KINETICS Kinetics – Rates and Mechanisms

Rates and Mechanisms

What I Absolutely Have to Know to Survive the AP Exam Collision Theory of Reactions Con’t…
The following might indicate the question deals with kinetics: rate; reactant concentration; order; rate constant; When the temperature is increased, the molecules speed
mechanisms; rate determining step; intermediate; catalyst; half-life; instantaneous rate; relative rate; activation energy; up and collide more frequently with more energetic
integrated rate law; rate expression; rate law collisions.

Only those particles represented by the area to the right

FACTORS THAT AFFECT REACTION RATE of the activation energy mark will react when they
Reaction rate increases with increasing temperature – “heat `em up, speed `em up” collide. The majority don't have enough energy, and
Temperature The higher the temp the more likely there are more collisions that are able to overcome the will simply bounce apart.
activation energy and form products
Phases of matter play a role, chemical identity (ions of opposite charge typically react faster; If we increase the temperature from T1 to T2, more
Nature of the molecules are energetic enough to achieve the Ea, thus
molecules with more bonds to break and form and substances with stronger bonds react more
Reactants slowly) more molecules react and the overall reaction rate
Reaction rate typically increases with increasing concentration of reactants (pressure changes increases.
Concentration of the
have the same effect on gaseous reactions) – more reactants the more effective collisions, the
Reactants faster the reactions proceeds Notice how many more molecules are to the right of the
Reaction rate increases with the addition of a catalyst; not a part of the reaction and is not used activation energy and thus will react when they collide.
Catalyst up but typically participates in the rate determining step of the reaction (slowest step) – it
LOWERS the activation energy! A general rule of thumb is that reaction rate doubles
Reaction rate increases with increased surface area of the reactant; reactions occur at the for each 10°C increase in temperature!
exposed surface of the two substances (except in g or aq) thus the greater the surface area the
Surface Area
more exposure the greater chance of effective collisions, the greater the rate. Aqueous
solutions offer the ultimate exposure.
DON’T FALL FOR THIS – adding an inert gas will NOT effect the reaction rate; it is not part
Inert Gas
of the reaction mechanism thus is has NO EFFECT

Collision Theory of Reactions EXPRESSING REACTION RATE

For a reaction to happen two things must occur:
1. The molecules must collide with the appropriate orientation for a reaction to occur Reaction rate is expressed in terms of how fast the concentration of a substance changes. It does not matter whether you
2. Molecules must collide with enough kinetic energy to react – i.e. they must meet or exceed the energy of activation, measure the rate the products are formed or the rate at which the reactants are consumed – they are stoichiometrically
Ea linked – just focus on either the disappearance of the reactants (–) or the appearance of the (+).
In other words the collisions MUST BE EFFECTIVE. ∆[product] ∆[reactant]
Rate of reaction = or Rate of reaction = –
If this happens the product of an effective collision is at the peak of the energy hump (activated complex or the transition time time
state. This complex can either fall back to reactants or produce products For example:
Ea − the activation energy… 2 N2O5(g) → 4 NO2(g) + O2(g)
! Is a measure of the energy barrier colliding molecules must overcome if they are to react rather than recoil from The relative rate can be expressed as:
one another. !
! It is assumed that reacting species with energy less than Ea will not react and those with energy greater than Ea and 1 ∆[N 2O5 ] 1 ∆[NO 2 ] ∆[O 2 ]
ally react.
the proper orientation will typically rate = − = =
2 ∆t 4 ∆t ∆t

Translated…
! The rate of consumption (disappearance) of N2O5 is equal to half the rate of the production (appearance) of NO2
and equal to twice the production (appearance) of O2
Or better yet…
! NO2 is produced at twice the rate at which N2O5 is consumed
! O2 is produced at half the rate at which N2O5 is consumed

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 Kinetics – Rates and Mechanisms Kinetics – Rates and Mechanisms

Differential Rate Laws – Concentration and Rate Con’t…

Instantaneous Rate Using the experimental data shown below you can determine the order of each reactant, the overall reaction order, and
Instantaneous rate is the rate at any one point in time during the experiment. To find instantaneous reaction rate you find calculate the rate constant, k.
the slope of the curve at the time in question (for those of you in calculus aka…derivative) i.e. the slope of the tangent line
to that point in time.

Examine the data with an analytical eye. Look for two trials where the concentration of ONE reactant was held constant.
Then compare how the other reactant changed and its effect on the initial rate.
! Look at Experiments 1 & 4
[A] was held constant and [B] doubled – the initial rate of the reaction doubled, therefore the reaction is
FIRST ORDER with respect to reactant B.
! Look at Experiments 1 & 3
[B] was held constant and [A] doubled – the initial rate of the reaction was unchanged, therefore the
reaction is ZERO ORDER with respect to reactant A.
rate = k[A]0[B]1
or
rate = k[B]
! Use experiment 5 (can use any of them) to solve for the rate constant, k.
rate = k[B]
rate 1.50 × 10−2
=k= = 0.025 hr −1
[B] 0.60

Reaction Mechanisms
Differential Rate Laws – Concentration and Rate Reaction mechanisms attempt to describe the stepwise sequence of elementary reactions that take reactants to products.
The rate law is a mathematical equation relating the instantaneous rate at a particular point in the progress of a chemical The mechanism describes in detail the bonds that are broken and formed as the reaction proceeds.
reaction to the concentration of the reacting species. Each elementary step of a mechanism typically involves one or two reactants forming products.
! Rate generally refers to the initial rate.
! The initial rate is the fastest rate of the reaction and occurs at the very beginning of the reaction. Every mechanism consists of a series of stepwise reactions. Each reaction in the mechanism has a rate associated with it.
! At this point there are few competing reactions, little chance for the reverse reaction (think equilibrium) to get The overall speed of the reaction depends upon the slowest step of the mechanism. The rate law of this step is identical or
involved, etc. equivalent to the experimental rate law. The slow step of the mechanism is also called the rate-determining step of the
! It should be noted when using the initial rate the concentration of the reactants are initial concentrations. mechanism. The sum of all the steps of the mechanism must equal the overall balanced chemical equation.
For the following reaction…
2X+Y→Z The coefficients of the reactants in the rate-determining step of the mechanism must correspond to the exponents or order
the general form of the rate law is… of the reactants in the experimental rate law.
rate = k[X]m [Y]n Catalysts and Intermediates…
Where… ! A catalyst is used up early in a reaction (reactant) and is regenerated (product) in a subsequent step.
! k is the rate constant ! A catalyst is a substance that acts to increase the rate of a chemical reaction by providing an alternate path for the
! The exponent m represents the order of the reaction with respect to reactant X reaction to occur. This means that there will be a change in the magnitude of the rate constant and possibly a
! The exponent n represents the order of the reaction with respect to reactant Y change in the order of the reaction.
! The sum of m + n represents the overall order of the reaction. ! An intermediate is produced early in the reaction (product) and used up (reactant) in a subsequent step.

Reactant orders must be determined experimentally; they cannot be written from the overall balanced equation

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 Kinetics – Rates and Mechanisms

Kinetics Cheat Sheet

Relationships
Differential Rate Law (concentration vs. rate data): Rate = k [A]x[B]y

Be able to explain with algebraic equations or words how an Mechanisms – must agree with the stoichiometry of the
order is determined. It is important to state which reaction and the “summary rate law” must agree with
concentration(s) is/are held constant and which concentration the slow step; identify intermediates and catalysts and
is varied as well the effect that has on the rate of the reaction if clearly state that the correct mechanism “agrees with
you choose not to justify with algebraic equations. the experimentally determined rate law”.
Discuss number of effective collisions in relation to increasing Ea predicts speed but the relationship is an inverse one;
or decreasing rates high = slow rate; low = fast rate
Instantaneous rate = slope of the line tangent to the time
“rate in terms of” is code for “relative rates” – use point in question
stoichiometry ratios on rate value

2 N2O5(g) → 4 NO2(g) + O2(g)

1 ∆[N 2O5 ] 1 ∆[NO 2 ] ∆[O 2 ]

rate = − = =
2 ∆t 4 ∆t ∆t

Catalyst – lowers Activation Energy and provides an alternate Distinguish between catalyst and intermediate –
pathway/mechanism especially in the steps of a mechanism!
Temperature increases of approx.. 10°C
Connections
Stoichiometry − “using up” one component of the system Electrochemistry − if reaction is redox in nature, rate
might indicate a limiting reactant in effect problems could come into play
Thermochemistry − Ea and ∆H°rxn and reaction diagrams
Potential Pitfalls
Units on k ! Make sure you can solve for units for k

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 KINETICS Kinetics – 2
Integrated Rates — Putting it All Together

What I Absolutely Have to Know to Survive the AP Exam Integrated Rate – Concentration and Time
The following might indicate the question deals with kinetics: rate; reactant concentration; order; rate constant; Where the differential rate law expresses rate as a function of reactant concentration(s) at an instant in time (hence
mechanisms; rate determining step; intermediate; catalyst; half-life; instantaneous rate; relative rate; activation energy; instantaneous rate), integrated rates express the reactant concentrations as a function of time.
integrated rate law; rate expression; rate law
To solve integrated rate problems, construct a graph with time on the x-axis and then make 3 plots where the y-axis is
! Concentration of A [A] vs. t
! Natural log of the concentration of A ln [A] vs. t
Instantaneous Rate
1
Instantaneous rate is the rate at any one point in time during the experiment. To find instantaneous reaction rate you find ! Reciprocal of [A] vs. t
the slope of the curve at the time in question (for those of you in calculus aka…derivative) i.e. the slope of the tangent line [A]
to that point in time. LINEAR IS THE WINNER
! Zero Order reaction are linear for [A] vs. t
! First Order reactions are linear for ln [A] vs. t
1
! Second Order reactions are linear for vs. t
[A]
Think y = mx + b
It is imperative that you can determine reaction order simply by analyzing a graph.
What is important?
! What is plotted on each axis?
! What does the slope of the line indicate?

If you know this, the order and rate constant can easily be determined.

Zero Order Reactions

For the reaction…
A(g) → products

∆[ A]
rate = – = k[A]0
∆t
When this relationship is integrated from t to tt then…
[A]t = −kt + [A]0

y = mx + b
Where…
! [A]t is the concentration at time t – [A]t represents what is plotted on the y-axis
! [A]0 is the initial concentration
! t is the time – represent what is plotted on the x-axis
! k is the rate constant - which is the SLOPE of the graph!
! Notice that in this equation k has a negative sign; thus the SLOPE of the graph is negative not the rate constant
If the reaction is zero order then the graph will be linear with a negative slope.

slope = −k
[A]

time

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 Kinetics – 2 Kinetics – 2

Second Order Reactions

First Order Reactions For the reaction…
For the reaction… A(g) → products
A(g) → products
∆[ A]
rate = – = k[A]2
∆[ A] ∆t
rate = – = k[A]1
∆t When this relationship is integrated from t to tt then…
When this relationship is integrated from t to tt then… 1 1
= kt +
ln [A]t = −kt + ln [A]0 [ A] [ A]0

y = mx + b y = mx + b
Where… Where…
! [A]t is the concentration at time t – ln [A]t represents what is plotted on the y-axis
1
! [A]0 is the initial concentration ! [A]t is the concentration at time t – represents what is plotted on the y-axis
[A]
! t is the time – represent what is plotted on the x-axis
! k is the rate constant – which is the SLOPE of the graph! ! [A]0 is the initial concentration
! Notice that in this equation k has a negative sign; thus the SLOPE of the graph is negative not the rate constant ! t is the time – represent what is plotted on the x-axis
! k is the rate constant – which is the SLOPE of the graph!
If the reaction is ILUVW order then the graph will be linear with a negative slope. ! Notice that in this equation k is positive; thus the SLOPE of the graph is positive

If the reaction is 2nd order then the graph will be linear with a positive slope.

slope = −k
slope = +k
ln[A]

1
[A]

time
Half life…
! the time required for the initial concentration, [A]0, to decrease to ½ of its value. time
ln [A]t = −kt + ln [A]0
ln 1 = −kt + ln 2
1
ln = −kt
2
−0.693 = −kt
0.693
=t
k

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 Kinetics – 2

Kinetics Cheat Sheet

Relationships
Differential Rate Law (concentration vs. rate data): Rate = k [A]x[B]y

Integrated Rate Laws (concentration vs. time data): Zero order [A] = (−)kt + [A]0
First order ln [A] = (−)kt + ln[A]0
1 1
Second order = kt +
[A] [A]0
0.693
t1/2 = for first order reactions and all nuclear decay
k
Connections
Stoichiometry − “using up” one component of the system Electrochemistry − if reaction is redox in nature, rate
might indicate a limiting reactant in effect problems could come into play
Thermochemistry − Ea and ∆H°rxn and reaction diagrams
Potential Pitfalls
Units on k ! Make sure you can solve for units for k

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 Name: __________________

AP Chemistry Free Response Review

Unit 5

Directions: Below are a student’s answer to a free response. Every question is either incorrect or partially incorrect.
You need to tell me why it is wrong and provide the correct answer.

Free Response 1
X (g) + 2Y (g)  Z (g)
1. The above reaction was studied at 25oC. The data collected are shown in the table below:

Initial rate of formation of Z

Experiment [X] [Y]
(mol L-1 s-1)

1 0.200 0.200 1.20 x 10-5

2 0.200 0.400 2.40 x 10-5

3 0.100 0.200 6.00 x 10-6

a. Calculated the initial rate of disappearance of substance Y in experiment 2

1 1 Correct response
𝑅𝑎𝑡𝑒𝑌 = =
2𝑅𝑎𝑡𝑒𝑧 2(1.2 × 10−5 )

𝑀
𝑅𝑎𝑡𝑒𝑌 = 6.00 × 10−6
𝑠

What is wrong?
 b. Determine the order of the reaction with respect to each reactant. Justify your answer
I. X:

The reaction is first order with respect to X. Correct response

What is wrong?

II. Y:

The reaction is first order with respect to Y. Correct response

What is wrong?

c. Write the rate law for this reaction

∆[𝑋] ∆[𝑌] ∆[𝑍] Correct response

𝑅𝑎𝑡𝑒 = − =− =+
∆𝑠 2∆𝑠 ∆𝑠

What is wrong?

d. Calculate the value of the rate constant, k. Be sure to include proper units

𝑅𝑎𝑡𝑒 = 𝑘[𝑋][𝑌] Correct response

𝑅𝑎𝑡𝑒
=𝑘
[𝑋][𝑌]

6.00 × 10−6
=𝑘
0.1(0.2)

3.00 × 10−4

What is wrong?
 e. Three possible mechanisms for this reaction are shown below:

i. Select the rate law that is most consistent with the experimental data. Justify your choice

Mechanism 3 because it lists both X & Y in the first Correct response

reaction.

What is wrong?

ii. Identify substance D as an intermediary or catalyst. Justify your answer.

Substance D is a catalyst because it is not listed in the Correct response

reagents of the original reaction and therefore would
have to be added and extracted separately.

What is wrong?
 f. In an experiment where the concentration of Y was at 10.0 M, the concentration of X was monitored as a
reaction occurred over 15 minutes. The data below was obtained and the following graphs were created.

Time
[X] (mol L-1)
The natural log of concentration
(min) of X over 15 mins
0 0.1
0
2 0.088
0 5 10 15

[X] (mol L-1)

6 0.069 -1
y = -0.0604x - 2.308
10 0.054 -2 R² = 0.9997
14 0.043 -3
?? 0.030 -4
time (min)

The concentration of X over 15

mins The inverse of the concentration
0 of X over 15 mins
0 5 10 15
-1 0
[X] (mol L-1)

y = -0.0041x + 0.0968 0 5 10 15
-1
-2 R² = 0.9834 [X] (mol L-1) y = 0.9422x + 9.4962
-3 -2 R² = 0.9901

-4 -3
time (min)
-4
time (min)

i. Does this data support your previous rate of the reaction with respect to X (question 1bi)?
Explain.

This data shows that the reaction is zero order with Correct response
respect to X, so it does NOT support our previous
experimental data

What is wrong?

ii. What is the value of k for THIS experiment? Include units

k = -0.0041 Correct response

What is wrong?
 iii. How long would the experiment have to run for [X] to reach a concentration of 0.030M?

[𝑿] = −𝟎. 𝟎𝟎𝟒𝟏𝒕 + 𝟎. 𝟎𝟗𝟔𝟖 Correct response

[𝑿] − 𝟎. 𝟎𝟗𝟔𝟖 = −𝟎. 𝟎𝟎𝟒𝟏𝒕

[𝑿] − 𝟎. 𝟎𝟗𝟔𝟖 [𝟎. 𝟎𝟑] − 𝟎. 𝟎𝟗𝟔𝟖

=𝒕=
−𝟎. 𝟎𝟎𝟒𝟏 −𝟎. 𝟎𝟎𝟒𝟏

𝒕 = 𝟏𝟔. 𝟑 𝒎𝒊𝒏𝒔

What is wrong?