Physical Chemistry

CHM 241

3 Units

Dr. Segun OLAOYE

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 Course Outline

✓Kinetics of Chemical Reactions

✓Rate equations, Order, and Molecularity
✓Temperature Effects on reactions and catalysis
✓Enzyme catalysis.

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 CHEMICAL KINETICS
INTRODUCTION
➢The study of the rates of chemical reactions is called chemical kinetics.
The word kinetics is derived from the Greek kinetikos, meaning “putting
in motion.”
• Kinetics is inherently an experimental science; many factors influence the
rate of a reaction. Chemical reactions typically occur when reactant
species strike each other and interact to form new species, called
products.
• Chemists study the kinetics of reactions in an effort to determine which
molecules collide, how many, under what conditions, and soon. This
information is used to improve the production of materials, minimize
pollution, and increase the energy efficiency of manufacturing processes.
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 Rate of Reactions
➢ The rates of reactions and the factors that influence those rates are crucial components of our knowledge of chemical
reactions. The study of reaction rates is important to the synthesis of chemicals and the design of reactors, and
provides fundamental insight into chemical reactivity as it applies to biological, geological, and industrial processes

• In chemistry, the rate of reaction is measured in terms of a change in concentration per unit time.

∆𝑐
Rate = ∆𝑡

Consider a reaction of the type

reactant → product

∆[𝑝𝑟𝑜𝑑𝑢𝑐𝑡] ∆[𝑟𝑒𝑐𝑎𝑡𝑎𝑛𝑡]
+𝑣𝑒 = (−𝑣𝑒)
∆𝑡 ∆𝑡

Why the –Ve and +Ve signs ? ?

NOTE: It is important to remember that the rate of reaction is always expressed as a positive number, regardless of which
species is measured, which explains the negative sign in the preceding equation.
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 Work-to-do!!!
• Consider the formation of ammonia from the elements:
N2(g) + 3H2(g) 2NH3(g)

(a) If the ammonia concentration is increasing at a rate of 0.024 M/s, what is the rate of
reaction?
(b) What is the rate of disappearance of hydrogen?

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 Experimental Rate Laws
• A good starting point for learning about rates of reactions is to consider the kinetics of
a chemical system (experiment) in which two compounds, A and B, react:
aA + bB products
• A general observation from this experiment is that the rate of reaction is not just proportional to the
concentrations of the reactants, but the rate is proportional to the product of the concentrations of the
reactants, each raised to some power. These observations can be summarized by an equation called the
rate law that relates the rate of reaction to the concentrations of the reactants:

Rate = k[A]x[B]y

• The exponents, x and y, are the orders of the reaction. Th e order is usually a small
positive integer, but occasionally it can be zero, negative, or fractional. The rate law is
described as xth order in A and yth order in B. For example, if x = 1 and y = 2, then the
reaction is first order in A and second order in B. The sum of the orders, termed the
overall order, is three for this example
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 Work-to-do!!!
A scientist (‘’Blossomu’’) has collected the following data in her laboratory. She needs to determine the rate law and
evaluate the rate constant for this reaction
H2O(g) CH3Cl(g) CH3OH(g) HCl(g)

It is important to emphasize that

the rate law cannot be predicted
from the reaction stoichiometry.

From the data above, derive the rate expression, rate law, and evaluate the overall order of reaction and rate constant

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 First-Order and Half Life
• Suppose a chemical reaction is of the form A B, the
rate for 1st order reaction
Radioactive decay processes follow a first-order rate law. The
rate of decay is proportional to the amount of material present,
so doubling the amount of radioactive material doubles the
measured counting rate of decay products. When the amount
of material remaining is one-half of the original amount, the
time expired is called the half-life.

At the point where the time elapsed is equal to one half-life, t =

When the integration is performed, we obtain t1/2, the concentration of A is one-half the initial concentration
or [A]o/2. Therefore, we can write:

The half-life is then given as

In this case, we see that the half-life is independent on the

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initial concentration of A.
 Zero Order and Half Life
• Suppose a reaction can be written as
• Another way to describe the speed of the reaction
A B is by the half-life, designated t1/2, which is the time
needed for the concentration of a reactant to
reaction follows a rate law of the form decrease to half its original value. A short half-life
𝑑𝐴
R𝑎𝑡𝑒 = − = 𝑘[𝐴]0 indicates a rapid reaction.
𝑑𝑡
• we can determine the half-life of the reaction
because [A]0 = 1. Therefore, we can write the equation as because after one half-life, [A] = [A]o/2. Therefore

So that the half life for zero order is of the form:

In this case, we see that the half-life is directly

Rearranging and compare with the linear equation: proportional to [A]o, the initial concentration of A.

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 Work-to-do
• The pesticide fenvalerate, C25H22ClO3N, is a member of a class of compounds called pyrethrins. Fenvalerate is one of four
compounds approved by New York City to combat the mosquitoes that spread West Nile virus. These compounds were
originally isolated from plants (including chrysanthemums) that exhibited a tendency to repel insects. It degrades in the
environment with first-order kinetics and a rate constant of 3.9 x 10-7 s-1. An accidental discharge of 100 kg fenvalerate into a
holding pond results in a fenvalerate concentration of 1.3 x 10-5 M. Calculate the concentration 1 month (2.6 x 106 s) after the
spill. Ans = 4.7 x 10-6 M
• Dinitrogen pentoxide decomposes to nitrogen dioxide and oxygen. When the reaction takes place in carbon tetrachloride
(CCl4), both nitrogen oxides are soluble, but the oxygen escapes as a gas.

The rate of reaction can be measured by monitoring the volume of oxygen gas that is produced by the reaction. Quantitative
analysis of the gas generated in such an experiment shows that the rate law is first order in N2O5 with a rate constant of 8.1 x 10-5
s-1 at 303 K. If the initial mass of [N2O5] is 0.032 g , how long does it take for the mass to decrease to 0.015 g ?
Ans = 9.4 x 103 s
• The age of Chioma, a witty girl, was determined by carbon-14 (14C) dating. 14C is a radioactive isotope with a half-life
of 5730 years. A sample of carbon-containing material was found to have 52.7% of its original amount of 14C. Use this
information to calculate how long ago Chioma lived.

Ans = 5.29 x 103 years

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 Second-Order and Half Life
Such a rate law might result from a reaction that can be written as

Rearranging the equation to form a linear

A reaction that is second-order in one reactant or component obeys equation:
the rate law

After a reaction time equal to one half-life, the concentration

of A will have decreased to one-half its original value.

/
If the equation is integrated between limits on
concentration of [A]o at t=0 Therefore, solving for t1/2 (half life)
and [A] at time t, we have

Please note, in the case of a second-order reaction, the half-life is

inversely proportional to the initial concentration of the reactant.
Performing the integration gives the integrated rate law

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 Work-to-do
The gas-phase reaction

Whose half-life is inversely proportional to the concentration of NO3. At a temperature of 20°C and an initial concentration of
NO3 equal to 0.0500 mol/L, the concentration after 60.0 minutes is equal to 0.0358 mol/L. Find the value of the rate constant.

Ans: 2.2 × 10−3 L mol−1 s−1

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 The Temperature Dependence of Rate
Constants
• Reaction rates depend strongly on temperature, nearly always increasing when the temperature is raised. The first
quantitative studies of the temperature dependence of rate constants were published in the last half of the 19th century, and
various empirical formulas were proposed.
• The Arrhenius relation, which was proposed in 1889, is widely used because it is based on a physical picture of elementary
processes and because it usually fits experimental data quite well.

The Arrhenius equation is of the form:

=

Where:
k = Rate constant
A = Pre-exponential factor
Ea = Activation Energy
R = Gas constant = 8.314 Jmol-1K-1
T = Absolute Temperature in Kelvin
Work to-do: Considering two experiments, derive an expression for the temperature-rate constant (T-k) relationship

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 Work-to-do
• Consider the decomposition of nitrogen dioxide

At 650 K , the rate constant is 1.66 L/mol∙s ; at 700 K , it is 7.39 L/mol∙s . Use these rate
constants to determine the activation energy. Ea = 1.13 105 J/mol = 113 kJ/mol

• A reaction rate doubles when an investigator increases the temperature by 10 °C, from 298 to
308 K . What is the activation energy?
Ea = 5.3 104 J/mol = 53 kJ/mol
 Catalysis
✓ One way to improve the productivity of collisions is to add a
catalyst—a substance that increases the rate of reaction but is not
consumed in the reaction.
✓ A catalyst is intimately involved in the course of the chemical
reaction; it helps to make and break bonds as the reactants form
products, but it does not undergo a permanent change.

➢ A catalysed reaction proceeds by a different set of steps than does an

uncatalyzed reaction. The catalysed reaction generally has lower activation
energy, and thus a greater reaction rate at any given temperature
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Figure 1: An energy-level diagram for a chemical reaction. The activation energy of the catalyzed reaction is
lower than that of the uncatalyzed reaction. The catalyzed reaction is faster at any given temperature.

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 Homogeneous Catalysis
A homogeneous catalyst is one that is present in the same phase as the reactants. The bromide-catalyzed decomposition of
hydrogen peroxide is an example of homogeneous catalysis.

Chemists believe that the catalyzed reaction occurs in two steps. First, bromide ion and the H+ found naturally in water reacts
with hydrogen peroxide to form bromine and water.

STEP 1:

In a second step, the bromine formed in the first step reacts with additional hydrogen peroxide to form oxygen.

Step 2:

The sum of the two steps gives the overall reaction.

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Figure 2: Bromide-catalyzed decomposition of hydrogen peroxide. Shortly after a bromide salt such as sodium or potassium
bromide is added to a hydrogen-peroxide solution, the yellow colour of bromine is seen together with bubbles of oxygen. The
yellow colour fades at the conclusion of the reaction

Adding bromide ion results in violent bubbling because of the generation of oxygen gas and simultaneous appearance
of the yellow colour of bromine. At the end of the reaction, the bubbling stops and the yellow colour disappears,
because all the bromine is present then as the colourless bromide ion. Bromide ion is a catalyst because it increases
the rate of reaction but is not consumed.
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Figure 3: Energy-level diagram for the bromide-catalyzed decomposition of hydrogen peroxide.

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 Heterogeneous Catalysis
Metals such as platinum, palladium, and nickel and many metal oxides catalyse many reactions, particularly those that involve
small gas molecules. Th ese solids are examples of a heterogeneous catalyst, one that is in a different phase from the
reactants. The formation of methanol, CH3OH, from hydrogen and carbon monoxide is extremely slow if it is not catalysed by
metal surfaces.

The uncatalyzed reaction has a high activation energy and needs high temperatures if the reaction is to proceed at a
satisfactory rate. Unfortunately, high temperatures favour the reverse reaction, and methanol breaks up into hydrogen and
carbon monoxide if heated at too high a temperature.

A better approach is to use a platinum surface to catalyze the formation of methanol from hydrogen and carbon
monoxide so low temperatures can be used. We write the catalyzed reaction by naming the catalyst and placing it over
the arrow:

To study how heterogeneous catalysts work, scientists studied a simpler system: the metal-catalyzed hydrogen
deuterium reaction. Studying simple systems with the idea of extrapolating the knowledge to more complex systems
is one important aspect of scientific research. The chemical equation for the reaction of hydrogen with deuterium is

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 Figure 4: Energy-level diagram for the reaction of hydrogen with deuterium

Scientists learned that when a hydrogen or deuterium molecule forms a weak bond to the metal surface, the H-H or D-D
bond weakens. If a D2 molecule bonds to the surface near an H2 molecule, the product can form. This process is illustrated
schematically in Figure 4.
Many scientists believe that this bond-weakening process explains why so many gas-phase reactions, including the
production of methanol from H2 and CO, proceed rapidly at certain metal surfaces.
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Catalyst can actually determine the nature of the product. For instance, Platinum and nickel
catalysts lead to different products from the reaction of hydrogen and carbon monoxide.

The CO bond is retained in the reaction at the platinum surface but is broken in the reaction at the nickel surface.

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 Enzyme Catalysis
Enzymes are large molecules that catalyse specific biochemical reactions. Scientists believe that some enzymes increase
the rate of reaction by increasing the value of the steric factor rather than by decreasing the activation energy.
• These enzymes interact with the reactant molecules in a way that places them in the correct geometry to form the
products.

Figure 5: Model Structure of Alcohol dehydrogenase

Enzyme Metabolism
Alcohol dehydrogenase (ADH) is an enzyme that catalyses the oxidation of ethyl alcohol to acetaldehyde and other species.

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The reaction is thought to follow the Michaelis–Menten mechanism, which is illustrated in the following equations. Let E
represent the enzyme and S represent the substrate, which is the compound on which the enzyme acts. In this particular
example, E is ADH and S is ethanol. The first step is a rapid reversible one in which E and S form
a complex. The Michaelis–Menten mechanism
involves a fast, reversible step to form the
enzyme-substrate complex, followed by a
slow step in which the complex forms the
products.
The second step is the formation of the product and enzyme from the enzyme-substrate complex.
This second step limits the rate of reaction.

Note that the enzyme is “recycled.” It is a catalyst and not consumed in the reaction; therefore, it can act on another
substrate molecule. Let us define CE as the total concentration of the enzyme. The enzyme is present in two forms: free
enzyme, E, and bound enzyme, ES.

Under normal conditions, the substrate is present in much greater concentration than is the enzyme, and nearly
all the enzyme is bound to the substrate.
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