ENGI 9628 – Environmental Laboratory

Lecture 5:
The Chemistry of Natural
Waters
Faculty of Engineering & Applied Science

Friday, July 3, 2009

Hydrologic Cycle

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 Importance of Water
• All life forms on earth depend on water. Each human being
consumes several L water per day to sustain life.

• 97% is seawater: unsuitable for drinking and most agriculture.

• ¾ of the fresh water is trapped in glaciers and icecaps.

• Lakes and rivers are one of the main sources of drinking water.

• Although only 10% of the world’s population in 2000 lived under

conditions of water stress and scarcity, expect to rise to 38% by
2025.

• Important to understand the types of chemical activity that

prevail in natural waters.

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Major Water Quality Issues

• Acidification – acid rain, acid mine drainage
• Eutrophication – nutrient overload
• Metals e.g. Pb, Cd, Mg, Al, etc.
• Organic contamination
• – Organic contaminants e.g. DDT, PCBs
• – Organic matter e.g. sewage, manure
• Pathogens
• Salinization
• Sediment load
• Diversions, dams
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 Concentration

• Solutions  ‐‐ Reporting  Concentrations  and 

Solubility

• Concentration can be expressed as:
– Mass/Volume units
– temperature dependent!
– Mass/Mass units

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Concentration (mass/volume)

• Molarity (M, mol/L)
– Number  of  moles  of  solute  per  litre of 
solution

• Normality (N, eq/L)
– Equivalents of solute per litre of solution
– Also expressed as meq/mL

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 Normality

• The weight of one equivalent depends on the type of 
reaction considered
eq = M/n
M = Molar mass
n = number of protons donated
=  no.  of  moles  of  H+ or  OH‐ produced  per  mole  of 
acid/base
= total change in oxidation number of a compound
= charge on an ion

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Concentration (Mass/Mass)
• Modality (m, mol/kg)
• – number of moles of solute per kilogram of solvent
• Mole Fraction (XA)
• – Number of moles of a component divided by the total
number of moles of all components in the solution
• Weight Percent (%)
• – Mass of solute per 100 g of solution
• Parts per million (ppm)
• – Grams of solute per million grams of solution (or mg/L)
• – Can also use ppb or ppt

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 Equilibrium Constant

aA + bB → cC + dD

[C ]c [ D]d
K=
[ A]a [ B]b

• K = Equilibrium Constant

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Solubility

• E.g. gypsum
CaSO4 ( S ) → Ca 2+ + SO4 2−
Ksp = [Ca 2+ ][ SO4 2− ]
[Ca 2+ ] = [ SO4 2− ]

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 Ion Activity Product

• • IAP = Ksp Saturated solution
• • IAP < Ksp Unsaturated solution
• • IAP > Ksp Supersaturated solution

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Water Chemistry
• Two common reaction categories: Acid base reactions
and oxidation-reduction (redox) reactions.
• Acid base and solubility phenomena predominantly
control the concentrations of dissolved inorganic ions,
such as carbonate.
• Redox reactions dominate the organic matters.

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 Oxidation Reduction: Dissolved Oxygen

• The most important oxidizing agent in natural waters

is dissolved oxygen, O2.
• Each of the oxygen atoms in O2 is reduced from zero
oxidation state to -2 state.

O 2 + 4H + + 4e − →

O 2 + 2H 2 O + 4e − →

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Dissolved Oxygen, Cont’d
• The concentration of DO in water is small and
therefore precarious from ecological point of view.
• The dissolution process

O 2 (gas) ⇔ O 2 (dissolved)
• The equilibrium constant is the Henry’s Law
constant KH

O 2 (dissolved)
KH =
Partial Pressure O2

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 DO: Problem 1
• Confirm by calculation the value of 8.7mg/L for the
solubility of Oxygen in water at 25oC. (given that
KH=1.3x10-3 mol/L atm at 25 oC, PP O2= 0.21atm)

ENGI 9628 – Environmental Engineering Laboratory

DO: Thermal Pollution
• River and lake water that has been artificially
warmed can be considered to have undergone
Thermal Pollution. Why?
• Gas solubility decreases with increasing
temperature.
• Warm water contains less oxygen than cold water.
To sustain life, most fish species require at least 5
ppm of DO.
• Consequently, their survival in warm water can be
problematic.

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 Oxygen Demand
• The most common substance oxidized by DO in
water is Organic Matter of biological origin (dead
plant matter and animal wastes).
• The reaction process

• Oxidation state of carbon increases from 0 to +4, it

is oxidized, the state of O2 decreases from 0 to -2.

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Oxygen Demand:  Problem 2
• Show that 1L water saturated with oxygen at 25oC is
capable of completely oxidizing 8.2 mg of CH2O.

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 Oxygen Demand
• Water that is aerated by flowing in shallow streams
and rivers is constantly replenished with oxygen.
• Stagnant water or that near the bottom of a deep lake
is usually almost completely depleted of oxygen
because of the reaction with OM.
• Biological Oxygen Demand (BOD): the capacity of
the organic and biological matter in a sample of
natural water to consume oxygen, a process
catalyzed by bacteria present.

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Biochemical Oxygen Demand (BOD)
¾ Concept
BOD = amount of oxygen required (by bacteria) to decompose organic 
waste to carbon dioxide and water. 

ƒ an indirect measure of organic‐matter concentration in water bodies
ƒ most widely used for measuring organic pollution in wastewater & surface water
ƒ High BOD concentration = high organic‐matter concentration = poor water quality
¾ BOD Kinetics
ƒ If we introduce some organic matter into water

==>     Initial amount of organic matter ==> initial BOD (BODinitial)

==>    Bacteria keep decomposing organic matter

==>    Amount of organic matter keeps decreasing

==>     remaining BOD keeps decreasing (BODremaining)
 BODremaining(at time t) = BODinitial10 –Kt
where K = reaction constant (day ‐1); and t = time (day). 

¾ Define: BODutilized = BODinitial − BODremaining

==> BODutilized(at time t) = BODinitial − BODinitial10 –Kt

==>  BODutilized(at time t) = BODinitial(1 − 10 –Kt)

ƒBODutilized at day 5 = BODinitial(1 − 10 –5K)

ƒBODutilized at day 10 = BODinitial(1 − 10 –10K)
ƒRight figure shows the usual curve for BOD 
and is actually BODutilized. Also shown is 
the 5 day BOD.

Example: The 5‐day BOD for some wastewater 
has been found to be 200 mg/L. With reaction 
constant K = 0.1 day ‐1, find 
10‐day BOD and BODinitial?

¾Measurement of BOD
ƒDecomposition of organic matter is a slow process

20 days ==> decompose 95 to 99% of organic matter 
5 days ==> decompose 60 to 70% of organic matter

ƒStandard way to measure BODutilized during the first 5 days (at 20 °C) 

==> named       "5‐day BOD" or BOD5

==> employed by the standards of many countries, e.g. Canada, USA and EU.

ƒImplication of BOD measurement:
‐ BOD5 for domestic sewage = several hundreds mg/L
‐ BOD5 for industrial sewage = several thousands mg/L

ƒTherefore, when the sewage is discharged to water 

==>    quick depletion of oxygen => would kill fish
IMPACT FACTORS ‐ (1) Temperature

ƒTemperature  ==> affect biochemical reaction rates (and thus reaction 
constant K) 
==> different BOD values

ƒK value at temperature different from 20 oC:

KT = K20θ(T‐20)
where θ = temperature coefficient (between 1.056 to 1.135).

Example: The initial BOD concentration of a sewage is 300 mg/L. 
Reaction constant K is 0.1 day‐1 at 20 oC. Calculate BOD5 for this 
sewage at 30 oC (θ = 1.056).

IMPACT FACTORS ‐ (2) Effect of Nitrification
Organic nitrogen in sewage 

Converted to ammonia during decomposition 

Oxidation of ammonia to nitrite and nitrate requires oxygen

Second‐stage BOD (nitrogenous oxygen demand) 

At 20 oC, reproduction rate of 
nitrifying bacteria 
==> very slow (need 6 to 10 
days to exert measurable 
oxygen). 

Í Influence of 
Nitrification
¾APPLICATION of BOD:
ƒ measure waste loading to treatment plants
ƒ evaluate efficiency of treatment systems
ƒ determine relative O2 requirements of treated effluents & polluted 
waters
==> useful in
‐ sewage treatment & water quality management  
‐ sizing of waste treatment facilities 
‐ measuring efficiency of treatment processes

(5) Oxygen Sag Curve
¾when sewage is discharged into a receiving water, two simultaneous 
actions follow:
ƒ decomposition of organic matter by bacteria => consume O2
ƒ reaeration from atmosphere ==> bring O2 to water 

==> their combination produces an oxygen sag curve

ƒ initial stage
==> DO curve drops (i.e. rate of O2 consumption by   
bacteria > rate of reaeration with atmosphere)
ƒ at the point where [DO] = minimum 
==> rate of consumption = rate of reaeration
ƒ beyond minimum point
==> rate of consumption < rate of reaeration (DO level 
eventually returns to normal)
This sequence is called "natural self‐purification of water"
 Chemical Oxygen Demand (COD)
• A fast determination of oxygen demand can be made by
evaluating the Chemical Oxygen Demand (COD) of a
water sample.
• The basis for the COD test is that nearly all organic
compounds can be fully oxidized to carbon dioxide with a
strong oxidizing agent under acidic conditions.
• For many years, potassium permanganate (KMnO4) has
been used.
• Other oxidizing agents such as ceric sulfate, potassium
iodate, and potassium dichromate have been used to
determine COD.
• Of these, potassium dichromate (K2Cr2O7) has been
shown to be the most effective: it is relatively cheap, easy
to purify, and is able to nearly completely oxidize almost
all organic compounds.

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Chemical Oxygen Demand (COD)

• Dichromate ion, can be dissolved as one of its salts,
such as Na2Cr2O7 or Na2Cr2O7 in sulfuric acid, this
mixture is a powerful oxidizing agent.

• It is this mixture, rather than O2, that is used to

ascertain COD values.

• Moles of O2 is 6/4=1.5 times that of the moles of

dichromate, since the latter accepts 6 electrons per
ion whereas O2 accepts only 4

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 COD: Problem 3
• A 25-mL sample of river water was titrated with
0.001M Na2Cr2O7 and require 8.3 mL to reach the
endpoint. What is the chemical oxygen demand
(COD) in mg of O2 per liter of the sample?
(0.001 M = 0.001 mole/Liter)

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Chemical Oxygen Demand (COD)

• Dichromate is such a strong oxidant that it oxidizes
substances that are very slow to consume oxygen in
natural waters.
• In another word, Dichromate oxidizes substances that
would not be oxidized by O2 in determination of BOD.
• Therefore, the COD is slightly greater than BOD.
• In many water pollution cases, the O2 required by OM is
higher than DO. If the water is not aerated, the O2 will be
soon depleted, and fish will die.
• Wastewater need to be treated to reduce BOD.

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Acid‐base Chemistry: Carbonate System
• Natural waters, even when “pure” contains
significant quantities of dissolved carbon dioxide
CO2, and the anions it produces (CO32-, HCO3-), as
well as Calcium and Magnesium cations (Ca2+,Mg2+).
• The pH of the natural waters is rarely exactly 7.0, the
value expected for pure water.
• Equilibrium (carbonate, bicarbonate)

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Calcareous Waters
• Natural waters that are exposed to limestone are
called calcareous waters.
• The limestone rocks are largely made up of
calcium carbonate, CaCO3.
• Almost insoluble, a small amount dissolves when
water passes over it.

CaCO 3 ( s ) ⇔ Ca 2 + + CO 32 −
• Dissolved carbonate acts as a base, producing
bicarbonate ion and hydroxide ion, OH-

CO 32 − + H 2 O ⇔ HCO 3− + OH −
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 Reaction Among Three Phases
Air CO2 (gas)

H2CO3 ÍÎH+ + HCO3-

H2O
Water
CO32- + H2O ÍÎOH- + HCO3-
+

Ca2+

CaCO3 (solid)
Rock, Soil or Sediments

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Water in Equilibrium with Solid CaCO3
• Consider a hypothetical case: water is in equilibrium with
excess solid CaCO3, all other reaction are of negligible
importance.
• Equilibrium constant in this case is Ksp, the solubility
product, equals to the product of the concentration of
ions.
K sp = [Ca 2+ ][CO32− ]

• Ksp=4.6x10-9 (25oC), S=[Ca2+]=[CO32-]

S2=4.6x10-9, S=6.8x10-5 M, or 6.8x10-5 mol/L

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