CE 307 Weeks2and3

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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

-1

0.0005486

Proton

+1

1.0088925

Neutron

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

Covalent bond

Strong bonds between atoms

Eg.: H2, CH4, NH3

Van der Waals forces

Eg.: HF

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+

NaHCO3

a2 NaOH a3 Ca(OH)2+ a4

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.
2+ Fe2+ is the complex ion, and water is the ligand.
Eg: In Fe(H2O)6

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 W0

Mass per volume (mg/l)

W=Solvent mass (eg: water,


air)
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

H2O 1

2O

C D
K
a
b
A B
c

EQUILIBRIUM CONSTANT

Equilibrium in case of solubility calculations

AaBb(s)aAx++bBy-

Ks A

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

Here: x is equilibrium mole fractions


ng is gmoles of
l gas
nl is moles of liquid

n n

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++CO322 CO3 +H2O HCO3 +OH

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)
It

is 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+]
2 [CO3 ]=0

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.

We use Eriochrome Black T (EBT)as a titrant to see


if total hardness is removed.

EDTA+M [M.EDTA]complex

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

kT=1.047
k 20 T 20

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

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