CIVE 350

Water Chemistry
Pascal E. Saikaly
Department of Civil and Environmental
Engineering
American University of Beirut

Outline
Water Chemistry
Introduction
Physical properties of water
Chemical reactions
Acid/Base, Precipitation/Dissolution,
Complexation, Oxidation/Reduction
Chemical units
Stoichiometry
Chemical equilibrium
Precipitation reactions
Acid-Base reactions
The carbonate system
Solubility of gases in water

Water chemsitry
Almost

every pollution problem that we face

has a chemical basis (e.g. greenhouse effect,
ozone depletion, toxic wastes, groundwater
contamination, disinfection, softening, air
pollution, and acid rain).
A knowledge of the fundamentals of water
chemistry is essential to the understanding
of processes governing water quality and
wastewater treatment.

Physical Properties of Water

Density: mass per unit volume
Specific gravity

S =

(Kg/m3)

M
V

The subscript denotes the density of water at

3.98oC, 1,000 Kg/m3.
A measure of friction is viscosity (higher friction: harder
to pump liquid)
Dynamic viscosity or absolute viscosity, , has
dimensions of mass per unit length per time, with
units Pa . S.

2
Kinematic viscosity (m /s) =

Physical properties of water at 1 atm

Chemical Reactions
Important types of chemical reactions in environmental
engineering

Acid/Base (e.g. dissociation of bicarbonate)

HCO3H+ + CO32-

Precipitation/dissolution
CaCO3 (s)
Ca2+ + CO32-

Ion-association or complexation
Fe3+ + OHFeOH2+

Redox reactions: Oxidation/Reduction (valence changes and

transfer of electrons)
Fe
Fe2+ + 2e(Oxidation, loss of electrons)
2H+ + 2eH2(g)
(Reduction, gain of electrons)

Chemical Units
Methods of expressing concentration of a given material in
aqueous solution

One mole of a substance contains: 6.023 X 1023 molecules.

Number of moles = mass/molecular weight (g)/(g/mole)

Molarity, M (mol/L): The number of moles of a specific species per

liter of solution.
1-molar solution (1 M) is 1 mole/L
Molarity is related to mg/L by
mg/L = molarity X molecular weight X 103
mg/L = (moles/L) X (g/mole) X (103 mg/g)

Molality, m (mol/Kg): The number of moles of a specific species

per Kg of solvent.

Chemical units

Normality, N (equivalents/L): The number of equivalent weights of acid, base, or

redox-active species per liter of solution.

Mass of substance per liter

Normality =
Equivalent weight
Equivalent weight =

or

Normality = Molarity n

Molecular weight
n

where,
1. For Acid/Base rxn
n = number of protons (H+) or hydroxyl ions (OH-) that react in an acid-base
reaction
2. For Redox rxn
n = number e- transferred per mole of species
3. For precipitation rxn
n = the valance of the element in question (see table next page)
4. For compounds
n = number of hydrogen ions that would be required to replace the cation

Typical valences of elements and compounds in water

Example 1
Find the normality of the following solutions
A) 155 mg Ca3(PO4)2/liter given that Ca3(PO4)2
participates in the dissolution rxn
Ca3(PO4)2

3Ca2+ + 2PO43-

B) 49 mg H3PO4/L with respect the rxn

H3PO4

2H+ + HPO42-

C) 45 mg CO32-/L with respect the rxn

CO32- + H2O

HCO3- + OH-

D) Equivalent weight of O2 for the reduction rxn

O2 + 4H+ +4e-

2H2O

E) Equivalent weight of Ca2+

Example 1
A) n = 6. Each Ca3(PO4)2 forms 6 + and 6 charges. MW of
Ca3(PO4)2 is 310 g/mole.
Equivalent weight = (310 g/mole)/(6 eg/mole) = 51.67 g/eg or
51.67 mg/meq
Normality = (155 mg/L)/(51.67 mg/meq) = 3 meq/L
B) n = 2. Equivalent weight = (98 g/mole)/ (2 eq/mole) = 49 g/eq
or 49 mg/meq
Normality = (49 mg/L)/(49 mg/meq) = 1 meq/L
C) n =1. Equivalent weight = (60 g/mole)/(1 eq/mole) = 60 g/eq or
60 mg/meq
Normality = (45 mg/L)/(60 mg/meq) = 0.75 meq/L
D) n = 4. Equivalent weight = (32 g/mole)/(4 eq/mole) = 8 g/eq
E) n = 2. Equivalent weight = ( 40.08 g/mole)/(2 eq/mole) = 20.04
g/eq

Example 2
Find the weight of sodium bicarbonate, NaHCO3,
necessary to make a 1 M solution. Find the
normality of the solution.
Na+ + HCO3NaHCO3
HCO3H+ + CO32HCO3- + H2O
H2CO3 + OH-

Example 2
The molecular weight of NaHCO3 is 84. using the
equation
mg/L = molarity X molecular weight X 103
= (1 mole/L)(84 g/mole)(103 mg/g) = 84,000
HCO3- is able to give or accept only one proton;
therefore n = 1.
Equivalent weight = (84 g/mole)/(1 eq/mole) = 84
g/eq or 84 mg/meq
Normality = (84,000 mg/L)/(84 mg/meq) = 1000
meq/L or 1 eq/L

Stoichiometry
Chemical reaction
Qualitative information: Which chemicals are interacting to
produce which end products
Quantitative: Principle of conservation of mass
Stoichiometry: The balancing of equations so that the same number
of each kind of atom appears on each side of the equation and the
subsequent calculations, which can be used to determine amounts
of each compound involved.
Atomic weight of an atom is the mass of the atom measured in
atomic mass units.
Molecular weight of a molecule is the simply the sum of the atomic
weights of all the constituent atoms (e.g. CH4, atomic weight of C is
12 and atomic weight of H is 1. Therefore, the MW of methane = 12 +
4(1) = 16 g/mole).

Stoichiometry
Various ways to express the oxidation of methane
CH4
+ 2O2
CO2
+ 2H2O
1 molecule +
of methane
or,
1 mole
+
of methane
or ,
16 g
+
of methane

2 molecules
of oxygen

1 molecule of + 2 molecules of
carbon dioxide
water

2 mole
of oxygen

1 mole of
+ 2 moles of
carbon dioxide
water

64 g
of oxygen

44 g of
+ 36 g of
carbon dioxide
water

The mass is conserved in the last expression ( 80 g = 80 g)

Example 3
Consider a 1.67 X 10-3 M glucose solution that is completely
oxidized to CO2 and H2O. Find the mg/L of oxygen required to
complete the reaction.
C6H12O6 + 6O2
180 g
192g

6CO2 + 6H2O
264g 108 g

It takes 192 g of oxygen to oxidize 180 g of glucose

mg/L = molarity X molecular weight X 103
= (1.67 X 10-3 M )(180 g/mole)(103 mg/g) = 301 mg/L
So the oxygen requirement would be
300 mg/L X (192 g O2/180 g glucose) = 321 mg/L O2

Chemical Equilibrium
Different approaches may be used in predicting aqueous chemistry
speciation (i.e. concentration of products & reactants)
Chemical kinetics: The rate at which a reaction proceeds
toward equilibrium
Chemical equilibrium: tell you what the chemistry will be at
equilibrium, but not the kinetic rate at which the system
reaches the equilibrium state. This is the most widely used
method for obtaining chemical speciation.
Most chemical reactions are, to some extent, reversible, proceeding
in both directions at once. When products are being formed on the
right at the same rate as they are being formed on the left, the
reaction is said to have reached equilibrium .
aA + bB
cC + dD
The small letters a, b, c, and d are coefficients corresponding to the
number of molecules or ions

Chemical Equilibrium
aA + bB
At equilibrium we can write

K=

cC + dD

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

where the [ ] represents the concentration of the substance at

equilibrium, expressed in moles per liter (molarity). DO NOT USE mg/L.

K is the equilibrium constant

K: Dissociation constant or ionization constant
Ks: Solubility product
KH: Henrys constant; equilibrium constant describing the
concentration of gas in the water in equilibrium with the
concentration of gas in the air.
X = 10 pX

pX = logX

Precipitation Reactions
All solids are to some degree soluble, although some are much more
than others (e.g. NaCl is very soluble, whereas AgCl are very insoluble).
A generalized equation describing the equilibrium condition in which a
solid is dissociating into its ionic components (dissolution) at the same
rate that ionic compounds are recombining into the solid form
(precipitation)
Solid
aA + bB

[A] a [B] b
K=
[solid]
As long as there is still solid present at equilibrium, its effect can be
incorporated into the equilibrium constant
K s = [A] a [B] b
Ks values are often reported as pKs

pK s = logK s

Selected solubility product constants at 25oC

Solid
aA + bB
If we place solid in water, for every a moles of A that dissolves, b
moles of B will dissolve until equilibrium is reached.
When precipitating ions, it is possible to have a higher
concentration of ions in solution than dictated by the solubility
product. This is called a supersaturated solution.

Solubility product constants at 25oC

Example 4
How many mg/L of PO43- would be in solution at equilibrium with
AlPO4(s)?
Al3+ + PO43AlPO4(s)
pKs for aluminum phosphate is 20 (see table in previous slides)
K s = 10 20 = [Al 3 + ][PO4 3 ]

For every mole of AlPO4(s) that dissolves, one mole of Al3+ and
one mole of PO43- are released into solution. At equilibrium, the
molar concentration of Al3+ and PO43- in solution will be equal.
[Al 3 + ] = [PO4 3 ] = X
K s = 10 20 = X 2
Solving for X, we find PO43- = 10-10 moles per liter
mg/L = molarity X molecular weight X 103 = (10-10 moles/L)(95 g/mole)(103
mg/g) = 9.5 X 10-6

Example 5
If 50 mg of CO32- and 50 mg of Ca2+ are present in 1 L of water,
what will be the final (equilibrium) concentration of Ca2+?
Ca2+ + CO32CaCO3(s)
Molecular weight of Ca2+ is 40.08 and CO32- is 60.01, resulting in
initial molar concentration of 1.25 X 10-3 moles/L and 8.33 X 10-4
moles/L for Ca2+ and CO32-, respectively.
K s = 10 pK s = 10 8.305 = [Ca 2 + ][CO3 2 ]

For every mole of Ca2+ that is removed from solution, one mole of
CO32- is removed from solution. If the amount removed is given by
10 8.305 = 4.95 10 9 = [1.25 10 3 Z][8.33 10 4 Z]
Z, then
1.04 10 6 (2.08 10 3 )Z + Z 2 = 0
Z=
=

b 2 4ac
2a

2.08 10 3

= 8.28 10 4

4.34 10 6 4(1.04 10 6 )
2

Example 5
So that the final Ca2+ concentration is
[Ca2+] = 1.25 X 10-3 8.28 X 10-4 = 4.22 X 10-4 M
or,

mg/L = molarity X molecular weight X 103 = (4.22 X 10-4

moles/L)(40 g/mole)(103 mg/g) = 16.9 mg/L

Acid-Base Reaction
In 1923, Bronsted and Lowry suggested a new concept
of acid and base behavior. They proposed that an acid is any
substance that can donate a proton to another substance.
HNO3(aq) + H2O(l)
H3O+(aq) + NO3-(aq)
HNO3(aq)
H+(aq)
+ NO3-(aq)
And a base is a substance that can accept a proton from any other
substance.
NH3(aq) + H2O(l)
NH4+(aq) + OH-(aq)
If a compound is stronger acid than water, then water will act as a base.
If a compound is a strong base than water, then water will act as an
acid.
The acid/base chemistry centers on water and it is important to know
how strong an acid water is
H+(aq) + OH-(aq)
H2O(l)
+

[H ][OH ]
K =
[H 2O]

Acid-Base Reaction
Since water dissociates only slightly, the molar concentration after
ionization is not changed enough to be a of significance, so [H2O] is
essentially constant and can be included in the equilibrium constant
+

14
o
[H ][OH ] = K w = 1 10
at 25 C
where Kw is the dissociation constant of water (pKw = 14). Kw is
temperature dependent.
A solution is said to be acidic if [H+] is greater than [OH-], neutral if
equal, and basic if [H+] is less than [OH-].
Neutral solution , then [H+] = [OH-] = 10-7 M.
A convenient expression of the hydrogen ion (proton) is pH.

pH = log[H + ]

where

[H + ] = 10 pH

Acid-Base Reaction
Therefore, a neutral solution at 25oC has a pH of 7, an
acidic solution has a pH < 7, and a basic solution has a pH
> 7.
Strong acids

Note the use of single arrow to signify that, for practical

purposes, we may assume that the reaction proceeds
completely to the right.

Acid-Base Reaction
Selected weak acid dissociation constants at 25oC

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 week acid
is
HA(aq)
H+(aq) + A-(aq)
[H + ][A ]
Ka =
[HA]

pK a = logK a

Example 6
If 100 mg of H2SO4 (MW = 98) is added to 1L of water, what is the
final pH?

100mg

1
1
= 1.02 10 3 mole/L

1L H2O 98g/mole 3
10 mg/g

2H+ + SO42H2SO4(aq)
Therefore 2 X (1.02 X 10-3)M H+ is produced. The pH is:
pH = -log(2.04 X 10-3) = 2.69.

Example 7
If 15 mg/L HOCl (hypochlorous acid) is added to a potable water for
disinfection and the final pH is 7.0, what percent of the HOCl is not
dissociated ? Assume the temperature of water is 25oC.
HOCl(aq)
pKa = 7.54

H+(aq) + OCl (aq)

K a = 10 7.54 = 2.88 10 8
[H + ][OCL ]
Ka =
[HOCL]

2.88 10

[10 7 ][OCL ]
=
[HOCL]

Solving for the HOCL concentration

[HOCl] = 3.47[OCl-]

Example 7
Since the fraction of HOCl that has not dissociated plus the OClthat was formed by the dissociation must, by the law of
conservation of mass, equal 100% of the original HOCL added
[HOCl] + [OCl-] = 100%
then
3.47[OCl-] + [OCl-] = 100%
[OCl-] = 23.37%
[HOCl] = 77.6%

The Carbonate System

Buffer solution: A solution which resists large changes in pH when an
acid or base are added.
Atmospheric carbon dioxide, CO2(g), produces a natural buffer through
the following reactions:
2+
CO2(aq) + H2O
H2CO3
H + HCO3
2H+ + CO3
CO2(g)
where H2CO3 = carbonic acid
HCO3 = bicarbonate ion
2CO3
= carbonate ion
CO2(g) = carbon dioxide gas
CO2(aq) = aqueous carbon dioxide
Aqueous CO2(aq) is formed when atmospheric CO2(g) dissolves in
water; we can find its concentration in fresh water using Henrys law
Where KH = Henrys law constant (mol/L . atm); PCO2 = partial pressure
of CO2 in the atmosphere
[CO2 ]aq = K H PCO2

The Carbonate System

The carbonate system is the most important buffer system in water and
wastewater treatment. Also, it is the most important acid-base system
in natural waters because it largely controls its pH.
H+

CO2(aq) + H2O
H2CO3
+ HCO3
2H+ + CO3
CO2(g)
Any change in the system components to the right of CO2 causes the
CO2 either to be released from solution or to dissolve.
Le Chateliers Principle: A system at equilibrium, when subjected to a
perturbation, responds in a way that tends to minimize its effect.

2-

Examine the character of the buffer system in resisting a change in pH

assuming 4 cases (system exposed to atmosphere, system is open)
Case I: Acid is added to the system (it unbalances the system by
increasing H+ concentration)
Case II: Base is added to the system (base consumes H+)
Case III: CO2 is bubbled into the carbonate system
Case IV: carbonate buffer is stripped of CO2

Behavior of carbonate buffer system with the addition of

acids and bases or the addition or removal of CO2
Case I and II
are common
in natural
settings when
a reaction
proceeds over
a relatively
long period
The pH will
change more
dramatically
because the
atmosphere is
no longer a
source or sink
of CO2

Case III and

IV are not
common in
natural
settings. They
are used in
water
treatment to
adjust the pH

The Carbonate System

In natural waters in equilibrium with atmospheric CO2, the amount of
CO32- in solution is quite small in comparison to the HCO3 in solution.
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. As a consequence it
precipitates from solution
CaCO3(s)

Ca2+ + CO32-

The Carbonate System

Alkalinity: is the sum of all titratable bases down to about pH of 4.5. It
is found experimentally by determining how much acid it takes to lower
the pH of water to 4.5. In most waters the only significant
contributions to alkalinity are the carbonate species and any free H+ or
OH-. The total H+ that can be taken up by a water containing primarily
carbonate species is
Alkalinity = [HCO3 ] + 2[CO3 2 ] + [OH ] [H + ]
In most natural water situations (pH 6 to 8), the OH- and H+ are
negligible such that

Alkalinity = [HCO3 ] + 2[CO3 2 ]

Note that [CO32-] is multiplied by two because it can accept two
protons.
H2CO3
HCO3-

H+ + HCO3H+ + CO32-

pKa1 = 6.35
pKa2 = 10.33

pC-pH diagram for carbonate system

HCO3 -

H2CO3

pKa1

pKa2

< 4.5

> 12.3

OH CO3

2-

H+

1. Below pH of 4.5, essentially all the carbonate species are present as

H2CO3, and the alkalinity is negative (due to H+).
2. At pH of 8.3 most of the carbonate species are present as HCO3-, and
the alkalinity equals HCO3-.
3. Above pH of 12.3, essentially all of the carbonate species are present
as CO32-, and the alkalinity equals 2[CO32-] + [OH-].

Titration curve for a hydroxide-carbonate mixture

Source:
Sawyer,
McCarty,
and Parkin,
1994

The figure shows the change of species described above

as the pH is lowered by the addition of acid to a water
containing alkalinity.
At about pH 8.3 the carbonate is essentially all converted to
bicarbonate

The Carbonate System

By convention, alkalinity is not expressed in molarity units, but rather
in mg/L as CaCO3.

EWCaCO
3
mg/L as CaCO3 = (mg/L as species)
EW species

The alkalinity is then found by adding all the carbonate species and the
hydroxide, and then subtracting the hydrogen ion. When using the
units mg/L as CaCO3 the terms are added directly. The multiple of
two CO32- has already been accounted for in the conversion.

Example 8
A water contains 100.00 mg/L CO32- and 75.0 mg/L HCO3- at a pH
of 10. Calculate the alkalinity exactly at 25oC. Approximate the
alkalinity by ignoring [OH-] and [H+].
The equivalent weight are:
CO32-: MW = 60, n = 2, EW = 30
HCO3-: MW = 61, n = 1, EW = 61
H+: MW = 1, n = 1, EW = 1
OH-: MW = 17, n = 1, EW = 17
pH = 10; therefore [H+] = 10-10 M.
mg/L = (10-10 mole/L)(1 g/mole)(103 mg/g) = 10-7
[OH-] = Kw/[H+] = 10-14/10-10 = 10-4 moles/L
mg/L = (10-4 mole/L)(17 g/mole)(103 mg/g) = 1.7

Example 8
EWCaCO
3
mg/L as CaCO3 = (mg/L as species)
EW species

mg/L as CaCO3 is found using the equation

The equivalent weight of CaCO3 = MW/n where n = 2

EW CaCO3 = 100/2 = 50
CO32- = 100.0(50/30) = 167
HCO3- = 75.0(50/61) = 61
-7
-6
= 5 X 10
H+ = 10 (50/1)
OH- = 1.7(50/17) = 5.0
The exact alkalinity (in mg/L) is found by
Alkalinity = 61 + 167 + 5.0 (5 X 10-6)
= 233 mg/L as CaCO3
Alkalinity = 61 + 167 = 228 mg/L as CaCO3

Solubility of Gases in Water

When air comes in contact with water, some of it dissolves into the
water.
The relationship between the equilibrium concentration of gas
dissolved in solution and the partial pressure of the gas defined by
Henrys law:

[gas] = K H Pg

where
[gas] = concentration of dissolved gas (mol/L)
KH = Henrys law constant (mol/L . atm)
Pg = the partial pressure of the gas in air (atm)
Pg is simply the volumetric concentration times the atmospheric
pressure. For example, oxygen makes up about 21 percent of the
atmosphere, so at 1 atm: Pg would be 0.21 X 1 atm = 0.21 atm.
Henrys law constant varies both with temperature (solubility
decreases as temperature increases) and with concentration of other
dissolved gases and solids (the solubility decreases as other
dissolved material in the liquid increases).

Solubility of Gases in Water

Because atmospheric pressure varies with altitude, Pg will change as
well
(Thomson and Mueller, 1987)

P = P0 1.15 10 4 H

Where
P = atmospheric pressure at altitude H (atm)
H = altitude (m)
P0 = atmospheric pressure at altitude H (atm)

Example 9
By volume, the concentration of oxygen in air is about 21 percent.
Find the equilibrium concentration of O2 in water (in mol/L and
mg/L) at 25oC and 1 atm of pressure. Recalculate it for Denver at
an altitude of 1,525 m.
Pg = 0.21 X 1 atm = 0.21 atm.
At 25oC, KH for O2 = 0.0012630 mol/L . Atm
[O2] = KHPg = 0.0012630 X 0.21 = 2.65 X 10-4 mol/L
In Denver, at 1,525 m, atmospheric pressure can be estimated
using the equation
P = P0 1.15 10 4 H = 1 - 1.15 10 -4 1,525 = 0.825 atm
Pg = 0.21 X 0.825 atm = 0.17325 atm.
[O2] = KHPg = 0.0012630 X 0.17325 = 2.19 X 10-4 mol/L

Alkalinity vs. Alkaline

Buffer solution: A solution which resists large changes in pH when an
acid or base are added.
Alkalinity serves as a measure of buffering capacity.
The greater the alkalinity, the greater the buffering capacity.
Alkaline water: water that has a pH greater than 7.
High alkalinity water: water with high buffering capacity.
An alkaline water may or may not have a high buffering capacity.
Likewise, a water with high alkalinity may or may not have a high pH.