DR.

ARMAN TABASSUM
Assistant Professor
DEPARTMENT OF CHEMISTRY

FEDERAL URDU UNIVERSITY OF ARTS, SCIENCE AND TECHNOLOGY

GULSHAN-E-IQBAL CAMPUS
KARACHI
INDUSTRIAL CHEMISTRY (CHEM-521)
M.Sc (P), (Semester I)
Unit: Water, Conditioning and Treatment for
Industrial Purposes

Topic: Hardness of water and its estimation

Date: 15th December 2020
 What is Hard Water?
• Hard water is usually defined as water which contains a high concentration of calcium and
magnesium ions.
• Measurements of hardness are given in terms of the calcium carbonate equivalent, which is
an expression of the concentration of hardness ions in water in terms of their equivalent
value of calcium carbonate.
• Water is considered to be hard if it has a hardness of 100 mg/L or more as calcium
carbonate.
• Hard water makes soap precipitate out of water and form a scum, such as the ring which
forms around bathtubs.
• Excessively hard water will nearly always have to be softened in order to protect the water
treatment plant equipment and piping systems.
• At a hardness of greater than 300 mg/L as calcium carbonate, scale will form on pipes as
calcium carbonate precipitates out of the water.
• The scaling can damage equipment and should be avoided.
 Types of Hardness
The type of anion found in these salts distinguishes between the two types of hardness -
carbonate and non carbonate hardness.
 Temporary & Permanent Hardness
• Carbonate hardness is sometimes called temporary hardness because it can be removed
by boiling water.
• Non carbonate hardness cannot be broken down by boiling the water, so it is also known
as permanent hardness.
• In general, it is important to distinguish between the two types of hardness because the
removal method differs for the two.
• When measuring hardness, we typically consider total hardness which is the sum of all
hardness compounds in water, expressed as a calcium carbonate equivalent.
• Total hardness includes both temporary and permanent hardness caused by calcium and
magnesium compounds.
The Guidelines for Drinking Water Quality Hardness divide
hardness into the following categories:

Health Canada, Guidelines for Canadian Drinking Water Quality Supporting Documents.
http://www.hc-sc.gc.ca/ewh-semt/pubs/water-eau/doc_sup-appui/index_e.html
Hardness Problems
 Chelation Chemistry
Chelate:
• Is a compound containing a ligand (typically organic) bonded to a central
atom at two or more points in a cyclic or ring structure.
• Chelates are more stable than nonchelated compounds of comparable
composition, and the more extensive the chelation—that is, the larger the
number of ring closures to a metal atom—the more stable the compound.
This phenomenon is called Chelate Effect.
• Ligands that can attach to the same metal ion at two or more points are
known as polydentate ligands. All polydentate ligands are chelating agents.
 Uses of Chelating agents
• In medical practice, chelating agents, particularly EDTA & its salt are widely used for direct
treatment of metal poisoning because they bind the toxic metal ions more strongly than do
the vulnerable components of the living organism.
• Chelation therapy is an antidote for poisoning by mercury, arsenic, and lead.
• Many commercial dyes and a number of biological substances,
including chlorophyll and hemoglobin, are chelate compounds.
• Chelating agents are also employed as extractants in industrial and laboratory separation of
metals and as metal-ion buffers and indicators in analytical chemistry.
• Chelation in the intestinal tract is a cause of numerous interactions between drugs and metal
ions (also known as "minerals" in nutrition). As examples, antibiotic drugs of
the tetracycline and quinolone families are chelators of Fe2+, Ca2+, and Mg2+ ions.
• They are used in fertilizers to provide micronutrients.
• They are used to determine the hardness of water.
 Estimation of Hardness of Water
• Complexometric Method (EDTA Method)
• EDTA= Ethylene Diamine Tetra Acetic acid
 Ethylene Diamine Tetra Acetic acid
• It is an aminopolycarboxylic acid and a colourless, water-soluble solid.
• Its conjugate base is ethylene diamine tetra acetate.
• It is widely used to dissolve limescale.
• Its usefulness arises because of its role as a hexadentate ("six-
toothed") ligand and chelating agent, i.e., its ability to sequester metal ions such
as Ca2+ and Fe3+.
• After being bound by EDTA into a metal complex, metal ions remain in
solution but exhibit diminished reactivity.
• EDTA is produced as several salts, notably disodium EDTA, calcium
disodium EDTA, and tetrasodium EDTA (typically as the hydrate).
 Ethylene Diamine Tetra Acetic acid
Characteristics:

• It is available in pure form.

• It is strong chelating agent.
• Its chelate formation is faster than other chelating agents.
• It is hexadentate (4 oxygen and 2 nitrogen)
• In solution: In aqueous solution, two Na-ions are ionized (from its Na-salt).
• When pH becomes 6.3, one of H-atom gets removed from it.
• At pH 11.5 second H-atom is removed.
• Stability of EDTA is possible with low pH. It decomposes at higher pH.
Sodium salt of Ethylene Diamine Tetra Acetic acid
Chelate action of EDTA
 Eriochrome Black T (EBT)
• Eriochrome Black T is a complexometric indicator that is used
in complexometric titrations, e.g. in the water hardness determination process.
• It is an azo dye.
In its deprotonated form, Eriochrome Black T is blue. It turns red when it
forms a complex with calcium, magnesium, or other metal ions.
 Complexometric Titration
• Analytical technique called “complexometric titration” is used to analyze the amounts of
dissolved metals in solutions.
• The technique involves placing the metal-containing solution in a flask and adding a
complexing agent, such as EDTA, dropwise from a buret.
• The complexing agent binds to the metals and, after all the metals have been complexed,
the next drop of complexing agents binds to an indicator-metal to induce a color change.
• The color change allows the chemist to know when the titration is complete.
• Eriochrome black T, or EBT, represents one of the color-changing compounds for such
titrations.
• EBT, however, is a solid and must be prepared as a solution prior to its use as an
indicator.
EDTA Titration
https://www.youtube.com/watch?v=CWOJW4357Bg