.

MODULE 2: Determination of Water/Wastewater hardness by

EDTA Titrimetric Method

EXPERIMENT 3

I. OBJECTIVES

To determine the hardness of water or wastewater by EDTA Titrimetric Method

II. THEORETICAL BACKGROUND

Originally, water hardness was understood to be a measure of the capacity of water to

precipitate soap. Soap is precipitated chiefly by the calcium and magnesium ions present.
Other polyvalent cations also may precipitate soap, but they often are in complex forms,
frequently with organic constituents, and their role in water hardness may be minimal and
difficult to define. In conformity with current practice, total hardness is defined as the sum
of the calcium and magnesium concentrations, both expressed as calcium carbonate, in
milligrams per liter. Water with high hardness values are referred to as "hard," while those
with low hardness values are "soft".

When hardness numerically is greater than the sum of carbonate and bicarbonate
alkalinity, that amount of hardness equivalent to the total alkalinity is called ‘‘carbonate
hardness’’; the amount of hardness in excess of this is called ‘‘noncarbonate hardness.’’
When the hardness numerically is equal to or less than the sum of carbonate and
bicarbonate alkalinity, all hardness is carbonate hardness and noncarbonate hardness is
absent. The hardness may range from zero to hundreds of milligrams per liter, depending on
the source and treatment to which the water has been subjected.

Table 1.1: Classes of Water Hardness Based on Hardness Range

Hardness Range Hardness

(mg/L as CaCO3) Description
0 - 50 Soft
151 – 300 Hard
>300 Very Hard

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EDTA Titrimetric Method

Ethylenediaminetetraacetic acid and its sodium salts (abbreviated EDTA) form a chelated
soluble complex when added to a solution of certain metal cations. If a small amount of a
dye such as Eriochrome Black T or Calmagite is added to an aqueous solution containing
calcium and magnesium ions at a pH of 10.0 ± 0.1, 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 a
satisfactory end point. To insure this, a small amount of complexometrically neutral
magnesium salt of EDTA is added to the buffer; this automatically introduces sufficient
magnesium and obviates the need for a blank correction.

The sharpness of the end point increases with increasing pH. However, the pH cannot be
increased indefinitely because of the danger of precipitating calcium carbonate, CaCO3,
or magnesium hydroxide, Mg(OH)2, and because the dye changes color at high pH values.
The specified pH of 10.0 ± 0.1 is a satisfactory compromise. A limit of 5 min is set for the
duration of the titration to minimize the tendency toward CaCO3 precipitation.

III. APPARATUS AND REAGENTS

A. APPARATUS
Buret clamp
Erlenmeyer flask Iron Stand
Pipet Iron ring
Pipetol Wire gauze
Graduated cylinder Bunsen burner
Buret Wash bottle

B. REAGENTS

1. Buffer solution

Dissolve 16.9 g ammonium chloride (NH4Cl) in 143 mL conc ammonium hydroxide (NH4OH).
Add 1.25 g magnesium salt of EDTA (available commercially) and dilute to 250 mL with
distilled water.

If the magnesium salt of EDTA is unavailable, dissolve 1.179 g disodium salt of

ethylenediaminetetraacetic acid dihydrate (analytical reagent grade) and 780 mg
magnesium sulfate (MgSO4⋅ 7H2O) or 644 mg magnesium chloride (MgCl2⋅ 6H2O) in 50 mL
distilled water.

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Add this solution to 16.9 g NH4Cl and 143 mL conc NH4OH with mixing and dilute to 250 mL
with distilled water. To attain the highest accuracy, adjust to exact equivalence through
appropriate addition of a small amount of EDTA or MgSO4 or MgCl2. Store Solution 1) or 2)
in a plastic or borosilicate glass container for no longer than 1 month. Stopper tightly to
prevent loss of ammonia (NH3) or pickup of carbon dioxide (CO2). Dispense buffer solution
by means of a bulb-operated pipet. Discard buffer when 1 or 2 mL added to the sample
fails to produce a pH of 10.0 ± 0.1 at the titration end point.

2. Eriochrome Black T:

Sodium salt of 1-(1-hydroxy-2-naphthylazo)-5-nitro-2-naphthol-4-sulfonic acid; No. 203 in the

Color Index. Dissolve 0.5 g dye in 100 g 2,2′,2′′-nitrilotriethanol (also called triethanolamine)
or 2-methoxymethanol (also called ethylene glycol monomethyl ether). Add 2 drops per 50
mL solution to be titrated. Adjust volume if necessary.

3. Standard EDTA titrant, 0.01M:

Weigh 3.723 g analytical reagent-grade disodium ethylenediaminetetraacetate dihydrate,

also called (ethylenedinitrilo)tetraacetic acid disodium salt (EDTA), dissolve in distilled water,
and dilute to 1000 mL. Standardize against standard calcium solution. Because the titrant
extracts hardness-producing cations from soft-glass containers, store in polyethylene
(preferable) or borosilicate glass bottles. Compensate for gradual deterioration by periodic
restandardization and by using a suitable correction factor.

4. Standard calcium solution:

Weigh 1.000 g anhydrous CaCO3 powder (primary standard or special reagent low in
heavy metals, alkalis, and magnesium) into a 500-mL Erlenmeyer flask. Place a funnel in the
flask neck and add, a little at a time, 1 + 1 HCl until all CaCO3 has dissolved. Add 200 mL
distilled water and boil for a few minutes to expel CO2. Cool, add a few drops of methyl red
indicator, and adjust to the intermediate orange color by adding 3N NH4OH or 1 + 1 HCl, as
required. Transfer quantitatively and dilute to 1000 mL with distilled water. (Note: 1 mL = 1.00
mg CaCO3)

5. Sodium hydroxide, NaOH, 0.1N.

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IV. METHODOLOGY

A. Standardization of EDTA Titrant Against Standard Calcium Solution

1. Place 10 mL standard calcium solution in an Erlenmeyer flask.

2. Add 1 to 2 mL buffer solution.
3. Add 1 to 2 drops of EBT indicator.
4. Titrate the sample with EDTA titrant slowly, with continuous stirring, until the last reddish
tinge disappears. Add the last few drops at 3- to 5-s intervals. At the end point the solution
normally is blue.
5. Repeat all procedures for two more trials.

B. Determination of the Total Hardness of Water

1. Shake the water sample well

2. Place 50 mL water sample in an Erlenmeyer flask.
3. Add 1 to 2 mL buffer solution. Usually 1 mL will be sufficient to give a pH of 10.0 to 10.1.
The absence of a sharp end-point color change in the titration usually means that an
inhibitor must be added at this point or that the indicator has deteriorated.
4. Add 1 to 2 drops of EBT indicator.
5. Titrate the sample with standard EDTA titrant slowly, with continuous stirring, until the last
reddish tinge disappears. Add the last few drops at 3- to 5-s intervals. At the end point the
solution normally is blue. Daylight or a daylight fluorescent lamp is recommended highly
because ordinary incandescent lights tend to produce a reddish tinge in the blue at the
end point.
6. Repeat all procedures for two more trials.

C. Determination of the Permanent Hardness of Water

1. Boil around 250 mL water sample for 15 minutes.

2. Cool the water sample to room temperature.
3. Place 50 mL water sample in an Erlenmeyer flask.
4. Add 1 to 2 mL buffer solution. Usually 1 mL will be sufficient to give a pH of 10.0 to 10.1.
The absence of a sharp end-point color change in the titration usually means that an
inhibitor must be added at this point or that the indicator has deteriorated.
5. Add 1 to 2 drops of EBT indicator.
6. Titrate the sample with standard EDTA titrant slowly, with continuous stirring, until the last
reddish tinge disappears. Add the last few drops at 3- to 5-s intervals. At the end point the
solution normally is blue. Daylight or a daylight fluorescent lamp is recommended highly
because ordinary incandescent lights tend to produce a reddish tinge in the blue at the
end point.
7. Repeat procedures 3 - 6 for two more trials.

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Calculation

The standardized concentration of the standard EDTA solution was computed utilizing the
dilution formula:

�1 �1 = �2 �2

Total Hardness = Permanent Hardness + Non − Permanent Hardness

�� (� � �) � 1000
�� ����3 =
� �� ������

Where A is mL EDTA used during titration and B is the mg CaCO3 equivalent to 1.00 mL
EDTA titrant.

V. REFERENCES

Standard Methods for the Examination of Water and Wastewater, 20th Edition.

CONNORS, J.J. 1950. Advances in chemical and colorimetric methods. J. Amer. Water
Works Assoc. 42:33.

DIEHL, H., C.A. GOETZ & C.C. HACH. 1950. The versenate titration for total hardness. J. Amer.
Water Works Assoc. 42:40.

BETZ, J.D. & C.A. NOLL. 1950. Total hardness determination by direct colorimetric titration. J.
Amer. Water Works Assoc. 42:49.

GOETZ, C.A., T.C. LOOMIS & H. DIEHL. 1950. Total hardness in water: The stability of standard
disodium dihydrogen ethylenediaminetetraacetate solutions. Anal. Chem. 22:798.

DISKANT, E.M. 1952. Stable indicator solutions for complexometric determination of total
hardness in water. Anal. Chem. 24:1856.

BARNARD, A.J., JR., W.C. BROAD & H. FLASCHKA. 1956 & 1957. The EDTA titration. Chemist
Analyst 45:86 & 46:46.

GOETZ, C.A. & R.C. SMITH. 1959. Evaluation of various methods and reagents for total
hardness and calcium hardness in water. Iowa State J. Sci. 34:81 (Aug. 15).

SCHWARZENBACH, G. & H. FLASCHKA. 1969. Complexometric Titrations, 2nd ed. Barnes &
Noble, Inc., New York, N.Y.

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Davis, Mackenzie. Introduction to Environmental Engineering, 5th Ed. McGraw-Hill

Education, c2012.

Metcalf & Eddy. Wastewater Engineering: Treatment, Disposal and Reuse, 3rd Edition.
McGraw-Hill Education, c1991.

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