Environmental Engineering

(CE3030)
Dr. Praveena G
Assistant Professor
Civil Engineering
IIT Palakkad

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3. Acidity, Alkalinity, and Hardness

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 Acidity and Alkalinity
Buffer system: Resist pH changes when acid or alkali adds to the system
Eg: Carbonate buffer system

CO2 + H2O H2CO3 (dissolved carbon dioxide or carbonic acid)

H2CO3 H+ + HCO3 - (Bicarbonate ion)

HCO3 - H+ + CO3 - (carbonate ion)

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CO2 + H2O H2CO3 (carbonic acid)

H2CO3 H+ + HCO3 - (Bicarbonate ion)

H2CO3 2H+ + CO3 - (carbonate ion)

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Acidity
• Base neutralizing capacity

(i) CO2 acidity (ii) Mineral acidity (iii)Total acidity

• CO2 acidity is due to the presence of CO2

https://science4fun.info/lakes/

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Mineral acidity
• Sources: Industrial wastes (metallurgical industry), abandoned mines,
metal bearing wastewater
bacteria
2S + 3O2 + 2H2O 4H++ 2SO42-

bacteria
FeS2 + 3.5O2 + H2O Fe2+ + 2H+ + 2SO42-

FeCl3 + 3H2O Fe(OH)3(s)+ 3H+ + 3Cl-

https://stateimpact.npr.org/penns
ylvania/2016/07/05/tracking-co2-
emissions-from-mine-water/
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 Alkalinity
• Alkalinity is a measure of the ability of a water to neutralize the acids.

Constituents of alkalinity in natural water systems include:

(1) CO32-, HCO3-, OH- - Natural sources , dissolution of minerals

(2) PO43-, HPO42- , H2PO4 – Detergents in wastewater
(3) S2-, HS- , H2S – Decomposition of organic matter by microbes

The mot common constituents of alkalinity are CO32-, HCO3-, OH-

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 Determination
Reagents required:

• 0.02 N H2SO4 (to be filled in the burette)

• Phenolphthalein Indicator

• Methyl orange indicator (or Bromocresol

green methyl red indicator)

http://www.webassign.net/question_assets/ncsugenchem102labv1/lab_9/images/figure9-1.png

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Determination
OH - + H+ H2O
mL of acid used to bring down the pH to 8.3
CO3 - + H+ HCO3-
equals the alkalinity of OH- + 1/2 CO32-
mL of acid used to bring down the pH to 4.5
pH 8.3 equals the alkalinity of 1/2CO32- + HCO3-

HCO3 - + H+ H2CO3
pH 4.5

mL of acid used to bring down the pH to 4.5

equals the alkalinity of OH- + CO32- + HCO3-

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Measuring the water alkalinity

• Alkalinity is measured by titrating the water sample with standard acid (usually 0.02N
H2SO4).

• Based on 1L water sample, each 1mL of the acid is equivalent to 1mg of alkalinity
expressed as mg/L as CaCO3.

𝐸𝑊 𝑜𝑓 𝐶𝑎𝐶𝑂3
mg/L as species X = 𝑚𝑔/𝐿 as CaCO3
𝐸𝑊 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠

E.g., CO32-: concentration = 50 mg/L; EW = 60/2

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50 mg/L X = 83.33 𝑚𝑔/𝐿 as CaCO3
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Total Alkalinity (mg/L as CaCO3) = [HCO3-] + [CO32-] + [OH-] - [H+]

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Problem
A 200 mL sample of water has an initial pH of 10. 30 mL of 0.02 N
H2SO4 is required to titrate the sample to pH 4.5. What is the total
alkalinity of the water in mg/L as CaCO3?

Answer 1 mL of H2SO4 will neutralize 1 mg of alkalinity

Total alkalinity = (30 mg/200 mL )X (1000 mL/L) = 150 mg/L

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Problem
A water contains 100.0 mg/L CO32- and 75.0 mg/L HCO3- at a pH of 10. Calculate
the alkalinity exactly at 25oC.

ion MW n EW
CO32- 60 2 30
HCO3- 61 1 61
H+ 1 1 1
OH- 17 1 17

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Solution
Alkalinity, mg/L = [HCO3-] + [CO32-] + [OH-] - [H+]
𝐸𝑊 𝑜𝑓 𝐶𝑎𝐶𝑂3
mg/L as species X = 𝑚𝑔/𝐿 as CaCO3
𝐸𝑊 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠

ion Concentration Concentration CaCO3 in Concentration

in mg/L in mg/eq. mg/eq. in mg/L
expressed as
CaCO3

CO32- 100 30 50 166.67

HCO3- 75 61 50 61.47
H+ 1 X 10-7 1 50 5x10-6
OH- 1.7 17 50 5

Alkalinity = 233 mg/L as CaCO3

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Environmental significance
(i) Unpalatable
(ii) Chemical coagulation –
chemicals used for coagulation of water and wastewater react with
water to form insoluble hydroxide precipitates. To maintain desirable
pH conditions, alkalinity is required.
(iii) Water softening-
Alkalinity is considered in calculating the lime and soda requirements in
softening of water
(iv) Buffering capacity

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(v) pH changes during aeration of water:
A water with higher alkalinity would tend to have a higher pH upon
aeration, and one with lower alkalinity would tend to have a lower pH

(vi) pH changes in the presence of algal blooms:

(vii) Alkalinity of Boiler water

https://www.cdc.gov

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 Hardness
• Hardness is defined as the sum of all polyvalent cations
Cations causing hardness Anions
Ca2+ HCO3-

Mg2+ SO42-
Sr2+ Cl-
Fe2+ NO3-
Mn2+ SiO32-

https://h2ocare.com/

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Soap consumption
2 NaCO2C17H33 + caton2+ caton2+(CO2C17H33)2 + 2 Na+
Soap Precipitate

• Lathering does not occur until all of the hardness

ions are precipitated.

• The precipitate may stain clothing, dishes,

and other items.

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• Hardness in mg/L as CaCO3

Types of Hardness
I. With respect to the metallic ion
II. With respect to the anions associated with the metallic ion
III. Pseudo- Hardness

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With respect to the metallic ion
Cations causing hardness
Ca2+

Mg2+
Sr2+
Fe2+
Mn2+

Total Hardness = Ca2+ + Mg2+

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(ii) With respect to the anions associated with the metallic ion

Cations causing hardness Anions Types of Hardness

Ca2+

Mg2+

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(ii) With respect to the anions associated with the metallic ion

Cations causing hardness Anions Types of Hardness

HCO3-
Carbonate Hardness
Ca2+

Mg2+

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(ii) With respect to the anions associated with the metallic ion

Cations causing hardness Anions Types of Hardness

HCO3-
Carbonate Hardness
Ca2+
SO42-
CI–
Noncarbonate Hardness
NO3 -
Mg2+

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Total Hardness = Carbonate hardness + Non carbonate hardness
TH = CH + NCH

Hardness range (mg/L CaCO3) Description

0-75 Soft
75-100 Moderately Hard
100-300 Hard
300 Vary Hard
Problem: A water has an alkalinity of 200 mg/L as CaCO3. The Ca2+
concentration is 160 mg/L as the ion, and the Mg2+ concentration is 40
mg/L as the ion. The pH is 8.1. Find the total, carbonate, and non-
carbonate hardness.

Total Hardness expressed as CaCO3 = Ca2+ + Mg2+

TH = CH + NCH
TH = 160 mg/L * (50/20) + 40 mg/L * (50/12) = 567 mg/L as CaCO3
NCH = TH – CH
NCH = 367 mg/L as CaCO3
Example: Given the following analysis of a ground water, construct a bar
chart of the constituents, expressed as CaCO3. Determine carbonate,
noncarbonate and total hardness.

Ion mg/L EW ion EW mg/L as

CaCO3/E CaCO3
W ion

Ca2+ 103 20
Mg2+ 5.5 12.153
Na+ 16 22.98
HCO3- 255 61
SO42- 49 48.03
Cl- 37 35.5
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 Ion mg/L EW ion EW mg/L as
CaCO3/E CaCO3
W ion

Ca2+ 103 20 2.50 258

Mg2+ 5.5 12.153 4.12 23
Na+ 16 22.98 2.18 35
HCO3- 255 61 0.82 209
SO42- 49 48.03 1.04 51
Cl- 37 35.5 1.41 52

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 Ion mg/L EW ion EW mg/L as Total Hardness
CaCO CaCO3
3/EW
Carbonate Noncarbonate
ion Hardness Hardness
258 281 316
Ca2+ 103 20 2.50 258
Cations Ca2+ Mg2+ Na+
Mg2+ 5.5 12.153 4.12 23
Na+ 16 22.98 2.18 35 Anions HCO3- SO42- Cl-

HCO3- 255 61 0.82 209 209 260 312

SO42- 49 48.03 1.04 51

Cl- 37 35.5 1.41 52

Total Hardness = 281 mg/L Ion Concentration, mg/L as CaCO3

Carbonate Hardness = 209 mg/L

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Noncarbonate Hardness = 209 mg/L – 281 = 72 mg/L
Case 1
• When alkalinity < total hardness

Carbonate hardness = alkalinity

250

Ca2+ Mg2+

HCO3- Cl-

200 250

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Case 2

When alkalinity ≥ total hardness,

Carbonate hardness = total hardness

250 275

Ca2+ Mg2+ Na+

HCO3-

275

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• Thank you

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