Unit 4 Water Chemistry

Purest form
 Water Quality Parameters
chemical
physical, and
biological properties

Physical parameters:
• Turbidity
• Temperature
• Color
• Taste and odor
• Electrical conductivity (EC)

one of the main parameters used to determine the suitability of water for irrigation and firefighting

Chemical parameters : Biological parameters :

pH Dissolved oxygen (DO)
Dissolved oxygen (DO) Biological oxygen demand (BOD)
Total Dissolved solids (TDS) Chemical oxygen demand (COD)
Major ions Microorganism bacterial counts
Trace elements
Hardness
Alkalinity
Hardness of Water
 Hardness of Water

Clark’s Process
Permanent Hardness Removal
Permanent Hardness Removal
 Permanent Hardness Removal

The resins used are generally organic, cross-linked and insoluble polymers with some
functional groups responsible for the ion-exchange properties

Water is known as de-ionized or demineralized water

Permanent Hardness Removal
Permanent Hardness Removal
Permanent Hardness Removal
 Permanent Hardness Removal

In lime-soda process, hard water is treated with lime (CaO or Ca (OH)2) firstly, after that
with soda. In this process, the hardness is removed by sedimentation as calcium carbonate
or magnesium hydroxide. Lime is added either as calcium hydroxide or calcium oxide, and
soda is added as sodium carbonate. The

This process is now obsolete but was very useful for the treatment of large volumes of hard
water
Permanent Hardness Removal
Permanent Hardness Removal
Permanent Hardness Removal
 Scale and sludge formation

In a boiler, water is continuously evaporated and converted into steam. As a result the water
becomes saturated due to increase in the concentration of dissolved impurities. Finally a
stage is reached where the ionic products of these salts exceeds their solubility product and
are thrown out as precipitates on the inner walls of the boiler.
Scale and sludge formation
 Scale and sludge removal

Phosphate conditioning
It is used equally in low- and high-pressure boilers. Magnesium chloride which hydrolyses to
form Mg(OH)2 scale can be removed by adding appropriate sodium phosphate NaH2PO4,
Na2HPO4, or Na3PO4.
The phosphate reacts with calcium/magnesium salts forming loose sludge of calcium or
magnesium phosphate
 Scale and sludge removal

For precipitation ionic product must exceed the solubility product

 Estimation of hardness by EDTA method
Hardness is due to Ca2+ and Mg2+ salts, therefore their concentration is measured using EDTA
(Ethylene diamine tetra acetic acid)

• EDTA dissolves in water with great difficulty, but its disodium salt dissolves quickly &
completely
• It is hexa dentate ligand. Can form 4 or 6 coordinate bonds.
• It binds the metal ions in water to give stable chelate complex.
• Hence it is called as complexometric titration method.

Zwitter ion in water

• EDTA forms colorless stable 1:1 complexes with Ca2+ and Mg2+ ions present in water at pH =
9-10
• To maintain the pH of the solution at 9-10, buffer solution (NH4Cl + NH4OH) is used.
• Eriochrome Black-T (E.B.T) is an azo dye and is used as an indicator. It forms soluble, wine-red
colored complex s with Ca2+ and Mg2+. Its unionized form is black in color
 Estimation of hardness by EDTA method

Procedure:
1. Standardize given EDTA solution
2. Determination of Total hardness: Take 20 ml of unknown water solution in an Erlenmeyer flask.
3. Add 1 mL of buffer solution.
4. Add two drops of indicator solution. The solution turns wine red in colour.
5. Add the standard EDTA titrant slowly with continuous stirring until the last reddish tinge
disappears from the solution. The colour of the solution at the end point is blue under normal
conditions.
6. Note down the volume of EDTA added (V1)
 Estimation of hardness by EDTA method

Determination of Permanent hardness:

Take sample water, boil it to reduce the volume half, cool it. Filter the carbonate salts,
temporary hardness is removed, now make up the water again and titrate it as per previous
method
Calculations
1. Standardization of EDTA
M1V1 = M2V2
Where, M1 = Molarity of standard hard water
V1 = Volume of standard hard water in conical flask
M2 = Molarity of EDTA
V2 = Volume of EDTA consumed (burette reading)

2. Determination of Total hardness

M2V2 = M3V3
Where, M3 = Total hardness of sample water
V1 = Volume of sample hard water in conical flask
 Estimation of hardness by EDTA method
3. Determination of Permanent hardness
M2V2 = M4V4
Where, M4= Permanent hardness of sample water
V4 = Volume of sample hard water in conical flask

4. Determination of Temporary hardness

Temporary hardness = Total hardness – Permanent hardness

Result: The hardness of the given water sample has been found to be as follows:

Total hardness = ------------------------------------ ppm

Permanent hardness = ------------------------------ ppm

Temporary hardness = ----------------------------- ppm

 Alkalinity
• water's ability to neutralize acid
• Due to bicarbonates (HCO3-), carbonates (CO32-), and hydroxides (OH-)
Following situations may arise due to the presence of the ions causing alkalinity
OH- only
CO32- only
HCO3- only
OH- & CO32- both
CO32- & HCO3-
OH- & HCO3- & OH-, HCO3-, and CO32- do not exist together as the reaction between hydroxide and
carbonate will take place
The pH and the alkalinity level of the well water can be affected by various factors such as acidic sanitizers,
rain, fill water, and other product applications that can change the alkalinity level over time.
The majority of alkalinity in the surface water is from calcium carbonate, CaCo3, leached from soil and
rocks.
Can be estimated by titration against standard acids using phenolphthalein and methyl
orange as indicators
Alkalinity
Alkalinity
Alkalinity
Alkalinity
Alkalinity
Alkalinity
Alkalinity
 Biological oxygen demand (BOD)
• Water bodies contain small amounts of oxygen, in the form of dissolved oxygen (DO) which may come
from the photosynthesis by aquatic plant

• the presence of a sufficient concentration of dissolved oxygen is critical to maintaining the aquatic life
and aesthetic quality of streams and lakes

• BOD helps in determining how organic matter affects the concentration of dissolved oxygen (DO) in a
stream or lake

• decay of organic matter in water is measured as biochemical or chemical oxygen demand

• BOD represents the amount of oxygen consumed by bacteria and other microorganisms while they
decompose organic matter under aerobic (oxygen is present) conditions at a specified temperature

• BOD is used, often in wastewater-treatment plants, as an index of the degree of organic pollution in
water

• It symbolizes the amount of organic pollution present in an aquatic ecosystem. BOD measures the extent
of pollution of waste water, sewage and industrial effluents. Higher value means low DO. Which is usually
lower in summer months

• The microorganisms feed on the biodegradable matter in the presence of oxygen (aerobically) to form
stable, non objectionable end products.

• The BOD value is most commonly expressed in milligrams of oxygen consumed per liter of sample during
5 days of incubation at 20 °C
 Biological oxygen demand (BOD)

H2S, NH3
Method of determination: BOD 5: 5 day BOD test
based on the determination of dissolved oxygen over a period of 5 days
Procedure:
1. A known volume of sample of sewage is diluted with a known volume of distilled water
2. The dissolved oxygen is determined on the first day (D1).
3. This is kept for 5 days at 20 ºC in a stoppered bottle, away from light (incubation period).
4. The dissolved oxygen is measured again after 5 days.
5. The difference (D1–D2) indicates the oxygen consumed in five days for oxidizing the organic
matter present in the water sample.

BOD = (D1–D2) × dilution factor

 Biological oxygen demand (BOD)

Pure water ~ 1 ppm

Moderately clean ~ 2-8 ppm
Highly polluted water > 17 ppm

mg/L
There are two stages of decomposition in the BOD test:
A carbonaceous stage and
a nitrogenous stage

The carbonaceous stage, or first stage, represents that portion of oxygen demand
involved in the conversion of organic carbon to carbon dioxide
Org mat → CO2

The nitrogenous stage, or second stage, represents a combined carbonaceous plus nitrogenous demand,
when organic nitrogen, ammonia, and nitrite are converted to nitrate.

Nitrogenous oxygen demand generally begins after about 6 days.

For some sewage, especially discharge from wastewater treatment plants utilizing biological treatment
processes, nitrification can occur in less than 5 days if ammonia, nitrite, and nitrifying bacteria are present

In this case, a chemical compound that prevents nitrification should be added to the sample if the intent is
to measure only the carbonaceous demand. The results are reported as carbonaceous BOD (CBOD), or as
CBOD5 when a nitrification inhibitor is used
 Chemical oxygen demand (COD)
BOD does not measure the inorganic matter
COD is a measure of both organic as well inorganic matter
COD reveals the actual organic content and inorganic nutrients present in water
It is the amount of oxygen required by organic and inorganic matter in a sample of water for its
oxidation by a strong chemical oxidizing agents such as K2Cr2O7 in 50 % H2SO4 solution
COD is always higher than BOD for the same waste water sample

Measurements:
A measured quantity (say 50 mL) of the sample is refluxed with a known excess of standard
potassium dichromate solution and dilute H2SO4 in the presence of Ag2SO4 – HgSO4 as a
catalyst.
The amount of K2Cr2O7 before the reaction and excess K2Cr2O7 left after the reaction is
determined by titrating against a standard ferrous ammonium sulphate solution (Mohr’s
salt) using ferroin as an indicator.
The difference between the K2Cr2O7 originally present and that remaining unreacted gives
the amount of K2Cr2O7 used for the oxidation of oxidizable impurities in water
Chemical oxygen demand (COD)