IS : 3025 ( Part 21 1 - 1983
UDC 620.11’3: 643’32 ( Third Reprint JANUARY 1998 ) (J3oaffh.d 1996 )
Indian Standard
METHODS OF SAMPLING AND TEST ( PHYSICAL AND
CHEMICAL ) FOR WATER AND WASTE WATER
PART 21 TOTAL HARDNESS
f First Revision J
1. Scope- Prescribes two methods for determination of total hardness, namely:
. a) Ethylenediamine tetraacetic acetate acid ( EDTA ) method, and
i
; b) Method based on analytical data.
b
.
1.1 The first method is based dn the reaction of calcium and magnesium salts with ethylenediamine
I
1tetra acetic acid o! its disodium salt and is applicable to all types of water but not applicable to waste
t \water. The analytlcal data method IS based on computation from analytical results of the sample and is
4applicable to water and waste water. In case of dispute, the method based on analytical data shall be
1 ’ssed.
, I2. EDTA Method
I
, :2.1 Principle - This method depends on ability of ethylenediamine tetraacetic acid ( Cl0 HIa Oe NI )
1 HOOCH& CH&OOH
I
I > NH& - CHIN <
I HOOCH& CHICOOH
,
! (>r its disodium salt to form stable comrjlexes with calcium and magnesium ions. When the dye
1 tirriochrome black T ( EBT ) ( GO Hu. NsOTS )
I
I
I
/ NaO,S N=N&
I
w /
OzN
is added to a solution containing calcium and magnesium ions at pH 10’0 a wine red complex iq
formed. This solution is tit!a!ed with standard solution of disodium salt of EDTA, which extracts
calcium and magnesium from the dye complex and the dye is changed back to its original blue colour.
Eriochrome black T is used to indicate the end-point for the titration of calcium and magnesium
together.
Mg+++ EBTPEMg-EBT]‘+ H+
( Pink Complex)
[Ma- EBTI- + EDTA--+ I:Mg- EDTA]‘- + [EBT]” + H+
( Blue)
2.2 Interferences
22.1 The EDTA forms stable complexes with iron, manganese, copper, lead, cobalt, zinc and nickel.
Heavy metal interferences can be eliminated by complexing the metals with cyanide. In the presence
>f cyanide, the procedure may be used even when iron, copper, zinc or lead concentrations are as high
as 10 mg/l.
Adopted30 December1983 0 September 1986, BIS I
Or2
I
BUREAU OF INDIAN STANDARDS
MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG
NEW DELHI 110002
IS : 3025 ( Part 21 ). - 1983
2.2.2 The higher oxidation states of manganese above Mn++ react rapidly with the indicator to form
discoloured oxidation products. Hydroxylamine hydrochloride reagent may be used to reduce man-
ganese to divalent state. The divalent manganese interference can be removed by addition of one or
two small crystals of potassium ferrocyanide.
2.2.3 In presence of high aluminium concentrations, the blue colour near end point starts disappea-
fing and reverts to red.
2.2.4 Phosphate and carbonate ions may precipitate. calcium at the pH of titration.
2.3 Reagents
2.3.1 Buffer solution - Dissolve 16’9 g ammonium chloride ( NH&l ) in 143 ml concentrated
ammonium hydroxide ( NHIOH ), add 1’25 g of magnesium salt of EDTA and dilute to 250 ml with
distilled water.
Store the solution in a polyethylene bottle tightly stoppered to prevent loss of ammonia or pick-
up of carbon dioxide for no longer than ‘1 month. Dilute 10 ml of the solution to 100 ml with
distilled water and check that the pH value is 10’0 f 0’1.
2.3.2 In the absence of magnesium salt of EDTA, dissolve 1’179 g disodium salt of EDTA (AR
quality) and 780 mg magnesium sulphate ( MgSOa.7H,O ) or 644 mg magnesium chloride ( Mg
Cl,. 6H,O) in 50 ml of distilled water. Add this solution to 16’9 g ammonium chloride and 143 ml
concentrated ammonium hydroxide with mixing and dilute to 250 ml with distilled water. To attain
the highest accuracy, adjust to exact equivalance through appropriate addition of a small amount of
EDTA or magnesium sulphate or chloride. The’exact amount can be determined by taking an appro-
priate aiiquot of buffer and titrate it with disodium salt of EDTA as in 2.4.1. Keep the solutions tightly
stoppered to prevent loss of ammonia or absorbance of carbon dioxide and do not store for more than
a month. Dilute 10 ml of the solution to 100 ml with distilled water and check that the pH value
is 10’0 f 0’1.
2.3.3 Standard calcium solution - 1’00 ml = 1’00 mg calcium carbonate ( CaCOs ). Dry analyti-
cal grade calcium carbonate ( CaCOs ) in an oven at 180°C for 1 hour. Weigh 1’000 g, suspend it in
distilled water and add con.centrated hydrochloric acid AR quality, diopwise slowly to dissolve the
solid. Use minimum amount of acid. Boil for a few minutes, cool, add a few drops of methyl red
indicator and adjust to orange colour with 3N ammonium hydroxide. Dilute to 1 000 ml with distilled
water.
23.4 Eriochrome black 1 indicator solution - Dissolve 0’40 g eriochrome black T and 4’5 g
hydroxylamine hydrochloride ( NH,OH HCI ). in 100 ml 95 percent ethanol. This indicator is stable
for more than 2 months. Alternatively, dissolve 0’5 g eriochrome black T in 100 ml triethanolamine
or 2-methoxyethanol or mixed 0’5 g EBT dye and 100 g soduim chloride in a pestle and mortar.
Store in a tightly stoppered bottle. All indicator formulations tend to deteriorate especially when
exposed to moisture. If the end point colour change is not sharp enough it is either due to, the pre-
sence of some interfering ions or due to deterioration of the indicator. In the latter case, addition of
inhibitor sodium cyanide or sodium sulphide ( NaCN or Na& ) does not sharpen the end point colour
change.
2.3.5 Inhibitors - For most waters inhibitors are not necessary. If interfering ions are present,
inhibitors given in 2.3.5.1 to 2.3.5.4 may be used.
2.3.5.1 Hydroxylamine hydrochloride solution - Dissolve 45 g hydroxylamine hydrochloride
( NHsOH.HCI) in demineralised water and dilute to 1 litre, or dissolve 4’5 g hydroxylamine
hydrochloride in 100 ml of 95 percent ethanol or isopropanol.
2.3.5.2 Potassium ferrocyanide crystals
2.3.5.3 Sodium sulphide inhibitor - Dissolve 5’0 g sodium sulphide ( NarS.9HIO) or 3’7 g NarS.
5HI0 in 100 ml distilled water. Tightly stopper so as to avoid excessive contact with air.
2.3.5.4 Sodium cyanide solution - Dissolve 2’5 g sodium cyanide ( NaCN 1 in demineralised
water and dilute to 100 ml. As sodium cyanide is extremely poisonous, it should be handled with
care. The solution should not be made acidic and should be flushed down the drain with large
amounts of water when it is to be disposed off.
2
IS : 3025 ( Part 21 ) - 1983
2.3.6 Standard EDTA solution - Dissolve 3’723 g EDTA ( NasH&laHlrO N2.2 H*O) which has
been dried overnight in ti sulphuric acid desiccator, in demineralised water and dilute to i 000 ml.
The reagent is stable for several weeks and large volume is usually prepared. Check the reagent by
titrating 25 ml of standard calcium solution as described in 24.1. Store in polyethylene bottles.
2.4 Procedure
2.4.1 Standardization - Pipette 25’0 ml ‘of standard calcium solution in- a porcelain basin and
adjust the volume to 50 ml with distilled water. Add 1 ml buffer solution (2.3.1 ). Add 1 to 2
drops of indicator ( 2.3.4). titrate slowly with continu.ous stirring until the redish tinge disappears,
adding last few drops at 3 to 5 second interval. At the end point the colour is sky blue.
2.4.2 Procedure for drinking, surface and saline waters - Pipette an aliquot of water sample,
maximum 50 ml, in a porcelain dish or 150-ml beaker and adjust the volume to approximately 50 ml.
Add 1 ml hydroxylamine hydrochloride ( NH:OH.HCI ), solution. Add 1 to 2 ml buffer solution so
as to achieve pH of 10’0 to 10’1. If the end point is not sharp ( as determined by practice) add 2 ml
sodium cyanide or sodium sulphide inhibitor solution. The addition of sodium cyanide or. sodium
sulphide may be omitted if ‘copper, zinc, lead, cobalt and nickel are absent and if the sample contains
less than 0’25 mg of iron and 0’025 mg of manganese. If manganese is present, add 1 or 2 small
crystals of potassium ferri cyanide [k Fe (CN)s. 3H10 1. Stir and wait for at least 5 minutes until
sodium ferri cyanide precipitates. Add 2 ml eriochrome black T indicator solution, titrate with
standard EDTA solution stirring rapidly in the beginning and slowly towards the end till end
point is reached when all the traces of red and purple colour disappear and solution is clear sky blue
in colour.
2.4.3 Procedure for waste waters and highly polluted waters - Digest an aliquot of the sample
with 3 ml of distilled concentrated nitric acid in a beaker on a hot plate and evaporate to near dryness
cautiously making sure that the sample does not boil. Repeat digestion with nitric acid till the,
digestate is light in colour. Evaporate to near dryness and cool the beaker. Add a small quantity of
1 : 1 hydrochloric acid ( 5 ml ) and warm on a hot-plate or steam-bath to dissolve the residue. Cool,
adjust to a suitable volume and take an aliquot of this digested sample. Proceed as given in 2.4.2.
Note 1 - For water with very low hardness ( less than 5 mg/l ) micro burette may be used.
Note 2 - Selection of sample size may be made such that the result lies between 200 to 300 mg/l of hardness
( as CaCOI ).
2.5 Calculation - Calculate the hardness as follows:
1 000 VI
Total hardness ( as CaCOs ), mg/l = ,,
,
where
v, = volume in ml of the EOTA standard solution used in the titration, and
v, = volume in ml of the sample taken for the test.
2.6 Report - Report hardness in mg/l as CaC03 rounded to the first decimal place when the value
is less than 10 mg/l and to the nearest unit if the value is more than 10 mg/l.
2.7 Precision and Accuracy - The precision is within 1 mg/l. The accuracy depends on the inter-
fering substances present. In the absence of any interference, it is within 1 mg/l.
Note - Standarddeviation of 1’2 mg/l has been reported.
3. Method Based on Analytical Data
3.1 Principle - Total hardness computed from the concentration of the different metallic cation (other
than alkali metals ) in the sample but most often the cations taken into account are calcium, magne-
sium, iron, aluminium; zinc, strontium, barium and manganese.
3.2 Calculation
Total hardness ( as CaCO3 ), mgll = ( 2’497 X mg/l Ca ) +( 4’116 x mg,4 Mg ) + ( 2’69 x mg/l Fe ) +
( 5’567 X mg/l Al ) -I-( 1’531 X my/l Zn )+ ( 1’822 xmg/l Mn ) +
( 0’894 x mg/l Ba ) + ( 1’319 x mg/l Sr ).
EXPLANATORY NOTE
Total hardness of water is the sum of the concentrations of all the metallic cations other than
cations of alkali metals, expressed as equivalent calcium carbonate concentration. In most natural
waters, hardness is mainly due to calcium and magnesium ions. In some waters, measurable con-
centrations of iron, aluminium, manganese, barium, zinc and other metals may be present. when the
hardness is numerically greater than the sum of carbonate alkalinity and bicarbonate alkalinity; the
amount of hardness which is equivalent to total alkalinity is called ‘carbonate hardness’ and the
amount of hardness in excess of this is called ‘non-carbonate hardness’. Some waters containing high
concentrations of borafes, phosphates, silicates, may contribute to total alkalinity.
3
Reprography Unit, BIS, New Delhi, India
AMENDMENT
NO. 1 JANUARY 2000
TO
1s 3025 ( PART 21) : 1983 METHODS OF SAMPLING
AND TEST (PHYSICAL AND CHEMICAL) FOR WATER
AND WASTEWATER
PART 21 TOTAL HARDNESS
( First Revision )
(Page 2, clause 2.3.3, iinc 3 ) - Substitute ‘I :l ’ for ‘concentrated’.
( Pqe 2, clnust 2.3.3, line 5 ) - Insert ‘or 1 :l hydrochloric acid’ after
‘3 N ammonium hydroxide’.
( Page 3, clause 2.4.2, last line ) - Insert the following at the end of Ihe
clause:
‘Blank titration, carried out in a similar way as that for sample, may be
used for comparison.’
(Page 3, ck0rrse 2.5 ) -Substitute the following for the existing:
‘2.5 Calculation - Calculate the hardness as follows:
Total hardness as (C&03), r-t@ = [lo0 (VI-&)/ti] x CF
where
VI = volume in ml of the EDTA standard solution used in the
titration for the sample,
V2 = volume in ml of the EDTA solution used in the titration for
blank,
V3 = volume in ml of the sample taken for the test,
CF = Xl/.X;! = correction factor for standardization of EDTA,
Xl = volume in ml of standard calcium solution taken for
standardization, and
X2 = volume of ml of EDTA solution used in the titration.’
(CHDl2)
Reprography Unit, BlS, New Delhi, India
