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Hardness of Water


To determine the extent of hardness Date: present in the given water sample

CONCEPT: Hard water is water that has high mineral content (in contrast with "soft water"). Hard water is generally not harmful to one's health, but can pose serious problems in industrial settings, where water hardness is monitored to avoid costly breakdowns in boilers, cooling towers, and other equipment that handles water. In domestic settings, hard water is often indicated by a lack of suds formation when soap is agitated in water. Wherever water hardness is a concern, water softening is commonly used to reduce hard water's adverse effects. Water's hardness is determined by the concentration of multivalent cations in the water. Multivalent cations are cations (positively charged metal complexes) with a charge greater than 1+. Usually, the cations have the charge of 2+. Common cations found in hard water include Ca2+ and Mg2+. These ions enter a water supply by leaching from minerals within an aquifer. Common calcium-containing minerals are calcite and gypsum. A common magnesium mineral is dolomite. Rainwater and distilled water are soft, because they contain few ions. The following equilibrium reaction describes the dissolving/formation of calcium carbonate scales: CaCO3 + CO2 + H2O Ca2+ + 2HCO3Calcium and magnesium ions can sometimes be removed by water softeners. Temporary hardness Temporary hardness is a type of water hardness caused by the presence of dissolved carbonate minerals (calcium carbonate and magnesium carbonate). When dissolved, these minerals yield calcium and magnesium cations (Ca2+, Mg2+) and carbonate and bicarbonate anions (CO32-, HCO3-). The presence of the metal cations makes the water hard. However, unlike the permanent hardness caused by sulfate and chloride compounds, this "temporary" hardness can be reduced either by boiling the water, or by the addition of lime (calcium hydroxide) through the process of lime softening. Boiling promotes the formation of carbonate from the bicarbonate and precipitates calcium

carbonate out of solution, leaving water softer upon cooling. Permanent hardness Permanent hardness is hardness (mineral content) that cannot be removed by boiling. When this is the case, it is usually caused by the presence of calcium and magnesium sulphates and/or chlorides in the water, which become more soluble (and not precipitate as in case of Temporary hardness) as the temperature rises. This hardness of the water can only be removed using a water softener, or ion exchange column. Water hardness calculator For permanent hardness we can use this formula for calculation. TOTAL PERMANENT HARDNESS = CALCIUM HARDNESS + MAGNESIUM HARDNESS The calcium and magnesium hardness is the concentration of calcium and magnesium ions expressed as equivalent of calcium carbonate. The molar mass of CaCO3, Ca2+ and Mg2+ are 100.1 g/mol, 40.1 g/mol and 24.3 g/mol respectively.

The ratio of the molar masses are:

So total permanent water hardness expressed as equivalent of CaCO3 can be calculated with the following formula:

Interpreting Test Results The hardness of your water will be reported in grains per gallon, milligrams per liter (mg/l) or parts per million (ppm). One grain of hardness equals 17.1 mg/l or ppm of hardness. The Environmental Protection Agency (EPA) establishes standards for drinking water which fall into two categories -- Primary Standards and Secondary Standards. Primary Standards are based on health considerations and Secondary Standards are based on taste, odor, color, corrosiveness, foaming, and staining properties of water. There is no Primary or Secondary standard for water hardness. Water hardness is classified as follows: Concentration as CaCO3 0 to 17.1 mg/L 17.1to 60 mg/L 60 to 120 mg/L 120 to 180 mg/L >180 mg/L Grains per gallon 0-1 1 3.5 3.5 - 7 7 10.5 > 10.5 Indication Soft water Slightly hard water Moderately hard water Hard water Very hard water

Disodium salt of EDTA is used to estimate the various hardness of the given sample of water containing Ca2+ and Mg2+ ions. When EDTA is added to sample, it reacts with Ca and Mg ions present to form stable EDTA metal complexes. From the volume of EDTA consumed, hardness can be calculated. Erichrome Black T is used as indicator. This indicator forms a weak complex with the metal ions present in the sample and gives a wine red colour.
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Hard water

Weak complex of wine red colour

When EDTA is added to sample water, metal ions form a stable metal complex with EDTA leaving from the weak complex with the indicator. When all the metal ions have formed this strong & stable complex with EDTA, the wine red colour changes into steel blue colour, marking the end point. Metal EDTA complex is stable at pH 8-10. Hence this pH value has to be maintained, by adding ammonia buffer solution (NH4Cl + NH4OH)
( ) ( ) Steel blue colour

PRINCIPLE: We shall use a titration method where Calcium ions do not interact with the indicator dye, whereas Magnesium ions react and causes the colour of dye to change. A small dose of complexometrically neutral magnesium salt EDTA is introduced into the titer through the addition of buffer to carry out titration. Disodium salt of Ethylene Diamine Tetra Acetic acid (EDTA) is a good complexing agent; its chemical structure is given below.

Stable colourless

REQUIRED APPARATUS & CHEMICALS: APPARTUS 1. Burette with stand 2. Conical flask 3. Hot plate 4. Pipette CHEMICALS 1. Erichrome black T (EBT) 2. Ammonium Chloride 3. Ammonia Solution 4. EDTA







1. EBT Indicator: a. Dissolve 0.2 gm of pure solid EBT in 15 ml of methanol b. Dissolve 250 mg of pure solid EBT in 100 ml of methanol or ethanol.

2. Standard EDTA titrate 0.02 N (0.01 M): a. Take 0.5 gm of EDTA and heat it to 80C for 30 minutes and then cool it to room temperature. b. Take 0.37 gms of this cooled EDTA salt and add distilled water to make a 100 ml titrate. It is to be noted that 1 ml of exactly 0.02 N EDTA is equivalent to 1.0 mg of CaCO3. 3. Ammonia Buffer solution: a. Dissolve 0.7 gm of NH4Cl in 5.7 ml concentrated ammonia solution and dilute it to 100 ml with distilled water. PROCEDURE: (For Total hardness)

TABULATION: 1. For TOTAL Hardness Run No. Burette Reading Initial Final ml ml EDTA vs. SAMPLE Sample volume ml Indica tor End point


Wine red colour changes to steel blue colour

3 1. Take 20 ml of SAMPLE in a conical flask. 2. Add 2 ml of buffer solution. 3. Add a couple of drops of EBT indicator. Colour of sample becomes wine red. 4. Note the initial reading in the titration burette. 5. Titrate with the EDTA solution till the samples colour changes to blue. PROCEDURE: (For non-carbonate hardness) 1. Boil the 20 ml of SAMPLE for 30 minutes. 2. Steps 2 to 5 as above. 1 Wine red colour changes to steel blue colour

2. For Non- Carbonate Hardness -


AFTER BOILING the SAMPLE for 30 minutes Run No. Burette Reading Initial Final ml ml Sample volume ml Indica tor End point

OBSERVATIONS: Source of sample Date Time Temperature


CALCULATION: 1. Total hardness (expressed in mg of CaCO3)


Total hardness (expressed in mg of CaCO3) = from Table 1 = mg/l

Carbonate hardness (expressed in mg of CaCO3) = mg/l

2. Non-carbonate hardness (expressed in mg of CaCO3) = from Table 2 Non-Carbonate hardness (expressed in mg of CaCO3) = mg/l

3. Carbonate hardness (expressed in mg of CaCO3) = Total hardness - Non-carbonate hardness

SIGNIFICANCE: Hard water has adverse effect on soap and renders less lather and reduces soaps effectiveness. It also renders scaling of boilers, leading to inefficiencies and safety problems causing the boilers to burst.

APPLICATION and UTILITY OF THIS EXPERIMENT: 1. To ascertain waters suitability for domestic and industrial use. 2. To evaluate the feasibility and designing the appropriate water softening plants and schemes.