CE-307

WEEKS-2 AND 3

Dr. Sri Harsha Kota

Department of Civil Engineering
IITG
OTHER PHYSICAL EFFECTS
Color
Humic acid present in organic debris imparts
yellowish brown color to water
Iron Oxide Causes reddish color to water.
Manganese Oxides cause brown or blackish color
water.
5 Hazan units (desirable limit.)
OTHER PHYSICAL EFFECTS
Taste and odor:
Water tastes bitter when contaminated with
alkaline impurities and salty when impurities are
metallic salts.
Biological decomposition of organic debris impart a
odor of rotten eggs. Which is mainly due to
Hydrogen sulphide (H2S).
INTRODUCTION TO ENVIRONMENTAL
CHEMISTRY
CONSTITUENTS OF AN ATOM
An atom is an extremely small particle of matter that retains its
identity during chemical reactions.
Symbol Charge Mass (amu)
Electron e -1 0.0005486
Proton p +1 1.0088925
Neutron n 0 1.0088665

amu= Unified atomic mass unit

1/12 of the mass of an atom in unbound neutral
carbon-12
Atomic number= Number of protons
Mass number= Number of neutrons +
protons
Isotopes are forms of an element with same
atomic number but different mass numbers.
For example: Carbon-12 and Carbon-14 are
Isotopes.
CHEMICAL BONDS AND INTERMOLECULAR
FORCES

Ionic bond
Eg.: HF
Covalent bond Strong bonds between atoms
Eg.: H2, CH4, NH3
Van der Waals forces
Eg.: Between neutral
molecules of Cl2
Hydrogen bonding
Between CH3OH, H2O Weak forces between molecule
CHEMICAL REACTIONS
Stoichiometric coefficients

2C8H18+25O216CO2+18H2O

Reactants Products

Atoms are neither created nor destroyed

Net charge of reactants=products
BALANCING CHEMICAL REACTIONS
a1 C3H8+ a2 O2 a3 CO2 + a4 H2O
a1 Ca(HCO3)2+ a2 NaOH a3 Ca(OH)2+ a4
NaHCO3
TYPES OF CHEMICAL REACTIONS
Precipitation-Dissolution Reactions
CaCl2+Na2CO3 CaCO3(s)+2Na++2Cl-
If reaction proceeds to right its precipitation (formation of
calcium carbonate), else its dissolution (dissolution of calcite).
Acid-Base Reactions
Acid is a substance that can donate a proton to the base.
HCl+H2O H3O++Cl-
Here HCl is acid and water acts like a base.
This reaction leads to a conjugate acid (H3O ), and a base (Cl )
+ -

NaOH+H3O+ 2H2O+Na+
Here NaOH is the base and water acts like an acid.
This reaction leads to a conjugate acid (Na ), and a base (H2O)
+
TYPES OF CHEMICAL REACTIONS
Acid-Base Reactions
pH=-log{H+}
pH in natural waters should be in the range of 6-9 to
support most life.
These reactions which are fast (with half life of
milliseconds) can be a part of biological reactions, passage of
water through soils, acid rains, and direct release from
municipal, households and industries.
Complexation Reactions
It occurs in natural waters whenever the coor-dination of
two (or more) atoms, molecules, or ions results in the
formation of a stable product.
Complex ion + Ligand Stable product
They form through coordinate covalent bonding
Ligand is a base attached to the complex ion.

Eg: In Fe(H2O)6
2+ Fe2+ is the complex ion, and water is the ligand.
TYPES OF CHEMICAL REACTIONS
Complexation Reactions
Effects the biological update of the chemical species,
the toxicity, removal efficiency of the metal.
Oxidation-Reduction Reactions
Photosynthesis and respiration are a sequence of
redox (oxidation-reduction) reactions.
Corrosion of iron metal
Fe+H2O+O2 Fe2O3
 Reactions involving gases
Diffusion of oxygen from air to water helps the
survival of aquatic life
Dissolution of CO2 gas in water leads to acidity of
pure rain water (pH=5.6).
UNITS FOR CONCENTRATION
Weight Percent (P)
W
P 100% W=Solvent mass (eg: water,
W W0 air)
Mass per volume (mg/l) W0=Solute mass
Converting mg/l to ppm for water
For dilute solutions, its assumed that water has a density
of 1 g/ml and is not effected by mass of solute.
UNITS FOR CONCENTRATION
Molarity
Number of moles per liter of a solution
Mole: Avagadros number of molecules of a substance.
How many molecules does a mole of Benzene have? Whats
its molecular weight?
 Normality
Number of equivalent moles per liter
Equivalent moles=mole/n
n is number of
electrons transferred in redox reactions

Hydrogen ions transferred in acid-base reactions

Hydrogen ions required to replace the cation in

precipitation reactions
Whats a cation?
H2SO4, Ca2+, CO32-, CaCO3
PROBLEM-CONCENTRATION UNITS
84g of sodium bicarbonate (NaHCO3) added to 1
L of water in a volumetric flask. Express the
concentrations in mg/l, ppm, molarity and
normality.
CONCENTRATION UNITS
Expressing in CaCO3 equivalent
mg/l as CaCO3=(mg/l as species)(EW of CaCO3)/(EW
of species)
Convert 1M of NaHCO3 into CaCO3 equivalent
CONCENTRATION UNITS
For gases g/m3 and ppm are usually used
As in dilute aqueous solutions which have a fixed
density of 1g/ml, airs density isnt fixed.
At normal conditions, convert the 1-hr
average Ozone concentration of 300 g/m3
to ppm
CHEMICAL EQUILIBRIUM
Rate of forward reaction=rate of reverse reaction
Equilibrium constant (K)
aA+bB cC+dD

NaCl+H2O Na++Cl-+H 2O
K
C D
c d

A B
a b

H2O 1
EQUILIBRIUM CONSTANT
Equilibrium in case of solubility calculations
AaBb(s)aAx++bBy-

Ks A B
x a
Mg(OH)2(s)Mg2++2OH-
y b
PROBLEM
The solubility product for the dissociation of
magnesium hydroxide at 250C is 9E-12.
Determine the concentrations of Mg2+ and OH- at
equilibrium.
EQUILIBRIUM CONSTANT
Acid-base reactions
Strong acids completely dissociate in water.
Weak acids only partially dissociate
PROBLEM
Acetic acid solution was prepared by adding 60
mg of CH3COOH to a volumetric flask, and
adding water to 1 L mark. Despite of this, the
water was neutral. What are the concentrations
of individual constituents in the solution?
Assumed that the temperature is 25oC. pKa is
4.75
EQUILIBRIUM CONSTANT
Gas-Liquid Equilibrium
The relation between partial pressure of a gas and
its corresponding concentration in aqueous solution
is given by Henrys Law.
Pgas=KHCaq
Pgas is partial pressure of a gas (kPa)

Caq is aqueous concentration of dissolved gas in water

(mol/L)
What are units of KH?

Whats the relation when concentration of gas is expressed

in mol/m3?
PROBLEM
The concentration of a gas in water is 1M. Whats
the partial pressure, in the units of kPa, of that
gas in air? Use, Henrys constant for that gas as
1M/atm.
EQUILIBRIUM CONSTANT
Gas-Liquid Equilibrium
If concentrations are expressed in mole fractions
x=Pgas/KH,m

ng
x
Here: x is equilibrium mole fractions
n n
ng is gmoles of
l gas
nl is moles of liquid
PROBLEM
Calculate the solubility of air in water at 00C and
1 atm pressure. Assume other dissolved material
is negligible.
KH,m=4.32E+4 atm/mol fraction
M.Wt. of air=28.9 g/mol
ALKALINITY
Alkalinity is the ability of water bodies to
neutralize added acids.
This acid-neutralizing capacity is important to
figure out how buffered the water is against
sudden changes in pH.
Its primarily due to presence of bicarbonate,
carbonate and hydroxide ions.
Salts of weak acids such as borates, silicates and
phosphates may also contribute, but to a lesser
extent
ALKALINITY
Prominent ways of carbonates entering into water
bodies:
Water flowing through limestone or marble
CaCO3 (s) Ca2++CO32-
CO3 +H2O HCO3 +OH
2- - -

Storm water runoff through lawns and agricultural

fields, which use lime (calcite etc.). Lime is used to
neutralize clay soil and ammonia based fertilizers
which produce acid when they are decomposed.
ALKALINITY
Transfer of CO2 from air to water
CO2+H2O H2CO3
H2CO3 HCO3-+H+

HCO3- CO32-+H+

Note: Unlike CaCO3, carbonic acid to

carbonate conversion leads a falls in
p H.
ALKALINITY-MEASUREMENT
Alkalinity is expressed as mg/l of CaCO3
Usually 0.02N H2SO4 is used in the titration

1 ml of acid will neutralize 1mg of alkalinity as CaCO3

H+ ions from acid react with the alkaline species as:

OH-+H+ H2O
CO32-+H+ HCO3-
HCO3-+H+ H2CO3
ALKALINITY-MEASUREMENT
Two infliction points
pH=8.3; Phenolphthalein Alkalinity
OH-+1/2 CO32-
Phenolphthalein is used as indicator, and color changes

from pink to colorless

pH=4.5; Total Alkalinity
1/2 CO32- + HCO3-
Methyl orange is used as indicator, and color changes from

orange to red
PROBLEM
A 200-ml sample of water has an initial pH of 10.
30 ml and 11 ml of 0.02N H2SO4 is required to
titrate the sample to pH of 4.5 and 8.3
respectively. Determine the quantity of each
species and total alkalinity.
HARDNESS
Hardness is defined as sum of all multivalent
cations in solution.
They are two types:
Temporary Hardness or carbonate
Hardness (CH):
Carbonates and bicarbonates of calcium and
magnesium.
They can be removed by boiling
HARDNESS
Permanent Hardness or non-carbonate
hardness (NCH)
Itis usually caused by the presence of calcium and
magnesium sulfates, nitrate and chlorides in the water,
which become more soluble as the temperature rises.
Permanent hardness is hardness of water that cannot be
removed by boiling.
This can be removed using a water softener, or ion
exchange column

NCH=TH-CH
HARDNESS
Impacts
Excessive soap consumption
2 NaCO2C17H33 +cation2+
cation2+(CO2C17H33)2 +2Na+
Soap Precipitate
Lathering doesnt occur untill all of the hardness ions
are precipitated.
The precipitate formed adheres to surfaces of tubs,
sinks, and dish washers, and may stain clothing,
dishes and other items.
Residues of the precipitate may remain in the pores,
so that skin may feel rough and uncomfortable.
 Fouling of water heaters and hot water pipes , because
of scaling of carbonate hardness precipitate.
Magnesium hardness, particularly associated with the
sulfate ion, has laxative effect on persons
unaccustomed to it.
 HARDNESS- MEASUREMENT
TH=Sum of all multivalent ions
Alkalinity=
[HCO3-]+[CO32-]+[OH-]-[H+]
@ pH of 6.5-8.3, its assumed that
[OH-]=[H+]
[CO3 ]=0
2-

CH is the least of TH or Alkalinity

NCH=TH-CH
Note: Units: mg/l as CaCO3 equivalent
PROBLEM
Estimate TH, NCH and CH for a neutral pH
ground water with mg/l of
Ca2+= 200
Mg2+= 14.6
HCO3-=600
HARDNESS- MEASUREMENT
EDTA Titrimetric method
Ethylenediaminetetraacetic acid (EDTA) reacts with
multivalent ions to form a complex.
EDTA+M [M.EDTA]complex
We use Eriochrome Black T (EBT)as a titrant to see
if total hardness is removed.
EBT+M Wine red color complex
When TH is converted to EDTA complex, then
aqueous solution changes from wine red to blue.
OXYGEN DEMAND
Theoretical Oxygen Demand (ThOD)
Its the amount of oxygen required to oxidize a substance to
CO2 , NH3, H2PO4, SO42-and H2O
Glucose oxidation

C6H12O6 + 6O2 = 6CO2 + 6H2O

Oxygen Required/demand=6 moles

632 g of Oxygen for 180 g of Glucose

If glucose concentration is 100 mg/L ;

THOD is?
 Chemical Oxygen Demand (COD)
Nearly all organic compounds can be oxidized
completely using a strong oxidizing agent under
acidic conditions
COD-MEASUREMENT
A sample is refluxed in strongly acid solution
with a known excess of potassium dichromate
(K2Cr2O7).
As we are using excess potassium dichromate
(K2Cr2O7), not all Cr6+ converts to Cr3+
The left over Cr6+ is estimated by titration with
ferrous ammonium sulfate with ferroin as
indicator.
 BIOCHEMICAL OXYGEN DEMAND (BOD)
The amount of oxygen consumed during microbial
utilization of organics, as a food source, is called BOD
L=oxygen equivalent of organic chemicals remaining
(mg/l)
k= reaction rate constant

dL
kL
dt
BODt L0 (1 exp( kt ))
L0= Maximum oxygen consumption possible
Are L0 and ThOD same?
BOD
k is temperature dependent
vant Hoff-Arhenius model

k 20 T 20
kT=1.047
PROBLEM
The BOD5 of a waste water is determined to be
150 mg/l at 200C. What would the BOD8 be if the
test was run at 150C? Assume k=0.23 day-1
BOD
BOD=CBOD+NBOD
Carbonaceous BOD (CBOD):
Its a result of breakdown of organic molecules like glucose
into CO2 and H2O
Nitrogenous BOD (NBOD):
Its a result of break down of organic molecules like
proteins (which have N) releasing N as NH3 in water.
At normal pH, this ammonia is in the form of NH4+
NBOD

PROBLEM
IITG has an wastewater treatment plant in
operation. It discharges 10,000 m3 day-1 waste,
with a BODu of 10 mg/l and a decay rate of 0.1
day-1, and DO of 2 mg/l. If the wastewater is
discharged into Brahmaputra river, which has a
flow rate of 1 m3s-1, with a BODu and DO of 1 and 6
mg/l. Estimate BODu and DO initially after mixing.
PROBLEM
Estimate BOD5 of 113 mg/l of C5H7O2N. Given
decay rate is 0.15 day-1
C5H7O2N+5O2 5CO2+2H2O+NH3
NH3+2O2 NO3-+H++H2O
DO SAG CURVE
All rivers have a self purifying capacity
As the waste inside a river increases, it looses its
capacity to cleanse itself.
If DO drops below 4 mg/l, most of the aquatic life
will be effected.

But isnt the oxygen in air always in equilibrium

with DO in water?
DO SAG CURVE
STREETER-PHELPS MODEL



 PROBLEM
The wastewater is found to have a maximum flow rate of
15000 m3/day, a BOD5 of 40 mg/l, a dissolved oxygen
concentration of 2 mg/l, and a temperature of 250C. A slow
moving stream, with a flow rate of 0.5 m3/s, a BOD5 of 3
mg/l, a dissolved oxygen concentration of 8 mg/l , and a
temperature of 220C. Complete mixing of wastewater and
stream is almost instantaneous, and the velocity of
mixture is 0.2m/s.
Where and when does the maximum DO deficit occur?
Assume:
k1= 0.23day-1
k2=0.4 day-1
Equilibrium concentration of DO at 22.80C= 22.8 mg/l