Userdata Paziras Chem102 Chap 13
Userdata Paziras Chem102 Chap 13
Userdata Paziras Chem102 Chap 13
CHEMICAL KINETICS
Chemical Kinetics:
I. Rates of Reactions
Reaction Rate:
OR
The expression above is referred to as: Average Rate over the time interval t
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Chemistry 102 Chapter 13
REACTION RATES
Reactant concentration decreases with time, while product concentration increases with time.
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Chemistry 102 Chapter 13
REACTION RATES
Any substance in the reaction can be used to express the Rxn. Rate
Since: [decrease in concentration of reactant] has a negative value the Reaction Rate will be positive
OR
Rate of increase of HI
= Rate of decrease of H2
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Chemistry 102 Chapter 13
REACTION RATES
Examples:
1. For the hypothetical reaction shown below, write a rate expression based on each reactant and product:
3A+ B 2C+4D
Rate based on A =
Rate based on B =
Rate based on C =
Rate based on D =
In the first 10.0 seconds of the reaction, the concentration of I– dropped from 1.000 M to 0.868 M.
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Chemistry 102 Chapter 13
RATE DETERMINATION
Rate determination is done by monitoring the change in concentration of reactant or product over time.
Method:
Withdraw samples from the reaction vessel at various times and analyze some of their physical or
chemical properties that give information on the concentrations present.
1. Color 2. Flammability
(if product or reactant absorbs light) ( difficult to measure quantitatively)
7. Density
(useful if : d(reactants) d(products)
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Chemistry 102 Chapter 13
RATE LAW
Experimental observation:
k Rate Constant
its units depend upon the form of Rate Law
depends on temperature
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Chemistry 102 Chapter 13
REACTION ORDER
Experimental observation:
Doubling [NO2] Doubles the Reaction Rate
Doubling [F2] Doubles the Reaction Rate
Reaction is:
First order with respect to NO2 (m=1)
First order with respect to F2 (n=1)
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Chemistry 102 Chapter 13
Examples:
1. 2 NO (g) + 2 H2 (g) N2 (g) + 2 H2O (g)
Reaction is:
2nd order in NO
1st order in H2
3rd order overall
H+
2. CH3COCH3 (aq) + I2 (aq) CH3COCH2I (aq) + HI (aq)
Reaction is:
1st order in CH3COCH3
0 order in I2 (does not depend on the concentration of I2 as long as some I2 is present)
1st order in the catalyst (H+)
2nd order overall
Effect of concentration change on reaction rates and orders can be summarized as:
Zero x 2 No Effect
First x 2 x2
Second x 2 x4
Negative x2 x½
Half x2 2
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Chemistry 102 Chapter 13
In determining the rate law for a reaction, first the order of reaction with respect to each
reactant and catalyst must be found.
Commonly a series of experiments are done in which the initial concentrations of reactants
are varied (usually doubled).
The results of these experiments will yield the respective orders of reaction.
It follows: m = 1 (21 = 2)
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Chemistry 102 Chapter 13
Examples:
1. Use the rate data below to
A) determine the reaction orders with respect to [H2O2], [I–] and [H+] and
B) find the rate constant k for the reaction shown below:
Solution
A) Compare two rate experiments in which all concentrations of reactants but one are held constant:
NOTE: Reaction Orders are not related to the coefficients of the overall equation
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Chemistry 102 Chapter 13
[H2O2] = 0.010 M
[I] = 0.010 M
Rate = 1.15 x 106 M/s
k=?
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Chemistry 102 Chapter 13
[N2O5]
Rate = – = k [N2O5]
t
Using calculus:
[N2O5] t [N2O5] t – kt
ln = – kt OR log =
[N2O5] 0 [N2O5] 0 2.303
In General:
a A Products
[A]
Differential Rate Law: – = k[A]
t
[A] t [A] t - kt
Integrated Rate Law: ln = - kt OR log =
[A] 0 [A] 0 2.303
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Chemistry 102 Chapter 13
Example 1:
Sulfuryl chloride, SO2Cl2, decomposes when heated:
[SO2Cl2] t
= 0.82 [SO2Cl2] t = (0.82) x [SO2Cl2] 0
[SO2Cl2] 0
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Chemistry 102 Chapter 13
Example 2:
Cyclobutane, C4H8 decomposes, when heated to give ethylene:
–0.10054 = –197.57 k
[C4 H8 ]827
= 0.6566
[C4 H8 ]0
Substituting [C4H8]0
[C4 H8 ]827
= 0.6566
0.00150 M
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Chemistry 102 Chapter 13
Half-life is the time it takes for the reactant concentration to decrease to one-half of its initial value.
[A]t -kt
log =
[A]0 2.303
1
[A]0
1 - k (t1/2 )
In one half-life (t1/2): [A]t = [A]0 log 2 =
2 [A]0 2.303
0.693
t1/2 =
k
NOTES:
Example:
Dinitrogen pentoxide, decomposes when heated in carbon tetrachloride solvent:
The rate law is first order in N2O5 with a rate constant of 6.2x10–4 min–1.
0.693 0.693
t1/2 = = -4 -1
= 1118 min = 1.1x103 min
k 6.2x10 min
(b) How long would it take for the concentration of N2O5 to decrease to 25 % of its initial value?
t25 % left = t1/4 left = 2 x t1/2 = 2 (1.1 x 103 min) = 2.2 x 103 min
(c) How long would it take for the concentration of N2O5 to decrease to 12.5 % of its initial value?
t12.5 % left = t1/8 left = 3 x t1/2 = 3 (1.1 x 103 min) = 3.3 x 103 min
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Chemistry 102 Chapter 13
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Chemistry 102 Chapter 13
In General:
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Chemistry 102 Chapter 13
The graph which best fits the experimental data gives the order of a reaction.
-kt
log [A]t = ( ) + log [A]0 (This is the equation of a straight line)
2.303
-k
log [A]t = ( ) t + log [A]0 y = mx + b
2.303
A plot of log [A] (y) versus time (x) should give a straight line for a first order reaction.
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Chemistry 102 Chapter 13
y (–2.538)–(–1.783) – 0.755
m = slope of the straight line = = = = – 2.10 x 104 s–1
x (3600 – 0) s 3600 s
-kt
Recall: log [A]t = ( ) + log [A]0 y = mx + b
2.303
It follows:
–k
m = k = –2.303 (– 2.10 x 104 s–1) = 4.84 x 104 s–1
2.303
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Chemistry 102 Chapter 13
aA Products
[A]
Rate = = k [A]2 Differential Rate Law
t
By using calculus:
1 1
= kt + Integrated Rate Law
[A]t [A]0
Example:
1. For the reaction
At 330 K:
1 1
= (0.775 M-1s-1 )(645 s) +
[A]t 0.0030 M
1
= (499.9 M-1 ) + (333.3 M -1 ) = 8.3x102 M-1
[A]t
[A]t = 0.0012 M
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Chemistry 102 Chapter 13
Half-life is the time it takes for the reactant concentration to decrease to one-half of its initial value.
1 1
For a second order reaction: Rate = k [A]2 and = kt +
[A]t [A]0
1 1 1
In one half-life (t1/2): [A]t = [A]0 = kt +
2 0.5[A]0 [A]0
1 1 1 1
kt1/2 = = t1/2 =
0.5[A]0 [A]0 [A]0 k [A]0
NOTES:
Example:
1. For a particular 2nd order reaction k = 0.775 M–1s–1.
a) How long does it take to the concentration to decrease from 0.0030 M to 0.0015?
1 1
t1/2 = = -1 -1
= 430 s
k [A]0 (0.775 M s )(0.0030 M)
1 1
t1/2 = = -1 -1
= 860 s Twice as long
k [A]0 (0.775 M s )(0.0015 M)
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Chemistry 102 Chapter 13
1 1
= k t +
[A]t [A]0
y = mx + b
slope intercept
Meaning:
1
A plot of (y) versus time (s) should give a straight line for a second order reaction
[A]t
Summary:
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Chemistry 102 Chapter 13
Example:
1. Given the experimental data listed below, determine if the reaction is 1st or 2nd order, and determine
the rate constant (k) for the reaction shown below:
Time [NO2]0
(s) (M)
0 1.00 x 10–2
60 0.683 x 10–2
120 0.518 x 10–2
180 0.418 x 10–2
240 0.350 x 10–2
300 0.301 x 10–2
360 0.264 x 10–2
Strategy:
We must first see if the data fits the Rate Law for 1st Order Reactions. If it does, the
reaction is of the 1st order
If it does not, we must see if the data fits the Rate Law for 2nd Order If it does, the
reaction is of the 2nd order
-kt
log [A]t = ( ) + log [A]0 Plot log [A]t as a function of t
2.303
y = mx + b
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Chemistry 102 Chapter 13
Graphical Plot
Rate Differential Integrated
Order Half-Life for a
Law Rate Law Rate Law
Straight Line
[A]t [A]0
0 k =k [A] = – k t + [A]0 [A] vs. t
t 2k
[A]t kt
log =
[A]0 2.303
[A]t 0.693
1 Rate = k [A] = k [A] or log [A] vs. t
t k
kt
log [A]t = ( ) + log [A]0
2.303
[A]t 1 1 1 1
2 Rate = k [A]2 = k [A]2 =kt+ vs. t
t [A]t [A]0 k[A]0 [A]0
Examples:
1. Ethylene oxide, C2H4O(g), decomposes when heated to give methane and carbon monoxide:
The following kinetic data were observed for the reaction at 688K
Find the Rate Law and the value of the Rate Constant.
Rate =
k=
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Chemistry 102 Chapter 13
Examples:
3. In a kinetic study of the reaction shown below, the following data were obtained for the initial
rates of disappearance of NO and O2 :
Rate =
k=
4. In the presence of excess thiocyanate ion (SCN) the following reaction is 1st order with respect
to Fe3+ with a rate constant of 1.27 s–1.
t1/2 =
b) How many seconds would be required for the initial concentration of Fe3+ to decrease to
each of the following values? (25.0 % and 12.5 %)
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Chemistry 102 Chapter 13
5. Methyl acetate (CH3COOCH3) reacts in basic solution to give acetate ion (CH3COO) and
methanol (CH3OH).
The overall order of reaction was determined by starting with methyl acetate, CH3COOCH3 and
hydroxide ion, OH , at the same concentrations, so [CH3COOCH3] = [OH] = x.
Determine the overall order and the value of the rate constant by plotting data assuming first- and
then second-order kinetics.
Time [CH3COOCH3]
(min) (M)
0.00 0.01000
3.00 0.00740
4.00 0.00683
5.00 0.00634
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Chemistry 102 Chapter 13
Recall:
Temperature k
NOTE:
In this case, “k” (the Rate Constant) is more than tripled for a 100 C increase in temperature.
Consequently, for this reaction, the Reaction Rate is also more than tripled for a 100 C
increase in temperature.
Why?
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Chemistry 102 Chapter 13
COLLISION THEORY
Collision theory states that for a reaction to occur, the reactant molecules must collide:
with an energy greater that some minimum value, called Activation Energy (Ea)
and
with the proper orientation
k = Z f p
(As “t” increases molecules move faster molecules collide more often)
3RT
u=
Mm
This does not explain the large increase in rate with temperature
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Chemistry 102 Chapter 13
-
Ea e = 2.718
f=e RT R = 8.31 J/molK
Ea= 8.5 x 104 J/mol
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Chemistry 102 Chapter 13
This theory explains the reaction resulting from the collision of 2 molecules, in terms of an
activated complex.
An Activated Complex (Transition State) is an unstable grouping of atoms that can break up
to form products:
O= N + Cl Cl
back to reactants
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Chemistry 102 Chapter 13
I. Endothermic Reactions
NOTEs:
1. Sum of (Kinetic Energy + Potential Energy ) is constant throughout the reaction. (Law of
Conservation of Energy)
2. From: Reactants Activated Complex
(NO + Cl2) (NOCl2*)
Potential Energy increases (outer electrons of molecules repel, as molecules get closer)
Kinetic Energy decreases (molecules slow down)
Kinetic Energy changes into Potential Energy
3. The reaction will yield product only if : PE(max) Activation Energy (Ea). This will only occur if
reactant molecules possess sufficient KE to start with.
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Chemistry 102 Chapter 13
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Chemistry 102 Chapter 13
ARRHENIUS EQUATION
e = 2.718
Ea Ea = Activation Energy
RT R = gas constant = 8.31 J/K x mol
k=Ae T = absolute temperature
A = frequency factor
A = frequency factor
Ea Ea
ln k = ln A log k = log A
RT 2.303 RT
Ea 1
log k = log A
2.303 R T
log k
Y = b + m x
Ea
Slope = m =
2.303 R
Ea can be obtained from the slope
Intercept = b = log A
1
T
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Chemistry 102 Chapter 13
Examples:
1. Sketch a potential energy diagram for the decomposition of nitrous oxide:
The activation energy for the forward reaction is 251 kJ; the H is +167 kJ. What is the
activation energy for the reverse reaction? Label the diagram appropriately.
2. The rate constant for a particular reaction was studies at various temperatures and a plot of
log k vs. 1/T was obtained as shown below. Determine the activation energy of this reaction
based on the graph below.
0.3
0.2
0.1
0
log K
-0.2
-0.3
-0.4
1/T
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Chemistry 102 Chapter 13
REACTION MECHANISMS
Reaction Mechanisms show the steps involved in the change from Reactants to Products
Mechanisms consist of a set of “Elementary Reactions” whose overall effect is the Net
Chemical Equation.
Elementary Reactions:
Elementary reactions are single molecular events that result in a reaction and are caused by
molecular collisions
NO2 (g) + CO (g) NO (g) + CO2 (g) Net Chemical Equation
Example 1:
The decomposition of Ozone (O3) is believed to occur in 2 steps:
Elementary Reaction 1: O3 O2 + O
Elementary Reaction 2: O3 + O 2O2
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Chemistry 102 Chapter 13
Example 2:
Sodium hydrogen carbonate (NaHCO3), also called sodium bicarbonate can been synthesized through a
sequence of 3 elementary steps:
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Chemistry 102 Chapter 13
MOLECULARITY
Molecularity is the number of molecules on the reactant side of an Elementary Reaction.
Unimolecular Reactions:
Unimolecular reactions are Elementary Reactions that involve ONE reactant molecule.
Bimolecular Reactions:
Bimolecular reactions are Elementary Reactions that involve TWO reactant molecules.
Termolecular Reactions:
Termolecular reactions are Elementary Reactions that involve THREE reactant molecules.
These are less common because the chance of three molecules coming together with the right orientation
is unlikely.
Example 1:
What is the molecularity of each of the following elementary reactions?
O + O2 + N2 O3 + N2*
Cl + H2 HCl + H
CS2 CS + S
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Chemistry 102 Chapter 13
Reasons:
The majority of reactions consist of several elementary steps.
The Rate Law is the combined result of the elementary steps
The rate of all the elementary reactions must be known in order to predict the rate law for
the overall equation.
II. For an Elementary Reaction, the Rate Law can be written directly from the Elementary Equations
The rate of an elementary reaction is proportional to the product of the concentrations of each
reactant molecule.
Reason:
The frequency of collisions is proportional to the number of A molecules (nA) and the number of
B molecules (nB)
Examples:
Write Rate Equations for each of the elementary reactions shown below
:
1) O3 + NO O2 + NO2
Rate =
2) CS2 CS + S
Rate =
Rate =
NOTE:
For Elementary Reactions ONLY, the coefficients of the balanced chemical elementary reaction are the
exponents to which the concentrations of the reactants are raised.
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Chemistry 102 Chapter 13
A Suggested Mechanism
Is considered correct if it agrees Is considered incorrect if it does not
with the experimentally determined agree with the experimentally determined
Rate Law Rate Law
Example 1:
Overall Equation: 2 NO2 (g) + F2 (g) 2 NO2F (g)
The predicted Rate Law does not agree with the experimental Rate Law
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Chemistry 102 Chapter 13
k1
NO2 + F2 NO2F + F (slow step)
k2
NO2 +F NO2F (fast step)
Reaction Intermediate: F
NOTE:
The Rate Law is determined by the slow step
THE SLOWEST STEP THE RATE DETERMINING STEP
Predicted Rate Law = RATE (rate-determining-step) = k1[NO2] [F2]
The predicted Rate Law agrees with the experimental Rate Law
This mechanism must be correct.
k1
O3 k -1
O2 + O (fast equilibrium)
k2
O3 + O 2 O2 (slow)
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Chemistry 102 Chapter 13
CATALYSIS
In practice, however, there is some loss of catalyst through other reactions that occur at the same
time (side-reactions).
Importance of Catalysts:
Catalysts allow reactions to occur much faster.
Characteristics of Catalysts:
Catalysts are often quite specific. They increase the rate of some reactions but not others.
A catalyst must participate in one step of a reaction and be regenerated in a later step.
The catalyzed reaction mechanism makes available a reaction path having an increased
overall rate of reaction by:
Ea
RT
k=Ae
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Chemistry 102 Chapter 13
Examples:
1. The commercial preparation of sulfuric acid, H2SO4 from SO2 (the early process)
NO catalyst
First step: 2 SO2 (g) + O2(g) 2 SO3 (g)
Proposed Mechanism:
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Chemistry 102 Chapter 13
Homogeneous catalysis is a catalyzed process in which the catalyst is in the same physical
phase as the reacting species.
Example:
The commercial preparation of sulfuric acid, H2SO4 from SO2 (the early process)
Catalyst (NO) and reactants (SO2 and O2) are all in gaseous phase.
Heterogeneous catalysis is a catalyzed process in which the catalyst exists in a different phase
from the reactants.
In these types the catalyst is usually a solid in contact with a gaseous or liquid solution of
reactants.
Heterogeneous catalysis occurs by the adsorption of the reactant molecules to the surface of the
solid catalyst.
Adsorption is the attraction of molecules to a surface and it can be of two types:
Physical Adsorption
The molecules are attracted to the catalyst surface by weak intermolecular forces.
Chemisorption
The molecules are attached to the catalyst surface by chemical bonds.
Examples:
3. Surface catalysts are used in the catalytic converters of cars to convert potential atmospheric pollutants
(such as CO and NO) into CO2 and N2.
Pt or Ni
C2H4 (g) + H2 (g) C2H6 (g)
ethylene ethane
Ethylene and Hydrogen chemisorb to the catalyst surface Ethane then diffuses of
the catalyst surface
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Chemistry 102 Chapter 13
ENZYME CATALYSIS
Enzymes are huge protein molecules (Molecular Weights over a million amu) that are highly
specific:
Each enzyme acts only on a specific substance or a specific type of substance.
E + S ES ES E + P
enzyme-substrate complex
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