration has no effect on the rate
12/12/10 75
Heterogeneous Catalysts
Hydrogenation of Ethylene (Ethene) to Ethane
catalyzed by Nickel (Ni), Palladium (Pd), or Platinum
(Pt) Ni, Pd, Pt
H2C=CH2(g) + H2(g) → H3C – CH3
Finely divided Group 8B metals catalyze by adsorbing
the reactants onto their surface
H2 lands and splits into separate H atoms chemically
bound to solid catalyst’s metal atoms
H – H + 1catM(s) → 2catM – H
Then C2H4 absorbs and reacts with two H atoms, one
at a time, to form H3C–CH3
The H-H split is the rate determining step providing a
lower energy of activation
12/12/10 76
Effect of A Catalyst
Comparison of Activation Energies in the Uncatalyzed and
Catalyzed Decompositions of Ozone
12/12/10 77
Practice Problem
Ethyl Chloride, CH3CH2Cl2, used to produce
tetraethyllead gasoline additive, decomposes, when
heated, to give ethylene and hydrogen chloride.
The reaction is first order. In an experiment, the
initial concentration of ethyl chloride was 0.00100
M. After heating at 500 C for 155 s, this was
reduced to 0.00067 M. What was the concentration
of ethyl
[A]o chloride after a total of 256 s?
ln = kt (1st order reaction)
[A]t
[A]o 0.00100M
ln ln
[A]t 0.00067M ln ( 1.492537 ) 0.400478
k= = = = = 0.0026 / s
t 155s 155 155
Determine concentration after t = 256 seconds
ln[A]t - ln[A]0 = - kt
ln[A]t = ln[A]0 - k t
ln[A]t = ln(0.00100 M) - 0.0026 / s × 256 s
ln[A]t = - 6.90776 - 0.6656 = - 7.57336
12/12/10 [A]t = 0.00052 M 78
Practice Problem
The rate of a reaction increases by a factor of 2.4
when the temperature is increased from 275 K to
300 K. What is the activation energy of the
reaction?
k 2 T1 × T2
Ea = -R × ln ×
k 1 T1 - T2
2.4 k 1 275o K × 300o K
Ea = - ( 8.314J / mol • K ) × ln × o o
k 1 275 K - 300 K
Ea = 65, 846.88J / mol
Ea = 65 kJ / mol
12/12/10 79
Practice Problem
The rate constant of a reaction at 250 oC is 2.69 x
10-3 1/M-s (L/mols). Given the activation energy for
the reaction is 250 kJ, what is the rate constant for
the reaction at 100 oC, assuming activation energy
is independent of temperature?
k 2 T1 × T2
Ea = -R × ln ×
k 1 T1 - T2
Ea T1 - T2
lnk2 = lnk1 + ×
-R T2 × T1
kJ 1000J
250 (250o C + 273.15)K - (100o C + 273.15)K
-3
lnk 2 = ln(2.69x10 L / mol • s + mol kJ ×
-8.314J / mol • K (250o C + 273.1)K ×(100o C + 273.15)K
250, 000J / mol 150o K
lnk 2 = 1.002694 L / mol • s + ×
-8.314J / mol • K 195, 213.4225o K 2
37, 500, 000
lnk 2 = 1.002694L / mol • s -
1, 623, 004.395
lnk 2 = 1.002694L / mol • s - 23.105298 = -22.102604
k 2 = 2.52x10-10 L / mol • s
12/12/10 80
Practice Problem
If the half-life of a first-order reaction is 25 min, how
long will it take for 20% of the reactant to be
consumed?
ln2 0.693
t1/ 2 = =
k k
0.693 0.693 0.693
k= = =
t1/ 2 t1/ 2 25min
k = 0.02772 / min
[A]o
ln = kt
[A]t
t=
ln
[ A] t
ln
= = (
1.0x10-9 mol / L ln 2.5x103) =
7.82405
k 1hr 3.9600 / hr 3.96 / hr
1.1x10-3 / s
3600s
t = 2.0 hr
12/12/10 83
Practice Problem
The indirect photolysis of the pesticide atrazine (Atr,
C8H14 ClN5) in air by hydroxyl radical (OH) is shown below
C8H14 ClN5 + OH → C8H13 ClN5 + H2O
12/12/10
Solution on next Slide 84
Practice Problem
Photolysis of Atrazine (con’t)
The 2nd order rate law (∆ [Atr]/∆ t = kph[Atr][OH]) is stated
in terms of two reactants
This would result in a different integrated form of the 2nd
order reaction, more complicated math
Since the concentration of hydroxyl, [OH], is constant,
the rate law can be reduced to a pseudo 1st order
reaction by combining the Kph & [OH] terms (both
constants) into a new15
rate constant:
-18 -3
k = k ph ×[OH] = 5.0 x 10 L / mol • s ×1.0 x 10 mol / L = 5.0 x 10 / s
Δ[Atr]
= k[Atr] (Restatement of 2nd order rate law into pseudo 1st order)
Δt
[A]o
ln = kt (Integrated 1st order Rate Law))
[A]t
[A]o -15
ln 2.5 x 10 mol / L
ln
[A]t 1.0 x 10 -18
mol / L ln(2.5 x 103 ) 7.824046
t= = = =
k 5.0 x 10-3 / s 5.0 x 10-3 / s 5.0 x 10 -3 / s
1min
t = 1.5648 x 103 s × = 26 min
60s
12/12/10 85
Practice Problem
A convenient rule of thumb is that the rate of a
reaction doubles for a 10 oC change in temperature.
What is the activation energy for a reaction whose
rate doubles from 10.0 oC to 20.0 oC?
a. 47.8 kJ b. 19.5 kJ c. 24.3 kJ d. 10.1 kJ e. 69.2
kJ k TT
Ea = - R × ln 2 × 1 2
k1 T1 - T2
At 20o C the rate constant k 2 = 2 k1
( ) ( )
o
o o o
2k1 10 C + 273.15 K × 20 C + 273.15) K
Ea = -8.314J / mol • K × ln ×
( ) ( )
k o
1 10o C + 273.15 K 1 - 20o C + 273.15)o K
8.30054 x 104o K 2
Ea = -8.314J / mol • K × ln ( 2 ) ×
-10o K
Ea = -8.314J / mol • K × 0.693147 × 8.30054 x 103o K
kJ
Ea = 4.783455 x 104 J / mol × = 47.8kJ / mol
1000J
12/12/10 86
Rate Equations - Summary
Integrated Rate Laws
Δ [ A]
rate = - = k[A]0 = k Zero Order Rate Reaction
Δt
[ A] 0
Rate Law : [ A ] t - [ A ] 0 = -kt Half - Life t1/ 2 =
2k
Δ [ A]
rate = - = k[A] First Order Reaction
Δt
ln2 0.693
Rate Law : ln[A]0 - ln[A]t = kt Half - Life t1/ 2 = =
k k
Δ [ A]
rate = - = k[A]2 Second Order Reaction
Δt
1 1 1
Rate Law : - = kt Half - Life t1/ 2 =
ln[A]t ln[A]0 k [A]0
12/12/10 87
Rate Equations - Summary
An Overview of Zero-Order, First-Order, and Simple
Second-Order Reactions
Integrated rate law [A] = -kt + [A] ln [A] = -kt + ln [A] 1/[A] = kt + 1/[A]
t 0 t 0 t 0
in straight-line form
12/12/10 88
Rate Equations - Summary
Activation Energy (Ea)
k = Zpf
f = e -Ea/RT
k = Zpe -Ea/RT = Ae -Ea/RT
k, rate constant
Z, collision frequency
f, fraction of collisions that are => activation
energy
p, fraction of collisions in proper orientation
A = frequency factor (pZ)
Ea = activation energy (J)
R = gas constant (8.314 J/molK)
T = temperature (K)
Arrhenius Equation
k TT
Ea = -R × ln 2 × 1 2
k 1 T1 - T2
12/12/10 89