Example: one thousand kilograms per hour of a mixture of benzene and toluene that

contains 50% by mass are separated by distillation into two fractions. The mass flow of
benzene in the top steam is 450 kg (benzene/hour) and toluene in the bottom steam is
475kg (toluene/hour). Write the material balance on benzene and toluene to calculate
the unknown components in the output stream.
• Total Material Balance :
---------------------------------------
F=D+B

1000 = D + B

Benzene Material Balance :

---------------------------------------
( F ) ( xFbz ) = ( D ) ( xDbz ) + ( B ) ( xBbz )

( 1000 ) ( 0.5 ) = ( D ) ( xDbz ) + ( B ) ( xBbz )

fbz = dbz + bbz

500 = 450 + bbz

29/12/2019 bbz = 500 - 450 = 50 kg/hr benzene 1

Toluene Material Balance :
---------------------------------------
( F ) ( xFtol ) = ( D ) ( xDtol ) + ( B ) ( xBtol )

ftol = dtol + btol

500 = dtol + 475

dtol = 500 - 475 = 25 kg/hr toluene

The distillate product, D , is thus :
---------------------------------------
D = dbz + dtol

D = 450 + 25 = 475 kg/hr Distillate product

xDbz = dbz / D

xDbz = 450 /475 = 0.9474 mass fraction benzene = 94.74 mass % benzene
xDtol = dtol / D

xDtol = 25 / 475 = 0.0526 mass fraction toluene = 5.26 mass % toluene

2
You have for the bottom product :
---------------------------------------...

B = F - D = 1000 - 475 kg/hr

B = bbz + btol

B = 50 + 475 = 525 kg/hr Bottom Product

xBbz = bbz / B

xBbz = 50 / 525 = 0.0952 mass fraction benzene = 9.52 mass % benzene

xBtol = btol / B

xBtol = 475 / 525 = 0.9048 mass fraction toluene = 90.48 mass % toluene

3
 POLLUTION

Pollution is the introduction of harmful substances or products

into the environment.
Pollutant is a substance present in nature , in greater abundance
due to human activity which ultimately affect the environment ,
living organisms and mankind.
Contaminant is a material which does not occur in nature, but it
is introduced by human activity in to the environment. e.g.
chlorine gas escaped from tank near a road.
Receptor is the medium which is affected by a pollutant.
Example:- man is a receptor of photochemical smog causing
irritation of eyes and respiratory tract.
Classification of pollution:
A. According to the environment:
1. Air Pollution.
2. Water Pollution.
3. Soil Pollution.
B. According to the pollutant:
The pollution caused by pollutants may be of a
number of types:-
1. Radioactive Pollution.
2. Noise Pollution.
3. Thermal Pollution.
4. Pesticide or Biocide Pollution.
5. Oceanic Pollution.
6. Chemical & Biological Pollution.
7. Industrial Pollution.
8. Population Pollution.
•The term “Environment” literally means “surrounding”.
It comprises of the following four major components:
1. Atmosphere.
2. Hydrosphere.
3. Lithosphere.
4. Biosphere.

• “ENVIRONMENT CHEMISTRY” is a branch of science

which deals with the chemical phenomena occurring in
the environment, i.e., study of origin, transport, reactions,
effects and fates of chemical species in the
environment.
Air (ATMOSPHRIC) POLLUTION:
Air pollution is defined as the addition of undesirable materials
into the atmosphere either due to natural phenomena or due to
human activity on the earth which adversely affect the quality of
the air and hence affects the life on the earth. It is also known as
“Atmospheric Pollution”
Atmospheric pollution is generally studied as Tropospheric and Stratospheric
pollution.
•Tropospheric pollution occurs due to the presence of undesirable solid or
gaseous particles in the air. The following are the major gaseous and
particulate pollutants present in the troposphere:
1. Gaseous air pollutants: These are oxides of sulphide, hydrocarbons, ozone
and other oxidants.
2. Particulate pollutants: These are dust, mist, fumes,
smoke, smog etc.
1.Gaseous Air Pollutants:
(a) Oxides of Sulphur:
Oxides of sulphur are produced when sulphur- containing fossil fuel is
burnt. The most common species, sulphur dioxide, is a gas that is
poisonous to both animals and plants. It has been reported that even
a low concentration of sulphur dioxide causes respiratory diseases.
However, the presence of particulate matter in polluted air catalyses
the oxidation of sulphur dioxide to sulphur trioxide.
2SO2 (g) + O2 (g) → SO3 (g)
SO2 (g) + O3 (g) → SO3 (g) + O2 (g)
SO2 (g) + H2O2 (l) → H2SO4 (as)
(b) Oxides of Nitrogen:
Dinitrogen and dioxygen are the main constituents of
air. These gases do not react with each other at a normal
temperature. At high altitudes when lightning strikes, they
combine to form oxides of nitrogen. NO2 is oxidized to nitrate ion.
When fossil fuel is burnt, dinitrogen and dioxygen combine to yield
significant quantities of nitric oxide (NO) and nitrogen dioxide
(NO2).
N2 (g) + O2 (g) → 2NO (g) [at 1483K]
2NO (g) + O2 (g) → 2NO2 (g)
NO (g) + O3 (g) → NO2 (g) + O2 (g)
(c) Hydrocarbons:
Hydrocarbons are composed of hydrogen and carbon only and are
formed by incomplete combustion of fuel used in automobiles.
Hydrocarbons are carcinogenic, i.e., they cause cancer. They harm
plants by causing ageing, breakdown of tissues and shedding of leaves,
flowers and twigs.
(d) Oxides of Carbon:
(i) Carbon monoxide: Carbon monoxide is one of the most serious air
pollutants. It is a colorless and odorless gas, highly poisonous to living
beings because of its ability to block the delivery of oxygen to the
organs and tissues. It is mainly released by automobiles. It
binds to haemoglobin to form carbonhaemoglobin, which is about 300
times more stable than the oxygen-haemoglobin complex. This results
in headache, weak eyesight, nervousness and cardiovascular disorder.
(ii) Carbon dioxide: Carbon dioxide is released into the
atmosphere by respiration, burning of fossil fuels for energy,
and by decomposition of limestone during the manufacture of
cement. Normally it is about 0.03% by volume of the
atmosphere. Green plants need carbon dioxide for
photosynthesis and they, in turn, emit oxygen, thus maintaining
the delicate balance. The
increase in mount of carbon dioxide in the air is mainly
responsible for global warming.
•Global Warming and Greenhouse Effect:
• About 75% of the solar energy reaching the earth is absorbed by
the earth’s surface, which increases its temperature. The rest of the
heat radiates back to the atmosphere. Some of the heat is trapped
by gases like carbon dioxide, methane, ozone, chlorofluorocarbon
compounds (CFCs) and water vapor in the atmosphere. Thus, they
add to the heating of the atmosphere. This causes “Global Warming”.
• Just as the glass in a greenhouse holds the sun’s heat near the
earth’s surface and keeps it warm.
This is called natural greenhouse effect.
Causes of Global Warming:
•Increase in concentration of carbon dioxide which is
emitted by automobiles, industries, etc,.
•Increase in concentration of methane which is emitted
when vegetation is burnt, paddy fields, coal mines etc,.
•Increase in concentrations of CFCs which is commonly
produced or emitted by refrigerators, etc,.
A greenhouse is a house made of glass. It has glass walls
and a glass roof. People grow tomatoes and flowers and
other plants in them. A greenhouse stays warm inside,
even during winter. Sunlight shines in and warms the
plants and air inside. But the heat is trapped by the glass
and cannot escape. So during the daylight hours, it gets
warmer and warmer inside a greenhouse, and stays
pretty warm at night too.
How is Earth a greenhouse?
Earth's atmosphere does the same thing as the greenhouse.
Gases in the atmosphere such as carbon dioxide do what the
roof of a greenhouse does. During the day, the Sun shines
through the atmosphere. Earth's surface warms up in the
sunlight. At night, Earth's surface cools, releasing the heat back
into the air. But some of the heat is trapped by the greenhouse
gases in the atmosphere.
That's what keeps our Earth a warm and snug 59 degrees
Fahrenheit, on average.

Greenhouse effect of Earth's atmosphere keeps some of the Sun's

energy from escaping back into space at night.
Stratospheric Pollution means depletion of the ozone layer (ozone
hole) by certain compounds like oxides of nitrogen,
chlorofluorocarbons (CFCs).
The upper stratosphere consists of considerable amount of ozone
which protect us from the harmful ultraviolet radiation coming
from the sun.
These radiation causes skin cancer in the humans.
ACID RAIN:
• We are aware that normally rain water has a pH of 5.6 due to
presence of hydrogen ions formed by reaction of rain water with
carbon dioxide present in the atmosphere.
H2O (l) + CO2 (g) ↔ H2CO3 (aq)
H2CO3 (aq) ↔ H+ (aq) + HCO3− (aq)
• When the pH of the rain water drops below 5.6, it is called acid rain.
Oxides of sulfur and nitrogen in the atmosphere produces acid rain.
Burning of fossil fuels such as coal and oil in power stations or petrol
and diesel in motor engines produce SO2 and NO2 after oxidation and
reaction with water are major contributors to acid rain.
• 2SO2 (g) + O2 (g) + H2O (l) → 2H2SO4 (aq)
• 4NO2 (g) + O2 (g) + H2O (l) → 4HNO3 (aq)
• Results of Acid Rain:
• Acid rain is harmful for agriculture, trees and plants as it dissolves
and washes away nutrients needed for their growth. It causes
respiratory ailments in human beings and animals.
• When acid rain falls and flows as ground water to reach rivers, lakes
etc. it affects plants and animal life in aquatic ecosystem. It corrodes
water pipes resulting in the leaching of heavy metals such as iron, lead
and copper into drinking water.

Fossil fuel is a fuel formed from the remains of plants and animals that
lived in an earlier era like coal, petroleum , natural gas.
2. PARTICULATE POLLUTANTS:
• Particulates pollutants are the minute solid particles or liquid
droplets in air. These are present in vehicle emissions, smoke particles
from fires, dust particles and ash from industries. Particulates in the
atmosphere may be viable or non-viable. The viable particulates e.g.,
bacteria, fungi, algae etc.,
are minute living organisms that are dispersed in the atmosphere.
They cause plant diseases.
• Non-viable particulates can be classified according to
their size and nature as follows:
(a) Smoke particulate consist of solid and liquid
particles formed during combustion of organic
matter. Ex. Cigarette and oil smoke.
(b) Dust is composed of fine solid particles, produced during
crushing, grinding of solid materials. Sand from sand blasting, saw
dust from wood works, cement and fly ash from factories etc.
(c) Mists are produced by particles of spray liquids and by
condensation of vapors in air.
(d) Fumes are generally obtained by the condensation of vapors
during sublimation, distillation, boiling and several other chemical
reactions.
• The effect of particulate pollutants are largely dependent on the
particle size. Air-borne particles are dangerous for human health.
COMPOSITION OF THE ATMOSPHERE:
•SMOG
•The word smog is derived from smoke and fog. This is the most
common example of air pollution that occurs in many cities
throughout the world. There are two types of smog:
(a) Classical smog occurs in cool humid climate. It is the
mixture of smoke, fog and sulfur dioxide.
Chemically it is a reducing mixture and so it is also called as reducing
smog.
(b) Photochemical smog occurs in warm, dry and sunny climate. The
main components result from the action of sunlight on unsaturated
hydrocarbons and nitrogen oxides produced by automobiles and
factories.
Photochemical smog has high concentration of oxidizing agents and
is, therefore, called as oxidizing smog.
•FORMATION OF PHOTOCHEMICAL SMOG
•When fossil fuels are burnt, a variety of pollutants are
emitted into the earth’s troposphere. A chain reaction
takes place between hydrocarbons and nitrogen oxide in
interaction with sunlight and forms nitrogen dioxide.
This nitrogen dioxide absorbs energy and breaks up into
nitric oxide and free oxygen atom.

(i)
Oxygen atoms are very reactive and combines with dioxygen to form
ozone.

(ii)

•The ozone formed in the above equation (ii) reacts rapidly with NO (g)
formed in equation (i) to regenerate nitrogen dioxide.

(iii) NO (g) + O3 (g) → NO2 (g) + O2 (g)

•Ozone is a toxic gas and both nitrogen dioxide and
ozone are strong oxidizing agents and can react with
unburnt hydrocarbons in the polluted air to produce
chemicals such as formaldehyde, acrolein and
peroxidyacetyl nitrate (PAN).
•EFFECTS OF PHOTOCHEMICAL SMOG:
•They damage metals, stones, buildings materials.
•Produce irritation in the eyes and respiratory system.
Formation of Ozone Layer:
Ozone is a product of UV radiations acting on oxygen
molecules.
The UV radiation splits molecular oxygen into free oxygen
atom. These oxygen atoms combine with molecular oxygen to
form ozone.
Ozone is thermodynamically unstable and decomposes to
molecular oxygen.
O2 (g) → O (g) + O (g)
O (g) + O2 (g) → O3 (g)
Ozone Layer Depletion:
The main reason for ozone layer depletion is believed to be the
release of chlorofluorocarbon(CFC), also known as freons.
These compound are non-reactive, nonflammable, non-toxic
organic molecules and therefore used in refrigerator, air
conditioner, and in the production of plastic foams.
A variety of indices have been in use in various regions around
the world. For instance, the Pollutant Standards Index (PSI)
established by the United States Environmental Protection
Agency (US EPA), the Common Air Quality Index in European
countries, and the Air Quality Health Index in Canada. Many
countries follow the AQI established by US EPA with an assigned
value of 0 to 500, and it can be divided into the categories
indicated in the following table:
Categories of Air Quality Index (AQI).

AQI Values Levels of Health Concern

0–50 Good
51–100 Moderate
101–150 Unhealthy for Sensitive Groups
151–200 Unhealthy
201–300 Very Unhealthy
301–500 Hazardous
Units and Dimensions:
The dimension of length (e.g., particle diameter) and mass may
take different units and the conversions are as follows:
• 1 mm = 1000 micrometer (μm).
• 1 μm = 1000 (nm).
• 1 gram (g) = 1000 milligram (mg) = 1,000,000 microgram (μg).
Concentrations of air pollutants and GHGs can be presented in
several dimensions, including mass per volume, volume ratio and
mass ratio. Mass per volume is usually presented with units of
kg/m3, mg/m3 or μg/m3; and, volume and mass ratios are
measured in units of parts per million (ppm) and percentages. At a
low concentration, ppm is used more often than percentage to
quantify the concentration of an air pollutant or GHG in the air.
One frequently encountered unit conversion is
between volume (or mass) percentage and ppmv (or ppmm):
ppm = percentage (%) x 10000
Percentage (%) = ppm ÷ 10000
Sometimes, it is necessary to specify the concentration by volume or
mass. Accordingly, ppmv and ppmm are used to express parts per
million by volume and mass, respectively. The density of a species is
needed in order to convert ppmv to ppmm:
ppmm = ppmv x density
The conversion between the volume concentration and the mass
concentration as determined by the density of the subject of concern
can be explained using the following example:
Example 1:
The National Ambient Air Quality Standard for carbon monoxide (CO) is
35 ppmv measured over a one-hour averaging time. What is the
equivalent concentration in (a) percentage, (b) mg/m3 under standard
condition when its density is 1.145 kg/m3?
Solution:
35 ppmv means that there is 35 m3 of CO in one million m3 of air.
Therefore,
(a) by volume percentage, 35 ppmv is 35/10000 = 0.0035 %
(b) by mass concentration, 35 ppmv of CO in air becomes:
1.145 kg/m3 x 35 /106 = 40.075 x 10-6 kg/m3 = 40.075 mg/m3
Unless otherwise stated, the standard ambient condition is at a
temperature of 25 °C and standard atmospheric pressure (1 atm or
1.013 x 105 Pa).
What is the molecular weight of dry air?
The value we are after should just be the weighted average of the
components in air, mostly nitrogen at 28 g/mol and oxygen at 32
g/mol (and perhaps a tad of argon at 40 g/mol). Thus,
MW of dry air = 0.78 x 28 + 0.21 x 32 + 0.01 x 40 = 29 g/mol

What is the volume of 1 mole of gas at 1 atm and 0o C?

(V/n) = (RT/P) = (0.082 L atm/mol K) x (273 K/1 atm) = 22.4 L/mol
What is the density of the Earth’s atmosphere at 0o C
and 1 atm pressure?
(n/V) x MW = (mol/ 22.4 L) x (29 g/mol) = 1.3 g/L = 1.3 kg/m3
Example 2:
An SO2 concentration is given as 830 μg/m3 at 25°C and 1 atm. Express
this concentration in parts per million (ppm).
Solution:
Concentration of SO2 is 830 μg/m3. AT STP conditions (25°C and 1 atm),
one mole of gas occupies 24.5 L.
(V/n) = (RT/P)
Molecular Weight of SO2 is 64 g/mol
ppm = (830 μg/m3 x 24.5 x 10-3 m3/mol)/(64 g/mol) = 0.32 ppm
Example 3:
The primary air quality standard for sulphur dioxide (SO2) measured
over 24 h averaging time is 0.14 ppmv. What is the equivalent
concentration in μg/m3 at 1 atm and 25 °C?
Concentration (μg/m3) =
[(0.14/106) x 64 x 106 μg/mol ]/24.5 x 10-3 m3/mol = 3.66 x 104

Example 4:
The national ambient air quality standard for ozone is 0.08 ppmv
measured over an eight hour averaging time. What is the equivalent
concentration in mg/m3 at 25 °C?
Concentration (mg/m3) =
[(0.08/106) x 48 x 103 mg/mol ]/24.5 x 10-3 m3/mol = 0.157
Example 5:
An exhaust gas containing 3.2 percent by volume SO2 is released at
25°C and 1 atm. Compute the concentration in mg/m3.
3.2 percent by volume = 3.2 x104 ppm
Concentration (mg/m3) =
[(3.2 x 104/106) x 64 x 103 mg/mol ]/24.5 x 10-3 m3/mol = 8.36 x 104
Example 6:
The primary air quality standard for nitrogen dioxide (NO2) as an
annual average is 100 μg/m3. What is the equivalent concentration in
ppmv at 1 atm and 25 °C?
ppm = (100 μg/m3 x 24.5 x 10-3 m3/mol)/(46 g/mol) = 0.053 ppm
Example 7:
The exhaust gas from automobile contains 8 ppmv of carbon
monoxide (CO).
A. What is the equivalent concentration in g/m3 at 1 atm and 25 °C?
B. What is the concentration in exhaust pipe in g/m3 if it is at 220 °C
and 1.2 atm?
Concentration (g/m3) =
[(8/106) x 28 g/mol ]/24.5 x 10-3 m3/mol = 9.14 x 10-3
(V/n) = (RT/P) = (0.082 L atm/mol K) x (493 K/1.2 atm) = 33.7 L/mol
Concentration (g/m3) =
[(8/106) x 28 g/mol ]/33.7 x 10-3 m3/mol = 6.647 x 10-3
Example 8:
The exhaust gas from automobile contains 20 μg/m3 of lead.
a. What is the equivalent concentration in ppmm at 1 atm and 25
°C?
b. What is the concentration in exhaust pipe in μg/m3 if it is at 200
°C and 1.1 atm?
Molecular Weight of Pb is 207.2 g/mol
ppm = (20 μg/m3 x 24.5 x 10-3 m3/mol)/(207.2 g/mol) = 2.365 x 10-3
(V/n) = (RT/P) = (0.082 L atm/mol K) x (473 K/1.1 atm) = 35.3 L/mol
Concentration (μg/m3) =
[(2.365 x 10-3/106) x 207.2 x 106 μg/mol ]/35.3 x 10-3 m3/mol = 13.9
Example 9:
Carbon Monoxide concentration at 90°C and 6 atm is 90 μg/m3.
Express this concentration in ppm.
(V/n) = (RT/P) = (0.082 L atm/mol K) x (363 K/6 atm) = 4.96 L/mol
ppm = (90 μg/m3 x 4.96 x 10-3 m3/mol)/(28 g/mol) = 0.016 ppm