Environmental Chemistry

Chemical Kinetics &

Chemistry of Atmosphere
for

CHEM-4181
Course Facilitators: Engr. Muhammad Suleman

Department of Chemical
Engineering
 Study Material for Lecture

Lecture Slides

Chapter 4 (The Chemistry of Processes

in the Atmosphere), pg. 69 - 77
Ibanez, Jorge G., et al. Environmental Chemistry
Fundamentals. Springer, 2007
OPTIONAL
Chapter 5 & 6
Girard, James E. Principles of environmental
chemistry. 3rd Ed, Jones and Bartlett, 2013.

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 TABLE OF CONTENTS

Basics of Chemical Kinetics

Chemistry of Atmosphere

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 TABLE OF CONTENTS

Basics of Chemical Kinetics

Chemistry of Atmosphere

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 What is Chemical Kinetics?

• how fast does a reaction proceed?

• Reaction speed: measured by the change in concentration with time.

• Besides information about the speed at which reactions occur, kinetics

also sheds light on the reaction mechanism (exactly how the reaction

occurs).

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Reaction Rate
• Rates of reactions can be determined by monitoring the change in concentration of either reactants or

products as a function of time t.

• For the reaction A B there are two ways of measuring reaction rate:

i. the speed at which the reactants disappear

ii. the speed at which the products appear

• Rate of Reaction can be defined as the variation of the concentration of a reactant or product in a

constant-volume (i.e., batch or intermittent) system.

• Important factors which affect rates of reactions: reactant concentration, temperature action of

catalysts, surface area, pressure of gaseous reactants or products

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Reaction Rate

• measuring the rate of the reaction is in terms of change in

concentration per unit time…

Rate  [A]
Rate = k[A]
[A] the molar concentration of A, in mol L-1
K the rate constant

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Reaction Rate

• Reaction rate is the change in the concentration of a reactant or a product with time.

A B
[A] decreases with time
rate = - Δ[A] / Δt

Δ[A] = change in concentration of A over time period Δt

rate = Δ[B] / Δt

Δ[B] = change in concentration of B over time period Δt

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Rate Constant

• the rate of a chemical reaction also depends on temperature

• This dependence is expressed by what is called the Arrhenius
equation:
−𝐸𝑎
𝑘 = 𝑍𝑒 ൗ 𝑅𝑇
K the rate constant
Ea the activation energy(measured in kl/mol)
R the gas constant (0.0821 L atm/mol K)
T the temperature in the Kelvin scale (absolute temperature)
Z the frequency factor that represents the collision frequency.

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Factors that Affect the
Reaction Rate Constant
1. Temperature: At higher temperatures, reactant molecules have more
kinetic energy, move faster, and collide more often and with greater
energy
Collision Theory: When two chemicals react, their molecules have to collide with
each other with sufficient energy for the reaction to take place.
Kinetic Theory: Increasing temperature means the molecules move faster.
2. Concentrations of reactants: As the concentration of reactants
increases, so does the likelihood that reactant molecules will collide.
3. Catalysts: Speed up reactions by lowering activation energy
4. Surface area of a solid reactant: More area for reactants to be in
contact
5. Pressure of gaseous reactants or products: Increased number of
collisions

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 TABLE OF CONTENTS

Basics of Chemical Kinetics

Chemistry of Atmosphere

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 What is Atmosphere

The atmosphere is the thin layer of gases that

envelop Earth. These gases are always in motion,
sometimes rising, sometimes falling, most of the time
moving across earth’s surface.

Altitude Temperature
Region Chemical Species
Range (km) Range (C)
Nitrogen, Oxygen, Water vapor,
Troposphere 0-20 15 to -56
Carbon dioxide
Startosphere 20-50 -56 to -2 Ozone
Mesosphere 50-85 -2 to -92 Oxygen, Nitric Oxide
Thermosphere 85-500 -92 to 1200 Oxygen, Nitric Oxide

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Functions of the Atmosphere

• Protection of all life from hazardous or deadly radiation from space (filter for UV- and x-rays from
sun)
• Letting pass the vitally important sunlight to the surface of the continents and oceans (energy
source)

• Transport of energy
• Transport of water vapor through dynamic processes of general air circulation
• Storage of huge amounts of nitrogen (important for plants)
• Reservoir for carbon dioxide and oxygen
• Dissipation and decomposition (oxidation, reaction with radicals, photolysis) of natural and
anthropogenic (man-made) emissions.

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Air / Atmosphere
• Air can be defined as a gaseous mixture that gives
sustenance to life on earth because of the
presence of dioxygen

• The main layers of concern in atmospheric

chemistry are the troposphere and the stratosphere
• The temperature of this layer of the atmosphere
decreases steadily as the distance from the Earth’s
warm surface increases
• The lower part of the troposphere is known as the
boundary layer. Pollutants emitted near the ground
accumulate in the boundary layer. Most weather
occurs in the boundary layer of the troposphere.

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Air / Atmosphere
• The upper part of the troposphere is free troposphere.
• The temperature of the free troposphere decreases with
rising altitude (approximately 6.5°C/km) and there are a
number of reasons.
• First, the top of the free troposphere continuously
radiates energy upward, cooling the upper troposphere.

• Second, the troposphere itself does not efficiently

absorb solar radiation.
• Third, this region receives warmed air that rises from
the surface. Because atmospheric pressure also
decreases with increased altitude, the warm air enters a
region of lower pressure. The warm air expands and as a
result cools, resulting in a decrease of temperature with
increasing height.

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Air / Atmosphere
• Above the troposphere is the stratosphere, which
extends to approximately 50 km (30 miles) and
includes the ozone layer.
• The temperature remains constant in the lower
part of the stratosphere but begins to rise with
increasing altitude
• The formation of ozone in the stratosphere,
which absorbs UV radiation from incoming solar
radiation and converts the radiant energy into
heat, causes this rise in temperature
• Collectively, the troposphere and the stratosphere
are known as the lower atmosphere.

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Air / Atmosphere
• There are two ways represent the amount (or mass) of a substance:
Air Components Concentration/
the concentration and the mixing ratio. Mixing Ratio ?
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑣𝑜𝑙𝑢𝑚𝑒 Nitrogen 78.084%
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 =
𝑉𝑜𝑙𝑢𝑚𝑒 Oxygen 20.946%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑣𝑜𝑙𝑢𝑚𝑒 Argon 0.934%
𝑀𝑖𝑥𝑖𝑛𝑔 𝑅𝑎𝑡𝑖𝑜 =
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎𝑙𝑙 𝑡ℎ𝑒 𝑎𝑖𝑟 𝑐𝑜𝑛𝑠𝑡𝑖𝑡𝑢𝑒𝑛𝑡𝑠 𝑖𝑛 𝑣𝑜𝑙𝑢𝑚𝑒 Water 0.5–4%
Carbon dioxide 360ppm
• The mixing ratio remains unchanged by differences in pressure or
Neon 18.18ppm
temperature associated with altitude or meteorological variability,
Helium 5.24ppm
whereas the concentration is changed with pressure and Methane 1.7ppm
temperature Krypton 1.14ppm
• The mixing ratio may be expressed as (a) mole fraction, (b) mass Hydrogen 0.5ppm
fraction Xenon 0.087ppm

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Air / Atmosphere

Interactions of Atmosphere

Fin Atmosphere Fout

Fin = Fout Steady State A/ 

Fin = Fout Accumulation

Fin = Fout Depletion A is the total amount of the gas in the atmosphere
 is the residence time

EXAMPLES The average time a molecule spends in the atmosphere

after it is released or generated there.
Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere
 Classification of Air Constituents
based on origin

Geogenic activities of the Earth's crust without the participation of

living organisms

Air
Constituents Biogenic
biological activity that produces or consumes chemicals

Anthropogenic production of chemicals resulting from human activities

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Tropospheric Chemistry
• Troposphere means ‘turning sphere’, which symbolizes the fact that, in Oxidation of Methane in
Troposphere
this region, convective processes dominate over radiative processes
• Chemicals available are nitrogen, oxygen, carbon dioxide, water vapor
and some trace pollutants

• Oxidation of these pollutants can assist in getting rid of these pollutants

• Dioxygen is not the oxidizing agent, it’s the free hydroxyl radical which
oxidizes pollutants
• Reactions with dioxygen require higher activation energies than reactions
with free radicals
• Link of pollutant oxidation & residence time?

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Tropospheric Chemistry

• The major source of *OH radicals is ozone

• Ozone photolysis with short wavelength UV
radiation produces excited oxygen atoms, O(1D),
which rapidly react with water vapor, forming *OH

• Other radicals include NO3* and is less reactive than

*OH
• In day, it is no much functional as it is easily
photolyzed

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Physical Principles of the Greenhouse Effect

• In steady state systems, energy received

from the sun equals the energy emitted by
the Earth
• the emitted radiation can increase the
temperature which is green house effect.
• The radiation is absorbed by gases such
as water vapor, carbon dioxide, nitrous
oxide, methane, CFCs, and SF6 , known as
greenhouse gases

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Stratospheric Chemistry

• The main element of interest in stratosphere is ozone

• ozone protects life on the surface of the Earth by
screening the harmful UV light coming from the sun
• ozone absorbs UV radiation without being consumed;
the net result is to convert UV radiation into heat. This
is why temperature increases with altitude in the
stratosphere

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

 Aerosols

• solid and liquid particulates in

atmosphere, known as aerosols

• Sea salt, dust, and volcanic emissions are

natural sources of aerosols
• Aerosols alter the Earth's radiative
process and thus affect its temperature
and climate

• black carbon (soot)

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere

Course: Environmental Chemistry | Lecture: Chemical Kinetics & Chemistry of Atmosphere