Determination Of Total Hardness In Given Water Sample

Objectives

Objectives of this lab includes:

 To get knowledge of hardness in water

 To understand the concept and phenomenon about hardness
 To learn about the role of hardness in water quality
 To understand the precautions and procedures involved in the determination of
hardness in water

Hardness

“Hardness defined as the soap consuming capacity of water and ability to form scales in hot
water pipelines and boilers.” The water that cannot produce good lather is termed as hard
water. And that can produce good lather in water is known as soft water.

Water Hardness is also known as the

amount of dissolved calcium and
magnesium in the water. So, another
definition of water hardness is “the amount
of dissolved calcium and magnesium in
the water. Hard water is high in dissolved
minerals, both calcium and magnesium.”

Hardness is measured in units of mg/L as CaCO3.

Causes

Major contributors in hardness of water are divalent metallic cations (Ca 2+, Mg2+, Sr2+, Fe2+,
Be2+, anions (HCO3-, NO3-, SO4-, SO3-, Cl-), etc.

These ions are capable of reacting with soap to form precipitates and scales around the walls
of container during boiling.

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Types of hardness

1. Permanent hardness
It is also known as the total hardness of water. It is due to the presence of Ca 2+, and
Mg2+.
Sometimes, it is due to only calcium ions or magnesium ions or sum of both ions.
2. Carbonate Hardness
The part of total hardness that is equivalent to the carbonate and bicarbonate alkalinity
in the water is called as carbonate hardness. It is due to the presence of carbonates and
bicarbonates of calcium (Ca(HCO3)2) and magnesium (Mg(HCO3)2) in the water
sample. It is also known as temporary hardness.
3. Non-carbonate hardness
It is due to the presence of chlorides and sulphates of calcium and magnesium. These
salts are solvable in water and present as ions. This type is also known as permanent
hardness.
e.g. CaCl2, MgCl2, MgSO4, CaSO4, etc.

Environmental significance:

1. Human health:
Ca+2 and Mg+2 are very adventitious for human body for example, calcium makes
the bones strong while magnesium improves the metabolism. Also, there
concentration saves the heart from heart diseases but their higher concentration can
cause harmful effects such as calcium cause kidney stone if it is present in excess
amount. Hypertension and stroke is risk factor in several diseases. Adequate calcium
intake has been associated with lowered risk of elevated blood pressure in some but
not all studies.it is also helpful in insulin resistance.
2. Scale/precipitation formation:
High total hardness can result in abnormal cloudiness and the formation of scale.
However, levels of hardness that are too low could make the water corrosive and
more aggressive. Thus, industries that utilize equipment and machinery that handle
water should ensure that the total hardness levels are maintained at appropriate levels
to prevent the water from becoming corrosive.

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 3. Body washing effects:
Hard water is high in dissolved minerals, both calcium and magnesium. You may
have felt the effects of hard water, literally, the last time you washed your hands.
Depending on the hardness of your water, after using soap to wash you may have felt
like there was a film of residue left on your hands.
4. Aquatic life:
Against this continuous movement of water into or out of the body, fish have to
maintain a constant internal body fluid concentration – a process called
osmoregulation. The greater the difference in concentration between the fish’s body
fluids and the surrounding water – the greater the osmotic effect. As hard water is
more concentrated than soft, there will be less difference and therefore less water
influx and consequently the fish will not have to work so hard at osmoregulation. This
is particularly important in cases of bacterial ulceration where water can flood into
open tissues.
5. Corrosion and clogging:
Since hard water contain ions in high concentration and these ions can cause the
corrosion of the pipes of water supply system and can also cause the slow clogging of
pipes. Which is not good for supply of water and cause hurdles in the supply system
and also cause danger to the consumer of that water.

NEQS Guidelines

According to NEQS guidelines, hardness up to 500mg/L is tolerate able. Some limits of

hardness in water are given following:

Concentration of hardness degree of hardness

0-75 mg/L as CaCO3 soft water

75-150 mg/L as CaCO3 moderately hard

150-300 mg/L as CaCO3 hard water

>300 mg/L as CaCO3 very hard water

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 Hardness Measurement

The process of chelation determines the hardness of water. Most metal ions are capable of
sharing electron pairs with chelating agent that have a free electron pair to form coordinate
covalent bond.

Chelating Agent

If a molecule or ion has more than 1 free electron pairs that can be shared metal ion or similar
specie is called a chelating agent.

Its stability depends upon that how much no. of coordinate covalent bonds can be found
between the chelating agent and metal ions.

e.g., EDTA, etc.

Working principle

EDTA (Ethylene diamine tetra acetic acid) forms colorless stable complexes with Ca2+ and
Mg2+ ions present in water at pH = 9-10. To maintain the pH of the solution at 9-10, buffer
solution (NH4Cl + NH4OH) is used. Erichrome Black-T (E.B.T) is used as an indicator.

EDTA first forms a complex with the calcium ions which is colourless.

EDTA4- + Ca2+ (CaEDTA)2-

EBT is used as indicator to indicate the complex formation. EBT combines with the
magnesium ions present in water and produce a complex with wine red colour.

Mg2+ + EBT2- MgEBT (wine red colour complex)

As stated earlier, EDTA forms complex with calcium first and when it consumes all the
calcium in the water then it starts to make complex with the magnesium and colour starts to
turn blue from wine red. The colour of solution becomes completely blue when it consumes
all the magnesium ion.

This is an indication that calcium has been complexed by the EDTA.

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Collection and Sampling

 Container Type: should be plastic or glass

 Storage: Analyze samples as soon as possible if delay is inhabitable then store it in
refrigerator at 4 degrees Celsius and add H2SO4 to lower the pH of water less than 2.
 Holding Time: Holding time for the sample is 6 months.

Interferences During Sampling

Some of the substance which cause interferences in hardness samples are given in the
following:

 Acidity: 10,000 mg/L acidity as CaCO3 does not interfere.

 Alkalinity: 10,000 mg/L alkalinity as CaCO3 does not interfere.
 Aluminum: Interferes when the sample contains more than 0.20 mg/L aluminum.
Add 0.5 grams of potassium cyanide after the Hardness 1 Buffer Solution during the
test procedure to remove the interference from a maximum of 1 mg/L aluminum.
 Barium: Barium is titrated at the same time with calcium and interferes with this test,
but it is unusual to find high levels of Barium in natural waters.
 Chloride: The chloride level in seawater does not interfere. Solutions that are
saturated with chloride do not show a sharp endpoint.

Materials and Reagents

1. Materials
 Titration flask
 Burette
 Pipette
 Measuring flask
 Funnel
 Burette stand
2. Reagents
 Standard EDTA solution 0.01 M
 Buffer solution (ammonia)

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  Erichrome black T

Procedure

 Take 50ml of water sample in 250ml Erlenmeyer flask.

 Add 2ml of buffer solution (pH of buffer should be 10+(-0.1)) in the above sample to
maintain the pH of water between 7-9.
 Add 2 drops of EBT in the water sample solution. The colour of solution becomes wine
red colour.
 Fill the burette with standard 0.01M EDTA and titrate the solution against it. Until the
colour of the solution turns blue from red.
 Note down the mean volume of the EDTA used.
 Repeat the procedure at least 2 times or more to get set of number of readings.
 Also, repeat the procedure for the blank sample reading.
 Use following formula to calculate total hardness:
( A−B )∗molarity of EDTA∗molecular weight of CaCO 3∗1000
Total Hardness =
Vol . of sample

Observations and Calculations

Volume of sample = 50 ml
Volume of EDTA used =

Sr. No. Initial Final volume

1 0 16 16
2 16 32 16

16+16
Average =
2

= 16

Blank sample reading = 32.2 – 32 = .2 ml

( 16−.2 )∗100∗0.01∗1000
Total Hardness =
50

Total Hardness = 316 mg/l as CaCO3

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Results

The total hardness of given water sample is 316mg/L as CaCO3. The given water sample is
very hard water.

Comments

We have performed total hardness experiment on the water sample and have come to know
that the results are quite alarming for drinking water. So, proper attention is required in this
issue.

Also this experiment has enabled us to understand the hardness of water and all related
phenomenon which effects the total hardness of water. Also we have learnt the procedure to
measure total hardness from this lab which is quite interesting.

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