Week 5 Baseline Slides For Students

Welcome to class!
Week 5 Baseline Slides

Office Hours + General
Updates
• Office hours today, 7 – 8:30 PM on Zoom
• No office hours on Thursday
• No new assignments this week
• Assignment 3 closes on Sunday at 11:59 PM
Extent of Reaction Plot
(Example with ∆Gºrxn = 0)
Extent of Reaction plots show how the Gibbs free energy
changes as the composition of a reaction mixture changes.
100% 100%
Reactants Products
Extent of Reaction
∆Grxn and Equilibrium
∆Grxn indicates whether a reaction has reached
equilibrium (∆Grxn = 0 at constant T and P), and/or
which direction the reaction has to proceed to get to
equilibrium.
If (∆Grxn)T,P < 0, then under the given conditions,

the forward reaction is spontaneous.
If (∆Grxn)T,P > 0, then under the given conditions,

the forward reaction is not spontaneous.
∆Grxn and Equilibrium
A+B⇌C
(∆Grxn)T,P < 0 (∆Grxn)T,P = 0
for the forward reaction

A B
What is the sign of ∆G?
A B A. ΔG<0
B. ΔG=0
C. ΔG>0
100% A 100% B
A B
A B A. ΔG<0
B. ΔG=0
C. ΔG>0
100% A 100% B
A B

A B
A. ΔG<0
B. ΔG=0
C. ΔG>0
100% A 100% B
A B

A B
100% A 100% B
What is the value of K?

Extent of Reaction Plot
(Example with ∆Gºrxn > 0)
Where does ∆Grxn = 0?
100% 100%
Reactants Products
Extent of Reaction
∆Grxn vs ∆G°rxn
∆G°rxn has ONE value

for a particular reaction under particular conditions
100% 100%
Reactants Products
Extent of Reaction
∆Grxn vs ∆G°rxn
∆Grxn has MANY possible values. It depends on the
instantaneous composition of the reaction mixture
(i.e. the “extent of reaction”) and ∆G°rxn.
G For the forward reaction:

∆Grxn < 0 ∆Grxn > 0
100% ∆G = 0 100%
rxn
Reactants Products
Extent of Reaction
Relationship between ∆G and ∆G°
∆G = ∆G° + RT lnQ
Where Q = reaction quotient
aA + bB → cC + dD
{C}c {D}d
Q=
{A}a {B}b
At equilibrium, ∆G = 0, Q=K and so: ∆G° = −RT lnK

Q and K…
Q has a nearly infinite number of possible values

(instantaneous composition of reaction mixture)
K has one value for a reaction under specified

conditions (which depends on ∆G°).
At equilibrium, the composition of the reaction

mixture doesn’t change, and Q = K.
Q and K…
Q indicates the direction of spontaneity for the reaction
(to get to equilibrium).
{Products} {Products at eq’m}

Q= K=
{Reactants} {Reactants at eq’m}
For the forward reaction:

Q<K Q>K
Q = K at eq’m
A B
For this reaction:

A B
100% A 100% B
A B
100% A 100% B
Where is ∆G > 0?
(for the forward reaction)
What is the equilibrium ratio of the molecule to
the left compared to the molecule on the right
at 25°C? CH 3
H 3C
7.5 kJ/mol
higher in energy
I will do this question in a separate video for you all because it can
be hard to process during lectures. This type of question is
examinable for Midterm 2 and/or the final exam, so make sure you
watch the video and know how to do it!
  
∆G = ∆H −T∆S
Very useful relationship, but
∆H° and ∆S° are not always readily available
∆G = −RT ln K

Both T and K can be measured
Can we equate these two?
− RT ln K = ∆H −T∆S  
What assumptions are necessary for this to be valid?

What assumptions are necessary for this to
be valid?
1. Measurements must be carried out at

constant T and P
2. The temperature range is reasonable such

that ΔH and Δ S are “constant” over the
temperature range in question (it cannot include
any phase transitions).
− RT ln K = ∆H −T∆S  
Solve for ln K:
 
− ∆H ∆S
ln K = +
RT R
K and T are variables, ∆S°, ∆H°, and R are constants.
 − ∆H   1 ∆S 
ln K =   +
 R T R
 
y = m x + b
Plot ln K vs. 1/T to get enthalpy and entropy

van’t Hoff Plot
Does the following van’t Hoff plot depict an
exothermic or an endothermic reaction?
ln K
High T Low T
1/T
 − ∆H   1 ∆S 
ln K =   +
 R T R
 
Is this reaction endothermic or exothermic?
ln K
High T Low T
1/T
 − ∆H   1 ∆S 
ln K =   +
 R T R
 
In the van’t Hoff plot below, which of the
following (A, B, or C) provides information about
the entropy of this reaction?
A (y-intercept)
ln K
B (slope)
C (x-intercept)
High T Low T
1/T
 − ∆H   1 ∆S 
ln K =   +
 R T R
 
Given the following van’t Hoff plot,
 − ∆H   1 ∆S 
calculate ∆H° and ∆S°. ln K =   +
 R T R
 
This R2 value is for

the line of best fit!
R (the gas constant) = 8.314 J K-1 mol-1

Line of Best Fit: lnK = -3965/T + 24.71
 − ∆H 
 1 ∆S 
ln K =   +
 R T R
 
y = m x + b
Rearrange
m = -∆H°/R ∆H° = -mR = -(-3965)*8.314
algebraically
= 32.97 kJ
b = ∆S°/R ∆S° = bR = 24.71*8.314

= 205.4 J/K
Chemistry 123
Introduction to Thermodynamics,
Kinetics, and Organic Chemistry
Slide Set 05:
Introduction to Kinetics
2023
Chemical Kinetics Introduction
Thermodynamics informs on the direction of spontaneous change
and the extent the reaction will go before reaching equilibrium but not
about how fast it will proceed to equilibrium.
Take, for example, the following reaction:
H2(g) + 1/2 O2(g) H2O(g) ΔGο298 = -237 kJ and K = 3 x 1041
ΔGο298 is negative and K is very large! Given the sign of ΔG⁰, this
reaction is spontaneous as written at standard state. Given the
magnitude of K, when the reaction is at equilibrium, only products
(virtually no reactants) will be present. (Thermodynamics).
However, this reaction will not start unless initiated with a spark
(Kinetics).
What can we know with Kinetics?
• studies the rates at which chemical reactions occur
• gives information about how the reaction occurs, known as the

reaction mechanism
• Determining the reaction mechanism is the overall goal of

kinetic studies.
• Most chemical reactions are written as the overall reaction.
• These reactions proceed by complex mechanisms that involve

several elementary steps.
Collision Theory
In a chemical reaction, bonds are broken and new
bonds are formed. In order for molecules to react, they
must collide.
Collisions are either effective or ineffective due to

orientation of molecules.
Collisions must have enough energy to overcome the

energy of activation (in other words, the energy required
to “activate” the reaction).
The likelihood of an effective collision occurring is

controlled by concentration of reactants and the
temperature of the system. We will focus first on
concentration.
Molecular Collisions
Reaction Coordinate Diagrams
Energy diagram describing the path one molecule of
reactant follows as it reacts to become products
Reactants Products
Free
energy Reactants
Products
reaction coordinate
Reaction Coordinate Diagrams
Energy diagram describing the path one molecule of
reactant follows as it reacts to become products
Reactants Products
Tells you how fast a
reaction proceeds
(Kinetics)
Free ∆G‡
energy Reactants
∆Gº
Products
Tells you how far a reaction proceeds
(Thermodynamics)
reaction coordinate
Comparing Diagrams
Kinetics vs Thermodynamics
A reaction coordinate describes changes to atomic coordinates. It is an abstract

concept. For very simple reactions, it could be the length of a bond as it stretches
and breaks but generally it is not measured one way.
Free
Tells you how fast a
energy Reactants
∆G‡ reaction proceeds
(Kinetics)
∆Gº
Products
Tells you how far a reaction proceeds
(Thermodynamics)
reaction coordinate THE START AND END OF BOTH

DIAGRAMS IS THE SAME
BUT WHAT IS MEASURED IN
BETWEEN IS DIFFERENT
Reaction: A‾ + B-C → A-B + C‾
A B C
Free
energy
A⁻ + B-C
A-B + C⁻
reaction coordinate
δ δ
A B C
Free
energy
A⁻ + B-C
A-B + C⁻
reaction coordinate
δ δ
A B C
Free
energy
A⁻ + B-C
A-B + C⁻
reaction coordinate
δ δ
A B C
Free
energy
A⁻ + B-C
A-B + C⁻
reaction coordinate
A B C
Free
energy
A⁻ + B-C
A-B + C⁻
reaction coordinate
Transition State: The highest energy point of the
path in a reaction coordinate diagram going from
reactants to products, in either direction.
δ δ
A B C
Free
energy Reactants
Products
reaction coordinate
Gibbs Free Energy of Activation, ∆G‡: The free
energy of the transition state minus the free energy of
the reactants.
If there is not enough
energy for a reaction to
overcome the energy of
activation, it will not occur.
Free ∆G‡
energy Reactants
Products
reaction coordinate
‡
Rate and ∆G
Question: Which reaction (A or B) is slower?
A
Free
energy Reactants
∆Gº Products
reaction coordinate
Free
energy Reactants
B
∆Gº
Products
reaction coordinate
If the collision energy < energy of activation, the reactant
molecules cannot surmount the barrier and they simply
bounce apart.
If the collision energy is > energy of activation, and if the
collision orientation is correct, the reactants will be able to
surmount the barrier and be converted to products.
∆G
A-
Free
B-C
energy
A-B
C-
reaction coordinate
What can be modified to increase the energy and/or
frequency of collisions?
Temperature and Rate
Generally, as temperature increases, more molecules have
sufficient energy to overcome the energy of activation
Boltzman Distribution
At higher temperatures, more molecules will have adequate

energy to react. This increases the reaction rate.
Concentration and Rate
At higher concentrations, there are more collisions, increasing the
number of successful collisions.
If there is enough energy in the system to overcome the energy of
activation, this increases the reaction rate.
∆G
A-
Free
B-C
energy
A-B
C-
reaction coordinate
Reaction Kinetics
Kinetics: Focused on studying how fast a process is.
We accomplish this by measuring changes over time
Increasing Time
Reaction Kinetics
Overall Reaction: The balanced chemical equation
accounting for to total input and output of atoms and
molecules
Reaction Mechanism: The step-by-step process by
which bonds are reformed to transform the reactants
to products
Intermediates are species that are produced in an
earlier step and consumed in a later step. They do not
appear in the overall reaction.
Catalysts are species that are consumed in an earlier
step and regenerated in a later step. They do not
appear in the overall reaction (but are specified as part
of the reaction conditions).
Reaction Progress
Increasing Time
A B
[B]
[A]
Reaction Progress
A B
C D
How do we describe the speed of a reaction?
Reaction rate: the change in concentration of a
substance divided by the time interval during which
this change is observed.
𝑑𝑑(𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶)
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 =
𝑑𝑑(𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇)
A B
[B]
Is the rate of reaction the
same at the two points
indicated in the graph?
[A]
How do we mathematically describe the reaction rate?

Reaction rate = − d[reactant]
________ = d[product]
________
dt dt
A B
[B]
[A]
Stoichiometry and Mass Balance
Mass Balance: Concentration change for each
component is related to its stoichiometric coefficient
In general: aA + bB cC + dD
1 d [A] 1 d [B ] 1 d [C ] 1 d [D ]
Rate = − =− = =
a dt b dt c dt d dt
Specific example:
2 N2O5 (g) 4 NO2 (g) + O2 (g)
1 d [N 2O 5 ] 1 d [NO 2 ] 1 d [O 2 ]
Rate = − = =
2 dt 4 dt 1 dt
Stoichiometry and Mass Balance
2 N2O5(g) 4 NO2(g) + O2(g)
1 d [N 2O 5 ] 1 d [NO 2 ] 1 d [O 2 ]
Rate = − = =
2 dt 4 dt 1 dt
NO2
O2
N2O5
Rate Law
A rate law is an expression for the instantaneous
reaction rate in terms of the instantaneous
concentration of the species involved in the reaction.
aA + bB cC + dD
Rate = k[A]m[B]n
Specific example:
NaOH + HCl NaCl + H2O
Rate = k[NaOH][HCl]
Rate Constant
A rate constant is a proportionality factor in the rate
law relating reagent concentrations to reaction rate.
aA + bB cC + dD
Rate = k[A]m[B]n
Rate Constant, k
Rate Constants
• are unique to different reactions
• change with temperature
• are NOT equilibrium constants (K)
• have different units (Rate must be in conc/time)
Reaction Order
Reaction order is the exponential dependence on
each reagent on the rate of reaction
aA + bB cC + dD
mth order in A nth order in B
Rate = k[A]m[B]n
(m+n)th order overall
Overall order of a reaction: the total number of

concentration terms in a rate law (i.e. the sum of all of
the exponents).
Order with respect to a particular species: the exponent
in the rate equation for that particular species.
Which of the following rate laws describes a
second order reaction?
[More than one answer may be correct.]
A. Rate = k[A]
B. Rate = k[A]2
C. Rate = k[A][B]
D. Rate = k[A]2[B]
E. Rate = k
Which of the following rate laws describes a
reaction that is first order with respect to B?
[More than one answer may be correct.]
A. Rate = k[A]
B. Rate = k[A]2
C. Rate = k[A][B]
D. Rate = k[A]2[B]
E. Rate = k
Elementary Reactions
An elementary reaction occurs in a single step and
passes through a single transition state.
The molecularity is the number of reactant molecular

entities that come together in an elementary reaction.
It is always a whole number.
Unimolecular elementary reactions:

1 reactant molecule
Bimolecular elementary reactions:
2 reactant molecules
Termolecular elementary reactions:
3 reactant molecules (rare)
All of the following reactions are elementary.
Which one is bimolecular?
A. A→B
B. A→B+C
C. B-C → B + C
D. A→B+C+D
E. A+B→C+D
Rate Laws of Elementary Reactions
An elementary reaction occurs in a single step and
passes through a single transition state.
We can write the rate law for elementary reactions

directly using the stoichiometry of the reaction.
For the elementary reaction: A+B→C
𝑑𝑑 𝐴𝐴 𝑑𝑑 𝐵𝐵
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − =− = 𝑘𝑘 𝐴𝐴 𝐵𝐵
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
All the reactions below are elementary
reactions. Which one has rate = k[A]?
A. A+B→C+D
B. A+B→C
C. A→B+C
D. A+A→B
E. A+A→B+C
The reaction below occurs in a single
step. Which of the following is true?
2A→B
A. The reaction is unimolecular and elementary

B. The reaction is bimolecular and elementary
C. The reaction is unimolecular, but not elementary
D. The reaction is bimolecular, but not elementary
Rate Law, Rate Constant and Reaction Order
Rate laws are empirical.
A rate law is an experimentally determined

characteristic of the reaction and CANNOT IN
GENERAL be derived from the stoichiometry of the
chemical equation for the reaction.
F2 + 2 ClO2 2 FClO2
Experimental rate law: Rate = k[F2][ClO2]
Measurements need to be made to determine

reaction order and the rate constant.
Reaction Kinetics
The rate law must be measured and may not resemble
the stoichiometry of a balanced reaction.
Consider the three reactions:
H2(g) + I2(g) → 2 HI(g) 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘 𝐻𝐻2 𝐼𝐼2
𝑘𝑘 𝐻𝐻2 𝐵𝐵𝐵𝐵2 1⁄2

H2(g) + Br2(g) → 2 HBr(g) 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 =
𝐻𝐻𝐻𝐻𝐻𝐻
1 + 𝑘𝑘𝑘
𝐵𝐵𝐵𝐵2
H2(g) + Cl2(g) → 2 HCl(g) Only occurs in the

presence of light
Overall Reaction:
+ particle board pieces

Reaction Mechanism:
Each step within a
reaction mechanism is
an elementary reaction.
Reactions
Overall Reaction:
2 N2O5(g) → 4 NO2(g) + O2(g)
Reaction Mechanism:
Step 1: N2O5(g) → NO2(g) + NO3(g)
Step 2: NO2(g) + NO3(g) → NO2(g) + O2(g) + NO(g)
Step 3: NO(g) + N2O5(g) → 3 NO2(g)
This reaction mechanism has 3 elementary steps.

NO(g), NO2(g) and NO3(g) are intermediates.
So if reactions are empirical, and we cannot
necessarily tell the rate law just by looking at
them, how do we determine the rate law?
Experiments! Measurements need to be made to
determine reaction order and the rate constant.
• Generally we have two ways of measuring rate and

determining the reaction order.
• The first is the method of initial rates (focuses on the

very beginning of the reaction).
• The second is the integrated rate law (focuses on the

whole reaction).
Method of Initial Rates
Measure the rate of a reaction at the beginning.
We assume that at this time point:
A. very little change in reactant concentration
B. no product to interfere or complicate the
measurement
A+B C
[C]
d[X]
dt
[A]
Carry out a series of trials changing the initial concentration of
the reactants, measuring the initial rate for each trial separately
A+B C
[C]trial 1
[A]0 [B]0 rate Rate = k[A]?[B]?

0.1 0.1 0.25
A+B C
[C]trial 2
[C]trial 1
[A]0 [B]0 rate Rate = k[A]?[B]?

0.1 0.1 0.25
0.2 0.1 0.50
A+B C
[C]trial 2
[C]trial 1
[A]0 [B]0 rate Rate = k[A]1[B]?

0.1 0.1 0.25
The reaction is
0.2 0.1 0.50
first order in A.
[C]trial 3 A+B C
[C]trial 2
[C]trial 1
[A]0 [B]0 rate Rate = k[A]1[B]?

0.1 0.1 0.25
0.2 0.1 0.50
0.2 0.2 1.00
[C]trial 3 A+B C
[C]trial 2
[C]trial 1
[A]0 [B]0 rate Rate = k[A]1[B]1

0.1 0.1 0.25
The reaction is
0.2 0.1 0.50
first order in B.
0.2 0.2 1.00
A student sets up experiments with varying
concentrations of reactants to study the reaction:
NH4+ + NO2‾ → N2 + 2 H2O
What is the experimentally determined rate law?

NH4+ + NO2‾ → N2 + 2 H2O
What is the experimentally determined rate law?

NH4+ + NO2‾ → N2 + 2 H2O
What is the value for k at this temperature?

The reaction:
CH3O‾ + CH3I → CH3OCH3 + I‾
obeys the rate law: rate = k[CH3O‾][CH3I]
What happens to the rate when the concentration of
CH3I is doubled?
A. The rate doubles

B. The rate is halved
C. There is no change in rate
D. It is impossible to answer this question.
The reaction:
CH3O‾ + CH3I → CH3OCH3 + I‾
obeys the rate law: rate = k[CH3O‾][CH3I]
What happens to the rate when the concentration of
CH3OCH3 is doubled and the concentration of CH3I is
halved?
A. The rate doubles

B. The rate quadruples
C. The rate is halved
D. The rate is reduced by a quarter
E. There is no change in rate
The reaction rate changes over time.
If we know the rate law, can we use it to
calculate [A] and [B] as a function of time?
A B
[B]
[A]
Integrated Rate Laws
Describe how [A] changes over time for the reaction
A B
The reaction rate is defined in its differential form:
1 𝑑𝑑 𝐴𝐴 From reaction
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = −
1 𝑑𝑑𝑑𝑑 stoichiometry
The reaction rate can be determined experimentally

(using the method of initial rates):
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘[𝐴𝐴] From experiment

(orders will vary)
Integrated Rate Laws
Set the two expressions for rate equal to each other:
1 𝑑𝑑 𝐴𝐴
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = 𝑘𝑘[𝐴𝐴]
1 𝑑𝑑𝑑𝑑
From reaction From experiment

stoichiometry (orders will vary)
and integrate the differential form of the rate law.
NOTE: Different differential rate laws will give

different integrated forms
Calculus Aside (not examinable)
𝑑𝑑 𝐴𝐴
For a first order reaction: − = 𝑘𝑘[𝐴𝐴]
𝑑𝑑𝑑𝑑
Separate the variables (concentration and time):
1
𝑑𝑑 𝐴𝐴 = −𝑘𝑘𝑘𝑘𝑘𝑘
[𝐴𝐴]
Integrate the left side from [A]0 to [A]t, and the right
side from time = 0 to some later time, t.
𝐴𝐴 𝑡𝑡 𝑡𝑡
1
� 𝑑𝑑 𝐴𝐴 = � −𝑘𝑘𝑘𝑘𝑘𝑘 ⇒ ln 𝐴𝐴 𝑡𝑡 − ln 𝐴𝐴 0 = −𝑘𝑘𝑘𝑘
𝐴𝐴 0 [𝐴𝐴] 0
First Order
Integrated Rate Law
Integrated Rate Laws:
First Order Processes
The integrated rate law for a first order process is
ln 𝐴𝐴 𝑡𝑡 = −𝑘𝑘𝑘𝑘 + ln 𝐴𝐴 0
This applies to ANY first order reaction.
Algebraic manipulations:
𝐴𝐴 𝑡𝑡 𝐴𝐴 𝑡𝑡
ln = −𝑘𝑘𝑘𝑘 = e−𝑘𝑘𝑘𝑘 𝐴𝐴 𝑡𝑡 = 𝐴𝐴 0 e−𝑘𝑘𝑘𝑘
𝐴𝐴 0 𝐴𝐴 0
Given on
Formula Sheet
Example
The reaction:
Br2(aq) + HCOOH(aq) → 2 Br‾(aq) + 2 H3O+(aq) + CO2(g)
was studied experimentally and obeys the rate law:
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘[𝐵𝐵𝐵𝐵2]
The rate constant at 25°C is k = 3.5 x10-3 s-1.
If [Br2] = 2.8 M when the reaction was started, what
would you expect [Br2] to be after 10 minutes?
Recognizing First Order
Processes Graphically
A plot of [A] vs time will [B]
show that the instantaneous
rate slows down as the
reaction progresses.
[A]
For a first order reaction:
ln 𝐴𝐴 𝑡𝑡 = −𝑘𝑘𝑘𝑘 + ln 𝐴𝐴 0
y = mx+ b
A plot of ln[A] vs time will be

linear for reactions obeying m = -k
first order kinetics. b = ln[A]0
Recognizing First Order
When analyzing a new reaction, the ln[A] vs time plot
does not give a straight line. What can be concluded
about this new reaction?
Second Order Processes
Consider a more complex reaction:

A+A→B
that obeys the differential rate law:
𝑑𝑑 𝐴𝐴
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = 𝑘𝑘[𝐴𝐴]2
𝑑𝑑𝑑𝑑
Integrate the rate law to get:
1 1 Given on
= 𝑘𝑘𝑘𝑘 +
[𝐴𝐴]𝑡𝑡 [𝐴𝐴]0 Formula Sheet
2A B
[B]
[A]
Reaction rate (using the

stoichiometry of the reaction): Rate of disappearance of A:
𝟏𝟏 𝑑𝑑 𝐴𝐴 dB
𝑑𝑑 𝐴𝐴
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = −
𝟐𝟐 𝑑𝑑𝑑𝑑 dt 𝑑𝑑𝑑𝑑
2 2
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘1 𝐴𝐴 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘2 𝐴𝐴
1 1 NOTE: 1 1
= 2𝑘𝑘1𝑡𝑡 + = 𝑘𝑘2𝑡𝑡 +
𝐴𝐴 𝑡𝑡 𝐴𝐴 0 2k1 = k2 𝐴𝐴 𝑡𝑡 𝐴𝐴 0
Example
The reaction:
A+A→B
obeys the differential rate law:
𝑑𝑑 𝐴𝐴
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = 𝑘𝑘[𝐴𝐴]2
𝑑𝑑𝑑𝑑
with k = 6.19 x 10-4 M-1s-1 at T = 298 K.
How long will it take for the concentration of A to
reach 0.32 M if [A]0 = 1.6 M?
Recognizing Second Order
A plot of [A] vs time will show
that the instantaneous rate
rapidly slows down as the [B]
reaction progresses.
[A]
For a second order reaction:
1 1
= 𝑘𝑘𝑡𝑡 +
[𝐴𝐴]𝑡𝑡 [𝐴𝐴]0
y = mx+ b m=k
A plot of 1/[A] vs time will be b = 1/[A]0
linear for reactions obeying
second order kinetics.
What is the value of k for the reaction
𝑑𝑑[𝐴𝐴]
graphed below if 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − ?
𝑑𝑑𝑑𝑑
1/[A]
y = 10x + 20
Time (s)
A. -20 M-1 s-1

B. 20 M-1 s-1
C. -10 M-1 s-1
D. 10 M-1 s-1
A+B→C
𝑑𝑑 𝐴𝐴 𝑑𝑑 𝐵𝐵 𝑑𝑑 𝐶𝐶
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = − =
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘 𝐴𝐴 𝐵𝐵
The integrated form is complex (unless [A]0 = [B]0).
We can choose experimental conditions (initial

concentrations) such that the kinetics will follow
“pseudo-first order” conditions.
Pseudo-First Order Conditions
Pseudo-first order conditions: increase the
concentration of one of the two components relative
to the other so its concentration appears constant
over the course of the reaction.
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘 𝐴𝐴 𝐵𝐵
Make [B]0 large that it can be treated as a constant:
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘′ 𝐴𝐴 where k’ = k[B]
Collect data for k’, algebraically solve for k.

Zero Order Processes
Consider some complex reaction:
A+B→C
That obeys an experimental rate law:
𝑑𝑑 𝐴𝐴 0
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = 𝑘𝑘 𝐴𝐴 = 𝑘𝑘
𝑑𝑑𝑑𝑑
Integrate the rate law to get:
𝐴𝐴 𝑡𝑡 = −𝑘𝑘𝑘𝑘 + 𝐴𝐴 0
Rearranged: Given on
𝐴𝐴 𝑡𝑡 − 𝐴𝐴 0 = −𝑘𝑘𝑘𝑘 Formula Sheet
Recognizing Zero Order
A plot of [A] vs time will show [B]
that rate is constant with time
and is independent of [A]
𝑑𝑑 𝐴𝐴 [A]
− = 𝑘𝑘
𝑑𝑑𝑑𝑑
𝐴𝐴 𝑡𝑡 = −𝑘𝑘𝑘𝑘 + 𝐴𝐴 0
b = [A]0
y = mx+ b
m = -k
A plot of [A] vs time will be
linear for reactions obeying
zero order kinetics.
Half-Life
The amount of time (𝑡𝑡1⁄2 ) needed for a reaction to
consume ½ of its starting material.
[A]t = ½ [A]0
Different order processes (zero, first, second) will have
different expressions to calculate the half-life.
Zeroth Order First Order Second Order

Processes Processes Processes
ln 2 1
𝑡𝑡1/2 = 𝐴𝐴 0 /2𝑘𝑘 𝑡𝑡1� = 𝑡𝑡1� =
2 𝑘𝑘 2 𝑘𝑘[𝐴𝐴]0
Notice that half-life for first order processes are

independent of [A] and only depend on k
Half-Life
Zeroth Order First Order Second Order

Processes Processes Processes
ln 2 1
𝑡𝑡1/2 = 𝐴𝐴 0 /2𝑘𝑘 𝑡𝑡1� = 𝑡𝑡1� =
2 𝑘𝑘 2 𝑘𝑘[𝐴𝐴]0
𝑡𝑡1/2 is getting shorter 𝑡𝑡1/2 is constant 𝑡𝑡1/2 is getting longer

Example
The half life of a pharmaceutical is 64 minutes
before it is metabolized in the body in a first
order process.
What is the rate constant for the metabolism of
the pharmaceutical?
Example
Radioactive decay is a first order process.
60Co is a synthetic radioactive isotope with a half-life
of 5.26 years. How long does it take a sample of
60Co to decay until only 3.125% of the initial sample
remains?
Summary
For zeroth order reactions 𝐴𝐴 → 𝐵𝐵
Integrated rate law Half-life
A0
[A]𝑡𝑡 − A 0 = −𝑘𝑘𝑘𝑘 𝑡𝑡1/2 =
2𝑘𝑘
For first order reactions 𝐴𝐴 → 𝐵𝐵

Integrated rate law Half-life
𝑙𝑙𝑙𝑙𝑙
ln 𝐴𝐴 = −𝑘𝑘𝑘𝑘 + 𝑙𝑙𝑙𝑙[𝐴𝐴]0 𝑡𝑡1/2 =
𝑘𝑘
For second order reactions 𝐴𝐴 + 𝐴𝐴 → 𝐵𝐵

Convention Integrated rate law Half-life
1 𝑑𝑑 𝐴𝐴 1 1 1
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = 𝑘𝑘1 [𝐴𝐴]2 = 2𝑘𝑘1 𝑡𝑡 + 𝑡𝑡1/2 =
2 𝑑𝑑𝑑𝑑 A 𝐴𝐴 0 2𝑘𝑘1 𝐴𝐴 0
𝑑𝑑 𝐴𝐴 1 1 1
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = − = 𝑘𝑘2 [𝐴𝐴]2 = 𝑘𝑘2 𝑡𝑡 + 𝑡𝑡1/2 =
𝑑𝑑𝑑𝑑 A 𝐴𝐴 0 𝑘𝑘2 𝐴𝐴 0
The reaction A + B → C obeys the rate law,
rate = k. Which of the following is true?
A. The half-life will increase with time.

B. The reaction is bimolecular and elementary.
C. A plot of ln[A]0 vs time will be linear.
D. The reaction will be slower when the concentration
of C is large.
E. The reaction cannot be an elementary reaction.

Week 5 Baseline Slides For Students

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Week 5 Baseline Slides For Students

Uploaded by

Copyright:

Available Formats

Welcome to class!

Week 5 Baseline Slides

If (∆Grxn)T,P < 0, then under the given conditions,

If (∆Grxn)T,P > 0, then under the given conditions,

(∆Grxn)T,P < 0 (∆Grxn)T,P = 0

for the forward reaction

What is the sign of ∆G?

What is the sign of ∆G?

What is the sign of ∆G?

What is the sign of ∆G?

What is the value of K?

Where does ∆Grxn = 0?

∆G°rxn has ONE value

G For the forward reaction:

Where Q = reaction quotient

At equilibrium, ∆G = 0, Q=K and so: ∆G° = −RT lnK

Q has a nearly infinite number of possible values

K has one value for a reaction under specified

At equilibrium, the composition of the reaction

{Products} {Products at eq’m}

For the forward reaction:

For this reaction:

Both T and K can be measured

Can we equate these two?

What assumptions are necessary for this to be valid?

1. Measurements must be carried out at

2. The temperature range is reasonable such

Plot ln K vs. 1/T to get enthalpy and entropy

This R2 value is for

R (the gas constant) = 8.314 J K-1 mol-1

b = ∆S°/R ∆S° = bR = 24.71*8.314

Slide Set 05:

Take, for example, the following reaction:

H2(g) + 1/2 O2(g) H2O(g) ΔGο298 = -237 kJ and K = 3 x 1041

• studies the rates at which chemical reactions occur

• gives information about how the reaction occurs, known as the

• Determining the reaction mechanism is the overall goal of

• Most chemical reactions are written as the overall reaction.

• These reactions proceed by complex mechanisms that involve

Collisions are either effective or ineffective due to

Collisions must have enough energy to overcome the

The likelihood of an effective collision occurring is

A reaction coordinate describes changes to atomic coordinates. It is an abstract

reaction coordinate THE START AND END OF BOTH

At higher temperatures, more molecules will have adequate

How do we mathematically describe the reaction rate?

Overall order of a reaction: the total number of

The molecularity is the number of reactant molecular

Unimolecular elementary reactions:

We can write the rate law for elementary reactions

For the elementary reaction: A+B→C

A. The reaction is unimolecular and elementary

A rate law is an experimentally determined

Experimental rate law: Rate = k[F2][ClO2]

Measurements need to be made to determine

H2(g) + I2(g) → 2 HI(g) 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑘𝑘 𝐻𝐻2 𝐼𝐼2

𝑘𝑘 𝐻𝐻2 𝐵𝐵𝐵𝐵2 1⁄2

H2(g) + Cl2(g) → 2 HCl(g) Only occurs in the

+ particle board pieces

Step 2: NO2(g) + NO3(g) → NO2(g) + O2(g) + NO(g)

Step 3: NO(g) + N2O5(g) → 3 NO2(g)

This reaction mechanism has 3 elementary steps.

• Generally we have two ways of measuring rate and