Characterizing Air Pollution:

Nature of Matter

ENE 250 LECTURE 3.2

ANALIZA P. ROLLON
DEPARTMENT OF CHEMICAL ENGINEERING
COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES
 Air Pollution: The Pollutant & Its Media

 The inherent properties of the air pollutant are influenced

and changed by the extrinsic properties of the air and other
media in which the pollutant resides in the environment.

 Thus, to characterize air pollution, the physical and

chemical properties of the pollutant and the air or the other
media must be considered together.
Basic Chemical Concepts

ENVIRONMENTAL CHEMISTRY
 Atoms & Elements

Atoms
 Nucleus
 protons (+ charge)
 neutrons (0 charge): determines
mass of an atom
 Electrons
 - charge

 Number of protons = number of electrons

 Atomic number  number of protons
 Atomic mass  number of neutrons
 Atoms contain equal numbers of electrons and protons.
Hence atoms has no net charge, i.e. electrically neutral.
 Atoms & Elements

 Elements – collection of atoms

that contain the same number of
both protons and electrons
 Known 109 elemnts; 92 Occur
naturally on earth; 17 made in
nuclear reactions

 Isotopes – variant of atoms (vary

in the number of neutrons)
 Electronic Structure

Electron Structure Model:

 Electrons reside in concentric shells about the nucleus.
Each shell consists of a fixed number of orbits in which
electrons can be found.
 Electronic Structure

Electron Structure Model:

 The shell closest to the
nucleus is of lowest energy
(has maximum of 2
electrons), while next shell
has higher energy and the
orbit farther away from the
nucleus has an even higher
energy, and so on.
 The shell closest to the
nucleus is filled first (and is
of lowest energy).
 Electron Orbital

 Configuration of Electron Orbital

 Atoms & Elements

 Processes involved in chemical reactions underlie virtually

all environmental phenomena!

 Atoms enter into chemical reactions through their electron

clouds. Hence, the electronic structure of atoms is
important in predicting how atoms react.
 Interactions Between Atoms and Valence
Electrons

Valence electrons
 The electron containing shell that is furthest away from the nucleus of
any given atom is called its valence shell and the electrons it contains
are known as valence electrons.

 When atoms interact to make

compounds, they do so by either
sharing or exchanging valence
electrons
 Valence Electrons & Valency

 Many ions have 8 electrons in their outermost shell (called

complete octets).
 Complete octets may be achieved on ion formation from
neutral atoms either by the loss of all valence electrons or
by the gain of sufficient electrons to fill the valence shell.
 The number of valence electrons of an atom determines its
valency (the combining power of an atom).
 Molecules & Covalent Compounds

 Molecules are groups of atoms bonded together by shared

electrons. Bond of this type is called covalent bonds.
Compounds that contain atoms bonded together in this way
are called covalent compounds.
Shared electrons spend most of
their time in the region of space
between the bonded atoms.

It is the neutral attractions between

the shared electron and the nuclei
that binds the atoms together.
 Molecules & Covalent Compounds

Bonds can be single (1 electron pair shared),

double (2 electron pairs shared), or triple
(3 electron pairs shared).
Valence Electrons & Structure of a Molecule

 The valence electron structure determines the shape of a molecule.

Lone electron pairs repel

other electron pairs.
Valence Electrons & Structure of a Molecule

 Electrons repel each

other
 Electron pairs (shared
or lone) stay as far
away as possible from
other electron pairs
 Lone pairs tend to
‘push’ other shared
pairs away
Valence, Charge & Structure

 Number valence
electrons
determine the
charge of ions:
 (-) if electrons are
gained to form an
octet;
 (+) if electrons are
given away to
form an octet
 Ions & Ionic Compound

 In interacting with other atoms, atoms form an octet of

electron in outermost orbital.  sharing electron

Electron pair tends to stay close to the

more electronegative atom:

Example: Chlorine atom is more

electronegative than sodium atom.
 electron goes to Cl (instead of sharing
with Na atom).
 Ions & Ionic Compound

 Atoms become ions when

they either lose or gain one
or more electrons.

  anions: negatively charge,

formed by atoms that contain
more electrons than protons

  cations: positively charge,

formed by atoms that contain
more protons than electrons
 Ions & Ionic Compound

 Ions of opposite charge attract one another strongly. Ions of like charge
repel one another strongly.
 Anions and cations are found together and in such proportions that the
overall material has no net charge.

 strong attraction
between an anion and a
cation  ionic bond.
 an ionic bond is a
chemical bond.
 Ions & Ionic Compound

 Group of atoms or ions bonded together by chemical bonds

are called compounds.
 Ionic compounds: ionic bonds involved
 Molecules & Covalent Compounds

Molecular Ions (Polyatomic ions)

 Molecular ions are molecules that carry a net overall charge.
 Structure of Ionic Compounds

Structure and properties of ionic compounds

 Structure: maximize interaction between attracting pairs
(opposite charge) and minimize those between repelling
pairs (similar charge)  alternate cation and anion

 Ionic bond is very

strong  pure ionic
compounds are hard
solids with high
melting points.
 Properties of Ionic Compound

 Structure and properties of ionic compounds

The ability of water to dissolve ionic compounds is a vital

part of many environmental phenomena, including
chemical weathering and many nutrient cycles.

Why should water be such a good solvent for so many ionic

compounds?
 Structure of Water Molecule

Structure of water
 Water (H2O): 2 Hydrogen atoms and 1 Oxygen atom
 Valence shell of an oxygen atom: 6 electrons.
 2 atoms, each shared with H atom (2 electrons of 2 hydrogen atoms
(1 electron each)
 4 electrons form 2 lone pairs (i.e. unshared)
 Hence, completing the octet of electrons in its valence shell.
 Structure of Water Molecule

Structure of water

 The unshared electron pairs are situated

around the oxygen nucleus such that
these pairs are as far away as possible
from each other. tetrahedral (when 4
electron pairs are also considered).

 The oxygen atom (more electronegative)

draws the electrons closer so that the O
part has a partial negative charge, while
the 2 H part of the water molecule have
partial positive charge  uneven
distribution of charge  polar
molecule.
 Dissolution of Ionic Compounds in Water

 Due to uneven distribution of charges, cations will be attracted to the O

atoms of water while anions will be attracted to the H.
 Thus, water can dissolve ionic compounds by breaking up the ionic lattice
and producing ions in solution surrounded by water molecule.

In ionic solutions, total

positive charge = total
negative charge.
 Dissolution of Ionic Compounds in Water

 Acid rain can cause aluminum ions to dissolve in water and

form insoluble aluminum hydroxides, which forms at
surface of fish gills, often resulting in death of fish.
 Polar Molecules & Electronegativity

Polar Molecules
 In most covalent bonds, electrons are
not evenly shared between the
bonded atoms. One has greater
attraction for the bonding electrons
(i.e. more electronegative).
 In order of decreasing
electronegativity: F, O, N, Cl, Br
 Molecules that involve covalent
bonds of atoms of these
electronegative elements will be
significantly polar  will have
uneven distribution of charge.
 Polar Molecules & Electronegativity

Polar Molecules
 The polar nature of water has environmental consequences.
 The environmental properties of many other molecules are affected
by the degree of their polarity.

 Example: CO2,
chlorofuorocarbons (CFCs) are
polar molecules in the
atmosphere.
 It is the polar nature of their
bonds that allows them to
absorb infrared radiation 
causing them to act as
greenhouse gases.
 Dative Bonds & Complexes

Dative Bonds
 Single covalent bonds may also be formed in which only one of the two
atoms involved provides both the bonding electrons. Such bonds are
called dative bonds or coordinate bonds. Molecules that contain
one or more of these bonds are called complexes.
 Dative Bonds & Complexes

Dative Bonds
 Ions or molecules that have lone pairs are called Lewis
bases or ligands (chelating agents).
 The complexes they form are called chelates.
 Dative Bonds & Complexes

Dative Bonds
 Intermolecular Bonds

 Bonds Within and Between Molecules

 Intramolecular bonds - bonds within molecule

 Example:
 Bonds within molecules in covalent compounds

 Intermolecular bonds - bonds between molecules (generally

weak)
 Examples:
 Bonds between molecules in covalent compounds;

 Ionic bonds between anionic and cationic molecules  strong

bonds
 Intermolecular Bonds

 Compounds that contain small discrete molecules (either

liquids or gases at normal temperature and pressure):

Weak intermolecular attraction  easy to overcome

 low boiling point  low melting point (under normal
conditions): Ex: CO2, H2O, CH4
 Intermolecular Bonds

 Compounds that are made up of giant molecules that

extend in all directions (three-dimensional network
macromolecular solids):

 Crushing, melting, dissolving involves breaking of strong bonds 

hard  have high melting point
 soluble in water to a very limited extent unless they react with
water.
 Example: SiO2 (silica)
 Intermolecular Bonds: Hydrogen Bond

 An example of covalent bonds is the hydrogen bond –

when H atoms are directly bonded to highly
electronegative atoms in molecules that contain atoms
with lone pairs of electrons. Example: H2O.
 Valency & Periodic Table of the Elements

Valency – the combining power of an atom.

 The more the number of valence electrons, the more the
number of “hands” an atom can use to hold the “hands” of
other atoms.

 In many compounds (covalent or ionic), the atoms or ions have

complete octet (set of eight electrons).
 To achieve these octets, the atoms of an element must, in general,
either gain, lose, or share electrons.
 The number of electrons that must be gained, lost, or shared is the
same as the valency of the atom.
 Valency & Periodic Table of the Elements

 The number of valence electrons of an atom (N) is related

to its valency (V).
 As a rule,
 V = N (example: Na, K, Mg, Ca)

 Or V = 8 – N (example: Cl)
 Valency & Periodic Table of the Elements

 In Periodic Table of the Elements, elements with similar

properties (example: valency) are grouped together.

 Vertical columns: Groups – similar valency

 Horizontal rows:
 Group 1: V = 1
 Group 2: V = 2
 Group 13 – 18: V = X – 10 or V = 8 – (X-10) where X = group
number of the element concerned
 Group 4-11: Variable valency
Valency & Periodic Table of the Elements
Properties of Elements: Trends in the Periodic Table

Metallic character:

Most non-metallic
Increasing non-metallic

Increasing metallic

Most metallic
Properties of Elements: Trends in the Periodic Table

Atomic size: function of the principal quantum number of the

valence electrons and the effective nuclear charge.

Smallest atom
Decreasing Size

Increasing size

Largest atom
 Properties of Elements: Trends in the Periodic Table

Ionization energy: The minimum amount of energy required to remove the

most loosely held electron of an isolated gaseous atom or ion.
Electronegativity: A measure of the relative tendency of an atom to attract
electrons to itself when chemically combined with another atom.

Most electronegative
Increasing ionization energy Greatest ionization
Increasing electronegativity energy

Decreasing ionization energy

Decreasing electronegativity

Least electronegative
Smallest ionization
energy
Properties of Elements: Trends in the Periodic Table

Structure of the oxides of the elements

Acidity of the oxides of the elements
Ion formation

molecular covalent
acidic oxides
anion formers

ionic
basic oxides
cation formers
 Oxidation State

 Oxidation state – the actual charge on an atom or a

notional charge.
 The oxidation state of an element in an elemental form (i.e.
not in compound) is zero.
 For monoatomic ion (ex. Na+, Cl-, Mg2+), the oxidation state
is the actual charge on the ion.
 Oxidation State

 In compounds (ex. H2O) or molecular ions (ex. SO42-), the oxidation

state of the constituent elements are notional charges based on the
charge distribution that would occur if the available valence electrons
were placed on the most electronegative atom present.

 The sum of the oxidation state = the overall charge of the compound
(zero) or ion.
 Compound, Mixtures, Chemical Species

 Compound –
collection of atoms of
different elements that
are bonded together by
chemical bonds.
 Mixture – collection
of different compounds
and/or elements that
are not chemically
bonded together.
 Compound, Mixtures, Chemical Species

 Compound – collection of atoms of different elements that are

bonded together by chemical bonds.
 Mixture – collection of different compounds and/or elements that
are not chemically bonded together.
 Compound, Mixtures, Chemical Species

 Chemical species (‘species’) – an atom, ion, or molecule with

identifiable chemical properties.
 Chemical speciation – collection of chemical species in which an
element is found.
 Example: S8, SO2, SO3, SO32-, SO42-, S2-, H2S

 Chemical formula: Shows the ratio at which atoms combine.

 Molecular formula – shows actual number of atoms in a molecule

 Emperical formula – shows the simplest ratio at which atoms in a

molecule combine (ex. CH2O for carbohydrates).
 Chemical Reactions

 Chemical Equations – Elemental symbols and/or chemical formula

that shows the proportions in which chemicals react.
 All chemical equations should be balanced, i.e. there are as many
atoms of a kind in the reactant as there are atoms of the same kind in
the products.
 Physical state of reactants and products are frequently indicated in a
chemical equation.
Example: CH4 (g) + 2O2 (g)  CO2 (g) + 2 H2O (g)
s – solid, l – liquid, g – gas,
aq – dissolved in water as solution
 Properties of Substances
Related to Chemical Reactions
 Dissociation & Acid-Base
Reactions

DISSOCIATION CONSTANTS OF ACIDS AND BASES,

FACTORS AFFECTING DISSOCIATION OF ACIDS & BASE,
ACID RAIN
 Acid-Base Dissociation

Acid Base Reactions

Bronsted-Lowry theory: Acid – donor of H+; Base – acceptor of H+

HA + B  A- + HB+
acid base base acid

HA + B  A- + HB+
acid base base acid

 A- is the conjugate base of acid HA.

 HB+ is the conjugate acid of base B.
 HA + H2O  A− + H3O+.
 Acid-Base Dissociation

 When an acid donates H, it becomes a conjugate base.

 The conjugate base of a weak acid is a strong base.

 When a base accepts H, it becomes a conjugate acid.

 The conjugate acid of a weak base is a strong acid.
 Acid-Base Dissociation

Acid Rain
HNO3, a component in acid rain
HNO2, a minor component of acid rain (much weaker than HNO3)
H2SO4

HNO3 + H2O ↔ NO3- + H3O+

Strong acid weak base
(very good proton donor) (very poor proton acceptor)

 Forward reaction predominates over reverse reaction.

HNO2 + H2O ↔ NO2- + H3O+

H2SO4 + H2O  SO42- + 2 H3O+

In the above reactions, water act as a base

Acid-Base Dissociation
 Acid-Base Dissociation

NH3 + H2O ↔ NH4+ + OH-

base acid acid base
(water acts as an acid!)

NH4+ - conjugate acid of NH3

OH- - conjugate base of H2O

NH4+ as acid is stronger than H2O and OH- as a base is stronger than NH3.
Thus, reverse reaction predominate.
In NH3-NH4+ system, most N is present as NH4+.

Chemical species that are capable of acting as either an acid or base

depending on the nature of the other reactants are called amphoteric.
Acid-Base Dissociation
 Acid-Base Dissociation Constants

 Acid dissociation constant, Ka, (also known as acidity constant, or acid-

ionization constant) is a quantitative measure of the strength of an acid in
solution.
 It is the equilibrium constant for a chemical reaction known as dissociation in
the context of acid-base reactions.

HA + H2O  A− + H3O+.
 Acid-Base Dissociation Constants

Polyprotic acids
 acids that can lose more than one proton.
 The constant for dissociation of the first proton may be denoted as Ka1 and the
constants for dissociation of successive protons as Ka2, etc.
 Example: Phosphoric acid, H3PO4

equilibrium pKa value

H3PO4  H2PO4− + H+ pKa1 = 2.15
H2PO4−  HPO42− + H+ pKa2 = 7.20
HPO42−  PO43− + H+ pKa3 = 12.37
Acid-Base Dissociation Constants
 Acid-Base Dissociation Constants

pKa values of acids in different solvents

pKa values at 25 °C for acetonitrile (ACN) and dimethyl sulfoxide (DMSO)

HA A− + H+ ACN DMSO water
p-Toluenesulfonic acid 8.5 0.9 strong
2,4-Dinitrophenol 16.66 5.1 3.9
Benzoic acid 21.51 11.1 4.2
Acetic acid 23.51 12.6 4.756
Phenol 29.14 18.0 9.99
BH+ B + H+ ACN DMSO water
Pyrrolidine 19.56 10.8 11.4
Triethylamine 18.82 9.0 10.72
Proton sponge 18.62 7.5 12.1
Pyridine 12.53 3.4 5.2
Aniline 10.62 3.6 4.6
 Acid-Base Dissociation Constants

DMSO is widely used as an alternative to water because it has a lower

dielectric constant than water, and is less polar and so dissolves non-
polar, hydrophobic substances more easily.
It has a measurable pKa range of about 1 to 30.
Acetonitrile is less basic than DMSO, and, so, in general, acids are weaker
and bases are stronger in this solvent.

Solvent Donor number Dielectric constant

Acetonitrile 14 37
Dimethylsulfoxide 30 47
Water 18 78
 Acid-Base Dissociation Constants

Conjugate acids of bases

Compound Equilibrium pKa ΔH /kJ·mol−1 TΔS /kJ·mol−1

B = Ammonia HB+  B + H+ 9.245 51.95 0.8205
B = Methylamine HB+  B + H+ 10.645 55.34 5.422
B = Triethylamine HB+  B + H+ 10.72 43.13 18.06
 Acid-Base Dissociation Constants

Equilibrium (all in aqueous

Acid or Ion Ka pKa pKb Kb
solution)
Perchloric HClO4  H+1 + ClO4-1 very large ------- ------- -------
Hydroiodic HI  H+1 + I-1 very large ------- ------- -------
Hydrobromic HBr  H+1 + Br-1 very large ------- ------- -------
Hydrochloric HCl  H+1 + Cl-1 very large ------- ------- -------
Sulphuric H2SO4  H+1 + HSO4-1 very large ------- ------- -------
Nitric HNO3  H+1 + NO3-1 40 1.6 ------- -------
Chromic(VI) H2CrO4  H+1 + HCrO4-1 10 1.00 14.00 1.0 x 10-14
Trichloroethane CCl3CO2H  H+1 + CCl3CO2-1 2.3 x 10-1 0.64 13.36 4.37 x 10-14
Iodic(V) HIO3  H+1 + IO3-1 1.7 x 10-2 0.78 13.22 6.03 x 10-14
 Acid-Base Dissociation Constants

Acid or Ion Equilibrium (all in aqueous solution) Ka pKa pKb Kb

Oxalic HO2CCO2H  H+1 + HOOCCOO-1 5.4 x 10-2 1.27 12.73 1.86 x 10-13
Dichloroethanoic CHCl2COOH  H+1 + CHCl2COO-1 5.0 x 10-2 1.30 12.70 2.00 x 10-13
Sulphurous H2SO3  H+1 + HSO3-1 1.5 x 10-2 1.82 12.18 6.61 x 10-13
Phosphoric H3PO4  H+1 + H2PO4-1 1.6 x 10-2 1.80 12.20 6.31 x 10-13
Chloric(III) HClO2  H+1 + ClO2-1 1.0 x 10-2 2.00 12.00 1.00 x 10-12
Hydrogen sulphate HSO4-1  H+1 + SO42- 1.0 x 10-2 2.00 12.00 1.00 x 10-12
Phosphoric(V) H3PO4  H+1 + H2PO4-1 7.9 x 10-2 2.10 11.90 1.26 x 10-12
Iron(III) ion Fe(H2O)63+  H+1 + Fe(H2O)5(OH)2+ 6.0 x 10-3 2.22 11.78 1.66 x 10-12
 Acid-Base Dissociation Constants

Acid or Ion Equilibrium (all in aqueous solution) Ka pKa pKb Kb

Aluminum ion Al(H2O)63+  H+1 + Al(H2O)5(OH)2+ 1.0 x 10-5 5.00 9.00 1.0 x 10-9
Dihydrogen phosphite H2PO3-1  H+1 + HPO32- 6.3 x 10-7 6.21 7.79 1.62 x 10-8
Carbonic H2O + CO2  H+1 + HCO3-1 4.5 x 10-7 6.35 7.65 2.24 x 10-8
Hydrogen chromate HCrO4-1  H+1 + CrO42- 3.2 x 10-7 6.50 7.50 3.16 x 10-8
Hydrogen sulphide H2S  H+1 + HS-1 8.9 x 10-8 7.05 6.95 1.12 x 10-7
Hydrogen sulphite HSO3-1  H+1 + SO32- 6.2 x 10-8 7.21 6.79 2.0 x 10-7
Dihydrogen phosphate H2PO4-1  H+1 + HPO42- 6.2 x 10-8 7.21 6.79 2.0 x 10-7
Hypochlorous HClO  H+1 + ClO-1 3.7 x 10-8 7.43 6.57 3.0 x 10-7
Telluric H5TeO6  H+1 + H4TeO6-1 2.0 x 10-8 7.70 6.30 5.02 x 10-7
Hypobromous HBrO  H+1 + BrO-1 2.1 x 10-9 8.68 5.32 4.8 x 10-6
Boric H3BO3  H+1 + H2BO3-1 5.8 x 10-10 9.24 4.76 1.74 x 10-5
Ammonium ion NH4+1  H+1 + NH3 5.6 x 10-10 9.25 4.75 1.78 x 10-5
 Acid-Base Dissociation Constants

Acid or Ion Equilibrium (all in aqueous solution) Ka pKa pKb Kb

Hydrogen carbonate HCO3-1  H+1 + CO32- 4.8 x 10-11 10.32 3.68 2.10 x 10-4
Hydrogen telluride H4TeO6-1  H+1 + H3TeO62- 1.0 x 10-11 11.00 3.00 1.0 x 10-3
Hydrogen peroxide H2O2  H+1 + HO2-1 2.4 x 10-12 11.62 2.38 4.17 x 10-3
Hydrogen silicate HSiO3-1  H+1 + SiO32- 1.3 x 10-12 11.89 2.11 7.76 x 10-3
Hydrogen phosphate HPO4-2  H+1 + PO43- 4.4 x 10-13 12.36 1.64 2.29 x 10-2
Hydrogen sulphide HS-1  H+1 + S2- 1.2 x 10-13 12.92 1.08 8.3 x 10-2
Water H2O  H+1 + OH-1 1.0 x 10-14 14.00 0.00 1.0
 Acid-Base Dissociation

 Acid rain formation

 Acid-Base Dissociation & pH

 Acids Rain: pH scale

 Acid-Base Reaction: Neutralization

A reaction between a strong acid and a strong base resulting

in ionic compound (called salt) is a neutralization reaction.

Example:
HCl + NaOH  NaCl + H2O
Dissolution & Precipitation

DISSOLUTION,
SOLUBILITY PRODUCT CONSTANT (KSP),
SOLUBILITY OF METAL SALTS,
FACTORS AFFECTING SOLUBILITY,
COMPLEX FORMATION,
PRECIPITATION
 Dissolution of Solids in a Solvent

 Solids  ions in aqueous solution

 Solubility: maximum amount that can be dissolved in the

solvent
 Based on dissociation constant (Ksp)
Solubility Product Constant

Ksp values for different metal salts

 Solubility of Various Metal Salts

http://web.deu.edu.tr/atiksu/ana52/ychem04.gif

 For most metals: solubility of the carbonate salts of metal > hydroxide > sulfide
Solubility of Ionic Compounds
 Solubility: Effect of Temperature

 Solubility values
The solubility of FeCl3,
Fe(OH)3, by what ions
are present in the
solution.

Common ions (Cl-)

decreases solubility of
the chloride salts of
Fe(III)

Common ions (OH-)

decreases solubility of
Fe(OH)3. Thus, low pH
increases solubility of
Fe(OH)3.

At pH > 8, solubility of
Fe(III) increases as pH
increases (i.e., OH-
increases)? Possible
complex formation at Solubility: Effect of pH
higher pH levels http://origin-ars.els-cdn.com/content/image/
Solubility: Effect of pH
 Solubility: Effect of pH

 Effect of pH
 Solubility: Effect of Complexation

 NH3 increases solubility of AgCl because NH3 forms

complex with NH3.
Complexation

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Complexation

Complex
formation
(complexation)
is a reaction that
results in dative
bonds.

Complexation
 Solubility: Common Ion Effect

Solubility in water without Cl- ions Solubility in water with Cl- ions

 The solubility (s) is smaller when common ion Cl- is present.

 Precipitation

Precipitation Reactions
Reactions that occur in solution in which one or more of the
products are insoluble in the solvent. Most environmentally
important precipitation reactions involve water as solvent.

Example: Impact of acid rain on fish in rivers and lakes.

Al3+(aq) + 3 OH-(aq)  Al(OH)3 (s)

Acid rain increases the solubility of aluminum in water, resulting in a

high concentration of Al3+ in water. This ion reacts with hydroxide ions,
produced at the gills of fish, resulting in the formation of gelatinous
precipitate, which builds up on the gills of fish resulting in the death of
fish.
 Precipitation
Precipitation Reactions
Reactions that occur in solution in which one
or more of the products are insoluble in the
solvent. Most environmentally important
precipitation reactions involve water as
solvent.
The absorption of
CO2 from air to water
may result in release
of H+ and HCO3- in
water and soil.

This has impacts on

pH and alkalinity of
water or soil
environment.
Minerals become
more soluble as pH
decreases.  metal
leaching
 Precipitation of
carbonates of leached Dissolution & Precipitation in
metals
Environment
Reduction-Oxidation

OXIDATION-REDUCTION REACTIONS,
REDUCTION POTENTIAL,
COMBUSTION REACTIONS,
FORMATION OF TOXIC COMPOUNDS
 Reduction-Oxidation Reactions

Reduction-Oxidation (Redox) Reactions

Reactions that involve the complete transfer of electrons from a

chemical species to another.

Reduction – gain of electrons

Oxidation – loss of electrons

Reducing agent (reductant) – one that readily gives up electrons

Oxidizing agent (oxidant) – one that readily accepts electrons
 Reduction-Oxidation Reactions

Redox Reaction in environment: Aerobic photosynthesis

2 H2O + CO2 + sunlight  CH2O + H2O + O2

Half reactions:
Reduction (oxidation state of C: +4  0):
CO2 + 4 e- + 4 H+  CH2O + H2O
Oxidation (oxidation state of O: -2  0):
2 H2O + sunlight  4 e- + O2 + 4 H+

Reduction and oxidation cannot happen independently in the environment.

This reaction – source of about 1 x 1017 g of organic matter per year

formation of virtually all O2 in the atmosphere
major sink of CO2 (a major greenhouse gas)
 Formation of Air Toxics
 1,4-Dioxin (also referred as dioxin or p-dioxin) is
a heterocyclic, organic, antiaromatic compound with the chemical
formula C4H4O2.
 There is anisomeric form of 1,4-dioxin, 1,2-dioxin (or o-dioxin).

 1,2-Dioxin is very unstable due to its peroxide-like characteristics.

Formation of Air Toxics
 Formation of Air Toxics

 Polychlorinated dibenzodioxins (PCDDs)

 Because of their extreme importance as environmental pollutants,

current scientific literature uses the name dioxins commonly for
simplification to denote the chlorinated derivatives of dibenzo-1,4-
dioxin, more precisely the polychlorinated dibenzodioxins (PCDDs),
among which 2,3,7,8-tetrachlorodibenzodioxin (TCDD), a
tetrachlorinated derivative, is the best known.
 Sources of Dioxins

 PCDDs are formed

 through combustion,
 chlorine bleaching and
 manufacturing processes.

 The combination of heat and chlorine creates dioxin.

 Because chlorine is often a part of the Earth's environment, natural

ecological activity such as volcanic activity and forest fires can lead to the
formation of PCDDs.
 Nevertheless, PCDDs are mostly produced by human activity.

 Polychlorinated dibenzofurans are a related class compounds to PCDDs

which are often included within the general term “dioxins”.
 Effects of Dioxins

 The polychlorinated dibenzodioxins, which can also be

classified in the family of halogenated organic compounds,
have been shown to bioaccumulate in humans
and wildlife due to their lipophilic properties, and are
known teratogens, mutagens, and carcinogens.
 Dioxin Exposure

 Famous PCDD exposure cases: Agent Orange produced

by Monsanto sprayed over vegetation during the Vietnam
war, the Seveso disaster, and poisoning.
Example: Formation of Air Toxics from Combustion Reactions
Formation of chlorinated dioxins and furans
Hydrocarbons in Ambient Air
 Hydrolysis Reactions

Hydrolysis Reactions

Hydrolysis reactions are reactions that involve water as one of

the reactants.

Acid hydrolysis reactions – involve acid solutions.

Base hydrolysis reactions – involve base solutions.
 Chemical Reactions: Free Radical

Free Radical Reactions

Example:
O3 + light  O2* + O* (a photochemical reaction)
O* + H2O  2 OH

OH  (hydroxyl radical) is a free radical.

Most free radicals are highly reactive.  generally found at
low concentrations in the environment.
Organic Chemistry

PHASE EQUILIBRIUM
Structures & Properties of Organic Compounds
Hydrocarbons
Halogen-Containing Compounds
Oxygen-Containing Compound
Carboxylic Acid Derivatives
Nitrogen-Containing Compounds
 Isomers

 Isomers: compounds of the same emperical formula but

different molecular structure
Chlorobenzenes
PCB Inventory
Hydrocarbons in Water
Volatility of Organic Compounds: Vapor Pressure

 In general, vapor pressure increases

with temperature.
 Relationship between vapor
pressure and temperature:
Antoine’s Equation

 At a given temperature, more

volatile substances have higher
vapor pressure.
Questions ??