Experiment.

No: 1 Date:
……..……….

DETERMINATION OF THE STRENGTH OF

UNKNOWN SOLUTION

Learning objectives:

• Select a suitable reaction for the estimation of acid/base by volumetric analysis

• Understand the role of standard solution
• Explore the significance of indicator(s)

Aim: To determine the strength of given NaOH solution

Chemicals required: A standard solution of 0.02N Na2CO3 and unknown (approximately

0.01N) HCl solution, Phenolphthalein, Methyl Orange
Indicators.

Apparatus required: Burette, Pipette, Beakers and Conical flask.

Theory:
i) 2 HCl + Na2CO3 → 2 NaCl + H2O + CO2
ii) HCl + NaOH → NaCl + H2O

Procedure:

Part A: Standardization of HCl solution: In this titration an unknown HCl solution is

titrated against standard Na2CO3 solution.
Rinse and fill the burette with the given HCl solution. Take 10 ml of Na2CO3 in a conical
flask with the help of pipette and add two drops of methyl orange indicator. The colour of
solution turns pale yellow. Titrate it with the HCl solution till a reddish pink colour is
obtained. Repeat the titrations to get successive concordant readings.

Observations:
Part A: Standardization of HCl solution:

S.No. Volume of Burette Readings Volume of

the solution the HCl
taken in Initial Final solution used
conical flask reading reading (ml)
(ml) (ml) (ml)
1.
2.
3.

Volume of the acid used = ------------ ml

Use Normality equation and explain the terms clearly.

Normality of HCl solution =
Calculation:
N1V1 (Na2CO3) = N2V2 (HCl)
Normality of HCl (N2) =

Volume of HCl (V2)=

Normality of Na2CO3 (N1) =

Volume of Na2CO3 (V1)=

Part B: Estimation of Strength of NaOH solution:

The given NaOH normality can be determined by titrating it with HCl (Known) using
phenolphthalein indicator.

Transfer 10 ml of NaOH solution in a clean conical flask with the help of pipette. Add two
drops of phenolphthalein indicator. The solution turns to pink. Titrate NaOH solution with
the HCl solution till the pink colour disappears. Repeat the titrations to get successive
concordant readings.

Part B: Estimation of NaOH solution:

S.No. Volume of Burette Readings Volume of

the solution the HCl
taken in Initial Final solution used
conical flask reading reading (ml)
(ml) (ml) (ml)
1.
2.
3.

Volume of the acid used = ------------ ml

Calculation:
N2V2 (HCl) = N3V3 (NaOH) Normality of HCl (N2) =
Volume of HCl (V2)=

Normality of NaOH (N3) =

Volume of NaOH (V3)=

Normality of NaOH solution =

Strength of NaOH solution = Normality of NaOH x Eq. wt of NaOH (40)

=
=

Result:

The strength of the given NaOH solution = ------------------ g/L

Review Questions:

1. HCl is a primary standard or a secondary standard? Explain?

2. Why anhydrous Na2CO3 is considered as primary standard?
3. How an exact N/10 solution of NaOH can be prepared?
4. Give the structure of phenolphthalein and Methyl orange?
5. Apply modern quinoid theory to explain the action of phenolphthalein and methyl
orange?

---oo0oo---
Experiment. No: 2 Date:
……..……….

Determination of alkalinity of water sample

Learning Objectives:
• Explore the alkalinity of various water samples
• Understand the species responsible for alkalinity
• Interpret the function of methyl orange and phenolphthalein indicators.
Aim: To determine alkalinity of a given water sample.
Apparatus required: Burette, Pipette, Conical flask, Measuring cylinder
Chemical required: Water sample, Unknown HCl solution (approximately 0.02N), 0.02N
Na2CO3 solution, Phenolphthalein indicator, Methyl orange indicator.
Theory:
The knowledge of alkalinity of water is necessary for controlling the corrosion, in
conditioning the boiler feed water (internally), for calculating the amounts of lime and
soda needed for water softening and also in neutralizing the acidic solution produced by
the hydrolysis of salts.
The alkalinity of water is due to the presence of hydroxide ion (OH-), carbonate ion
(CO32-) and bicarbonate ion (HCO3-) present in the given sample of water. These can be
estimated separately by titration against standard HCl solution, using phenolphthalein and
methyl orange indicators. The chemical reactions involved are shown below:

1. [OH-] + [H+] → H2O P

2. [CO32-] +
+ [H ] → [HCO3-] M
3. [HCO3-] + [H+] → H2O + CO2

The titration of the water sample against a standard acid upto phenolphthalein end-
point shows the completion of reactions (1) and (2) only. This amount of acid consumed
corresponds to hydroxide and half of the carbonate present. Further, titration of the water
sample against a standard acid (HCl) to methyl orange end-point marks the completion of
reactions (1), (2) and (3). Hence, the amount of acid consumed after the Methyl Orange
end-point corresponds to bicarbonate produced and already present. The total amount of
acid consumed (Phenolphthalein & Methyl Orange) represents the total alkalinity (due to
hydroxide, bicarbonate and carbonate ions).
The possible combinations of ions causing alkalinity in water are:
(i) OH- only,
(ii) CO32- only
(iii) HCO3- only.
(iv) OH- and CO32- together
(v) CO32- and HCO3- together
(vi) The possibility of OH- and HCO3- ions together is not possible since they
combine to form CO32- ions.
OH- + HCO3- → CO32- + H2O
Procedure:
Part A: Standardization of HCl solution: In this titration an unknown HCl solution is
titrated against standard Na2CO3 solution.
Rinse and fill the burette with the given HCl solution. Take 10 ml of Na2CO3 in a conical
flask with the help of pipette and add two drops of methyl orange indicator. The colour of
solution turns pale yellow. Titrate it with the HCl solution till a reddish pink colour is
obtained. Repeat the titrations to get successive concordant readings.

Observations:
Part A: Standardization of HCl solution:

S.No. Volume of Burette Readings Volume of

the solution the HCl
taken in Initial Final solution used
conical flask reading reading (ml)
(ml) (ml) (ml)
1.
2.
3.

Volume of the acid used = ------------ ml

Use Normality equation and explain the terms clearly.

Normality of HCl solution =
Calculation:
N1V1 (Na2CO3) = N2V2 (HCl)
Normality of HCl (N2) =

Volume of HCl (V2)=

Normality of Na2CO3 (N1) =

Volume of Na2CO3 (V1)=

Part B: Titration of water sample with HCl:

Rinse and fill the burette with standard HCl solution (from part A). Take 20 ml of
water sample into a conical flask with the help of pipette. Add 2 drops of phenolphthalein
indicator. The solution turns to light pink color. Titrate the water sample with N/50 HCl
till the pink color just disappears. Now add 1-2 drops of methyl orange indicator to the
same solution. The solution turns to yellow color. Continue the titration until red color is
appeared. Note down the reading and repeat the experiment to get concordant readings.
Observation tables for alkalinity:
Part B: Titration of water sample with HCl:

S.No. Volume of Initial Burette Readings Burette

water reading (Phenolphthalein) Readings
sample (ml) (Total/ Methyl
(ml) Orange)
Final reading Final reading
(ml) (ml)

1. 20 0
2. 20 0
3. 20 0

Calculations of Alkalinity:

Phenolphthalein Alkalinity in terms of CaCO3 equivalents:

Concentration of water: N2V2 (HCl) = N3V3 (water)

Phenolphthalein Alkalinity in terms of CaCO3 equivalents = Normality of water x Eq. wt

of CaCO3 =

Phenolphthalein Alkalinity (P) = --------- x 1000 mg/L or ---------- x 1000 ppm.

Total/Methyl Orange Alkalinity in terms of CaCO3 equivalents:
Concentration of water: N2V2 (HCl) = N3V3 (water)

Total Alkalinity in terms of CaCO3 equivalents = Normality of water x Eq. wt of CaCO3

=
Total Alkalinity (M) = --------- x 1000 mg/L or ---------- x 1000 ppm.
Interpretation of Results:

P- and M-
Hydroxyl (OH) Carbonate (CO3) Bicarbonate (HCO3 )
Alkalinity
P=O 0 0 M

P<½M 0 2P M – 2P
P=½M 0 M 0
P>½M 2P – M 2(M – P) 0

P=M M 0 0

Results:
The alkalinity of the given water sample is…………………ppm.

Review Questions:
1. What is the significance of determining alkalinity/acidity of water?
2. How phenolphthalein/methyl orange indicator does function in titration?
3. Why phenolphthalein is not a suitable indicator for titrating a weak base like
NH4OH against a strong acid?
4. Why methyl orange cannot be used as indicator for titrating weak acid, like acetic
acid against a strong base?
5. What is the pH range for phenolphthalein/methyl orange indicator?
6. What are the demerits of alkalinity/acidity in industry perspective?
7. How will you determine the alkalinity/acidity of soil sample?
Experiment No: 3 Date:
……..……….

ESTIMATION OF HARDNESS OF WATER BY COMPLEXOMETRY

Learning Objectives:

• Understand the concept of complexometry

• Analyze different types of hardness
• Explore the importance of buffer solution & EBT indicator

Aim: To determine the hardness of water by complexometric titration.

Apparatus Required: Pipette, Burette, Conical flask, Beakers etc.,

Chemicals Required: 0.01M ZnSO4, EDTA solution, Water sample, NH3-NH4Cl buffer
solution, Erio-chrome Black T (EBT) indicator.

Theory: The method is based upon the fact that Ethylene diamine tetra acetic acid forms
stable complex with all metals particularly with bi and polyvalent metals. For all practical
purposes the hydrated disodium salt of the EDTA is used which has the following
structure.

NaOOC H2C CH2COOH

N – CH2 – CH2 – N

HOOC H2C CH2COONa

Initially when EBT indicator is added to the hard water sample in presence of
buffer (pH 10) the solution turns wine red colour due to the formation of unstable Ca/Mg –
EBT complex. Now this solution is titrated against standard EDTA solution until the blue
colour appears (due to formation of stable complexes with Ca and Mg ions present in
water).

M2+ + EBT -------------------------- M- EBT

Wine- red complex
2+
M + EDTA --------------------- M- EDTA
Stable- colourless complex
M-EBT + EDTA ----------------- M-EDTA + EBT
Wine red Blue

(M = Ca or Mg)

Procedure:-
 A) Standardization of EDTA:-

Transfer 10 ml of 0.01M ZnSO4 solution into a conical flask with the help of
pipette. Add 2 ml of Ammonia and Ammonium chloride buffer solution and 2 drops of
EBT indicator. Solution turns wine red colour. Titrate with EDTA from the burette till
the colour changes to blue. Note the final burette reading. Repeat the procedure until
successive concordant readings are obtained.

Observations and Calculations:-

A) Standardization of EDTA:-

Molarity of ZnSO4 solution M1 = 0.01M

S.No. Volume of ZnSO4 Burette Readings Volume of

solution Initial (a) Final (b) EDTA
V1 solution
(b-a), V2
1. 10 ml
2. 10 ml
3. 10 ml

Molarity of EDTA solution = ZnSO4 = EDTA

M1V1 = M2V2

Calculation:

B) Determination of total hardness of water:-

Transfer 20 ml of water sample into a conical flask with the help of measuring
cylinder. Add 2 ml of Ammonia and Ammonium chloride buffer solution and 2 drops
of EBT indicator. The solution becomes wine red in colour. Titrate with EDTA
solution from the burette till the solution colour changes to blue. Note the final burette
reading. Repeat the procedure until successive concordant readings are obtained.
Determination of Total hardness of water:-

Molarity of EDTA = M2=

S.No. Volume of water Burette Readings Volume of

sample EDTA
Initial (a) Final (b)
V3 solution
(b-a)
1. 20 ml
2. 20 ml
3. 20 ml

EDTA = Water sample

M2V2 = M3V3
M3 = M2V2/ V3

Total Hardness of water = (1000 X M3 X 100) = ------------ ppm of CaCO3

Calculation:

C) Determination of Permanent Hardness:

Transfer 20 ml of boiled water sample into a conical flask with the help of measuring
cylinder. Add 2 ml of Ammonia and Ammonium chloride buffer solution and 2 drops of
EBT indicator. The solution becomes wine red in colour. Titrate with EDTA solution from
the burette till the solution colour changes to blue. Note the final burette reading. Repeat
the procedure until successive concordant readings are obtained.
Observations table for permanent hardness:
S.No. Volume of water Burette Readings Volume of
sample EDTA
Initial (a) Final (b)
V4 solution
(b-a)
1. 20 ml
2. 20 ml
3. 20 ml
EDTA = Water sample
M2V2 = M4V4
M4 = M2V2/ V4

Permanent water Hardness of water = (1000 X M4 X 100) = ------------ ppm of CaCO3

Results:
Total hardness of given water sample is ………………..ppm of CaCO3
Permanent hardness of the given water sample is……………ppm of CaCO3

Review Questions:

1. What is hardness of water?

2. What are soaps? Why hard water does not lather with soap?
3. What are carbonate and non-carbonate hardness?
4. How hardness of water is expressed?
5. What are the various units of hardness and how they are related to each other?
6. What is EDTA? In what form EDTA is used? Give its structure?
7. How does EBT acts as an indicator?
8. What are the disadvantages of hard water?
Experiment. No: 10 Date:
……..……….

ESTIMATION OF AMOUNT OF AN ACID USING pH- METRIC METHOD

Learning objectives:
• To understand the concept of pH
• To understand how pH-meter works
• To learn about electrodes involved
Apparatus: Electrodes, beaker, pipette, burette ctc.
Chemicals: Hydrochloric acid (HCl), sodium hydroxide (NaOH). buffer of pH = 4 and
9.2.
Instrumentation: pH-meter
Theory: Most of the chemical and biochemical processes are profoundly affected by the
acidity or alkalinity of the medium in which the reaction takes place. All acid dissociate in
aqueous solution to yield H+ ions. Some acids like HCl, H2SO4, HNO3 etc. are completely
ionized in aqueous medium where as CH3COOH, HCOOH etc. ionize to a small extent
only. The former is known as strong and the later as weak acid. pH of any solution is
defined as (–log H+) and has values between 0–14. pH < 7 indicate acidic solution, pH > 7
indicate basic solution and pH = 7 means neutral solution. The pH of a solution can be
measured accurately with the help of a pH meter. Measurement of pH is employed to
monitor the cause of acid-base titration. The pH values of the solution at different stage of
acid–base neutralization are determined and plotted against the volume of alkali added on
adding a base to an acid, the pH rises slowly in the initial stages as the concentration of H+
ion decreases gradually. But, at the equivalence point, it increases rapidly as at the
equivalent point H+ ion concentration is very small. Then it flattens out after the end point.
The end point of the titration can be detected where the pH value changes most rapidly.
However, the shape of the curve depends upon the ionisability of the acid and the base
used and also on the acidity of base and basicity of the acid.

Procedure:
0.1(N) NaOH solution is provided.
HCl solution of unknown strength is provided (100ml HCl).
Calibration of pH: Switch on the instrument and wait for 10–15 minutes so that machine
gets warmed up. Prepare the buffer solution by adding buffer tablets of pH = 4 and pH =
9.2 in 100 mL of water separately. Wash the electrode with distilled water. Then, dip the
electrode in the buffer solution (pH = 4) taken in a beaker, so that the electrode immersed
to the solution properly. Measure the temperature of the solution and set the temperature
compensate control accordingly. Set the pointer to pH = 7 exactly means of set = 0
control. Put the selector switch to proper pH range 0–7 (as the buffer pH = 4). So the
pointers to the known pH value of the buffer by burning the set buffer control. Put back
the selector at zero position. Wash the electrode with distilled water and standardize the
pH meter using basic buffer solution pH = 9.2.
pH-metric titration: Clean the electrode with distilled water and wipe them with tissue
paper or filter paper. Take 20 mL of HCl and about 40 ml distilled water in a 100 mL
beaker and immerse the electrode in it. Set the burette with NaOH solution. The reading
shown on the scale of pH meter is pH value of the HCl solution. Add NaOH solution drop
wise from the burette (maximum 1.0 mL at a time), shake the solution well and note the
corresponding pH values. Near the end point, volume of NaOH added should be as small
as possible because the acid is neutralized and there will a sharp increase in pH values.
Further addition of even 0.01 mL of NaOH, increase the pH value to about 9–10. Now plot
the graph between pH values and volume of titrant added. S shape curve is obtained. To
calculate the exact equivalence point from the graph, derivative curve is plotted between
∆pH/∆V and volume of titrant added.

Observation table:
S.No Volume of NaOH pH values ∆pH/∆V
added
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Calculation: N1V1 (NaOH) = N2V2 (HCl)
Result: The amount of HCl present in the given sample is………..g/mL