Chapter 16: Kinetics

Topic #1: Rates of reactions: rate laws, rate constraints, reaction orders
Reading: 16. 1-3, pp. 691 -701, 704
Units of the rate constant; reaction rate changes with time relative rates for different species taking
part in the reaction meaning of the rate law; order of a reaction
Heterogeneous reaction rates

Kinetics is the study of rates of reactions

(change in concentration of reactant(s) or product(s) with time)

Why?
Considered the most powerful method to study mechanisms of chemical reactions

Reactants to Products
Nuclear Substitution 1
Overall: CN3
Mechanism: cations and anion split in order to bond with

Reaction rates change in concentrations of products and reactants with time

Consider a balanced reaction that occurs in one step
One Reactant to One Product (1:1)
Products
rate = change of the concentration of the product / change of time = [P2]-[P1]/T2-T1
(units = mol/L/s)
[P1] = concentration of the product at time t1
[P2] = concentration of the product at time t2
rate= units (concentration/time)
T2-t1: time only goes forward therefore change of time is always > 0
Change of the concentration of the product is going to increase > 0
Rate is ALWAYS > 0
Reactants
Rate = -change of the concentration of the reactant / change of time = -([R2]-[R1])/T2-T1
[R1] = concentration of the product at time T1
[R2] = concentration of the product at time T2
Change of the concentration is < 0 therefore requires a - sign
Rate = change of the concentration of the product over time = (-) change of the concentration of the
reactants over time

Reactions in terms of different coefficients of reactants and products

N2O5 → 2NO2 + ½ O2
1. Make sure the reaction is balanced
1 mol of N2O5 reacts = 2 mols of NO2 and ½ mol of O2

aA + bB → cC + dD

Coefficients of the balanced equation are in the denominator

Rate is the slope of a [P] versus time graph

Rate is under loose conditions therefore it is not very accurate
Rate of a reactions depends on the concentration of reactant(s)
on the concentrations of the product(s)
Solvent
pH
salts
Temperature

Rate laws are much more talked about in order to regards of rates
Rate law is the rate as a function of the concentrations of reactants, sometimes products, pH, etc.

General Case: aA + bB → cC + dD
Only care about reactants in this class
Rate = k [A]x [B]y
k - rate constant, does not depend on the concentration of either A and B, does depend on
temperature, has units, and units depends on the order of the reaction
x - order vs reactant A
y - order vs reactant B
The sum of x and y are the overall order of the reaction
1. x and y are small integers (not often equal to a, b - the coefficients of the balanced equation)
x and y will determine the mechanism of a reaction
2. The units of the rate constant (k) depend on the overall order of the reaction
 3. The whole point of kinetics is to determine k, x, and y

Topic #2: Method of Initial Rates

Reading: 16.3, pp. 702-707

Point of this is to determine rate law

Consider A → B
Rate law: rate = k[A]x
Have to determine x and k
Rate depends on [A]
1. Measure the initial rate of a reaction at a known initial concentration of A
Rate1 @ [A]0,1 Use the
first few percent of the reaction bc you can assume that [A]B constant Ignore
reverse reactions Rate =
k [A]
2. Repeat with a different initial concentration of A
3. Two equations, 2 unknowns: now solve for x and then k

Example Problem #2
q=2
k= 2.00 x 10-4 M-1 s-1
(Kinetics was in the second trimester of AP chem just go refresh bc you got a score above 100 on that
test without studying easily)

What if you have more than one reactant?

aA + bB → cC
Rate law: rate = k [A]x [B]y

3 unknowns means 3 equations needed

1. Start by keeping the concentration of B constant and vary the initial concentration of A in
order to get x: the order vs reactant A
2. Keeping the concentration of A constant and vary the initial concentration of B in order to
get y: the order vs reactant B
3. Determine k

Rate = k [NO2]x [F2]y

Both are first order reactions
Rate = k [NO2]1 [F2]1
1.00 x 10-4 M/s = [1.00] [1.00] k
K = 1.00 x 10-4 M-1 S-1
Graphical determination:
A→B
Rate law: rate = k[A]x
Log rate = x log(k[A])
Log rate = x logk + xlog[A]
plot : y= b +ax
Always positive slope
Y- intercept = xlogk
[A] is 2nd order
[B] is 1st order
Rate law = 62.5 M-2 s-1 [A]2 [B]1

Topic #3: Integrated rate law for first order reactions

Reading: 16.4, pp. 707 - 714

First Order Reactions

A→B
Rate law: rate = k [A]1 = -(change of concentration of A) / change of time
Delta A / [A] = k (delta) t
Integrated Rate Law:
ln [A] - ln [A0] = -kt

[A] = 0.25 M
[A0] = 1.00 M
T = 10 seconds
What is k?
K = 0.14 s-1

Ln [A] = ln [A0] -kt

Y = b + ax
Negative slope on first order reaction
Y-intercept = ln [A0]
Only straight lines if the reaction is first order vs reactant A

Half Life
The time required for the initial concentration of A to decrease to half of its value
@ t1/2
[A] = [A0] / 2
@ t1/2 = ln2 / k = .0693 / k
The half life of a first order reaction is independent from the initial concentration of A
True for all 1st order reaction
All radioactive decay situations are first order
Topic #4: Integrated rate law for the first order reactions:
Applications to radioactive decay
Reading: Chap. 24 pp. 1073 - 1077 , 1083 - 1089

12.5% of the original amount

Half life is 5730 years

Zero Order Reactions

A→B
Rate law = k [A]0 = k = delta [A] / delta t
Integrated rate law: [A] = [A]0 - kt
[A] vs time gives a straight line with a negative slope
Slope = -k
Y-intercept = initial concentration of A
Units for k for zero order M s-1
Half life = k / 2
t1/2 = [A]0 / 2k

Second Order Reactions

2A → B
Rate law: rate = k [A]2 = -delta [A] / delta time
Integrated rate law: 1 / [A] = 1 / [A]0 + kt
Graph 1/[A] versus time
Straight line with a positive slope
k = slope
Y-intercept = 1 / [A]0
Units of k: M-1 s-1
@ t1/2
[A] = [A0] / 2
t1/2 = 1 / ( k [A0])

Rate constant, k, does not depend on the concentration of the reactants but it does depend on the
temperature
Reaction rates always increases with temperature
Therefore rate constant always increases with temperature increases
Arrhenius equation : k = A e (-Ea/RT)
k = rate constant
T = temperature (must be in kelvin, C + 273)
R = ideal gas constant = 8.314 J / mol K
A = frequency factor / collision factor
A function of the frequency of collisions between reactant molecules
A function of any geometry requirements for a reaction to take place
Ea = Activation energy, always positive
The amount of energy for a collision with the correct geometry to successfully lead to a
Reaction
Constant and does not change with temperature

T2 is greater than T1
At T2 greater fraction of collisions that have sufficient energy to lead to a reaction
As T increases, k increases but Ea is constant

Arrhenius equation : k = A e (-Ea/RT)

To solve using two different rate constants and temperatures to find Ea
Convert temps to Kelvin
Then do 1/T
Take the natural log of the rate constant
Then take the slope by ln K / (1/T)
This is equal to -Ea / R
So multiply by - R
To get the activation energy

Graphical determination:
ln(k) = lnA - Ea / RT
ln(k) vs 1/T
Straight line with a negative slope
Slope = -Ea / R
y- intercept: lnA
 2228 × 2184

Topic #7: Reaction energy diagram; transition state theory; activated complex
Reading: 16.5, pp. 715 -721

Topic #8: Mechanisms of chemical reactions; elementary reactions; rate - determining step
Reading: 16.6, pp. 721 - 727

Kinetics → get the mechanism of a reaction mechanism → reaction pathway → a series of

elementary reaction steps that occur in a specific order and that details how the reactants give
products

Elementary steps occur during a single collision

Has no intermediates
The sum of all the elementary steps must be equal to the balanced overall reaction

2A→C overall reaction

A→B 1st elementary step
B+A→C 2nd elementary step
B is the intermediate, it is produced and then consumed but doesn't appear in the balanced overall
reaction
B is a distinct species, therefore can be observed and occasionally may be isolated

Rate law: the order vs reactants are not necessarily equal to the coefficients of the balanced overall
reaction
BUT
The order vs reactants are equal to the coefficients of the slowest elementary step
The slowest elementary step is the rate - limiting step

Reaction that occurs in one step

A+B→C
Rate law: rate = k [A] [B] (can only be known if the reaction occurs in one step)

Kinetics shows the elementary steps up to and including the rate limiting step

Reaction Coordinate Diagrams (aka Reaction Energy Diagrams)

One - step reaction
A→B
OH- + CH3Br → CH3OH + Br-
Transition state: one bond is broken and another is formed, indicated by square brackets and a
crossed out equal sign as a superscript

Exothermic
Delta H is negative
The peak of the diagram is called the transition state or activated complex
The change in enthalpy is heat of products - heat of reactants
Ea is the forward reaction up to the the transition state
Transition state is not a distinct species, cannot be observed or isolated
Transition state will always be higher in energy than both your reactants and products
Ea = Energy of transition state - heat of reactants (forward reaction)
Endothermic
Delta H is positive
The peak of the diagram is still the transition state
Nothing changes in the calculations changes as:
Ea = Energy of transition state - heat of reactants (forward reaction)
It should be noted that the difference of the transition state energy and the heat of products is the Ea
of the reverse reaction
Heat of reaction = Ea (forward reaction) - Ea (reverse reaction)

If your reaction occurs in more than one step then there are intermediates
Intermediates in a reaction coordinate diagram = wells
A→B→C
There are two steps and each step has a different Ea for the forward reaction
As well as a different transition state per step
The difference of heat between the products and reactants are the enthalpy of the overall reaction
But each separate step has a certain enthalpy associated with it
The slower step is shown by the higher activation energy
The higher the Ea, the slower the reaction, the lower the k

Topic # 9: Catalysts
There are two ways to make a reaction go faster
Increase the temperature
Introduce the presence of a catalyst
All enzymes are catalysts

A catalyst is a compound that will increase the rate of a reaction by changing its mechanism
It will also change the reaction coordinate diagram
New mechanism with a smaller Ra for the rate limiting step
It will be consumed during the reaction but will be regenerated
Therefore doesn’t appear in the overall balanced reaction
The delta H of the overall reaction stays the same
Catalyst change the mechanisms, not just the Ea