Analysis of Water

To determine the hardness of a water sample

Requirements

250ml conical flask, funnel, beaker, burette, pipette.

Standard EDTA (Na2H2Y) solution (0.1M), buffer solution (pH=10), Eriochrome Black T (EBT)
indicator, Ammonium oxalate

Theory

Hard water is water that has high mineral content (in contrast with soft water). Hard water has
high concentrations of calcium and magnesium ions. These ions are called hardening ion. In low
concentrations, these ions are not considered harmful for domestic use, but when present in higher
concentrations these are harmful in many ways.

A General Classification Of Hard Water is given below:

Hardness (ppm CaCO3) Classification

<15ppm Very soft water

15ppm-50ppm Soft water
50ppm-100ppm Medium hard water
100ppm-200ppm Hard water
>200ppm Very hard water

Disadvantages of hard water

 It is difficult to form lather with soap.

 Scum may form in a reaction with soap thus wasting soap.

 Lime scale (a hard crust) forms inside kettles. This wastes energy whenever you boil a
kettle.

 Hot water pipes fur up. Lime scale starts to coat the inside of the pipes which can
eventually can get blocked up.

Thus these ions must be removed from water.

Total Dissolved Salts

The term total dissolved solids refer to materials that are completely dissolved in water. These
solids are non-filterable in nature. It is defined as residue upon evaporation of filterable sample.
The term total suspended solids can be referred to materials which are not dissolved in water and
are filterable in nature. It is defined as residue upon evaporation of non-filterable sample. Certain
components of TDS, such as chlorides, sulfates, magnesium, calcium, and carbonates, affect
corrosion or encrustation in water-distribution systems

Water containing TDS concentrations below 1000 mg/litre is usually acceptable to consumers,
although acceptability may vary according to circumstances. However, the presence of high levels
of TDS in water may be objectionable to consumers owing to the resulting taste and to excessive
scaling in water pipes, heaters, boilers, and household appliances

Environmental Significance

1. Dissolved minerals, gases and organic constituents may produce aesthetically

displeasing colour, taste and odour.

2. Some dissolved organic chemicals may deplete the dissolved oxygen in the receiving
waters and some may be inert to biological oxidation, yet others have been identified as
carcinogens.

3. Water with higher solids content often has a laxative and sometimes the reverse effect
upon people whose bodies are not adjusted to them.

4. High concentration of dissolved solids about 3000 mg/L may also produce distress in
livestock. In industries, the use of water with high amount of dissolved solids may lead to
scaling in boilers, corrosion and degraded quality of the product.

5. Estimation of total dissolved solids is useful to determine whether the water is suitable
for drinking purpose, agriculture and industrial purpose.

6. Suspended material is aesthetically displeasing and provides adsorption sites for chemical
and biological agents.

7. Suspended organic solids which are degraded anaerobically may release of noxious
odours.
 8. Biologically active suspended solids may include disease causing organisms as well as
organisms such as toxic producing strains of algae.

9. The suspended solids parameter is used to measure the quality of wastewater influent and
effluent.

10. Suspended solids determination is extremely valuable in the analysis of polluted waters.

11. Suspended solids exclude light, thus reducing the growth of oxygen producing plants

Chemistry Involved in removing hardness from water

The concentration of hardening ions in water can be determined by a titration technique, the
titrant is the disodium salt of ethylene-diaminetetraaceticacid

In aqueous solution Na2H2Y dissociates into Na+ and H2Y2- ions. Ca2+ and Mg2+ react with H2Y2-
to form stable complexes in a solution having pH of about 10. A buffer solution containing
ammonia and ammonium ions is used to maintain the pH of the solution around 10. For the
detection of the end point Eriochrome Black T (EBT) is used as indicator.

EBT forms complex ions with Ca2+ and Mg2+, but binds more strongly to Mg2+ ions.

EBT indicator is sky-blue in solution but its complex with Mg2+ ions, [Mg-EBT]2+, is wine red

Mg2+(aq) + EBT(aq) [Mg-EBT]2+ (aq)

Sky-blue wine red

Thus, during titration when indicator is added to hard water, the initial color is wine red. When the
titrant is added, H2Y2- complexes with free Ca2+ and Mg2+ present in water and finally removes
Mg2+ ions from the [Mg-EBT]2+ complex ions. As a result the color of the solution from wine red
to sky blue.

[Mg-EBT]2+ (aq) + H2Y2-(aq) MgY2- + 2H+(aq) + EBT(aq)

Wine red sky blue

Wine red to sky blue

Structure od Ca EDTA and Mg EDTA complex

 1. Procedure for determination of Total Ca and Mg content in hard water

Take about 20ml of tap water in a conical flask and add 10ml of buffer solution and mix. Add few
drops of Eriochrome Black T as an indicator. Titrate with standard EDTA solution, the end point
is permanent blue. Take three concordant readings.

Note : Note the total volume of EDTA used ‘a’

2. Procedure for determination of Magnesium

Take 20ml of water solution and precipitate out Calcium as calcium oxalate by using 5%
(NH4)2C2O4 solution and then titrate the remaining solution as discussed above.

Note the volume of EDTA used for Mg2+ titration ‘b’.

The amount of Ca is then found by difference.

Calculations

a) For Mg2+

EDTA = Hard water Mg2+

M1V1 = M2V2

0.1M × x ml = M2 × 20ml
0.1M × x ml
M2 = = ---------M
20ml

Molecular weight of Mg2+ = 24

Amount of Mg2+= 24× M2

b) For Ca2+

Volume for Ca2+ = Total volume of EDTA used for both Ca+2 and Mg+2 - Volume used for Mg2+

Volume for Ca2+ = a-b

EDTA = Hard water Ca2+

M1V1 = M2V2
0.1M × (a-b) ml = M2 × 20ml
0.1M ×(a−b) ml
M2 = = ---------M
20ml

Molecular weight of Ca2+ = 40

Amount of Ca2+= 40 × M2

3. Procedure to find total solids (TS)

Method

Gravimetric method was used for determination of solids

50ml of unfiltered water was taken in a weighed beaker and placed on hot plate for evaporation
and dryness. After dryness the beaker was placed in oven for complete evaporation. Then it was
allowed to cool and finally weighed.

Total solid was calculated by using following relation

𝒘𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝒓𝒆𝒔𝒊𝒅𝒖𝒆 (𝒈)

Total solids mg/l = × 𝟏𝟎𝟔
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒔𝒂𝒎𝒑𝒍𝒆 (𝒎𝒍)

4. Total Dissolved Solids (TDS)

50ml of filtered water was taken in a weighed beaker and placed on hot plate for evaporation and
dryness. After dryness the beaker was placed in oven for complete evaporation. Then it was
allowed to cool and finally weighed.

Total dissolved solid was calculated by using following relation

𝒘𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝒓𝒆𝒔𝒊𝒅𝒖𝒆 (𝒈)

Total dissolved solids mg/l = × 𝟏𝟎𝟔
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒔𝒂𝒎𝒑𝒍𝒆 (𝒎𝒍)

5. Conductivity Of Water

Conductivity of the sample was measured by conductivity meter at room temperature.

Specific conductance was calculated by the following relation

Specific conductance = conductivity × cell constant

 1
k = × C cm-1
𝑅

Where 1/R is conductance in milli Siemen and C is cell constant. The conductivity meter was
calibrated and the conductivity of water sample was then measured in mS. It was then multiplied
with cell constant to obtain specific conductance in mS cm-1

Cell constant = 1.15 cm-1 at 25ᵒC

Results

Explain your results and compare them with deionized water