BINDURA UNIVERSITY OF SCIENCE EDUCATION

FACULTY OF SCIENCE EDUCATION

DEPARTMENT OF CHEMISTRY

NAME : Maronga Chrispen

REG No : B1852150

PROGRAMME : HBSc.ed Chemistry

COURSE Description : Environmental technology

COURSE CODE : CH424

LEVEL : Part 3.2[2021]

Assignment No :1
 1. (a) Starting with reaction(s) involving the photolysis of oxygen, show how the OH
radical destroys ozone in the stratosphere. [10 marks]

Photolysis is the process which is initiated by energy in the form of light.

O2 + UV-C → 2O

O + O → O2 Thus any O2 molecule that absorbs a photon from light of wavelength

240 nm or shorter has sufficient excess energy to dissociate.

O2 + UV photon (λ< 240 nm) →2O

Far beyond the stratosphere, there is very thin film of air. It leads to the concentration of
molecules so low that most oxygen exists in atomic form, having been dissiociated from O2
molecules by UV-C photons from sunlight. The eventual collision of oxygen atoms with each
other leads to the re-formation of O2 molecules, which subsequently dissociate
photochemically again when more sunlight is absorbed.

In the stratosphere, the hydroxyl radical is produced when a small fraction of the excited
oxygen atoms resulting from the photochemical decomposition of trace amounts of
atmospheric ozone, O3, react with gaseous water to abstract one hydrogen atom from each
H2O molecule:

O3 + hѵ ( λ< 315 nm ) → O* + O2

H2O + hѵ → HO• + H

O* + H2O → 2OH

(b) Using bond energies, explain the reaction sequence of ozone – destroying in the
stratosphere of hydrocarbons containing the halogens: Br > Cl > F. [10 marks]

Bond enthalpies are as follows:

kJ mol-1

C – Br 276
C – Cl 338

C–F 484

According to observation of bond enthalpies, Carbon-Bromine bond is the weakest hence

involves the least quantity of energy to disrupt. The deep transmission of longer wavelength
radiation forms •Br radical into the atmosphere. This initiates reaction with ozone where it is
more intense that is lower in the stratosphere. The strongest bond is C – F which requires
shorter wavelengths that are higher in energy. They exist at higher altitude where ozone is not
as concentrated. So when the formed •F radical will not have as much ozone present to
counter with. We conclude that ozone is powerfull destroyed due to the presence of bromine-
containing compounds in the stratosphere. Chlorine drops amid Br and F and its radical •Cl is
also formed where ozone concentrations can be significantly affected.

2. (a) Draw a diagram showing the sequence of chemical species appearing during a
photochemical smog event. [10 marks]

The smog in the atmosphere differs with daytime. The Figure above show the sequence of
chemical species appearing for the period of a photochemical smog occasion concurrent
increase in the atmospheric concentrations of volatile hydrocarbons and nitric oxide, NO, is
observed at 6.00am in the morning as the motor traffic takes to the street. There is a swift
maximum increase in Nitric oxide concentration and then falls while at the same time the
nitrogen dioxide concentration decreases with detection in high levels of oxidizing agent and
aldehydes
A similar pattern is observed in the evening however the atmospheric concentrations are
relatively lower. The concentrations drop to initial levels and remain constant during the
night. The smog is comprised of a blend of partially oxidized hydrocarbons, ozone and other
oxidants.

(b) Describe the chemistry for the formation of peroxyacetic nitric anhydride (PAN)
from the oxidation of acetaldehyde with hydroxyl radical (OH). [10 marks]

peroxyacetic nitric anhydride (PAN) is formed b peroxyacetyl reacting (PA) radical

CH3C(O)OO with NO2. The dominance source of CH3C(O)OO are oxidation of acetaldehyde
CH3CHO and he photolysis of acetone and methylglyxoal CHCOCHO

CH3CHO + 3 OHCH C(O)OO + H 2O

2+ M
CH3C(O)OO + NOPAN + M

M typically is by product being O2 or O2

(c) Describe the chemical reactions by which the OH radical used in (b) is terminated in
the troposphere. [6 marks]

HOO + HO →H2O2 + O2

CO + HO → CO2 + H

CH4 + HO → CH3 + H2O

NO2 + HO → HNO3

3. (a)Suppose propene (CH2 = CH-CH3) is the hydrocarbon that reacts with the
hydroxyl radical. Beginning with the addition of OH, write the set of chemical
reactions that ultimately produces an aldehyde. [10 marks]

The addition of the hydroxyl radical is believed to occur across the double bond to yield both
the aldehyde and the ketone 'hydroxylated' species as shown below in their relative yields.
1) 67% CH2 = CH – CH3 + •OH → HO – CH2 – C• H – CH3
HO – CH2 – C• H – CH3 → O = CH – CH2 – CH3 (product 1) + •H
2) 33% CH2 = CH – CH3 + •OH → •CH2 – CH – CH3
OH

•CH2 – CH – CH3 → CH3 – C – CH3 (product 2) + •H

OH O

The aldehyde (product 1) is propanal. The ketone (product 2) is acetone. A second

mechanism

has dioxygen addition to the 'hydroxylated' radical species

O2•

3) HO – CH2 – C• H – CH3 + O2 → HO – CH2 – CH – CH3 which reacts with NO to give

NO2

O2• O•

HO – CH2 – CH – CH3 + NO → HO – CH2 – CH – CH3 + NO2

Decomposition leads to:

O•
HO – CH2 – CH – CH3 → HO – C• H2 + O = CH – CH3
acetaldehyde
HO – C• H2 + O2 → H2C = O + HOO•
formaldehyde
The two aldehyde products from this second mechanism (3) are acetaldehyde and
formaldehyde

(b) Discuss the relationship between the production of nitrogen – oxide species and the
formation of ‘acid rain’ and the role played by carbon monoxide, methane, and the
hydroxyl radical.[10 marks]
NOx species are formed primarily during combustion processes and are emitted into the
atmosphere. NO is oxidized to NO2 by species such as HOO•, ROO• and O3. The production
of HNO3 is a result of the reaction of HO• with NO2 in the presence of a third body (M).

HO• + NO2 + M → HNO3 + M

As a preventive measure, catalytic converters remove NO from exhaust gases by reaction

with CO and CH4.

CH4 + 4NO → 2N2 + CO2 + 2H2O

2CO + 2NO → N2 + 2CO2

CO and CH4 can also react with HO• to produce further reactive species

CO + HO• → CO2 + H•

H• + O2 + M → HOO• + M

CH4 + HO• → CH3• + H2O

CH3• + O2 + M → CH3OO•
+M

Both of these processes enhance the reactions that form NO2 and at the same time regenerate
the HO• and RO• radicals.

4. (a)(i) Estimate the total organic carbon (TOC) concentration of wastewater whose
chemical oxygen demand (COD) is 500 mg L-1 (O2). [10 marks]

COD = O2 required for decomposition of organic matter + O2 required for stabilization of

inorganic material

Assumed COD = 500 mg L-1 (as O2), the molar equivalent of {CH2O} is

500 mg L-1 ÷ 32 g mol-1 = 15.6 mmol L-1 (of O2 = {CH2O})

TOC is then equal to:

15.6 mmol L-1 {CH2O} = 15.6 mmol L-1 (as C)

15.6 mmol L-1 x 12 g mol-1 = 188 mg L-1 (or 188 ppm)
(ii) What fraction of the total (dissolved and particulate) solids content of 720 mg L-1 is
then made up of organic material? Assume the organic fraction can be represented
as {CH2O} [10 marks]

Using an estimate of 40% carbon of organic material,

TOC = 188÷(40÷100)
= 470 ppm

TS = 720 ppm % organic = 470 ÷ 720 x 100%

= 65 %

(iii) what might the remaining solids consist? [5 marks]

The 35 percent of remains are solids comprised of a diversity of Earthly materials such as
clay
minerals, Fe(OH)3 and, or Al(OH)3. Besides that there are inorganic particulates like
phosphates, nitrates, carbonates, calcium, magnesium and sodium. If an industry slightly
discharges water, then the composition of liquefied and particulate solids would reflect the
nature of the industry.

(b) (i) Describe the chemistry of the purification of water by chlorination[10

marks] A large-scale installation like municipal water treatment plants is generated by
dissolving molecular chlorine gas, Cl2, in water. At moderate pH values and low
concentrations, the equilibrium in the reaction of chlorine with water lies far to the right
and is achieved in a few seconds: Cl2(g) + H2O(aq) → HOCl(aq) + H(g)+ Cl(g)

Thus a very dilute aqueous solution of chlorine in water contains very little aqueous Cl2 itself.
If the pH of the reaction water were allowed to become too high, the result would be the
ionization of the weak acid HOCl to the hypochlorite ion, OCl, which is less able to penetrate
bacteria on account of its electrical charge. Once chlorination is complete, the pH of the water
is adjusted upward, if necessary, by the addition of lime.

In small-scale applications of chlorination, as in swimming pools, the handling of cylinders of

Cl2 is inconvenient and dangerous. The chlorine can be produced as needed on the spot by the
electrolysis of chloride ion in salt water swimming pools. More commonly, hypochlorous
acid instead is generated from the salt calcium hypochlorite, Ca(OCl)2, or is supplied as an
aqueous solution of sodium hypochlorite, NaOCl. In water, an acid–base reaction occurs to
convert most of the OCl in these substances to HOCl:

OCl + H2O → HOCl + OH

It is desirable to adjust the equilibrium point in the OCl → HOCl reaction so as to ensure a
good supply of the superior disinfectant molecular species, HOCl. Since the equilibrium
between HOCl and OCl shifts rapidly in favor of the ion between pH values of 7 and 9, the
acidity level must be meticulously controlled
Chlorine must be constantly replenished in outdoor pools since UV-B and the short-
wavelength components of UV-A in sunshine are absorbed by and decompose both
hypochlorous acid and especially the hypochlorite ion, thereby affecting the equilibrium in
the OCl → HOCl process toward forming the chloride ion:

UV

2 ClO → Cl2 + O2

(ii) What are the advantages of chlorination? [5 marks]

• In addition to being effective, disinfection by chlorination is relatively inexpensive

• Outstanding protection against recontamination
• Simplicity of use and acceptability
• Proven reduction of diarrheal disease incidence
• Flexible sanitation method for drinking water e.g uses powder or gas

(iii) What are its disadvantages? [5 marks]

• The handling of cylinders of Cl2 is inconvenient and dangerous

• Relatively low protection against protozoa
 • Lower disinfection effectiveness in turbid waters
• Potential taste and odor objections
• Must ensure quality control of solution
• Possible lasting effects of chlorination by-products

Referees

1. Colin Baird, Michael Cann, 2012 “ Environmental Chemistry” fifth edition,

2. DAISY DUNNE 2018 Explainer: Six ideas to limit global warming with solar
geoengineering, Potsdamer Platz, Berlin, Germany. Extracted from
https://www.carbonbrief.org/explainer-sixideas-to-limit-global-warming-with-solar-
geoengineering Aerosol injection
3. https://discoveringantarctica.org.uk/oceans-atmosphere-landscape/atmosphere-
weather-andclimate/the-ozone-hole/
4. https://uk-air.defra.gov.uk/research/ozone-uv/moreinfo?view=antarctica-hole-
explained
5. James E. Girard, , 2005” Principles of environmental chemistry” first edition
6. Lenore S. Clescerl; Arnold E. Greenberg; Andrew D. Eaton. Standard Methods for
Examination of Water & Wastewater (20th Ed.).
7. Manahan, Stanley E. 2001"Front matter" Fundamentals of Environmental Chemistry
Boca Raton: CRC Press LLC,.
8. World Meteorological Organization, 2010 Scientific assessment of ozone depletion
WMO, Geneva, Models and long-term trends of tropospheric ozone,.
9. https://www.sciencedirect.com/topics/chemistry/methane