CY307

ASSIGNMENT

GAYATHRI M
19IMMM23
TOPIC:

DETERMINATION OF HARDNESS
OF TAP WATER

This Photo by Unknown author is licensed under CC BY-SA-NC.

WHAT IS HARDNESS?

• Hardness of water is a measure of the total concentration of calcium and

magnesium ions expressed as calcium carbonate.

• Water is said to be hard when it contains Ca2+ and Mg2+ ions. These ions react
with soap to form an insoluble substance called soap scum

• It is the measure of capacity of water to precipitate the soap.

• The degree of hardness is measured in Parts per million(ppm) or Grams per
Gallon (GPG).

• Water with different degrees of hardness is used for different purposes such
as household and industrial purposes.

• Hard water is better for drinking because it

contains minerals.
• Soft water is better for cleaning because it
doesn’t form scum.
TYPES OF HARDNESS:
1. Temporary Hardness :

It is due to the presence of bicarbonates of calcium and magnesium. It can

be easily removed by boiling.

Eg : Ca(HCO3)2 CaCO3+CO2+H2O

2. Permanent Hardness :

It is due to the presence of chlorides and sulphates of calcium, magnesium, Fe3+

and SO42-. This type of hardness cannot be removed by boiling.
 WHY DETERMINE HARDNESS ?

• It is essential to know the hardness of the water

since it defines the purpose of it.
• Hard water is not a health hazard but it cannot
be used in industrial applications such as in
boilers, pipes etc.
• It has the tendency of
forming CaCO3 precipitate which later results
in sludge/scale formation .
 DETERMINATION OF HARDNESS
• The hardness of water can be estimated by methods such as gravimetric analysis,
EDTA titration, atomic absorption etc.

• In these methods, EDTA titration is the most inexpensive and simple way of
determining the hardness.

• Permanent hardness is usually determined by titrating it with a standard solution

of ethylenediaminetetraacetic (EDTA).

• The EDTA is a complexing, or chelating agent used to capture the metal ions. This
causes the water to become softened, but the metal ions are not removed from
the water.
• This method includes a series of titrations to determine the total, permanent,
temporary, Ca, Mg hardness of the given water sample.

• EDTA has a greater affinity for Ca2+ and Mg2+ when it is in the form of the
dihydrogen anion H2DTA2-. This is the ionic form of EDTA at pH 10.
• H2EDTA2- binds to a Ca2+ ion by by forming four special covalent bonds called
coordinate covalent bonds

• EDTA can form four or six coordination bonds with a metal ion.
• If Na2H2Y represents this salt, it ionizes in aqueous solution to H2Y2, which complexes
in a 1:1 ratio with either Ca2+ or Mg²+ ions (which are represented as M2+ ). The
reaction can be represented as follows:

H2Y2-+M2+ → MY2- + 2H+

• The indicator Eriochrome Black T is used to detect the end point. This is an indicator
that has a different color when complexed to metal ions than when it is a free indicator.
The reaction between the red indicator-metal complex and the EDTA reagent at the end
point can be represented as follows:

MIn- + H2Y2- → Hln2- + MY2- + H+

Wine red blue

• The figure shows the structure of Ca-EDTA complex where,
• carbons are black
• hydrogens are white
• oxygens are red
• nitrogen are blue
• calcium ion is the green ball.
• The EDTA complexes with the metal ions, while EBT is set free.
• In determining the Ca hardness, the water sample is heated to remove temporary
hardness and the Mg ions are precipitated by addition of 2N NaOH solution and it is
titrated against EDTA using murexide indicator.
• Necessary condition to be maintained while doing the titration is to keep the pH at about
10.
EXPERIMENTAL DETAILS
Requirements:

• Water sample

• Burette 25-30ml

• Glass funnel

• Pipette 1ml

• Flask Dropper

• Measuring cylinder
Reagents:
• EDTA

• Eriochrome Black-T

• NH4CL

• Ammonia Buffer

• Magnesium Carbonate

• 90% ethyl alcohol

• Distilled water
SOLUTION PREPARATION
• 250 ml 0.050 M std CaCO3 solution
SOLUTION PREPARATION
• .pH 10 Buffer

As a rule of thumb,
• The higher the pH (more basic solution), the sharper the endpoint
• The higher the formation of constant the lower the minimum pH
SOLUTION PREPARATION
• 500 mL 0.050 M EDTA
Why add 1.0 g MgCl2.6H20?

• Diverse ion effect: increase solubility (easier preparation)

• Sharper endpoint in titration

I. Ensures presence of Mg2+ in sample

II. Supposedly does not affect titration procedure

What exactly happens when we add MgCl2?

• Endpoint not as sharp if Mg2+ is not present in solution

• Only total hardness can be computed (Ca2+ and Mg2+)

STRUCTURE OF ERIOCHROME BLACK T-
MAGNESIUM COMPLEX
 REAGENT PREPARATION

1. EDTA solution: 4gm EDTA and 0.1gm magnesium bicarbonate dissolve in 800 ml
distilled water.
2. Eriochrome Black-T: 0.4gm Ericrome Black T, 4.5 gm hydroxylmine hydrochloride
add in 100ml 95% ethyl alcohol.
3. Ammonia Buffer: Stock A: 16.9gm of NH4CL in 143ml of conc. NH4OH, Stock B:
1.25gm magnesium salt of EDTA dissolve in 50 ml distilled water. Mix both stock
solutions and dilute to 250ml with DDW. Dilute 10ml of the solution to 100ml with
DDW.
 PROCEDURE:
1. The burette is filled with standard EDTA
solution to the zero level.
2. Take 50ml sample water in flask. If sample
having high Calcium content then take smaller
volume and dilute to 50ml.
3. Add 1ml Ammonia buffer.
4. Add 5 to 6 drop of Ericrome black – T
indicator. The solution turns into wine red
color.
5. Note the initial reading.
6. Titrate the content against EDTA solution. At
the end point color change from wine red to
blue color.
7. Note the final reading and record it. Repeat
the process till we get concordant value.
8. Take 50ml sample in another flask and
boiled it. (Add distilled water to get final
volume of water.)
9. Repeat step 3-7.
COLOUR CHANGE OF THE SOLUTION :

Starting point End point

SAMPLE ANALYSIS
• With MgCl2
SAMPLE ANALYSIS
• The amount of MgCl, that was supposed to be added was significant (0.0049

mol, compared to EDTA that has 0.025 mol)

• The addition of MgCl, should be negligible (EDTA:Mg~0) with respect to EDTA

in order for the titration to be unaffected.

• Back Titration with EDTA is possible

• Add standardized amount of EDTA .

• Back titrate with Mg2+ Activate.

CALCULATIONS :
• Total hardness of water mg/L (CaCO3 Scale) = ml of EDTA used

(unboiled)*103/ml of sample

• Permanent hardness of water mg/L (CaCO3 Scale) = ml of EDTA used (boiled)

*103 /ml of sample

• Temporary hardness of water mg/L (CaCO3 Scale) = Total hardness of water -

Permanent hardness of water

CONCLUSION :

• The color of soluble distilled water and R.O water instantly changed into blue

while tap water and pond water turned wine red when Erichrome black T was

added and therefore after turned blue when titrated against EDTA solution.
ADVANTAGES:

• It is a very simple and fairly accurate method.

• It also very cost efficient as only a burette and a conical flask are required.

• It also very quick and time efficient process when compared to gravimetric analysis.

DISADVANTAGES:

• A disadvantage is that there might be some human errors due to the solutions made up by
hand.

• EDTA grabs all the metal ions in the water, not just the Ca2+ ions. This gives us a value that
is not truly the concentration of Ca2+ ions. This causes an experimental error of about 1%,
but that is acceptable.