Mariano

MarianoMarcos
MarcosState
StateUniversity
University
College
CollegeofofHealth
HealthSciences
Sciences
Pharmacy
PharmacyDepartment
Department
City
CityofofBatac
Batac2906
2906Ilocos
IlocosNorte
Norte

PCHM 121: Pharmaceutical Inorganic Chemistry with Qualitative Analysis

1st Semester of A.Y. 2020-2021

Title
Chapter 5: Chemical Kinetics
Introduction

Chemical kinetics is the study of the rates and the mechanism of chemical
reactions. Commonly the measure of how fast the products are formed and the
reactants consumed is given by the rate values. The study of chemical kinetics has
been highly useful in determining the factors that influence the rate, maximum
yield and conversion in industrial processes. The mechanism or the sequence of
steps by which the reaction occurs can be known. It is also useful in selecting the
optimum conditions for maximum rate and yield of the chemical process.

Presentation of Outcomes

Having successfully completed this lesson the student must have:

1. Analyzed the basic concepts in chemical kinetics, including rate equations,
reaction order, and the effect of temperature and catalysts on the reaction rate.

Warm-up Activity
What’s your level of understanding of the topic?
I’m completely green
I have some basic knowledge
I have some solid background
I’m an expert

Central Activities

Learning Input 1 (Lecture)

Chemical Kinetics
• The study of the rates and the mechanism of chemical reactions.
• Deals with the study of the rate at which processes occur and mechanism of
chemical reaction.

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 • In the field of pharmacy, particularly in drug formulation, chemical kinetics
include a study of physical and chemical changes in drugs and dosage form,
factors influencing the rate of these chemical reactions, accelerated stability
testing and prediction of shelf-life.
• It applies to:
• Stability
• Incompatibility
• Dissolution
• Absorption
• Distribution
• Drug action at molecular level
• Elimination processes

Rate
• is a measure of how some property varies with time.
• It is a change in concentration over a time period: Δ[ ]/ Δt
Δ means “change in”
[ ] means molar concentration
t represents time.

Rate of chemical reactions

• The rate of a reaction tells us how fast the reaction occurs.
• It is a quantity that tells how a concentration of a given reactant or product
changes with time.
• Let us consider a simple reaction: A à B
• the rate of reaction is defined as the change in the concentration of any
reactant or product in the reaction per unit time.
• it is expressed by:

Factors that affect rates of reactions:

1. Physical state of the reactants
• The more readily the reactants collide, the more rapidly they react.
• Homogeneous reactions are often faster
• Heterogenous reactions that involve solids are faster if the surface area is
increased; i.e., a fine powder reacts faster than a pellet.
2. Concentration
• Increasing reactant concentration generally increases reaction rate since
there are more molecules/vol., more collision occur.
3. Temperature
• Reaction rate generally increases with increased temperature.
• Kinetic energy of molecules is related to temperature.

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 • At higher temperatures, molecules move more quickly, increasing numbers
of collisions and the energy the molecules possess during the collisions.
4. Catalysts
• Catalysts affect rate without being in overall balanced equation.
• Catalysts affect the kinds of collisions, changing the mechanisms (individual
reactions that are part of the pathway from reactants to products).

Rate Law/rate equation

• A mathematical expression that relates the rate of the reaction to the
concentration of the reactants.
• A rate law shows the relationship between the reaction rate and the
concentrations of reactants.
• For a general reaction:

• The rate law for the above equation is:

rate = k[A]a[B]b

*exponents a and b are called reaction orders. It tells the order of reaction with
respect to each reactant.
*k is known as the rate constant.

Reaction order
• It refers to the way in which the concentration of reactant/s influences the rate of a
chemical reaction.
• For a particular species in a reaction, the order is equal to the exponent for that
species in the rate law.
• Consider a reaction for which the rate law is:

rate = k[A]m[B]n

*if the exponent m is 1, the reaction is first order with respect to A. if m is 2, the
reaction is second order with respect to A. if n is 1, the reaction is first order in B.
if n is 2, the reaction is second order in B. if m and n is zero, the reaction is zero
order in A and B, respectively, and the rate of the reaction is not affected by the
concentration of the reactant.

Rate constant
• In the above general equation k represents the rate constant.
• Rate constant or velocity constant (or) specific reaction rate is defined as the rate of
the reaction when the concentration of each of the reactants is unity in the reaction
• When concentration of A and B is unity then, the rate constant is equal to the rate
of the reaction

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• When the temperature of the reaction mixture changes, the value of rate constant
changes.

Overall reaction order

• It is the sum of the orders with respect to each reactant.
• So, if m is 1 and n is 1, the overall order of the reaction is second order (m+n = 1+1
= 2)

Sample problem: An experiment shows that the reaction of nitrogen dioxide with
carbon monoxide is second order in NO2 and zero order in CO at 1000C. What is the
rate law for the reaction, orders with respect to each reactant and overall order of
the reaction?

NO2(g) + CO(g) à NO(g) + CO2(g)

Solution:
• The reaction will have the form:

rate = k[NO2]m[CO]n
• The reaction is second order in NO2; thus m=2. The reaction is zero order in CO;
thus n=0. The rate law is

rate = k[NO2]2[CO]0 = k[NO2]2

• A number raised to the zero power is equal to 1, thus [CO]0 = 1, which is why we
drop the concentration of CO from the rate equation: the rate of reaction is
solely dependent on the concentration of NO2.

• Order in NO2 = 2; order in CO = 0; overall order = 2

Integrated Rate Laws express the reaction rate as a function of the initial concentration
and a measured (actual) concentration of one or more reactants after a specific amount
of time (t) has passed; they are used to determine the rate constant and the reaction
order from experimental data.

a. Zero-order reactions (order is zero)

• The rate of a zero-order reaction is constant and independent of the
concentration of reactants. This rate is independent of the concentration of
the reactants. The rate law is:

rate = k, with k having the units of M/sec.

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 b. First-order reactions (order is one)
• Depends on the concentration of one reactant, and the rate law is:

• While other reactants can be present, each will be zero-order, since the
concentrations of these reactants do not affect the rate.

c. Second-order reactions (order is 2)

• Is second-order in only one reactant, or first-order in two reactants
• Depend on the concentration(s) of one second-order reactant or two first-
order reactants.
• Has a rate proportional to the concentration of the square of a single reactant
or the product of the concentration of two reactants. The formula is:

rate = k[A]2 (or substitute B for A or k multiplied by the concentration of

A times the concentration of B).

d. Half-life of a reaction
• Time required for the concentration of a reactant to reach one-half of its
initial value.
• A fast reaction will have a short half-life.
• Application: the duration of a drug is known as half-life. This is the period of
time required for the concentration or amount of drug in the body to be
reduced by one-half (50%).

Rate determining step

- Slowest step of a chemical reaction that determines the speed (rate) at which the
overall reaction proceeds.

Law of Mass Action

- States that the rate of a reaction is proportional to the product of the concentrations
of each reactant.
- Describes how the velocity of a chemical reaction is related to the molecular
concentrations of the reactants.

Collision Theory of Reaction Rates

- The rates of reaction are related to the properties of particles through a model called
collision theory
- Particles will only react if there is an effective or successful collision between them.
- In order for particles to react,

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 a. They must collide
b. They must collide in the correct orientation to form the activated complex

c. They must collide with a specific minimum amount of energy (activation energy)
to form the activated complex.

Collision theory and rate of reaction

- the following factors can increase the rate of a chemical reaction by increasing
the number of effective collisions that occur at a given time. Factors include
• concentration- if there is more of a substance in a system, there us a
higher chance that molecules will collide and speed up the rate of the
reaction. If there is less of something, there will be fewer collisions and
the reaction will probably happen at a slower speed.
• Temperature-raising the temperature of the system would cause the
molecules to bounce a lot more and more likely to collide.

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 • Catalyst-a substance that retards or speeds up a reaction but is
chemically unchanged. Types:
a. Positive catalyst/accelerators- speeds up a reaction. It acts by
decreasing the activation energy by accepting a smaller/shorter path.
b. Negative catalyst/inhibitors- slows down a reaction. It acts by
increasing the activation energy by taking a longer or alternative
path. It is used to control undesired reactions.
• Pressure- applies to gases. Increase pressure would increase the rate of
reaction
• surface area-the larger the surface area compared to the volume, the
faster a reaction can take place, as more simultaneous reactions can
occur.
• quality of mixing of reactants- if reactants are not thoroughly mixed, it
may slow the reaction rate.

Activation Energy (Ea)

- minimum amount of energy that is required to activate atoms or molecules to a
condition in which they can undergo chemical transformation or physical transport.
- It is the energy level that the reactant molecules must overcome before a reaction
can occur.

Heat of Reaction (Enthalpy)

- The amount of heat given off or absorbed in a chemical reaction.
- Heat of reaction is the difference in heat content of the products and reactants.

∆H = Hproducts - Hreactants
• ∆H = heat of reaction
• Hproducts = potential energy of the product(s)
• Hreactants = potential energy of the reactant(s)
• ∆H is measured in kJ (kilojoules)

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Endothermic and Exothermic Reaction

Endothermic reaction- heat (energy) goes into the system

- Enthalpy is positive (energy is absorbed)
- Products have higher energy than reactant
- A reaction that feels cold has hear going from your finger into the system is
endothermic

Exothermic reaction- heat (energy) goes out of the system

- Enthalpy is negative (energy is given off)
- Products have lower energy than reactants
- A hot reaction has heat coming out of the system is exothermic

Reversible Reactions and Chemical Equilibrium

Reversible reaction
- A reaction in which the conversion of reactants to products and the conversion
of products to reactants occur simultaneously
- Example is the reaction of hydrogen gas and iodine vapor to form hydrogen
iodide. The forward and reverse reactions can be written as:

- In the forward reaction, hydrogen and iodine combine to form hydrogen iodide.
In reverse reaction, hydrogen iodide decomposes back into hydrogen and iodine.
The reactions can be combined into one equation by the use of a double arrow.

- The double arrow is an indication that the reaction is reverse reaction.

Equilibrium
- The rate of the forward reaction and the rate of the reverse reaction are equal.

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Equilibrium Constants
- At equilibrium, the concentrations of the reactants and products are constant.
- At equilibrium, the concentrations can be used up to set up a relationship
between the reactants and the products.

- Equilibrium constant expression for a reversible chemical reaction:

Calculating Equilibrium Constants

Sample: In an experiment, the molar concentrations for the reactants and products at
equilibrium were found to be:

[H2]= 0.10 M
[I2] = 0.20 M
[HI] = 1.04 M

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 What is the value for the equilibrium constant?

Homogeneous and Heterogeneous Equilibria

Homogeneous equilibria- occur when all reactants and products are in the same phase

Heterogeneous equilibria- occur when reactant or product in the equilibrium is in a

different phase
- The value used for the concentration of a pure substance is always 1.
- Therefore, the concentrations of solids and liquids do not appear in the
equilibrium expression.

***as long as some CaCO3 or CaO remain in the system, the amount of CO2 above
the solid will remain the same.

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Le Chatelier’s Principle
- If a system at equilibrium is disturbed by a change in temperature, pressure or
the concentration of one of the components, the system will shift its equilibrium
position so as to counteract the effect of the disturbance.
- Example:

Activity 1

• You are requested to download the video related to the topic posted in the mVLE
course page on September 22, 2020, 1:00 PM.

Activity 2
• Practice writing rate of reaction, order of reaction, overall order of reaction,
equilibrium constant.

Learning Input 2 (Laboratory)

• The rate of a reaction is the speed at which a chemical reaction happens. If a
reaction has a low rate, that means the molecules combine at a slower speed
than a reaction with a high rate. Some reactions take hundreds, maybe even
thousands, of years while others can happen in less than one second. The rate of
reaction also depends on the type of molecules that are combining. If there are
low concentrations of an essential element or compound, the reaction will be
slower.

Activity 3
• Prepare clear cups, measuring cup, 6 Alka Seltzer tablets, stopwatch, mortar and
pestle, source of hot water, ice cubes

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Wrap-Up Activity
1. Discussion Forum (Open-ended questions)
• You are expected to participate in the discussion forum scheduled on
September 28, 2020 (unless otherwise rescheduled), Monday via the mVLE
BIGBlueButtonBN or ZOOM.
• An invitation link will be available in the mVLE course site.
• Open-ended questions will be asked randomly among students during the
discussion proper.
• In addition, students are also given opportunity to ask/raise any question or
make clarifications during the discussion.

Assessment (Post-Assessment)
Problem-Based Learning Task 5
Worksheet
• A detailed instruction will be available in the mVLE course page assignment portal
on September 22, 2020, 1:00 PM.
• Submit your output on or before 11:59 pm, September 27, 2020 (Sunday) via the
same portal in mVLE.
Laboratory-Based Learning Task 4
• A detailed instruction will be available on September 22, 2020, 1:00 PM. Submit
your laboratory report on or before 11:59 pm, September 27, 2020 via the
assignment part in mVLE.

Online Exam 4
• You are required to take the Post-Test on the topic learned.
• The link will be posted on September 28, 2020 (Monday) after the discussion forum
in the mVLE Quiz Portal.
• Accomplish and submit the said exam on or before 11:59 PM on the same date.
Course Facilitator

Kristian Gay D. Beltran

Assistant Professor II
Pharmacy Department
kdbeltran@mmsu.edu.ph

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