UNIT 5: WATER TECHNOLOGY

Introduction: Water is a universal solvent. It is one of the basic necessities of life and the most
abundant commodity in nature. Natural water may be classified as: Surface water, Underground water, Rain
water and Sea water. Other than drinking and household purposes, it is mainly required for agricultural and
industrial purposes.

Impurities in water: The natural water is contaminated due to different types of impurities. The
impurities present in water influence its characteristics such as colour, turbidity, taste, odour, acidity.

Hardness: Hardness of water is that characteristic which prevents the lathering of soap. The hardness
is imparted due to the presence of certain salts of multivalent cations like Ca2+, Mg2+, Fe2+, Mn2+ and Al3+
(heavy metals) dissolved in water.
Reaction:
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Sodium stearate Calcium stearate
(Sodium soap) (Insoluble)
The precipitate formed is called scum.

Comparison of Hard and soft water:

Sr. No. Hard water Soft water
1. It contains dissolved salts of higher valent It does not contain dissolved salts of
metal ions mainly Ca2+ and Mg2+ ions. hardness causing metal ions.
2. It does not give lathering with soap and It gives lathering with soap.
produces scum (precipitate).
3. Cleansing quality of soap is depressed, Cleansing quality of soap is not depressed,
hence soap is wasted during washing and hence soap is not wasted during washing
bathing. and bathing.
4. If hard water is used for cooking, boiling If soft water is used for cooking, boiling
point of water is elevated causing point of water is not elevated, hence no
unnecessarily wastage of time and fuel. wastage of time and fuel.

Hardness is classified as:

(1) Temporary hardness (Carbonate/Alkaline Hardness) is caused by the soluble bicarbonates of Ca2+
and Mg2+ ions. These soluble bicarbonates decompose to form insoluble precipitates when the water is heated.
Hence, temporary hardness is removed by mere boiling and filtering off the precipitates formed.
∆
Ca(HCO3)2 CaCO3 + H2O + CO2
1
 ∆
Mg(HCO3)2 Mg(OH)2 + 2CO2
Examples of salts causing temporary hardness are Ca(HCO3)2, Mg(HCO3)2 (i.e. bicarbonates of Ca2+ and Mg2+
ions).
(2) Permanent hardness (Non-carbonate/Non-alkaline Hardness) is due to the more soluble chlorides,
sulphates, nitrates of Ca2+, Mg2+, Fe2+ and other heavy metals ions. The permanent hardness removal needs
softening techniques. Examples of salts causing permanent hardness are CaCl2, MgSO4 etc.

Comparison of Temporary hardness and Permanent hardness:

Sr. No. Temporary hardness Permanent hardness
1. It is caused by the soluble bicarbonates of It is due to the soluble chlorides, sulphates,
Ca2+ and Mg2+ ions. nitrates of Ca2+, Mg2+, Fe2+ and other heavy
metals ions.
2. It is also called as carbonate or alkaline It is also called as non-carbonate or non-alkaline
hardness. hardness.
3. It can be removed by mere boiling and It cannot be removed by mere boiling. It can be
filtering off the precipitates formed. removed by softening techniques.
4. If water containing temporary hardness If water containing permanent hardness causing
causing salts is used in boilers, it leads to salts is used in boilers, it leads to formation of
formation of loose deposits of carbonate of adherent scales.
Ca2+ ion and hydroxide of Mg2+ ion.

Unit: mg/L or ppm (parts per million) of CaCO3 equivalent

mg/L = 1 mg /106 mg water, as 1 L water = 106 mg water, density of water being 1 g/cm3
i.e. 1 part /106 parts of water or parts per million (106)]
Other units:
1 ppm or 1 mg/L of CaCO3 equivalent = 0.1° French (Fr).
1 ppm or 1 mg/L of CaCO3 equivalent = 0.07° Clarke (Cl).

The CaCO3 equivalent for a given quantity of constituent (mg/L), is expressed as,

Weight of the constituent (mg/L) x Chemical equivalent of CaCO3 (Eq.wt of CaCO3)

________________________________________________________________________________________________________

Chemical equivalent of the constituent (Eq.wt of constituent)

2
Numericals:
Atomic weights:
H = 1, C =12, N = 14, O = 16, Na = 23, Mg = 24, Al = 27, Si = 28, S = 32, Cl = 35.5, K = 39, Ca = 40, Fe =
56

Example 1: Calculate the temporary, permanent and total hardness for a water sample in ppm containing
following salts: Mg(HCO3)2 = 18.25 ppm, Al(NO3)3 = 12 ppm, CaCO3 = 15 ppm, NaCl = 30 ppm.
Solution:
Constituent Quantity Eq.wt Conversion factor = CaCO3 Type of
(Salt/Chemical/Ion) (ppm) Quantity equivalent Hardness
x (ppm)
(Eq.wt of CaCO3/Eq.wt of constituent)
Mg(HCO3)2 18.25 73 18.25 x 50/73 12.5 Temporary
Al(NO3)3 12 71 12 x 50/71 8.45 Permanent
CaCO3 15 50 15 x 50/50 15 Temporary
NaCl 30 Does not contribute to hardness
Temporary hardness = 12.5 + 15 = 27.5 ppm
Permanent hardness = 8.45 = 8.45 ppm
Total hardness = Temporary hardness + Permanent hardness = 35.95 ppm

Example 2: Calculate the temporary, permanent and total hardness for a water sample in ppm containing
following salts: Mg(HCO3)2 = 7.3 ppm, Mg(NO3)2 = 18.5 ppm, Ca(HCO3)2 = 4.05 ppm, MgCl2 = 38 ppm,
MgSO4 = 18 ppm, SiO2 = 16 ppm.
Solution:
Constituent Quantity Eq.wt Conversion factor = CaCO3 Type of
(Salt/Chemical/Ion) (ppm) Quantity equivalent Hardness
x (ppm)
(Eq.wt of CaCO3/Eq.wt of constituent)
Mg(HCO3)2 7.3 73 7.3 x 50/73 5 Temporary
Mg(NO3)2 18.5 74 18.5 x 50/74 12.5 Permanent
Ca(HCO3)2 4.05 81 4.05 x 50/81 2.5 Temporary
MgCl2 38 47.5 38 x 50/47.5 40 Permanent
MgSO4 18 60 18 x 50/60 15 Permanent
SiO2 16 Does not contribute to hardness
Temporary hardness = 5 + 2.5 = 7.5 ppm
Permanent hardness = 12.5 + 40 + 15 = 67.5 ppm
Total hardness = Total hardness = Temporary hardness + Permanent hardness = 75 ppm

3
Example 3: How much of CaSO4 should be dissolved per litre to give 210 ppm hardness?
Solution:
The CaCO3 equivalent hardness caused by CaSO4 is 210 ppm
Equivalent of CaCO3 for CaSO4 =
Weight of the CaSO4 (mg/L) x Chemical equivalent of CaCO3 (Eq.wt of CaCO3)
____________________________________________________________________________________________________
Chemical equivalent of the CaSO4 (Eq.wt of CaSO4)

Weight of the CaSO4 (mg/L) x 50

∴ 210 = ___________________________________________
68

∴ Weight of the CaSO4 (mg/L) = 285.60

Determination of hardness of water by EDTA method: EDTA (ethylene diamine tetra acetic acid)
method is employed to determine hardness of water. It is a titrimetric, complexometric method. EDTA (written
as H4Y) has four carboxyl groups and two amine groups that can act as electron pair donors (Lewis base).
EDTA is used as the disodium salt (Na2H2Y). It yields an anion which forms complex with hardness causing
divalent cations like Ca2+ and Mg2+ ions (Figure 1).
M2+ + H2Y2- ⇌ MY2- + 2H+

(a) Structure of EDTA (b) Structure of disodium salt of EDTA

(c) Complex of disodium salt of EDTA with divalent metal ion

Figure 1 : Chemistry of EDTA to form complex

4
 The titration is carried out in a basic buffer solution where the H+ ions are removed as they are formed.
[This moves the position of equilibrium to the right and favours formation of the complex (Le Châtelier's
Principle). Also, for EDTA, pKa4 = 10.26.]
Thus, if the solution is buffered to about pH 10.3, most of the EDTA will exist as Y4-ions. The metal
ions will not have to remove the hydrogen ions from H2Y2-. They can react directly according to the equation,
M2++Y4-→ MY2-
Consequently, above pH 10.3, most metal ions react quantitatively with EDTA. Hence, during titration,
pH of water is maintained at pH 10 using NH4OH-NH4Cl buffer and then indicator is added. The indicator
used is Eriochrome black-T (EBT). Initially, EBT forms an unstable complex with Ca2+ and Mg2+ ions present
in water giving a wine-red colour. When the titration is carried out against di sodium EDTA solution, EDTA
replaces EBT and forms more stable complex of M-EDTA (where M = Ca2+ and Mg2+ ions) and in the process,
originally blue coloured EBT is set free. Hence, end-point is from wine red to blue.
pH = 10
M2+ + EBT [M-EBT] complex
Wine red

[M-EBT] complex + EDTA [M-EDTA] + EBT

Wine red Colourless Blue

In actual practice, while determining the hardness of unknown sample of water, standard hard water
(i.e. water whose concentration in terms of CaCO3 equivalent is known) is titrated against EDTA and the
concentration of EDTA in terms of CaCO3 equivalent is calculated. Now, the unknown sample of water is
titrated against the same EDTA and the hardness of water sample (i.e. its CaCO3 equivalent) is calculated.

Preparation of reagents for EDTA method:

(1) Preparation of Standard hard water: Dissolve 1 g CaCO3 in minimum quantity of HCl. Boil. Disslove
the residue in 1 litre distilled water. Concentration of solution is 1 mg CaCO3 per mL.
(2) Preparation of EDTA: Dissolve 4 g EDTA and 0.1 g MgCl2 in 1 litre of distilled water.
(3) Preparation of indicator (EBT-Erochrome Black T): Dissolve 0.5 g EBT in 100 mL alcohol.
(4) Preparation of buffer solution: Add 67.5 g NH4Cl to 570 mL concentrated NH3 solution, dilute to 1 litre
of distilled water.

Numericals:
With Standard hard water sample and unknown sample
Step 1: EDTA solution is standardized with standard hard water (SHW).
Step 2: Same EDTA of step 1 is used to titrate unknown hard water sample.
Method: 50 mL of standard hard water (SHW) requires V1 mL EDTA
(Given: Concentration of SHW = 1 mg/mL CaCO3)
5
50 mL of sample hard water requires V2 mL EDTA.
50 mL of sample hard water after boiling requires V3 mL EDTA
(i) To determine CaCO3 equivalent per mL EDTA (To determine concentration of EDTA),
50 mL SHW = V1 mL EDTA
V1 mL EDTA = 50 mL SHW
V1 mL EDTA = 50 x 1 = 50 mg CaCO3 (As concentration of SHW = 1 mg/mL CaCO3)

∴ 1 mL EDTA = (50/V1) mg CaCO3

(ii) To find total hardness,

50 mL sample hard water = V2 mL EDTA
= (V2 x 50/V1) mg CaCO3

∴ 1000 mL sample hard water = (V2 x 50/V1 x 1000/50) mg CaCO3

∴ Total hardness = (V2/V1 x 1000) mg/L or ppm

(iii) To find permanent hardness,

50 mL sample hard water after boiling and filtration = V3 mL EDTA
= (V3 x 50/V1) mg CaCO3

∴ 1000 mL sample hard water after boiling and filtration = (V3 x 50/V1 x 1000/50) mg CaCO3

= (V3/V1 x 1000) mg CaCO3

Permanent hardness = (V3/V1 x 1000) mg/L or ppm
(iv) To find temporary hardness,
Total hardness = Temporary hardness + Permanent hardness

∴ Temporary hardness = Total hardness – Permanent hardness

= (V2/V1 x 1000) – (V3/V1 x 1000)

= 1000/V1 [(V2 – V3)] mg/L or ppm

Example 1: 50 mL of standard hard water containing 1 mg of pure CaCO3 per mL consumed 30 mL of EDTA
solution. 50 mL of water sample consumed 35 mL of EDTA solution using EBT indicator. 50 mL of water
sample after boiling required 28 mL of EDTA solution using same indicator. Calculate temporary, permanent
and total hardness of water sample.
Solution:
Concentration (strength) of SHW,
Concentration of SHW = 1 mg/mL CaCO3

∴ 1 mL SHW = 1 mg CaCO3

(i) Standardization of EDTA,

50 mL SHW = 30 mL EDTA
30 mL of EDTA solution = 50 mL SHW
6
 = (50 x 1) mg CaCO3 equivalent
= 50 mg CaCO3 equivalent

∴ 1 mL EDTA = (50/30) mg CaCO3 equivalent

(ii) To calculate total hardness of water,

50 mL sample water = 35 mL EDTA
= (35 x 50/30) mg CaCO3 equivalent

∴ 1000 mL water = (35 x 50/30 x 1000/50) = 1166.66 mg CaCO3 equivalent

∴ Total hardness = 1166.66 mg/L or ppm

(iii) To calculate permanent hardness of water,

50 mL of boiled and filtered sample water ≡ 28 mL EDTA
= (28 x 50/30) mg CaCO3 equivalent

∴ 1000 mL boiled water ≡ (28 x 50/30 x 1000/50) = 933.33 mg CaCO3 equivalent

∴ Permanent hardness = 933.33 mg/L or ppm

(iv) To calculate temporary hardness of water,

Temporary hardness = Total hardness – Permanent hardness

∴ Temporary hardness = 1166.66 – 933.33 = 233.33 ppm

Example 2: 0.28 g of CaCO3 was dissolved in HCl and the solution made up 1 L with distilled water. 100 mL
of the above solution required 28 mL of EDTA solution. 100 mL of hard water sample required 33 mL of
EDTA solution. After boiling 100 mL of this water, cooling, filtering and then titration required 10 mL of
EDTA solution. Calculate each type of hardness.
Solution:
Concentration (strength) of SHW,
Standard hard water contains 0.28 g CaCO3 per 1000 mL = 0.28 g CaCO3 per 1000 mL

∴ Concentration of SHW = 0.28 mg/mL CaCO3

∴ 1 mL SHW = 0.28 mg CaCO3

(i) Standardization of EDTA,

100 mL SHW = 28 mL EDTA
28 mL of EDTA solution = 100 mL SHW
= (100 x 0.28) mg CaCO3 equivalent
= 28 mg CaCO3 equivalent

∴ 1 mL EDTA = 1 mg CaCO3 equivalent

(ii) To calculate total hardness of water,

7
100 mL sample water = 33 mL EDTA
= (33 x 1) mg CaCO3 equivalent

∴ 1000 mL water = (33 x 1 x 1000/100) = 330 mg CaCO3 equivalent

∴ Total hardness = 330 mg/L or ppm

(iii) To calculate permanent hardness of water,

100 mL of boiled and filtered sample water = 10 mL EDTA
= (10 x 1) mg CaCO3 equivalent

∴ 1000 mL boiled water ≡ (10 x 1 x 1000/100) = 100 mg CaCO3 equivalent

∴ Permanent hardness = 100 mg/L or ppm

(iv) To calculate temporary hardness of water,

Temporary hardness = Total hardness – Permanent hardness

∴ Temporary hardness = 330 – 100 = 230 mg/L or ppm

Example 3: 100 mL of standard hard water (1.2 g CaCO3/L) requires 38 mL of EDTA solution. 120 mL of
water sample consumes 18 mL EDTA. 150 mL of boiled and filtered water sample consumes 12 mL of EDTA.
Calculate the hardness of sample.
Solution:
Strength of SHW,
Standard hard water contains 1.2 g CaCO3 per 1000 mL = 1200 mg CaCO3 per 1000 mL

∴ 1 mL SHW = 1.2 mg CaCO3

(i) Standardization of EDTA,

38 mL of EDTA solution = 100 mL SHW
= (100 x 1.2) mg CaCO3 equivalent

∴ 1 mL EDTA = (100 x 1.2/38) = 3.158 mg CaCO3 equivalent

(ii) To calculate total hardness of water,

120 mL sample water = 18 mL EDTA
= (18 x 3.158) mg CaCO3 equivalent

∴ 1000 mL water = (18 x 3.158 x 1000/120) = 473.70 mg CaCO3 equivalent

∴ Total hardness = 473.70 ppm

(iii) To calculate permanent hardness of water,

150 mL of boiled and filtered sample water = 12 mL EDTA
= (12 x 3.158) mg CaCO3 equivalent

∴ 1000 mL boiled water = (12 x 3.158 x 1000/150) = 252.64 mg CaCO3 equivalent

8
∴ Permanent hardness = 252.64 ppm

(iv) To calculate temporary hardness of water,

Temporary hardness = Total hardness – Permanent hardness

∴ Temporary hardness = 473.70 – 252.64 = 221.06 ppm

Softening of water by Ion Exchange process:

Principle: A reversible exchange of ions occurs between the porous, stationary ion-exchange phase
and the external liquid phase. The cation exchange resins are capable of exchanging rapidly cations like Ca2+
and Mg2+from water by H1+ ions from cation exchange resin. The anion exchange resins are capable of
exchanging rapidly anions like Cl1-, SO42- from water by OH1- ions from anion exchange resin.
When ion exchange capacities are lost (resins are exhausted), the water will no longer be softened. The
exhausted cation exchanger is regenerated by passing dilute HCl or H2SO4. The exhausted anion exchanger is
regenerated by treating it with a dilute NaOH solution.
Ca2+ + RH2 RCa + 2H1+
2Cl1- + R’(OH)2 R’Cl2 + 2OH1-
H1+ + OH1- H2O
RCa + 2HCl CaCl2 + RH2
R’Cl2 + 2NaOH R’(OH)2 + 2NaCl
Total hardness of water ≡ Total volume of HCl (the acid) required for regeneration of
cation exchanger in terms of mg CaCO3 equivalent
Or
Total hardness of water ≡ Total volume of NaOH (the alkali) required for regeneration of
anion exchanger in terms of mg CaCO3 equivalent

For the purpose of hardness removal, cations like Ca2+ and Mg2+ are exchanged for H1+ ions from the
hydrogen cation exchanger along with other cations (non-hardness causing). Thus, the hardness factor of water
is removed. Further to improve, the quality of water, it is then passed through an anion exchanger where anions
like Cl-, SO42- are exchanged for OH1- ions from the anion exchanger. The water thus obtained is free from all
the dissolved salts and only H1+ + OH1- (H2O) is obtained. Thus, the demineralized water is obtained.
Ion exchange resins are soluble, cross-linked, long chain organic polymers with porous structure and
the functional group attached to the chains undergo the ion-exchange property. Resins containing acidic
functional groups (-COOH, -SO3H) are capable of exchanging their H1+ ions with other cations. Resins
containing basic functional groups [Quaternary ammonium salt (R1R2R3)-N1+OH1-] are capable of exchanging
their OH1- ions with other anions.
Ion exchangers have generally styrene-divinylbenzene as a basic unit. The cation exchange ion resins
are carboxylated or sulphonated styrene-divinylbenzene copolymers (Figure 2-a and b) and the anion

9
exchange ion resins are styrene-divinylbenzene copolymers containing quarternary ammonium groups (Figure
2-c).

(a) Cation exchanger resin (carboxylated) (b) Cation exchanger resin (sulphonated)

(c) Anion exchanger resin

Figure 2 : Ion exchange resins

Process: A known volume of water is first passed over a cation exchange column at a specific rate,
which removes cations from the water and equivalent amount of H1+ ions are released from column to water.
After the cation exchange, the same batch of water is passed through anion exchange column at a specific rate,
which removes anions from the water and equivalent amount of OH1- ions are released from column to water.
H1+ and OH1- ions released from the cation and anion exchange respectively get combined to form water
molecule (Figure 3). Thus, the treated water is free from cations as well as anions. Hence, it is called as
deionized or demineralised water. This exchange of ions continues till the exchange capacity of the ion
exchangers ceases.
Regeneration: The supply of hard water is stopped and the exhausted ion exchangers are regenerated.
The cation exchanger is regenerated by passing a solution of dilute HCl or H2SO4. The anion exchanger is
regenerated by passing a solution of dilute NaOH. The columns are then washed with deionized water.

10
 Figure 3 : Ion exchange process

Advantages:
(1) The residual hardness after the treatment is 0 ppm.
(2) The water can be used in high pressure boilers as it is free from alkalinity.
(3) The process is suitable to soften highly acidic or alkaline water.

Limitations:
(1) The equipment is costly and the ion exchangers are expensive.
(2) Turbid water reduces the process output. Hence, the turbidity must be removed initially by sedimentation,
coagulation or filteration.

Numericals:
Example 1: After treating 50000 L of water by ion exchanger, the cationic resin required 350 L of 0.5 N HCl
and anionic resin required 350 L of 0.5 N NaOH solutions for regeneration. Find the hardness of the above
sample of water.
Solution:
Total hardness of water ≡ Total volume of HCl or NaOH required for regeneration of ion exchange resin in
terms of mg CaCO3 equivalent
Total hardness of water = Quantity of water softened (L) x Hardness (mg/L)
Given, Total volume of HCl required for regeneration = 350 L of 0.5 N HCl
As 1000 mL (1 L) 1 N HCl ≡ 50 g CaCO3
350 L of 0.5 N HCl = (350 x 0.5 x 50) g CaCO3
= 8,750 g CaCO3
= 87,50,000 mg CaCO3
11
∴ Total volume of HCl required for regeneration = 87,50,000 mg CaCO3

∴ Total hardness of water = 87,50,000 mg CaCO3

∴ Quantity of water softened (L) x Hardness (mg/L) = 87,50,000 mg CaCO3

Given, Quantity of water softened = 50,000 L

∴ 50,000 x Hardness = 87,50,000

∴ Hardness = 175 mg/L

Alternate method:
Total hardness of 50000 L water ≡ 350 L of 0.5 N HCl
= 350 L of 0.5 N CaCO3 equivalent
= (350 x 0.5) L of 1 N CaCO3 equivalent
= 175 L of 1 N CaCO3 equivalent
= (175 x 50) g of CaCO3 equivalent
= 8750 g of CaCO3 equivalent

∴ Hardness in 1 L water = 8750/50000 = 0.175 g of CaCO3 equivalent

∴ Hardness (mg CaCO3 equivalent) in 1 L water = 175 mg of CaCO3 equivalent

∴ Hardness of water = 175 mg/L

Example 2: A water sample having hardness of 50 ppm was softened by ion exchange process. The exhausted
cation exchanger required 400 L of 0.25 N HCl whereas anionic resin required 400 L of 0.25 N NaOH
solutions for regeneration. Calculate the quantity of water softened using the ion exchange softner.
Solution:
Total hardness of water ≡ Total volume of HCl or NaOH required for regeneration of ion exchange resin in
terms of mg CaCO3 equivalent
Total hardness of water = Quantity of water softened (L) x Hardness (mg/L)
Given, Total volume of HCl required for regeneration = 400 L of 0.25 N HCl
As 1000 mL (1 L) 1 N HCl ≡ 50 g CaCO3
400 L of 0.25 N HCl = (400 x 0.25 x 50) g CaCO3
= 5,000 g CaCO3
= 50,00,000 mg CaCO3

∴ Total volume of HCl required for regeneration = 50,00,000 mg CaCO3

∴ Total hardness of water = 50,00,000 mg CaCO3

12
∴ Quantity of water softened (L) x Hardness (mg/L) = 50,00,000 mg CaCO3

Given, Hardness = 50 mg/L

∴ Quantity of water softened x Hardness = 50,00,000

∴ Quantity of water softened x 50 = 50,00,000

∴ Quantity of water softened = 1,00,000 L

BOD, COD- Definition, significance:

Biological Oxygen Demand (BOD): It is defined as the amount of milligrams of oxygen required by
microorganisms to oxidize the organic matter present in 1000 mL of water over a period of 5 days under
aerobic conditions at 20℃.

Determination of BOD:
(1) A known volume of waste water sample (V mL) is diluted with distilled water to known volume (V1 mL).
(2) Equal quantities of the diluted water sample are taken in two BOD bottles.
(3) In the first bottle, (DO)1 is determined immediately.
(4) Second bottle is incubated under aerobic conditions for 5 days under aerobic conditions at 20℃ and (DO)2
is determined.
[(DO)1 - (DO)2] gives the amount of dissolved oxygen consumed by microorganisms.

BOD is calculated as,

Volume of sample after dilution (V1)
BOD = [(DO)1 - (DO)2] x __________________________________
Volume of initial sample water taken (V)

Unit: mg/L

Significance: The BOD indicates the amount of decomposable organic matter in sewage, hence, BOD
can be used as a gauge to check the effectiveness of wastewater treatment plants. The higher the BOD of a
sample, the higher the amount of decomposable organic matter in the sample and the higher the pollution of
the sample. Thus, its significance in pollution control is unique since it provides the degree of pollution at any
time in the sewage stream. BOD test is the best test for assessing the organic pollution which serves as a
guideline for Regulatory Authorities to check the quality of effluents discharged into water bodies.

Chemical Oxygen Demand (COD): It is defined as the amount of milligrams of oxygen required to
oxidize the oxidizable material present in 1000 mL of water using a strong oxidizing agent such as acidified
potassium dichromate (K2Cr2O7).
13
Determination of COD:
(1) A known excess of K2Cr2O7 is titrated against standard (known normality) ferrous ammonium sulphate
(FAS). The titre value gives Blank titration reading.
(2) A known volume of water is refluxed with known excess of K2Cr2O7 and dilute H2SO4 in presence of
Ag2SO4 (catalyst) for 2-3 hours.
(3) The unreacted K2Cr2O7 after oxidation is titrated against standard ferrous ammonium sulphate (FAS). The
titre value gives Back titration reading.
(Blank - Back) gives the volume of oxidizing agent consumed.

COD is calculated as,

Volume of oxidising agent consumed x Normality of FAS x 8 x 1000

COD = _____________________________________________________________
Volume of water taken

(Blank – Back) x Normality of FAS x 8 x 1000

COD = ________________________________________
Volume of water taken
Blank = Volume of burette solution (FAS) required to consume the total (i.e. known excess) K2Cr2O7 added.
Back = Volume of burette solution (FAS) required to consume the excess K2Cr2O7 left over after oxidizing
the oxidisable matter in the water.

Unit: mg/L

Significance: The COD value is not affected by the presence of toxins and other unfavourable
conditions for the growth of microorganisms. It measures the effect of pollutants on dissolved oxygen. It is
taken as a basis for calculation of efficiency of treatment plant. It is important in proposing standards for
discharging domestic and industrial effluents in various kinds of water. Due to its rapid determination over
BOD, it has become important in the management and design of treatment plants.

Comparison of BOD and COD:

Sr. No. BOD COD
1. It is defined as the amount of milligrams of It is defined as the amount of milligrams of
oxygen required by microorganisms to oxygen required to oxidize the oxidizable
oxidize the organic matter present in 1000 material present in 1000 mL of water using a
mL of water over a period of 5 days under strong oxidizing agent such as acidified
aerobic conditions at 20℃. potassium dichromate (K2Cr2O7).
2. It requires 5 days for determination. It requires 2-3 hrs for determination.

14
 3. The process of determining of BOD is slower The process of determining of COD is rapid
than COD. than BOD.
4. It measures the oxygen demand of It measures the oxygen demand of
biodegradable pollutants only. biodegradable as well as non- biodegradable
pollutants.
5. BOD value is lower than COD. COD value is greater than BOD.
6. The method of determining BOD is less The method of determining COD is more
stable measurement as it uses stable measurement as it uses potassium
microorganisms which are susceptible to pH, dichromate which oxidises oxidisable matter
temperature and other variables in water. in matter regardless of water conditions.

Numericals:
Example 1: 60 mL of water sample was diluted to 100 mL. Equal volumes of it are taken for DO estimation.
The DO on day-1was 770 ppm and DO after incubation for 5 days was 340 ppm. Calculate the BOD of the
sample.
Solution:
Volume of initial sample water taken = 60 mL
Volume of sample after dilution = 100 mL
(DO)1 = 770 ppm
(DO)2 = 340 ppm
Volume of sample after dilution (V1)
BOD = [(DO)1 - (DO)2] x __________________________________
Volume of initial sample water taken (V)
= (770 – 340) x (100/60)
= 716.67 ppm

∴ BOD of water sample = 716.67 ppm

Example 2: 30 mL of waste water is mixed with 35 mL of acidified potassium dichromate and refluxed. The
unreacted potassium dichromate required 12.5 mL of 0.25 N ferrous ammonium sulphate. The blank titration
reading was 26.4 mL. Calculate COD of water sample.
Solution:
Volume of water taken = 30 mL
Blank reading = 26.4 mL
Back reading = 12.5 mL
Normality of ferrous ammonium sulphate (FAS) = 0.25 N
Volume of oxidising agent consumed x Normality of FAS x 8 x 1000
COD = _____________________________________________________________
Volume of water taken
15
 (Blank – Back) x Normality of FAS x 8 x 1000
COD = ________________________________________
Volume of water taken
(26.4 – 12.5) x 0.25 x 8 x 1000
COD = __________________________
30
COD = 926.67 mg/L

∴ COD of water sample = 926.67 mg/L

Example 3: 20 ml of waste water is mixed with 40 mL of acidified potassium dichromate and refluxed. The
volume of oxidising agent consumed was 10.2 mL of 0.1 N ferrous ammonium sulphate. Calculate COD of
water sample.
Solution:
Volume of water taken = 20 mL
Volume of oxidising agent consumed = 10.2 mL
Normality of ferrous ammonium sulphate (FAS) = 0.1 N
Volume of oxidising agent consumed x Normality of FAS x 8 x 1000
COD = _____________________________________________________________
Volume of water taken
10.2 x 0.1 x 8 x 1000
COD = _____________________
20
COD = 408 mg/L

∴ COD of water sample = 408 mg/L

16