Determination of the Hardness of Water

Introduction
Depending on the area of the country, tap water contains various amounts of ions such as
calcium, iron, magnesium, etc. The higher the concentration of these ions the harder the
water is. Hard water is characterized by the inability of soap to form lather and the formation of
scum in sinks and bathtubs.
To determine the concentration of the two most common hard water ions, Ca 2+ and Mg2+, a
titration is performed with a chealating agent, ethylenediaminetetraacetic acid (EDTA). Using a
burette, the exact amount of EDTA needed to react with the concentration of ions in the water is
determined. The molar concentration of EDTA is 0.005. Due to steric hindrances, EDTA will
complex with calcium and magnesium in a one-to-one molar ratio.
In this experiment the indicator Eriochrome Black T (EBT) is used to signal the presence of ions in
the water sample. EBT binds with free metal ions in the water to form a pink complex. EDTA has
a stronger affinity for the metal ions than EBT so when EDTA is added it replaces the EBT and the
EBT returns to its blue, uncomplexed color. The blue color is used as the end point in the
titration.
Both EDTA and EBT are weak acids and their actions are very pH dependent; thus we use a pH
buffer to hold the solutions at an appropriate pH for both the EDTA and the EBT indicator to work
well. The titration is carried out at a pH of 10 which keeps the EDTA in a half-neutralized form,
where it complexes with Group IIA ions very well but does not tend to react as readily with other
cations such as Fe+ that might be present as impurities in the water.
Total water hardness is usually expressed as the milligrams of CaCO 3 equivalent to the total
amount of calcium and magnesium present in one liter of water (mg/L, i.e. ppm).
The classification of the degree of water hardness according to the US Geological Survey is as
follows:
Soft
0 60
Moderately Hard 61 120
Hard
121 180
Very Hard
> 180

ppm CaCO3 equivalents

ppm CaCO3 equivalents
ppm CaCO3 equivalents
ppm CaCO3 equivalents

Pre-Lab Questions: These are due at the beginning of tomorrows lab (0800). Late answers
will result in a decrease of one letter grade on your lab.
1.
2.
3.
4.
5.

Why is it important to estimate the hardness of potable water?

At what pH condition is the titration performed? Why?
What indicator is used in the analysis? What is its color change?
What is the most common way to soften hard water in households?
A 50.0 mL sample of tap water was analyzed using the EDTA procedure. An average
volume of 16.34 mL of EDTA was required for the titration. Answer the following
questions:
a. Calculate the moles of EDTA used.
b. Calculate the molarity of metal ion present in the water sample (Remember: EDTA
binds to metal ions on a 1:1 molar ratio).

c. Water hardness is often expressed as ppm CaCO 3 even though there may be several
metal ions present. Find the parts per million calcium ion concentrations in the
sample based on your results from question b.

Objective
A sample of tap water is treated with EBT indicator. If the indicator turns from blue to pink, metal
ions such as calcium and magnesium are present. To determine the concentration of ions
present, the sample is titrated with a known molar concentration of EDTA.

Chemicals and Equipment

EDTA 0.2% solution
Buffer solution pH 10
EBT indicator solution
50 mL graduated cylinder
250 mL Erlenmeyer flask
50 mL burette, burette clamp and ring stand
150 mL beaker (for waste)
Magnetic stirrer and accessories

Safety Equipment Required:

Rubber gloves
Aprons
Safety goggles
Safety Note: The pH buffer and EDTA solution are basic. Wash contaminated area
immediately with water. The EBT indicator is an alcohol solution which is flammable.
Keep away from all sources of ignition.

Procedure
1. Rinse the burette with 5 mL EDTA solution.
2. Set up two burettes on ring stand with burette clamps. Fill one burette with 20 mL EDTA
solution. Fill the other burette with 20 mL tap water. The tap water burette will be used
only if you overshoot your endpoint (its easier than you think!!). Take an initial volume
reading of each burette and record it on your datasheet. Set up a magnetic stirrer
underneath the EDTA burette.
3. Use a graduated cylinder and eye dropper to put 50.0 mL of tap water into an Erlenmeyer
flask and add 5-10 drops of the EBT indicator and about 10 mL of buffer. The color change
from blue to pink is an indication of the presence of ions in the water sample.
4. To perform the titration, turn the stopcock on the burette so that the EDTA is added one
drop at a time. Be sure to go drop wise as you approach the endpoint. When you
get close to the end point the solution will turn purple.
5. Continue to add the EDTA one drop at a time until one drop turns the solution blue.
Record the final volume of EDTA in the burette on your datasheet.
6. If you overshoot the endpoint, add a known volume of tap water from the tap water
burette and record it on your datasheet.
7. Empty the flask, triple rinse with de-ionized water and dry. Repeat the titration two more
times to get the exact endpoint.

Chemical Disposal: Since the products of these titrations are dilute, non-hazardous
solutions, it is safe to flush these solutions down the drain with copious amounts of
water.