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HEC4842 ENVIRONMENTAL ENGINEERING

LECTURE 2:
ENVIRONMENTAL
CHEMISTRY

2.1: Units of Measurement


Environmental quantities are measured and reported in both U.S.
Customary System (USCS) and the International System of Units (SI).
It is common to encounter both extremely large quantities (energy use of
a country measured in terawatts [TW]) and small ones (concentration of
toxic substance measured in parts per billion [ppb].

Common Prefixes

Units of Measurement - Liquids


Concentrations of substances dissolved in water expressed in terms of
1. mass or number per unit volume of mixture
Mass milligrams (mg), micrograms (g)
Number moles (mol)
(one mole of any substance has Avogadros number of molecules
in it [6.02 1023 molecules/mol] and has a mass equal to its
molecular weight)
Volume Litre (L) or cubic meter (m)
2. mass of substance per mass of mixture
- parts per million (ppm) [1 drop of ribena in 56.87L water]
- parts per billion (ppb) [1 drop of saliva in 70m swimming pool]
(practically 1L mixture has a mass of 1,000g)
1 mg/L = 1 g/m = 1ppm (by weight)
1 g/L = 1 mg/m = 1 ppb (by weight)
mg/L = ppm specific gravity (in cases where conc. so high it affect SG)

Example 2.1 Fluoridation of Water


The fluoride concentration in drinking water may be increased to help
prevent tooth decay by adding sodium fluoride; however, if too much
fluoride is added, it can cause discolouring (mofttling) of the teeth. The
optimum dose of fluoride in drinking water is about 0.053mmol
(millimole/liter). If sodium fluoride (NaF) is purchased in 25kg bags, how
many m of drinking water would a bag treat? (Assume there is no
fluoride in the water)
How many people would it cater for?
Malaysia water usage: 225 litres per capita per day
(Ans: 11,198m, 49,768 person per day)

Common Dimensions
Density,

Concentration,

(kg/m)

Mass flow rate, QM (kg/s) = Density,


(m/s)
Retention time, t =

,
.

(kg/m, mg/L)

(kg/m) Volume flow rate, QV

,

,

Retention time: time an average particle of the fluid spends in the container
through which the fluid flows.

2.2: Unifying Theories


Law of conservation of mass:
When chemical reactions take place, matter
is neither created nor destroyed (except in
nuclear reactions, mass can be converted to
energy)
Law of conservation of energy:
Energy cannot be created or destroyed
(with the birth of the nuclear age)
Law of conservation of mass and energy :
Total amount of energy and matter is constant.
Exchange between mass and energy is not an issues in environmental
application. Thus, there are generally two separate balances for mass and
energy.

2.3: Stoichiometry
A chemical equation provides both qualitative (which chemicals) and
quantitative (how much of each compound) information.
Stoichiometry balancing of chemical equations so that the same
number of each kind of atom appears on each side of the equation and
calculation to determine amounts of each compound involve.
1st step: Balance the equation
CH4 + O2 CO2 + H2O (combustion of methane)
CH4 + 2 O2 CO2 + 2 H2O
2nd step: Calculate the mass of each substance
Atomic weight mass of the atom measured in atomic mass units (amu)
Atomic number number of protons in the nucleus
Molecular weight sum of atomic weights of all the constituent atoms
Moles =

1 mole contain 6.021023 molecules (Avogadros number)

Atomic weight of C = 12, H = 1, O = 16


CH4 = 12 + 4 1 = 16 g/mol
O2 = 2 16 = 32 g/mol
CO2 = 12 + 2 16 = 44 g/mol
H2O= 2 1 + 16 = 18 g/mol
CH4

2 O2

CO2

2 H2O

1 molecule of methane + 2 molecules of oxygen 1 molecule of carbon dioxide + 2 molecules of water


1 mol of methane

16 g of methane

+ 64 g of oxygen

Conservation of mass:

2 mol of oxygen

(16g + 64g =) 80g

1 mol of carbon dioxide

2 mol of water

44g of carbon dioxide

36g of water

(44g + 36g =) 80g

2.4: Water Chemistry


INTRODUCTION
Water chemistry is important in the design of water and wastewater
processes and in the remediation of environmental pollution.
Alkalinity chemistry natural alkalinity in the environment maintains the
waters of the world at a near neutral pH. It prevents many contaminants
from dissolving into the water. This balance protect water sources, used
in treatment of water to render it potable or more aesthetically acceptable
for consumption or to treat waste streams for discharge.
Water treatment - add chemicals to react with impurities to remove them
(precipitation) or render them harmless (oxidation, redox reaction). We
must know chemical doses, chemical type, reaction kinetics (rate of
reaction [to determine reactor size]), phase transfer from water to air (for
volatile contaminants in water)

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Basic Water Properties and Units


Physical Properties of Water:
Density measure of the concentration of matter
1. Mass density, - mass per unit volume (kg/m3). Dissolved impurities
change the density in direct proportion to their concentration and their
own density. Common to ignore for low concentration impurities but
not high concentration (thickened sludge or commercial liquid
chemicals)
2. Specific weight, - weight (force) per unit volume (kN/m).

= g
3. Specific gravity, S = /o = /o
the subscript zero denotes the density of water at 3.98C, 1,000 kg/m3, and the
specific weight of water, 9.81 kN/m.
The density of water at normal temperature is taken as 1,000 kg/m (1 kg/L) with
a specific gravity = 1.00.

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Viscosity - A measure of the friction


1. Dynamic viscosity, or absolute viscosity, , - mass per unit length per
time, (Pa.s). Represents a measure of a fluids internal resistance to
flow. Important for analysis of liquid flow, (designing pumps)
2. Kinematic viscosity, , = / (m/s). Used to evaluate the friction
coefficient for flow in pipes.
States of Solution Impurities
substances can exist in water in three classificationssuspended,
colloidal, or dissolved.

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Dissolved substance - truly in the solution (there is only one phase),


homogeneously dispersed in the liquid. Involve change of phase to
remove/separate the substance (distillation, precipitation, adsorption,
extraction, or passage through ionic pore-sized membranes)
Suspended solids are large enough to settle out of solution or be
removed by filtration. There are two phases present (liquid and
suspended-particle solid phase). Removed from water by physical
methods such as sedimentation, filtration, and centrifugation.
Colloidal particles - size range between dissolved substances and
suspended particles. They are in a solid state and can be removed from
the liquid by physical means (very high-force centrifugation or filtration
through membranes with very small pore spaces).
Tyndall effect - when light passes through a
liquid containing colloidal particles, the light
is reflected by the particles.
Degree to which a colloidal suspension
reflects light at a 90 angle to the entrance
beam is measured by turbidity.

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Particle counting - counts the number of particles in a water sample and


reports the results by particle size, generally from 1 to 30mm. A technique
used to evaluate water quality.

Particle distribution changes through treatment.

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Chemical Units
Molarity is the number of moles in a liter of solution. A 1-molar (1 M)
solution has 1 mole of substance per liter of solution.
mg/L = Molarity Molecular weight 10
= (moles/L)(g/mole)(10mg/g)
Equivalent weight (EW) - molecular weight divided by the number (n) of
electrons transferred in redox reactions or the number of protons (H+)
transferred in acid/base reactions.
In a precipitation reaction, n is the valence of the element. For
compounds, n is equal to the number of hydrogen ions that would be
required to replace the cation.
Eg. 2 H+ are needed to replace the calcium in CaCO3, therefore, n = 2.
Normality (N) is the number of equivalent weights per liter of solution.
N = Mn

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Example 2.2
Commercial sulfuric acid, H2SO4, is often purchased as a 93 weight
percent solution. Find the mg/L of H2SO4 and the molarity and normality
of the solution. Sulfuric acid has a specific gravity of 1.839.
Solution. Since 1 L of water weighs 1,000 g, 1 L of 100% H2SO4 weighs
1,000(1.839) = 1,839 g
(0.93)(1,839 g) = 1,710 g of H2SO4 , or 1.7106 mg/L of H2SO4 in a 93%
solution.
The molecular weight of H2SO4 = 2 (1) + 32 + 4 (16) = 98 g/mole
mg/L = Molarity Molecular weight 10
Molarity = 1.7106 mg/L of H2SO4 / 98 g/mole 10 mg/g
= 17.45 mole/L or 17.45 M
H2SO4 can give up 2 H+ and therefore n = 2 equivalents/mole:
N = Mn
N = 17.45 mole/L (2 equiv/mole) = 34.9 equiv/L

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Chemical Reactions
There are four principal types of reactions of importance in environmental
engineering: precipitation, acid/base, ion-association, and
oxidation/reduction.
Most chemical reactions are to some extent reversible. They reach
equilibrium when the rates of reaction are the same for both directions
(products are being formed on the right at the same rate as they are
being formed on the left)
aA + bB cC + dD
a, b, c, d = number of molecules or ions in a balanced equation
At equilibrium,

[ ] = concentrations of substances at equilibrium in moles per liter


(molarity) Do not use mg/L!
K = equilibrium constant (ratio of products to reactants)

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Precipitation Reactions
phase change reaction of dissolved ions to solid state
Ca2+

+ CO

precipitation

dissolution

CaCO3(s)

Often, out of convenience, we talk about compounds when in reality a


compound (CaCO3) does not exist in water. In fact the water consists of
the unassociated ions: Ca2+ and CO .
All complexes are soluble in water to a certain extent. Likewise, all
complexes are limited by how much can be dissolved in water.
Solubility reaction: AaBb(s) aAb+ + bBaExample:

Ca3(PO4)2(s) 3Ca2+ + 2PO


solid

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Interestingly, the product of the activity of the ions is always a constant for
a given compound at a given temperature. That constant is called the
solubility constant, Ks.
solubility constant, Ks =
Ks values are often reported as pKs , where
pKs = -log Ks

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Example 2.3
How many mg/L of PO
AlPO4(s)?

would be in solution at equilibrium with

Solution. The pertinent reaction is


AlPO4(s) Al3+ + PO

The associated pKs = 20.0 and calculated as


Ks = 10-20.0 = [Al3+][PO ]
For every mole of AlPO4 that dissolves, one mole of Al3+ and one mole of
PO are released into solution. At equilibrium, the molar concentration of
Al3+ and PO in solution will be equal, so
[Al3+] = [PO ] = X
10-20.0 = X2
X = [PO ] = 10-10 moles per litre in solution.
The molecular weight of PO is 95 g/mole,
(95 g/mole)(103 mg/g)(10-10 moles/L) = 9.5 10-6 mg/L

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Acid/Base Reactions
Acids are defined as those compounds that release protons.
Bases are those compounds that accept protons.
HA H+ +AIn order for HA to release the proton (H+) , something must accept the
proton. Often that something is water, that is,
H+ + H2O H3O+

resulting in the net reaction


HA + H2O H3O+ +AIt is understood that water is generally present. Water acts as the base as
it accepts the proton. If a base is added to water, the water can act as an
acid.
B- + H2O HB + OHIn the above reaction the base (B-) accepts a proton from water. If a
compound is a stronger acid than water, then water will act as a base. If a
compound is a stronger base than water, then water will act as an acid.

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Acid/base chemistry centres on water and it is important to know how


strong an acid water is.
Water itself is ionized in water
H2O H++ OHThe degree of ionization of water is very small and can be measured by
what is called the ion product of water, Kw It is found by
Kw = [H+][OH-] = 10-14 (at 25C)
A convenient expression for the hydrogen ion concentration is pH,
pH = -log[H+]
A solution is acidic if [H+] [OH-], H+ 10-7M, pH < 7
neutral if [H+] = [OH-] = 10-7M, pH = 7
basic if [H+] < [OH-], H+ < 10-7M, pH 7

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Acids are classified as strong acids or weak acids. Strong acids have a
tendency to donate their protons to water. For example,
HCl H+ +Cl-

pKa for most strong acids are < 0.

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Weak acids are acids that do not completely dissociate in water. An


equilibrium exists between the dissociated ions and undissociated
compound. The reaction of a weak acid is
HW H+ +WAn equilibrium constant exists that relates the degree of dissociation:
H+][W]

HW
As with other K values,
pKa = -log Ka
By knowing the pH of a solution (which can be easily found with a pH
meter) it is possible to get a rough idea of the degree of dissociation of
the acid. If
pH = pKa (that is [H+] = Ka), then [HW] = [W] and the acid is 50%
dissociated.
[H+] is 2 orders of magnitude (100 times) < Ka, then 100 [H+] = Ka (or
H+][W]
+
or 100 [HW] = [W]. All acid is
pH >> pK).100[H ]
HW
dissociated (W >>HW).
pH << pK then [HW] >> [W], none of the acid is dissociated.

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Example 2.4
If 15 mg/L of HOCl is added to a potable water for disinfection and
the final measured pH is 7.0, what percent of the HOCl is not
dissociated? Assume the temperature is 25C.
Solution. The reaction is HOCl H++ OClpKa = 7.54
Ka = 10-7.54 = 2.55 10-8
Writing the equilibrium constant,
2.55 108

H+][OCl]
HOCl
107][OCl]
HOCl

[HOCl] = 3.47[OCl-]
Since the fraction of HOCl that has not dissociated plus the OCl- that
was formed by the dissociation must, by the law of conservation of mass,
equal 100 percent of the original HOCl added;

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[HOCl] + [OCl-] = 100% (of the total HOCl added to the solution)]
Then
3.47 [OCl-] + [OCl-] =100%
4.47 [OCl-] = 100%
[OCl-] = 100% /4.47 = 22.37%
and [HOCl] = 3.47 [OCl-] = 3.47 [22.37%] = 77.6%

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Buffer Solutions
A solution that resists large changes in pH when an acid or base is
added or when the solution is diluted is called a buffer solution.
The most important buffer system in environment and water and
wastewater treatment is the carbonate buffer system.
CO2(g) CO2 + H2O H2CO3 H+ + HCO 2H+ + CO
carbonic acid

bicarbonate ion

carbonate ion

The presence of Ca2+ in the form of


limestone rock or other naturally
occurring sources of calcium results in
the formation of calcium carbonate
(CaCO3), which is very insoluble.

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Behaviour of the carbonate


buffer system with the
addition of acids and bases
or the addition and removal
of CO2.
Case I and II
(natural system)
Case III and IV
(use in treatment plant to
adjust pH)

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Alkalinity
Alkalinity is defined as the sum of all titratable bases down to about
pH 4.5. It is found by experimentally determining how much acid it takes
to lower the pH of water to 4.5.
Alkalinity (nature system)
= [HCO ] + 2 [CO ] + [OH-] [H+]
Alkalinity = HCO + CO + OH- - H+) mg/L as CaCO3
mg/L as CaCO3 = (mg/L as species)

alkalinity, buffering capacity

Titration curve for a hydroxidecarbonate mixture. (Source:


Sawyer, McCarty, and Parkin,
1994.)

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Example 2.5
A water contains 100.0 mg/L CO and 75.0 mg/L HCO at a pH of 10.
Calculate the alkalinity exactly at 25C. Approximate the alkalinity by
ignoring [OH- ] and [H+].
Solution. First, convert CO , HCO , OH-, and H+ to mg/L as CaCO3.
The equivalent weights are
CO : MW = 60, n = 2, EW = 30
HCO : MW = 61, n =1, EW = 61
H+ : MW = 1, n = 1, EW = 1
OH- : MW = 17, n = 1, EW = 17
and the concentration of H+ and OH- is calculated as follows: pH = 10;
therefore [H+] = 10-10M.
mg/L = (10-10 moles/L)(1 g/mole)(10 mg/g) = 10-7

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Kw = [H+][OH-] = 10-14
[OH-] = Kw / [H+] = 10-14 / 10-10 = 10-4 moles/L
mg/L = (10-4 moles/L)(17 g/mole)(10 mg/g) = 1.7
Now, find the mg/L as CaCO3 , taking the equivalent weight of CaCO3 to
be 50:
mg/L as CaCO3 = (mg/L as species)
CO

= 100.0

HCO = 75.0
H+ = 10-7
OH- = 1.7

=167
=61

=5 10-6
=5.0

The exact alkalinity (in mg/L) is found by


Alkalinity = 61 + 167 + 5.0 - (5 10-6 ) = 233 mg/L as CaCO3
It is approximated by 61 + 167 = 228 mg/L as CaCO3 . This is a 2.2
percent error.

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Reaction Kinetics
Many reactions in the environment do not reach equilibrium quickly.
(disinfection of water, gas transfer into and out of water, removal of
organic matter from water, and radioactive decay.)
Reaction kinetics - the study of how these reactions proceed
Rate of reaction, r - used to describe the rate of formation (+r) or
disappearance (-r) of a compound.
Homogeneous reactions -Reactions that take place in a single phase
(liquid, gas, or solid)
Moles or milligrams
r=
(Unit volume)(Unit time)
Heterogeneous reactions -Reactions that take place at surfaces between
phases
Moles or milligrams

r=
(Unit surface)(Unit time)

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Reaction rates are a function of temperature, pressure, and the


concentration of reactants. For a stoichiometric reaction of the form:
aA + bB cC
the change in concentration of compound A is equal to the reaction rate
equation for compound A:
d[A]
dt

[A], [B], [C] = concentrations of the reactants


, , = empirically determined exponents
k = reaction rate constant. [It is often not a constant, rather, is dependent
on the temperature and pressure]
order of reaction - the sum of the exponents in the reaction rate
equation. (my be either integers or fractions)

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For elementary reactions where the stoichiometric equation represents


both the mass balance and the molecular scale process, the coefficients
of proportionality (a, b, c) are equivalent to the exponents in the reaction
rate equation:
A B
The overall reaction rate, r, and the individual reaction rates are related:

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