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Experiment: # 1 Name: Title:

Leonie Lawrence Hardness of Water 0800383

Aim: To determine the hardness or softness of a river water sample and that of a
controlled sample of CaCo3 solution.


This experimental exercise was performed by method of titration. A standard sample of Ethylenediaminetetraacetic acid (EDTA) solution was titrated with a 100 ml river water sample and 100 ml CaCo3 standard solution. Hardness calculated for CaCo3 sample (16.9 ppm) was compared to the Lenntech Water Solution data table and result indicated this solution is hard once the value ranges between 121-180 ppm. The river water sample reading was (174 ppm) thereby indicating this solution was also hard.


Water hardness or softness is an expression for the sum/ amount of

calcium and magnesium cation concentration found in a water sample, as sited by the E-how article Water Hardness. These cations may enter a stream through the weathering of rocks such as limestone (CaCo3). Calcium occurs in water naturally and is known to give water a better taste. Calcium and magnesium cations however have the ability to form insoluble salts with soaps, decreasing soaps cleaning effectiveness, also forming hard water deposits in hot water heaters. The standard way to express water hardness is in ppm, and such water quality (harness or

softness) may be calculated using the formula: ml of EDTA used in Titration

/ml of H2O sample * 10 ppm. Another method of

calculation is Volume of Water sample used * 10 ppm (since 1ml of water sample contains 10 ppm). The laboratory exercise to determine water hardness or softness involves titrating the sample of river water and CaCo3 solution with a standard Ethylenediaminetetraacetic acid solution (ETDA) colour of the Erichrome black T indicator (EBT) until the wine red turns blue.


Procedure is as seen in the Environmental Chemistry Laboratory Manual CHY4005. Revised 2010 written by Dr Kerri-Ann Bartley-Hynes


Table 1.1 Demonstrating Titration of a river water sample and a controlled sample of CaCo3 solution. Trial 1 River Water Volume of Sample/ml Initial burette reading/ml Volume of EDTA added/ml PH 100 49.80 32.40 9.50 Trial 2 CaCo3 solution 100 49.80 32.90 9.58 16.90

Volume of EDTA used/ml 17.40

Observation: A colour change was noted from clear to wine red when Erichrome black T indicator was added to both river water and CaCo3 sample. Another change noted from wine red to bluish grey after titration had been complete with EDTA. Table 1.2 Showing water quality measurements by Lenntech water Quality Table.

Concentration (ppm) <61 61-120


Hardness Reading Soft Moderately hard Hard Extremely Hard


1. Calculate the hardness of the water sample: (1 ml of standard EDTA solution contains 10 ppm of CaC03) Hardness of river water: Volume of EDTA used * 10 ppm 17.40 ml* 10 = 170 ppm Hardness of CaCo3 solution: Volume of EDTA used * 10 ppm 16.90 ml * 10 = 169 ppm


The experimental results obtained demonstrated that the 174 ppm reading of the river water is an indication of the water sample being hard. The reference table 1.2 showed that ppm (parts per million) value between the range of 121-180 is regarded as Hard. 169 ppm was the obtained value for the CaCo3 sample, thereby demonstrating Hardness as well. Due to the conductivity of river water its ion concentration is more than that of the CaCo3 sample and therefore the Hardness measurement is higher. Calcium as an important determinant of water hardness functioned as a pH stabilizer in the experiment because of its buffering qualities. The PH value was calculated for NH3/NH4Cl to be: At the onset of the experimental exercise, EDTA solution was used to rinse the burette in order to condition it and prevent errors in the experiment. The 2 ml buffer solution indicated in the procedure was not enough to raise the required PH of the titration. Therefore a total of 4 ml was used for both the River water sample and the CaCo3 solution to provide a PH of 9.50 and 9.58 respectively. The Erichrome black T indicator imparted a red color to the solution in the presence of calcium and magnesium ions, thereby indicating it had not yet complex the EDTA solution. Once the endpoint had been reached and there was no more uncomplexed Ca or Mg, the indicator gave a blue colour. The known solution of CaCo3 was diluted to standard 100ml. Controlling the presence of calcium and magnesium ions in water is done by an ion exchanger known as water softeners. These usually contain Na+ ions, which are

released and substituted by Ca2+ and Mg2+ ions. Calcium compounds can also be applied for wastewater treatment. Drinking water pH and hardness may be altered by means of calcium carbonate and calcium hydroxide.

Using EDTA is a practical method of demonstrating water hardness or softness however there is a limitation to this procedure. If the water sample does not have a sufficient amount of Magnesium it will be extremely hard to titrate the sample to distinguish the endpoint. Other errors such as parallax could have been prevented when conducting the volumetric reading, as the eye must be positioned on the line directly perpendicular to the measuring rule on the burette and other apparatus.

Conclusion: It may be concluded that the aim was achieved and both samples of river
water and CaCo3 sample were found to be hard with water quality measurements of 174 ppm and 169 ppm respectively.

Answers to questions given:

1. Give reason and supporting equation why the buffer is added to the sample before titration. A buffer is added to the reaction solution in order to maintain the PH of the solution. Eg. The accepted experimental PH value should range 9.50-10. Equation:

2. Calculate PH of NH3/NH4CL buffer. (Kb of Nh3 is required)

3. Giving suitable examples explain why hardness is a suitable water quality indicator.

A Water Quality Assessment article defines stream water hardness as being the total concentration of cations, specifically calcium (Ca2+), magnesium (Mg2+), iron (Fe2+), and manganese (Mn2+) in the water. Water hardness is a specifically important water

quality indicator as it provides a measure of the influence of human activity on the water systems in specific areas. An example of this is Acid Mine Drainage which often results in the release of iron into a stream. The presence of iron produces extraordinarily high hardness readings. Other examples include foaming agents such as those in soaps and detergents. They do not work well in hard water. In addition hard water tends to leave hard; scaly calcium deposits on faucets accounting for the very reason many people install water softener systems in their homes.

References: University of Technology Environmental Chemistry Lab manual (CHY4005) 2010, by Dr. Kerri-Ann Bartley-Hynes pg 6. www.ganon.edu (sited definitions.) www.enow.com www.cotf.edu (water quality assessment article) www.lenntech.com (water quality measurements by The Lenntech water Treatment and Purification Solutions Limited)