Ex. No.
: 5
ESTIMATION OF WATER HARDNESS
Date:
Water hardness is a traditional measure of the capacity of water to precipitate soap.
Hardness of water is not a specific constituent but is a variable and complex mixture of
cations and anions. It is caused by dissolved polyvalent metallic ions. In fresh water, the
principal hardness causing ions are calcium and magnesium (Ca2+ and Mg2+) which
precipitate soap. Hardness is caused by compounds of calcium and magnesium, and by a
variety of other metals like iron, sulphates etc. Water’s hardness is determined by the
concentration of multivalent cations in the water. The total hardness is the sum of Ca and Mg
concentration, both expressed as CaCO3 in mg L-1. When hard water is heated, CaCO3
precipitates out; this then clogs pipes and industrial boilers. This leads to malfunction or
damage and is expensive to remove. By determination of Ca & Mg and by calculation
hardness of water is determined.
There are two types of hardness
a) Temporary Hardness
b) Permanent Hardness
The degree of hardness of drinking water has been classified in terms of the equivalent
CaCO3 concentration as follows:
Hardness rating Concentration of Calcium Carbonate (mg L-1)
Soft 0-75
Medium Hard 75-150
Hard 150-300
Very Hard 300 and above
Method
a) Hardness by calculation is applicable to all waters and yields the higher
accuracy. If a mineral analysis is performed, hardness by calculation can be
reported.
b) EDTA titration method measures the calcium and magnesium ions and may
be applied with appropriate modification to any kind of water. The procedure
described affords a means of rapid analysis.
Procedure
Hardness by Calculation
The preferred method for determining hardness is to compute it from the results of
separate determinations of calcium and magnesium.
Hardness, mg equivalent CaCO3/L = 2.497 [Ca, mg L-1] + 4.118 [Mg, mg L-1]
EDTA Titrimetric Method
Principle:
Hardness is determined by the EDTA method in alkaline condition; EDTA and its
sodium salts from a soluble chelated complex with certain metal ions. A water sample
containing calcium and magnesium is buffered to pH 10.0 ± 0.1 and added with a small
amount of a dye such as Eriochrome Black T (EBT – Indicator), the solution becomes wine
red. If EDTA is added as a titrant, the calcium and magnesium will be complexed, and when
all of the magnesium and calcium has been complexed the solution turns from wine red to
blue, marking the end point of the titration. Magnesium ion must be present to yield
satisfactory point of the titration. Hence, a small amount of complexometically neutral
magnesium salt of EDTA is added to the buffer. The sharpness of the end point increases
with increasing pH. However, the specified pH of 10.0 ± 0.1 is a satisfactory compromise. At
a higher pH i.e. at about 12.0 Mg++ ions precipitate and only Ca++ ions remain in solution. At
this pH murexide (ammonium purpurate) indicator forms a pink colour with Ca++. When
EDTA is added Ca++ gets complexed resulting in a change from pink to purple which
indicates end point of the reaction. To minimise the tendency towards CaCO3- precipitation
limit the duration of titration period to 5 minutes.
Apparatus
a. Conical flasks 100mL (or) Porcelain basin, b. Burette, c. Pipette, d. Spatula
Reagents
a) Murexide indicator: Weigh 0.2 g of ammonium purpurate and 40 g potassium
sulphate. Mix both the reagents thoroughly in a pestle and mortar.
b) Eriochrome black T: Dissolve 0.5 g of Eriochrome Black – T dye in 100 ml of 80 %
ethyl alcohol.
c) Sodium hydroxide: Weigh 100 g of pure NaOH in water and make volume to one lit.
d) Ammonia buffer solution: Ammonium chloride – Ammonium hydroxide buffer
solution Dissolve 67.5g of ammonium chloride in 570 ml of concentrated ammonium
hydroxide and make to one lit.
e) EDTA solution (0.02 N): Dissolve 3.723 g of disodium salt of EDTA in distilled
water to prepare 1litre of solution. Store in a polyethylene bottle.
TOTAL HARDNESS
Procedure
Calcium Alone
- Pipette out 25ml of the sample into a porcelain basin and add 10 ml of 10 % sodium
hydroxide and 50 mg of murexide indicator.
- Titrate with 0.02 N EDTA till the colour changes from pink red to purple or
violet. Volume of 0.02 N EDTA consumed for Ca (B mL)
- Repeat the titration for concordant values.
Calcium + Magnesium
- Pipette out 25 ml of the sample into a porcelain basin and add 10 ml of ammonium
chloride-ammonium hydroxide buffer solution and 2-3 drops of erichrome black- T
indicator.
- Titrate with 0.02N EDTA till the colour changes from wine red to sky blue.
- From the volume of 0.02 N EDTA consumed (A mL) calculate the Mg and Ca
contents.
- Repeat the titration for concordant values.
Calculation
Volume of the sample taken (V) = 25 ml
Volume of 0.02 N EDTA consumed for Ca+Mg = A ml
Volume of 0.02 N EDTA consumed for Ca alone = B ml
Volume of 0.02 N EDTA consumed for Mg alone = A-B ml
Calcium
1 ml of 0.02N EDTA = 0.0004 g of Ca
A ml of 0.02N EDTA = 0.0004 x A g of Ca
This is present in 25 ml of the sample
= 0.0004 x A x 1000 x 1000 mg L-1
25 (V)
Magnesium
1 ml of 0.02N EDTA = 0.00024 g of Mg
(A-B) ml of 0.02N EDTA = 0.00024 x (A-B) g of Mg
This is present in 25 ml of the sample
= 0.00024 x (A-B) X 1000 x 1000 mg L-1
25(V)
Total hardness (as CaCO3) can also be calculated from calcium and magnesium hardness titre
value (A)
Total Hardness (mg L-1) = ANE1000 V
Where,
E = Equivalent weight of CaCO3 (50)
V = volume of sample in ml
A = volume of titrant consumed (EDTA) in ml
N = Normality of EDTA
Results
Total hardness (as CaCO3) of given water sample is = ____________________ mg L-1
