1.

OBJECTIVE

To learn the cause and the effect of hard water and to determine the total Calcium and
Magnesium hardness of a water sample.

2. INTRODUCTION

Hardening ions present in natural water are the result of slightly acidic rainwater flowing over
mineral deposits of varying decompositions; the acidic rainwater reacts with the very slightly
soluble carbonate salts of calcium and magnesium and with various iron containing rocks. A
partial dissolution of these salts release the ions into the water supply, which may be surface
water or ground water.

CO2(aq) + H2O(l) + CaCO3(s) → Ca2 +(aq) + 2HCO3- (aq) (Eq.1)

Hardening ions, such as Ca2+, Mg2+, Sr2+ and Fe2+, from insoluble compounds with soaps and
causes many detergents to be less effective. Soaps, which are sodium salts of fatty acids such
as sodium stearate, C17H35CO2-Na+ , are very effective cleansing agents as long as they
remain soluble; the presence of hardening ions however cause the formation of a gray,
insoluble soap scum such as (C17H35CO2)2Ca.

This gray precipitate appears as a “bathtub ring” and its also clings to clothes, causing white
clothes to appear gray. Dishes and glasses may have spots, shower stalls and lavatories may
have a sticky film, clothes may feel rough and scratchy, hair may be dull and unmanageable,
and your skin may be irritated and sticky because of hard water.

Hard water is also responsible for the appearance and undesirable formation of “boiler scale”
on tea kettles. And pots used for heating water. The boiler scale is a poor conductor of heat
and thus reduces the efficiency of transferring heat. Boiler scale also builds on the inside of
hot water pipes causing a decrease in the flow of water. In extreme cases, this build up causes
the pipe to break.

Boiler scale consists primarily of the carbonate salts of the hardening ions and is formed
according to

Ca2+(aq) + 2HCO3-(aq) → CaCO3(s) + CO2(g) + H2O(l) (Eq. 2)

Note that this reaction is just reverse of the reaction for the formation of hard water (Eq. 1).
The same two reactions are also the key to formation of stalactites and stalagmites for caves
located in regions with large limestone deposits. Because of relatively large natural
abundance of limestone deposits and other calcium minerals such as gypsum, CaSO4.2H2 O,
it is not surprising that Ca2+ ion, in conjunction with Mg2+ is a major hardness contributing
ions in natural water. Thus, generally total hardness is taken as the sum of Ca and Mg
hardness.

Table 1: Hardness classification of water

Normally, water hardness is determined by titration technique. The titrant is

ethylenediaminetetraacetic acid (EDTA). EDTA reacts with hardening ions, Ca2+ and Mg2+ to
form very stable complex ions, especially in a solution buffered at a pH of about 10. In this
experiment, colorimetric method is utilized. This method supplements the conventional
trimetric method because the colorimetric method can measure very low levels of calcium
and magnesium. Also some metals that interfere in the titrimetric method may be
inconsequential when diluting the sample to bring it within the range of this test.

The indicator dye is calmagite, which forms a purplish-blue colour in a strongly alkaline
solution and changes to red when it reacts with free calcium or magnesium. Calcium and
magnesium determinations are made by chelating the calcium and magnesium with EDTA to
destroy the red colour due to both calcium and magnesium. By measuring the red colour in
the different states, calcium and magnesium concentrations are determined. The result are
measured at 522 nm.

To limit scale formation in boilers and pipes and reduces soap consumption, water softening
is practiced in region with high water hardness. Depending on the characteristics of the source
water, different types of softening treatment processes are employed. The processes are:

a. Single-stage lime process: For high calcium, low magnesium carbonate hardness (< 40
mg/L as CaCO3). No carbonate hardness
b. Excess lime process: For high calcium, high magnesium carbonate hardness. No
noncarbonated hardness. One or two stage process. 60mg/L excess lime is typically
added.
c. Single-stage lime-soda ash process: For high calcium, low magnesium carbonate hardness
(< 40 mg/L as CaCO3). Calcium noncarbonated hardness is present.
d. Excess lime-soda ash process: For high calcium, high magnesium carbonate hardness and
some noncarbonated hardness. One or two stage process. 60 mg/L excess lime is typically
added.
After precipitation process, the pH remains high and remaining calcium and magnesium is just at
the solubility equilibrium. To limit post-precipitation, water is usually stabilized by lowering pH
with the addition of H2SO4 or CO2.Precipitation softening cannot produce a water completely
free of hardness because of the solubility of calcium carbonate and magnesium hydroxide.
Furthermore, completion of the chemical reactions is limited by physical considerations, such as
adequate mixing and limited detention time in settling basins. Therefore, the minimum practical
limits of precipitation softening are 30 mg/L of CaCO3 and 10 mg/l of Mg(OH)2 expresses as
CaCO3.
Hardness level of 80 – 100 mg/L are generally considered acceptable for a public water supply,
but the magnesium content should not exceed 40 mg/L as CaCO3 in softened municipal water.

3. MATERIALS AND APPARATUS

3.1. Chemicals and Solutions

 Calcium and magnesium indicators solution (calmagite)

 Alkali for calcium and magnesium test
 EDTA solution
 EGTA solution
 Water sample

3.2. Equipment and Glassware

 Pipette
 500 and 1000 ml beakers
 100 ml volumetric flask
 DR2800 spectrophotometer
4. PROCEDURE

4.1. Pressed “Stores Programs” and “225 Hardness,Mg” was selected,

4.2. 100 ml of sample was poured into a 100 ml graduated mixing cylinder.
4.3. 1.0 ml of Calcium and Magnesium indicator solution using was added using a 1.0 ml
measuring dropper.
4.4. Stopper the cylinder and inverted it several times.
4.5. 1.0 ml of Alkali solutions and Magnesium Test using a 1.0 ml measuring dropper was
added.
4.6. Stopper the cylinder and inverted it several times.
4.7. 10 ml of the solutions was poured into each three square sample cells.
4.8. Blank preparation: One drop 1 M EDTA solution to the first cell was added. Swirl to
mix.
4.9. Magnesium preparation: One drop 1 M EGTA solution to the first cell was added. Swirl
to mix.
4.10. The blank (first cell) was inserted into cell holder with the fill line facing right. Pressed
“Zero”, the display will show: 0.00 mg/L MG CaCO3.
4.11. The magnesium sample (second cell) was inserted into cell holder with the fill line
facing right.
4.12. Pressed “Read”. Results are in mg/L magnesium as calcium carbonate. This value is the
amount of magnesium in the sample expressed as CaCO3.

4.13. Do not removed the cell from instrument. Pressed “Exit” and selected the test “220
Hardness, Ca”.
4.14. Pressed “Start” and then press “Zero”. The display will show: 0.00 mg/L CaCO3. The
second cell was removed.
4.15. Calcium sample: The third cell was inserted into the cell holder with the fill line facing
right.
4.16. Press “Read”. Result are in mg/L calcium as calcium carbonate. This value is the
amount of calcium in the sample expressed as CaCO3.
5. RESULTS AND CALCULATION

Parameter Results
pH 8.058
Calcium hardness 0.100
Magnesium hardness 2.120
Total hardness 2.220

mg/L total hardness = mg/L Ca as CaCO3 + mg/L Mg as CaCO3

= 0.10 + 2.12
= 2.22 mg/L

6. DISCUSSION

The results from this experiment were very reasonable. The hardness of water is
structured by a numerical range. Soft water has a ppm between 0 and 75. Moderately hard has
a range of 75-150. Hard is between 150 and 300. Anything over 300 ppm is considered very
hard. Our sample was in the soft range of the scale with 2.75 mg/L as CaCO3.

For the most accurate hardness test result, the test should be rerun on a diluted sample if the
calcium is over 1.0 or the magnesium is over 0.25 mg/L as CaCO3. Traces of EDTA or
EGTA remaining in sample cells from previous tests will give erroneous results. Rinse cells
thoroughly before use.

7. CONCLUSION

The colorimetric method for measuring hardness supplements the conventional titrimetric
method because it can measure very low levels of calcium and magnesium. Also some
interfering metals (those listed above) in the titrimetric method are inconsequential in the
colorimetric method when diluting the sample to bring it within the range of this test.

The indicator dye, calmagite, forms a purplish-blue color in a strongly alkaline solution and
changes to red when it reacts with free calcium or magnesium. Calcium is chelated with
EGTA to destroy any red color due to calcium and then the sample is chelated with EDTA to
destroy the red color due to both calcium and magnesium. Measuring the red color in the
different stages of chelation gives results as the calcium and magnesium hardness
concentrations.

In conclusion, the results from this experiment were reasonable. The hardness of a water
sample was successfully discovered by finding the calcium and magnesium content in the
 sample. The calcium and magnesium content 0.10 mg/L and 2.12 mg/L. This showed that the
water fell into the range of numbers indicating soft water. For most applications, total
hardness of 75mg/L resulting soft water is more compatible with soap and extends the
lifetime of plumbing.
8. QUESTIONS

8.1. What are the problems associated with hardness in water?

The problems that associated with hardness in water are clothes washed in hard water
often look dingy and feel harsh and scratchy, bathing with soap in hard water leaves a
film of sticky soap curd on the skin and washing dishes, especially in a dishwasher,
hard water may cause spotting and filming on your crockery. Hard water also
contributes to inefficient and costly operation of water-using appliances and solar
heating, often used for heating swimming pools is prone to lime scale buildup, which
can reduce the efficiency of the electronic pump and therefore the overall systems
performance will deteriorate.

8.2. What are the benefits of using soft water?

Hard water is not a health hazard. In fact, the National Research Council (National
Academy of Sciences) states that hard drinking water generally contributes a small
amount toward total calcium and magnesium human dietary needs. They further state
that in some instances, where dissolved calcium and magnesium are very high, water
could be a major contributor of calcium and magnesium to the diet. The ideal solution
would be to leave the calcium in the water, but alter its state so that it couldn’t form
lime scale. This is exactly what magnetic water conditioners do.

8.3. Give the disadvantages of using lime softening in water treatment?

Lime softening produces large volumes of a mixture of calcium carbonate and

magnesium hydroxide in a very finely divided white precipitate which may also contain
some organic matter flocculated out of the raw water. Processing or disposal of this
material may be a cost to the process.