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Testing the Hardness of Water

Purpose:
The purpose of this experiment is to determine the hardness of a water sample by measuring the
amount of calcium present. This analysis will utilize the method of titration.
Introduction:
All natural waters have salts dissolved in them. It is these salts that give water a unique taste.
Sometimes the water can contain too much of these salts and can cause problems when the water
is used for drinking or washing. These problems are caused mainly by the presence of calcium
and magnesium ions in the water. You may have experienced this problem if you have taken a
bath with water that contained too many calcium and magnesium salts. The problem is that you
cannot get the soap to lather and form suds. When this happens, we say that the water is hard.
In this experiment, you will analyze a sample of water to measure the amount of calcium (or the
water hardness) by performing titrations on water samples you provide from home or other
sources. In the previous experiment, you learned how to perform a titration and use a buret so an
in-depth explanation is not necessary. However, the reaction in this titration is not a
neutralization reaction as in the acetic acid titration. In this case, an EDTA (ethylenediamine
tetra-acetic acid) solution is the titrant, which will react or capture (also called chelate) the
calcium ions in the water as shown in equation 1 below.
O
-

OOCCH2
-

OOCCH2

CH2COO

2+

Ca

CH2COO

NON
Ca
OOO

O
4-

2-

(EDTA )

Eqn. 1

(CaEDTA )

The reaction between calcium ions and EDTA only occurs at a high pH; therefore, a solution that
has a constant pH of 10 (called a buffer) will to be added to the water sample.
Just as in the acid-base reactions, you must use an indicator to identify when the reaction is
complete. In this experiment, Eriochrome black T, a metal ion indicator, will be used to
visualize the endpoint.
OH
-

O 3S

OH

N N

O 2N

Eriochrome black T

A metal ion indicator is a compound whose color changes when it binds to a metal ion. For such
an indicator to be useful in the titration of a metal with EDTA, the indicator must give up its
metal ion to the EDTA. The indicator in its free form, i.e. not bound to any metal, is blue. A
small amount of indicator is added to the solution containing the Ca2+ forming a wine red
complex (Equation 2.) If we denote the indicator as In2-, we can write the reaction as:
Ca2+ +

In2(blue)

CaIn + EDTA4(wine red)

CaIn
(wine red)

Eqn. 2

CaEDTA2- + In2(blue)

Eqn. 3

In this experiment, the end point will be indicated when the original red solution turns to blue
(Equation 3) indicating that the EDTA has reacted with all the calcium ions in the water sample.
After the measurement, it will be necessary to calculate the amount of calcium ions present. The
concentration units used to measure the water hardness is normally parts per million (ppm.) In
this experiment you will measure calcium carbonate (CaCO3) in ppm. (One part per million is
the same as 1 mL/L.) You will be able determine the hardness of your water sample by
measuring the volume of your water sample and the volume (in mL) of the EDTA solution used
to react with all of the calcium in the water sample. You will calculate the ppm of calcium
carbonate in your water sample by using the following calculation
ppm CaCO3 = mL of EDTA used in titration X 1000 ppm
mL of water sample
Once the concentration in ppm is determined, it can be related to the hardness scale in Table 1.
Concentration (ppm)
< 61
61 120
121-180
> 180

Hardness Rating
Soft
Moderately hard
Hard
Very hard

Table 1: Water Hardness Scale

Procedure:
1. Bring at least 100 mL of water from home, your dormitory, or any local water supply to lab.
(Note: a 20 oz soda bottle contains 514 mL.)
2. Pour 25 mL of the water sample into a 250 mL Erlenmeyer flask.
3. Obtain 25 mL of DISTILLED water and add it to the same flask. (This water will
not affect the titration, but it makes the endpoint easier to recognize.)
4. Using an eye-dropper, add 20 drops of the pH 10 solution (called a buffer) to the same flask.
5. Using a spatula, add a pea size amount of indicator (in the form of a powder) to the same
flask. The color of the solution should be red.
6. Clean and fill your buret with the EDTA solution and record the initial volume.
7. Titrate until the solution has changed color from red to blue. When this happens record the
final volume. Remember, this first time is just a trial run to help you approximate the
equivalence point, this data does not go into your average value of ppm of CaCO3.
8. Repeat steps 1-6 three more times. Calculate the ppm of CaCO3 for each sample and then
calculate the average value for these three trials. Remember to provide a sample calculation
for your data in the space provided under calculations.

Question:
1. Based on the concentration of calcium (ppm) you calculated from your results, would you
say your water is soft, moderately hard, hard or very hard? Give a very brief explanation

Results:
Record your data in the table below and provide your sample calculations in the space provided
under calculations.
Titration

Trial Run

Volume of water
sample (mL)

_________

_________

_________

_________

Final buret reading of


EDTA solution (mL)

_________

_________

_________

_________

Initial buret reading of


EDTA solution (mL)

_________

_________

_________

_________

Volume of EDTA
added (mL)

_________

_________

_________

_________

ppm of CaCO3

_________

_________

_________

_________

Average ppm of CaCO3


(Do not include trial run)

_________

Water Hardness

_________

Sample Calculation(s):