4.A.

DETEREMINATION OF TOTAL HARDNESS OF WATER USING EBT AS

INDICATOR

Theory:
Before describing the experiment, it is necessary to acquaintance some terms used in its
discussion.
Hardness:
‘Hardness’ may be defined as the amount of metal cation in a particular given amount of the
water.
Total hardness:
Total hardness of water is defined as the concentrations of calcium and magnesium ions
expressed in terms of calcium carbonate.
CaCO3 or MgCO3 present in H2O reacts with EDTA in high pH(10). So this experiment requires
an alkaline buffer solution which can keep pH=10. In presence of EBT indicator. If we titrate
H2O containing CaCO3 and/or MgCO3 with EDTA, Ca2+ or Mg2+ ion reacts with EDTA and
complex formation occurs. The end point can be determined observing colour change occurred
by EBT indicator. The whole titration process is called complexometric titration.
Chemistry involved:
1. Required reagents:
a. Sample water
b. Buffer solution(pH=10)
c. EBT indicator
d. EDTA solution
2. Chemical reactions:
M+++HD-(blue)=MD(red)+H+
MD+EDTA=M-EDTA+HD-(blue)
Procedure:
At first 50ml of sample water is taken in a conical flask and 1ml buffer solution(pH=10) & 2-3
ml indicator is added. Then the solution is titrated against standardized EDTA solution until the
colour changes from red to blue.
Data table:

Table-1: Determination of total hardness of pond water:

Volume of Burette reading(ml)

No. of Volume of Average Volume of
pond
Obs. Initial Final EDTA(ml) EDTA(ml)
water(ml)
1 1.7 7.4 5.7
50 5.75
2 7.4 13.2 5.8
Table-2: Determination of total hardness of tap water:

Volume of tap Burette reading(ml) Volume of

No. of Obs.
water(ml) Initial Final MgSO4 ml
1 29.4 46.1
50 16.75
2 19.7 36.5
Calculation:
1ml 0.01M EDTA≡1.00mg CaCO3
∴5.75ml 0.01M EDTA ≡5.75mg CaCO3
≡115ppm(in pond water)
Again,
1ml 0.01M EDTA≡1.00mg CaCO3
∴16.75ml 0.01M EDTA ≡16.75mg EDTA
≡335ppm(in tap water)
Result:
Total hardness in sample Pond Water= 115 ppm.
Total hardness in sample Tap Water= 335 ppm.

Discussions:

 Hard water is not a health hazard, but it causes various problems.

 For the homemaker water hardness makes home cleaning operations more difficult.

 Hard water wastes soap and synthetic detergents.

 In the laundry, hard water leaves soap curd and detergent deposits on fabrics. This dulls
colors and gives a grey or yellow appearance to white fabrics. Also hard water soap curd
clings to fabric fibers, causing threads to become brittle and shortening the life of the
material.

 Hard water leaves unsightly soap scum rings in the bathtub.

 Hard water spots and streaks glassware and dishes.

 Hard water builds up scale deposits in all water-using appliances clogs hot water pipes.
 From the above experimental evidence we can see that the hardness of the pond water is
less than that of tap water. Lakes, rivers, reservoirs, ponds, etc., are termed surface
waters. They receive water directly from precipitation and surface run-off. These various
bodies of water also receive a portion of their total amount from underwater springs
connected with the groundwater supply. As we have seen, surface waters are generally
 lower in mineral content. So it have less hardness. On the other hand the tap water is
ground water. It is full of minerals & metal ions, so that it is too hard.
 This indicator EBT is not suitable for strongly acidic solutions. So, to maintain the
condition of pH a buffer solution was added at a pH of 10 to 10.2. In this pH range the
dye tends to polymerize to a red brown product. So we must have to add a buffer solution
of which is alkaline in nature.

 Water hardness can be managed with powdered or liquid water softeners or with an ion
exchange softening unit.

Name Of The Experiment:

Determination Of Calcium In Presence Of Magnesium.

Theory:
The experiment is necessary to know about the hardness of water of different sources & compare
it scientifically. Hard water is due to metal ions (minerals) that are dissolved in the ground water.
These minerals include Ca2+, Mg2+, Fe3+, SO42-, and HCO3-. Hardness of water is due to rain
moving through the vast amount of limestone, CaCO3 that occurs in our area to the aquifer. This
is why we measure hardness in terms of CaCO 3; the concentration of the Ca2+ ions is greater than
the concentration of any other metal ion in water.
If it is stated that water has invisible hardness minerals in the amount of CaCO 3, this hardness
may be due to calcium or magnesium carbonates, bicarbonates, sulfates or chlorides or any
combination of these compounds. But in every case the combined concentration is chemically
equivalent to calcium carbonate, and the various calculations involved can be made with
simplicity.
There are two types of water hardness, temporary and permanent.
Temporary Hardness is due to the bicarbonate ion, HCO3-, being present in the water. This type
of hardness can be removed by boiling the water to expel the CO2.
Permanent hardness is due to the presence of the ions Ca2+, Mg+2, Fe3+ and SO4-. Boiling cannot
eliminate this type of hardness. The water with this type of hardness is said to be permanently
hard.

When calcium ion is titrated with EDTA, a relatively stable calcium complex is formed. With
calcium ion alone, no sharp end point can be obtained with eriochrom black T indicator and
transition from red to blue is not observed. With magnesium ion a somewhat less stable complex
is formed. And the magnesium indicator complex is more stable than the calcium indicator
complex but fewer stables than magnesium –EDTA complex. Consequently during the titration
of a sample of Ca2+ and Mg2+ mixture with EDTA solution in presence eriochrom black, the
EDTA reacts first with the free calcium ions, then with the free magnesium ions, then calcium
indicator complex and finally with the magnesium indicator complex. Since the magnesium
indicator complex is wine red in color and the free indicator is blue between pH 7 to 11, the color
of the solution changes from wine red to blue at the end point. If magnesium ions are not present
in the solution containing calcium ions they must require be added since they are required for the
color change of the indicator.
 To determine the individual element, calcium may be evaluated by titration using a suitable
indicator as Patton and Reeder’s or calcon or by titration with EGTA using Zincon as indicator.
The calcon indicator with calcium form complex with EDTA at a pH 12 and wine red in color.
But magnesium colcon complex is more stable then calcium complex at pH 12. Approximately
nothing happens when to magnesium calcon complex when EDTA is added to the solution
relatively of calcium. And the end point comes when the color is pure blue.

Chemistry involve:
1. Required reagents:
a. Standard EDTA solution
b. Sample water ( Pond & Tap water)
c. Calcon indicator
d. Di-ethyl-amine as buffer
2. Chemical reactions:
Ca2+ + H2Y2- = CaY2- + 2H+
CaY2-+EDTA=Ca-EDTA+ H2Y2- (blue)

Procedure: We take 50 ml of sample water in a conical flask. We add 5 ml of diethylamine

(giving a pH of about 12) and add a few drops of calcon indicator. We titrate the solution with
standard EDTA solution until the colour change from wine red to blue.

Experimental Data:
Table-1: Data For Determination Of Total Calcium In Presence Of Magnesium In Pond Water.
Volume of Burette reading(ml)
No. of Volume of Average Volume of
pond
Obs. Initial Final EDTA(ml) EDTA(ml)
water(ml)
1 0.0 4.2 4.2
50 4.25
2 4.2 8.5 4.3

Table-2: Data For Determination Of Total Calcium In Presence Of Magnesium In Tap Water.

Volume of Burette reading(ml)

No. of Volume of Average Volume of
tap
Obs. Initial Final EDTA(ml) EDTA(ml)
water(ml)
1 8.6 19.0 10.4
50 10.45
2 19.3 29.8 10.5

Calculation:
Sample- Pond Water:
1ml 0.01M EDTA≡0.4008mg Ca
∴4.25ml 0.01M EDTA ≡4.25×0.4008mg Ca
≡34.068ppm(in pond water)
Sample- Tap Water
1ml 0.01M EDTA≡0.4008mg Ca
∴10.45ml 0.01M EDTA ≡10.45×0.4008mg Ca
≡83.77ppm(in pond water)

Result:
Ca2+ present in sample Pond Water= 34.068 ppm.
Ca2+ present in sample Tap Water= 83.77ppm.

Discussions:

 Here access indicator was added to mask the total magnesium ion.
 In this experiment the pH is maintained using Di-ethyl-amine.
 From the above experimental evidence we can see that the hardness of the pond water is
less than that of tap water. Lakes, rivers, reservoirs, ponds, etc., are termed surface
waters. They receive water directly from precipitation and surface run-off. These various
bodies of water also receive a portion of their total amount from underwater springs
connected with the groundwater supply. As we have seen, surface waters are generally
lower in mineral content. So it have less hardness. On the other hand the tap water is
ground water. It is full of minerals & metal ions, so that it is too hard.
 This calcon indicator is used at pH at 12 it is reasonable to recognize properly. Here both
calcium and magnesium makes a complex with the indicator & in this pH range the
complex of magnesium is more stable than the calcium. So only calcium reacts with
EDTA to form complex. This method of making magnesium inert is called masking.

Name of The Experiment: Determination Of Total Solid In Water.

Theory:

Total solids in water- Many dissolved inorganic water contaminants or impurities exist as ions in
solution. On the other hand there are some insoluble solids present in water. The most common
of these solids are:

Cations   Anions  
Calcium Ca+ + Bicarbonate HC09 Suspended solids
Magnesium Mg++ Chloride Cl Bacteria
Sodium Na+ Sulfate SO,- Algae
Iron Fe+ + Nitrate NO, Microorganisms
Manganese Mn+ + Carbonate CO,_ _ organic wastes

These electrically charged dissolved particles make ordinary natural water a good conductor of
electricity. Coversely, pure water has a high electrical resistance, and resistance is frequently
used as a measure of its purity.

Chemistry involved:

 Sample water

Procedure:
Total solids (TS) are determined by drying a known amount of a sample at a temperature of 103
to 105 C in a tare (pre-weighed) vessel, such as a porcelain dish, cooling in a dry atmosphere (in
a container known as a desiccators), weighing on an analytical balance, subtracting the tare
weight, and dividing by the original amount of sample. Results can be expressed in mg/L if the
sample was originally measured out by volume; or percent by weight, if the sample was
originally weighed. If the sample is then burned in a furnace at about 500 C, cooled, and
weighed, the fixed (FS) or volatile solids (VS) can be determined.

Grams of solid ×1000

=
Total solids (TS) Milliliters of sample g/L

If the original sample is filtered through a tare glass-fiber filter, which is then dried, the
weight of the material captured on the filter is used to figure the total suspended solids (TSS).
Burning the filter in the furnace allows measurement of volatile suspended solids (VSS) or fixed
suspended solids (FSS).

The dissolved solids (DS) can be estimated from the difference between the total solids and
the total suspended solids, but the official method calls for drying the filtrate (the liquid which
passes through the filter) in a dish at 180C. (And, of course, there are TDS, FDS and VDS).
The dissolved solids (DS) = Total solids (TS) - Total suspended solids (TSS)

Experimental Data:
Sample: Water
Volume of sample water = 200.00ml
Weight of blank beaker = 75.85 g
Weight of solid + beaker = 75.99 g
 Solid present in sample = 0.1360g

Calculation:

Grams of solid ×1000

=
Total solids (TS) in Water Milliliters of sample g/L
0 .1360×1000
=
200 g/L
=0. 680 g/L

Result:

Total solid in sample Pond Water = 0.68 g/L

Discussion:
 The water can be passed through a fine-pore filter which can be made of
paper, glass fibers, a cellulose acetate membrane, etc. when factorization
have done.
 The amount of total solid and total suspended particle may vary from
source to source because the composition of the water from various source
is also vary.
 Total solid: The maximum allowable total solid in drinking water is
500mg per liter of sample water. We can see that our value does not exit
this
 Salt: The average acceptable levels for freshwater fish are 0 - 5 ppm.
Seawater averages 25 to 70 ppm.The level that is toxic varies with the
species of aquatic animal..
 Inorganic Arsenic: Arsenic is toxic to marine organisms at the level of
2000 mg/L.
Name of the experiment: determination of dissolved oxygen in sample water

Theory:

The dissolved oxygen (DO) is oxygen that is dissolved in water.

Oxygen is stripped out of water by reaction with excess hydroxide (OH-) and manganese ion
(Mn+2). The reaction reduces oxygen (from 0 to -2), oxidizes Mn (from +2 to +3) and forms a
precipitate, Mn(OH)3.

Mn in the precipitate is later reduced (from +3 to +2) in the presence of acid and excess iodide
(I-), the iodide is oxidized to iodine (I 2). But there is still excess iodide in the sample, and it
combines with the iodine to form tri-iodide ( I-3).

Finally, the tri-iodide is reacted in yet another oxidation-reduction step back to iodide, in the
presence of thiosulfate ion (S2O3-2), with the formation of tetrathionate ion (S4O6-2):

The amount of oxygen in a water sample can be determined when the amount of thiosulfate
necessary to completely react all tri-iodide is known precisely. The amount of thiosulfate is
directly related to the amount of oxygen initially present; no additional thiosulfate is added.

MiligramsofOxygen×1000
=
Dissolved oxygen in terms of ppm SampleVolumeinMililitre

Chemistry involve:
1. Required reagents:
a. Sample water
b. Manganous sulfate
c. Alkaline potassium iodine
d. Starch solution
e. Standard sodium thiosulfate solution
f. Sulfuric acid (conc.)
2. Chemical reactions:

I-3(aq) + S2O3-2(aq) → 3I-(aq) + S4O6-2(aq)

I2(aq) + I-(aq) → I-3(aq)

 4Mn+2(aq) + 8OH-(aq) + O2(aq) + 2H2O(l) → 4Mn(OH)3(s)

4Mn(OH)3(s) + 2I-(aq) + 6H+ → 2Mn+2(aq) + I2(aq) + 6H2O(l)

Procedure:

Firstly, 250ml bottle with a well fitted ground glass stopper is filled with sample water. Then 3ml
alkaline KI solution and 1ml manganous sulfate is added and carefully the bottle is stoppered not
to let any air bubbles to enter the bottle. Then it is allowed to settle the flocculent precipitate of
manganius hydroxide. When the upper part of the solution becomes completely clear, then the
stopper is removed from the bottle and 1ml concentrated sulfuric acid is introduced in it. After
that, the bottle is closed and shaked. At last, the solution is titrated with standard sodium
thiosulfate solution using starch as indicator.

Data table:
Table-2: Data for Determination of strength of Na2S2O3.
Burette reading(ml) Volume of
No. of Volume of Average Volume of
Na2S2O3
Obs. K2Cr2O7(ml) Initial Final Na2S2O3(ml)
(ml)
1 0.03 10.4 10.1
10 10.15
2 10.4 20.6 10.2

Table-2: Data for Determination of Dissolved Oxygen in Pond Water.

Volume of Burette reading(ml) Volume of
No. of Average Volume of
pond Na2S2O3
Obs. Initial Final Na2S2O3(ml)
water(ml) (ml)
1 3.1 16.0 12.9
290 13.15
2 16 29.4 13.4

Table-2: Data for Determination of Dissolved Oxygen in Tap Water

Volume of Burette reading(ml) Volume of
No. of Average Volume of
tap Na2S2O3
Obs. Initial Final Na2S2O3(ml)
water(ml) (ml)
1 31.6 36.3 4.7
290 4.75
2 36.3 41.1 4.8

Calculation:

1. Standardization of Na2S2O3 with standard K2Cr2O7 solution:

Here, Volume of K2Cr2O7, V1 = 10 ml

 Volume of Na2S2O3, V2 = 10.15ml
Normality of K2Cr2O7, N1 = 0.01 N
V 1×N 1
Normality of Na2S2O3, N2 =
V2
10× 0.01
=
10.15
=0.0098N
Sample-pond water
1ml 1N Na2S2O3 ≡8mg O2
∴13.15ml 0.0098N Na2S2O3≡8×13.15×0.0098
≡1.03096mg O2(in 290ml)
=3.55ppm
Sample-tap water
1ml 1N Na2S2O3 ≡8mg O2
∴4.75ml 0.0098N Na2S2O3≡8×4.75×0.0098
≡0.3724mg O2(in 290ml)
=1.284ppm

Discussion:

We have to very careful about that in the flask there is not entered any oxygen after
starting the experiment.
 The dissolved oxygen content of the water being tested can be expected to change
with depth, turbulence, temperature, sludge deposits, light, microbial action, mixing,
travel time, and other factors. A single dissolved oxygen test does not reflect the
accurate overall condition of a body of water. Several samples taken at different
times, locations, and depths are recommended for most reliable results. Samples must
be fixed immediately upon collection.
 In this experiment while titration is going on more oxygen dissolve with the sample
time to time. If there is access Mn+2 in solution there will be more points after the first
end points. So the titration should be done quickly & the first end point should be
taken for calculation.
 The nitrite ion frequently interferes with the dissolved oxygen determination. Nitrites
occur primarily in effluents from sewage treatment plants, which use biological
processes, in river waters, and in incubated biochemical oxygen demand (BOD)
samples. Nitrite interference may be easily overcome by the use of sodium azide. It is
most convenient to incorporate the azide in an alkali-KI reagent. When sulfuric acid
is added, the nitrite is destroyed. In this way, nitrite interference is eliminated.

Name Of The Experiment: Determination Of Acidity And Alkalinity Of Water.

Theory:
The alkalinity of water may be defined as its capacity to neutralize acid. Alkali substances in
water include hydroxides or bases. They can be detected by their acrid taste and by the fact that
they cause red litmus paper to turn blue.

Alkalinity of water may be due to the presence of one or more of a number of ions. These

include hydroxides, carbonates and bicarbonates. As discussed in previous articles, hydroxide

ions are always present in water, even if the concentration is extremely small. However,

significant concentrations of hydroxides are unusual in natural water supplies, but may be

present after certain types of treatment.

Again the term acidity means that the moles of a mono protic acid need to neutralize a base of

1M 1000cm3 are the acidity of that base.

Chemistry involve:

1. Required reagents:
a. HCl,0.02N
b. NaOH,0.02N
c. Phenolphthalein
d. Methyl orange
2. Chemical reactions:
H+ + NaOH  H2O + Na+
OH- + HCl  H2O + Cl-

Procedure:
In the process of neutralizing an acid by adding a base, like sodium hydroxide, the amount you
would need to neutralize a strong acid could be calculated directly from the pH of the acid
solution. But for a weak acid, the pH does not tell the whole story; the total amount of base
needed would be a lot more. This is because as the OH- from the base reacts with the H+ in
solution to form water, more H+ will break loose from the undissociated portion of the acid to
take its place. The neutralization will not be complete until all of the weak acid has dissociated.
To measure the total acidity, also called base-neutralizing capacity (BNC) of a water sample, it
has to be titrated with base. That is, a solution of a base whose concentration is known must be
added to the water sample slowly until the neutralization is complete. By measuring the volume
of the base added, you can figure out the original concentration of acid.
 In a similar way, the acid-neutralizing capacity (ANC), or alkalinity of a water sample has to
be determined by titrating it with a solution of a strong acid of known concentration. . And from
that value we can estimate the acidity and alkalinity of the water solution. The total acidity is
calculated in terms of CaCO3.
When we have to determine the acidity of water we will use a acid to neutralize the weak base
(water). To easy the calculation and to do perfect the experiment we chose a mono protic strong
acid such as HCl. For such case the neutralization point found at P H above 7. So we chose a
indicator that changes its color at PH above 7.

Data table:
Table-1: Standardization of HCl with Na2CO3.
No. of Volume of Burette reading(ml) Volume of Average Volume of
Na2CO3
Obs. take(ml) Initial Final HCl(ml) HCl(ml)
1 33.8 43.7 9.9
2 10 2.3 12.1 9.8 9.87
3 12.1 22.0 9.9

Table-2: Determination of methyl orange acidity of water

No. of Volume of Burette reading(ml) Volume of Average Volume of
water
Obs. take(ml) Initial Final HCl(ml) HCl(ml)
1 1.8 12.4 10.6
2 50 12.4 23.1 10.7 10.63
3 23.1 33.7 10.6

Table-1: Standardization of NaOH with HCl.

No. of Volume of Burette reading(ml) Volume of Average Volume of
HCl
Obs. take(ml) Initial Final HCl(ml) HCl(ml)
1 8.6 18.5 9.9
2 10 18.5 28.6 10.1 10.0
3 28.6 38.6 10.0

Table-2: Determination of phenolphthalein alkalinity of water

No. of Volume of Burette reading(ml) Volume of Average Volume of
water
Obs. take(ml) Initial Final HCl(ml) HCl(ml)
1 2.3 4.2 1.9
2 50 4.2 6.3 2.1 2.0
3 6.3 8.3 2.0

Calculation:
1. Determination of methyl orange acidity of water
 Here, Volume of Na2CO3 V1 = 10 ml
Volume of HCl V2 = 9.87ml
Normality of Na2CO3 N1 = 0.02 N
V 1×N 1
Normality of HCl, N2 =
V2
10× 0.02
=
9.87
=0.02N

Again,
1 ml 0.02 N HCl ≡ 1 mg CaCO3
∴10.63 ml 0.02 HCl ≡1×10.63 mg CaCO3
= 10.63 mg CaCO3
50 ml H2O contains= 10.63 mg CaCO3
1000 ml H2O contains =10.63×1000/ 50 ml CaCO3
= 212ppm

2. Determination of phenolphthalein alkalinity of water

Here, Volume of HCl V1 = 10 ml
Volume of NaOHV2 = 10ml
Normality of HCl N1 = 0.02 N
V 1×N 1
Normality of NaOH N2 =
V2
10× 0.02
=
10
=0.02N
Again,
1 ml 0.02 N NaOH ≡ 1 mg CaCO3
∴2 ml 0.02 NaOH ≡1×2 mg CaCO3
= 2.0mg CaCO3
50 ml H2O contains= 2 mg CaCO3
1000 ml H2O contains =2×1000/ 50 ml CaCO3
= 40ppm

Result:
Alkalinity in terms of CaCO3 = 40 ppm
Acidity in terms of CaCO3 = 212 ppm

Discussions:
 The acidity of water is acid neutralizing capacity of water and this is produced for the
presence of anions of salts which is produced by neutralization reaction of strong acid
and week base.
 The alkalinity of water is base neutralizing capacity of and this is produced for the
presence of cataion of salts which is produced by neutralization reaction of week acid and
strong base.
 From the experimental evidence we can see that the alkalinity of water is greater than the
acidity. Moreover tap water is more alkaline than pond water.
 The acidity and alkalinity may also vary for variation of source of water as the anions and
actions may vary from source to source.
 In the experiment the main thing that must be known to a student is the different types of
indicator used according acid base strength’s point of view.