Experiment 1: Comprehensive Water Analysis

Aim:
To analyze hardness, chloride content, Total Dissolved Solids (TDS), pH, and sulfate
content of a locally available water sample and compare the water quality as per central
pollution control board (CPCB), India.

Part I - Estimation of Total Hardness of a given water sample

Aim: To determine the total hardness of the given water sample

Principle:

Hardness of a ground water sample is due to the presence of calcium and magnesium salts
present in it. There are two types of water hardness, namely temporary and permanent hardness.
Temporary hardness causing salts, Ca(HCO3)2 and Mg(HCO3)2 (bicarbonates of calcium and
magnesium) which can be removed by simple boiling. On boiling, these salts form precipitates
of CaCO3 and Mg(OH)2 which can be further removed by filtration. Permanent hardness is
caused by the presence of chlorides and sulphates of calcium and magnesium.
Ethylenediaminetetraacetic acid (EDTA) forms complexes with many cations including Ca2+
and Mg2+ at a basic pH (9-10). Basic pH of the water sample is maintained by using ammonia
buffer (NH4OH – NH4Cl). Hence, it is possible to determine the total hardness of water sample
using EDTA solution. As EDTA is insoluble in water, disodium salt of EDTA is generally used
for the complexation. EDTA has six binding sites (the four carboxylate groups and the two
amino groups, Fig. 1a.) providing six pairs of electrons.

(a) (b)

Structure of EDTA and EBT

To indicate the end of complexation, Eriochrome Black–T (EBT) indicator (Fig. 1b.) is used.
Ca2+ and Mg2+ ions form a wine red colored complex with EBT indicator in the presence of
ammonia buffer solution. When EDTA solution is added to the indicator complex, EDTA
replaces the indicator and a stable complex of Metal–EDTA is formed. The color of the solution
will be steel blue due to the release of EBT indicator into the solution.

Ca2+/Mg2+ + EBT → [Ca2+/Mg2+–EBT]

in water wine red color
(unstable)
[Ca2+/Mg2+–EBT] + EDTA → [Ca2+/Mg2+–EDTA] + EBT
wine red color colorless steel blue color
(stable)

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Requirements:

Reagents and solutions: Standard hard water (1mg/mL of CaCO3 equivalents), 0.01 N EDTA
solution, EBT indicator, hard water sample, NH3-NH4Cl buffer solution.

Apparatus: Burette, pipette, conical flask, standard flask, and burette stand.

Procedure:

Titration-I: Standardization of EDTA

20 mL of the standard hard water containing 1mg/mL of CaCO3 (1000 ppm) is pipetted out into
a clean conical flask followed by 3 to 5 ml of of ammonia buffer (NH4OH – NH4Cl) solution
to maintain the pH around 10. Three drops of Eriochrome Black – T (EBT) indicator was added
and titrated against the given EDTA solution taken in the burette. The end point is change of
colour from wine red to steel blue. Titrations are repeated to get concordant titre value. (V1).

Titration-I: Standardization of EDTA

Standard Hardwater vs. EDTA
S. No. Volume of standard Burette reading (mL) Volume of EDTA
hard water (mL) Initial Final (V1, mL)

Concordant titre value

Calculation:

20 mL of given hard water consumes V1 mL of EDTA

20 mg of standard hardwater requires V1 mL of EDTA for complexation

1 mL of EDTA requires = 20/V1 mg CaCO3 for complexation

Titration-II: Estimation of total hardness of hard water sample

Pipette out 20 mL of the given sample of hard water into a clean conical flask. Add one test
tube full of ammonia buffer (NH4OH – NH4Cl) solution and three drops of Eriochrome Black–
T (EBT) indicator. Titrate this mixture against standardized EDTA solution taken in the burette.

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The end point is the change of color from wine red to steel blue. Repeat the titration for
concordant titre value. Let ‘V2’ be the volume of EDTA consumed.

Titration-II: Estimation of Total hardness of water sample

Standard EDTA vs. given water sample
S. No. Volume of sample Burette reading Volume of EDTA
hard water (mL) (V2, mL)
Initial Final

Concordant titre value

From Titration 1, we have the following relation:

 1 mL of EDTA requires = 20/V1 mg CaCO3 for complexation

From Titration 2,

20 mL of sample hard water consumes = V2 mL of EDTA.

= V2 x 20/V1 mg of CaCO3 eq.

1000 mL of hard water sample consumes = V2 x 20/V1×1000/20

= V2/V1×1000 ppm

Total hardness of the water sample = _________ ppm

Result: Total hardness of the water sample = _______ppm

Part II - Estimation of Chloride content

Solutions of electrolyte conduct electricity due to the presence of ions. In case of

conductometric precipitation titration between AgNO3 and Chloride ions, the conductance
decreases slowly due to the removal of chloride ions as AgCl precipitate preceded by
replacement of sodium ions by silver ions up to the equivalence point. After the equivalence
point, where no chloride ions are present, the conductance increases rapidly due to silver ions
from the added AgNO3 solution.

Cl-(aq) + Ag+(aq) + NO3-(aq) → AgCl(s) + NO3-(aq)

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The obtained precipitate has a low solubility in water. In addition, because only halide and
sulfide ions precipitate in presence of AgNO3, such methods have a good selectivity in
quantitative analysis of chloride ions. The representative titration graph is given below.

Reagents and solutions: Standard AgNO3, and NaCl solutions

Apparatus: Burette, pipette, beaker, standard flask, burette stand, Pt electrode, a digital
conductometer and magnetic stir bar

Procedure:

The given unknown chloride solution is made up to the mark in the 100 mL standard measuring
flask using distilled water. 20 mL of this solution is pipetted out into a 100 mL beaker and 10
mL distilled water is added to it. A conductivity cell of known cell constant is dipped in it and
connected to the conductivity meter. The burette is then filled with ~0.01 N AgNO3 solution
(Bottle B). The conductivity of the unknown chloride sample without adding any AgNO3
solution from the burette (0th reading) is noted followed by 1 mL AgNO3 solution of known
concentration into the beaker with continuous stirring by magnetic stirrer. Addition of AgNO3
solution (1 mL each time) is continued and the conductance is measured after each addition.
The titration is continued beyond the equivalence point for about 5 mL A graph is now drawn
by plotting conductance vs volume of AgNO3 added. Intersection point from the plot gives the
volume of AgNO3 required for precipitating the chloride present in the water sample.

Model graph

Conductance measurement: Volume of AgNO3 added vs. Electrical Conductivity

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Tabulation:

S.No. Volume of Conductance

AgNO3 (mL) (mhos)

Calculations:

Volume of AgNO3 (from the graph) V1 = ______mL

Normality of AgNO3 N1 = 0.01 N
Volume of Water sample V2 = 20 mL
Normality of given water sample N2 = 𝑉1 𝑁1 /𝑉2
Amount of chloride present in 1L = Normality of given water sample x Equivalent weight of
Cl- (35.453)
Amount of chloride present in 100 ml of the sample solution =
𝑆𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 35.453 𝑥100
1000

= grams in 100 mL

Result: Amount of chloride in given water sample in 100 ml = _______ g

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 Part III - Estimation of Total Dissolved Solids (TDS) estimation
Aim: To determine the total dissolved solids of the given water sample

Principle: The use of electrical conductivity (EC) is based on the observed linear relationship
between specific conductance and ionic strength for fluids with conductance ranging from 10–
10,000 μS/cm. A common expression is:

𝑇𝐷𝑆 (𝑚𝑔⁄𝐿) = 𝑘𝑒 × 𝐸𝐶(𝜇𝑆⁄𝑐𝑚)

where ke is a constant of proportionality. The TDS-EC relationship is affected by the ionic

composition of the water and the concentration of dissolved species. For most natural waters,
the ke value varies from 0.55 to 0.85, and the average of these two extremes (0.7) is widely
used.

Apparatus: Conductivity meter, conductivity cell

Procedure:

The conductivity of the water sample is recorded. The recorded conductivity when multiplied
by 0.7 (ke) as per the equation, gives the total dissolved solids present in the given water sample.

𝑇𝐷𝑆 (𝑚𝑔⁄𝐿) = 𝑘𝑒 × 𝐸𝐶(𝜇𝑆⁄𝑐𝑚)

Result: Total Dissolved Solids of the given water sample = ______mg/L

Part IV - Determination of pH of the given water sample

Aim: To determine the pH of the given water sample

Principle:

The term “pH” refers to the measurement of hydrogen ion activity in the solution. Since the
direct measurement of the pH is very difficult, specific electrodes are needed for quick and
accurate pH determination. pH is measured on a scale of 0 to 14, with lower values indicating
high H+ (more acidic) and higher values indicating low H+ ion activity (less acidic). A pH of 7
is considered as neutral. Every whole unit in pH represents a ten-fold increase in or decrease in
hydrogen ion concentration. Most natural waters possess the pH values ranging from 5.0 to 8.5.
Rain water have a pH value of 5.4 to 6.0 which then reacts with the soils and minerals causing
the reduction in H+ ion concentration and thus the water may become alkaline with a pH 0f
8.0-8.5. More acid water (pH<5) and more alkaline (pH >9) and other immediate changes in
the hydrogen ion concentration (pH) suggest that the quality of the water is adversely affected
due to the introduction of some toxic contaminants in water bodies. pH is measured using pH
meter, which comprises a detecting unit consisting of a glass electrode, reference electrode,
usually a calomel electrode connected by KCl Bridge to the pH sensitive glass electrode and an
indicating unit which indicates the pH corresponding to the electromotive force is then detected.
Before measurement, pH meter should be calibrated by using at least two buffers.

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Procedure:

The pH electrode is just dipped in a beaker of sample water and the displayed pH value is
recorded. To avoid any kind of contamination a clean and dry beaker was used before pouring
the sample water.

Result: pH of the given water sample = ________

Part V - Estimation of Sulfate in the given water sample

Aim: To estimate the amount of sulphate present in the given water sample

Principle:

To estimate sulfate ions, it is converted to a barium sulfate suspension under controlled

conditions. The resulting turbidity is determined by a nephelometer and compared with a curve
prepared from standard sulfate solution.

(Reference: https://www.epa.gov/sites/default/files/2015-12/documents/9038.pdf)

𝐵𝑎𝐶𝑙2 + 𝑆𝑂42− = 𝐵𝑎𝑆𝑂4 ↓ +2𝐶𝑙 −

Schematic diagram of Light scattering in Nephelometry

Reagents and solutions: Conc. HCl, conditioning reagent, Na2SO4 stock solution (1420 ppm)
and BaCl2.

Conditioning reagent: It is prepared by mixing 30 mL of concentrated HCl dissolved in 300

mL of distilled water, 95% ethanol or isopropanol, and 75 g NaCl in a container. Further, to
this mixture, 50 ml of glycerol is added and used for the analysis.

Apparatus: Magnetic stirrer, Nephelometer, Stopwatch, Measuring spoon, 250 mL conical

flask, and 1L volumetric flask.

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Seven 100 ml standard measuring flasks are taken and labelled as 1, 2, 3, 4, 5, 6 and 7. Flask
labeled as 1 is used for the blank solution preparation and 7 is used for the given unknown
sample. Standard Na2SO4 solutions of concentrations, 50, 100, 150, 200 and 250 ppm are
prepared by diluting 3.5, 7, 10.5, 14, 17.5 ml of the stock solution of Na2SO4 using distilled
water and made up to 100 ml in the standard measuring flasks and are labelled as 2,3,4, 5 and
6. Different concentrations of sulphate solutions each as prepared are transferred completely to
250-mL Erlenmeyer flasks (conical flasks), including the blank. To the blank solution in the
conical flask, 5 ml of conditioning reagent is added and stirred in the orbital shaker exactly for
1 min and 0.6 g of BaCl₂ crystals alone are added while stirring, but without sulphate solution
. The blank solution is then transferred to the sample tube and turbidity value is adjusted to zero
using the turbidity meter. After calibrating the turbidity values using the blank solution,
turbidity values are to be found for the standard solutions. The made-up standard solutions in
the standard measuring flasks are transferred to the conical flasks. To the contents in the conical
flasks, exactly 5.0 mL of conditioning reagent is added to the sulphate solutions and stirred for
one minute using the orbital shaker. While the solution is being stirred, 0.6g of BaCl₂ crystals
is added. After stirring, each sample was transferred to the sample tube. Readings on the
turbidity scale (Nephelometric turbidity unit, NTU) is noted for all standard solutions one by
one. After measuring the NTU values for all the standard solutions, given unknown solution is
also analyzed using the same way. A calibration plot (straight line) is plotted using the NTU
values for the standard solutions against their concentrations. Concentration of unknown
solution was found by extrapolating the NTU value in ‘y’ axis (turbidity, NTU) to meet the
straight line and extrapolated to the ‘x’ axis (shown as ‘X’ in the plot).

Model plot of sulphate concentration range vs. turbidity values

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 Table

S.No. Concentration Turbidity

(ppm) (NTU)
1. 50

2 100

3. 150

4. 200

5. 250

6. Unknown

Comprehensive Report of Water Sample Analysis

Sample Collected from
Date of Collection
Recommended Values for
Recorded Deviation from the
Parameters drinking water as per BIS
Values standard (%)
(Acceptable limit)
Hardness (ppm) 200
Chloride content (ppm) 250
TDS (ppm) 500
pH 6.5 – 8.5
Sulfate content (ppm) 200
References (weblinks):

Water quality BIS standards - https://cpcb.nic.in/wqstandards/

TDS Estimation - https://pure.psu.edu/en/publications/relationship-between-total-dissolved-solids-and-electrical-conduc or
https://doi.org/10.2166/wst.2018.092)
pH measurement
(Reference: https://nitsri.ac.in/Department/Civil%20Engineering/CWE-
301_WATER_QUALITY_AND_ENVIRONMENT_pH_Meters.pdf

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