ENGINEERING CHEMISTRY

LABORATORY MANUAL
Standard operating procedures (SOP) 2080

KHWOPA ENGINEERING COLLEGE

LIBALI, BHAKTAPUR
 Contents
SAFETY INSTRUCTIONS.................................................................................................................................. ii
NOTES ON PRACTICAL REPORT FORMAT ..................................................................................................... iii
TO DETERMINE THE ALKALINITY OF THE GIVEN WATER SAMPLE A ............................................................. 1
TO DETERMINE THE ALKALINITY OF THE GIVEN WATER SAMPLE B ............................................................. 5
TO DETERMINE THE TOTAL HARDNESS OF THE WATER SAMPLE ............................................................... 13
TO DETERMINE THE PERMANENT HARDNESS OF THE WATER SAMPLE .................................................... 17
TO DETERMINE THE AMOUNT OF RESIDUAL CHLORINE IN THE GIVEN SAMPLE OF WATER ..................... 21
TO DETERMINE THE AMOUNT OF IRON IN MOHR’S SALT SOLUTION. ....................................................... 25
TO DETERMINE THE pH OF THE UNKNOWN ACIDIC BUFFERS BY USING STANDARD ACIDIC BUFFER
SOLUTIONS .................................................................................................................................................. 28
TO DETERMINE THE pH OF THE UNKNOWN BASIC BUFFERS BY USING STANDARD BASIC BUFFER
SOLUTIONS .................................................................................................................................................. 32
TO DETERMINE THE pH OF SOIL SAMPLES ................................................................................................. 36
TO ESTIMATE THE AMOUNT OF BARIUM IN THE GIVEN SAMPLE OF BARIUM CHLORIDE SOLUTION ....... 37
TO ESTIMATE THE AMOUNT OF SULPHATE IN GIVEN COPPER SULPHATE SOLUTION. .............................. 39
TO ETCH PCB CIRCUIT BOARD USING IRON(3) CHLORIDE .......................................................................... 41
VIVA VOCE QUESTIONS ............................................................................................................................... 43

i
SAFETY INSTRUCTIONS
1. Students must strictly follow the safety rules and instructions.
2. Students must know their working space, location of fire extinguisher.
3. Use a mask and gloves.
4. Avoid skin and eye contact with all chemicals.
5. Minimize all chemical exposures.
6. Assume that all chemicals of unknown toxicity are highly toxic.
7. Use equipment only for its designated purpose.
8. Combine reagents in their appropriate order, such as adding acid to water.
9. All laboratory personnel should place emphasis on safety and chemical hygiene at all times.
10. Never leave containers of chemicals open.
11. Do not taste or intentionally sniff chemicals.
12. Never consume and/or store food or beverages or apply cosmetics in areas where hazardous
chemicals are used or stored.
13. Wash exposed areas of the skin prior to leaving the laboratory.
14. Determine the potential hazards and appropriate safety precautions before beginning any work.
15. Procedures should be developed that minimize the formation and dispersion of aerosols/ fumes.

ii
NOTES ON PRACTICAL REPORT FORMAT
Students must firmly follow the following instructions while preparing practical reports.

1. Either use blue or black ink throughout the practical report.

2. Titles on the contents page must be in block letters, fill all necessary fields related to practical.
Example

S.N. Name of the Experiment Date Page No. Remark

1. TO DETERMINE THE ALKALINITY OF GIVEN WATER 2080-04-03 01-05
SAMPLE-A

2. TO DETERMINE THE ALKALINITY OF GIVEN WATER 2080-04-10 05-10

3. State Date of experiment and Experiment No. in the first page of each practical and mark page
numbers in every page of the report.
4. Write practical title in block letters first line onwards, not above margin. Example

Name of Experiment: Page No.: 01

Date: 2078-01-03

Experiment No: 01
TO DETERMINE THE ALKALINITY OF GIVEN WATER SAMPLE-A

Apparatus required
1. Conical flask
2. Beakers

5. Requirements, Theory, Procedure, Observations, Calculation, Results, Conclusion and

Precautions must be in order.
6. Consider present tense while writing theory and conclusion.
7. Procedure should be reported in past tense, in passive voice and in paragraph. Not point wise
and not in imperative sentence with verb in the beginning.
8. Observation tables must be filled with readings written in possible precision level. Tables should
not be left open, use pencil to draw table borders.
9. Never use pen in left page of the report, only pencils are permitted.
10. Write 3 to 4 precautions in points yourself.
11. Keep the report neat and clean.

iii
Experiment no. 1

TO DETERMINE THE ALKALINITY OF THE GIVEN WATER SAMPLE A

Requirements

1. Standard HCl solution of N/50

2. Phenolphthalein indicator

3. Methyl orange indicator

4. Water sample

5. Arrangement for titration with 100 ml pipette

Theory:

The alkalinity of water is a measure of the ability of water to neutralize acids. The alkalinity in water
samples may be due to the presence of either

a. Soluble hydroxides only or

b. Soluble carbonates only or

c. Soluble bicarbonates only or

d. a mixture of soluble hydroxides and soluble carbonates or

e. a mixture of soluble carbonates and soluble bicarbonates.

The type and degree of alkalinity of a water sample is usually determined by titration with a double
indicator. A fixed volume of the water is titrated with a standard acid first to the phenolphthalein
endpoint, and then continuing the titration to the methyl orange endpoint. Hence this titration is generally
known as double indicator titration.

The reactions taking place in the first half i.e. up to the phenolphthalein endpoint are

OH- + H+ → H2O ................1

CO3- - + H+ → HCO3- .............2

That means, the volume of the acid used up to the phenolphthalein endpoint corresponds the complete
neutralization of hydroxide ions (OH-) and only half neutralization of CO3- - ions to HCO3- ions.

After that, we add methyl orange and continue the titration up to the methyl orange endpoint. The
reaction taking place in the second half i.e. after the phenolphthalein endpoint is

HCO3- + H+ → H2CO3 ..........3

That means, the volume of the acid used after the phenolphthalein endpoint corresponds to the
neutralization of all HCO3- to carbonic acid H2 CO3.

Let x = volume of acid required up to phenolphthalein endpoint

1
y = volume of acid required from beginning to methyl orange endpoint

Note: y corresponds to the total alkalinity and represents the completion of all neutralization reactions
from 1 to 3

Hence, the results can be summarized as follows:

Summary of results

Hydroxide(OH-) Carbonate (CO3- -) Bicarbonate (HCO3-)

Conditions
If x = 0 nil nil y
If x = y y nil nil
1 nil 2x nil
if x = 𝑦
2
1 2x - y 2 (y - x) nil
If x > 2𝑦
1 nil 2x y-2x
If x < 2𝑦

Procedure:

1. 100 ml of the given water sample in the 250 ml conical flask and add 2 drops of phenolphthalein
indicator.

2. Titrate the water sample against the standard HCl acid from the burette until the pink colour is just
discharged. Note the burette reading as the phenolphthalein endpoint (x)

3. Now, add 2 drops of methyl orange indicator to the same solution and continue the titration until the
colour changes from yellow to just orange. Note the whole titre value from the beginning to the end as
the methyl orange endpoint ( y ).

4. Repeate the whole process until concurrent reading is obtained.

2
Observation:

Volume of water sample (A) taken for each titration = 100 ml

Indicator used = Phenolphthalein and then methyl orange
Normality of standard HCl acid = N/50 (f = 1.05)

Burette reading

No. of obs. Initial Phenolphthalein Methyl orange endpoint (y) Concurrent x Concurrent y
endpoint (x) ml ml
1 0.0 12.2 14.3 12.0 14.0
2 0.0 12.1 14.1
3 0.0 12.0 14.0
4 0.0 12.0 14.0
Calculations:

Here x = 12.0 ml of N/50 (f = 1.05) HCl and y = 14.0 ml of N/50 (f = 1.05)

1
Since x > 2 𝑦 , the water sample contains only OH- and CO3- - ions and no HCO3- ions.

Alkalinity due to OH- ions:

The volume of the standard HCl acid equivalent to OH- ions in 100 ml of the water sample = 2x - y

= 2 x 12 - 14

= 10 ml
𝑁
That is, 100 ml of water sample = 10 ml of 50
( f= 1.05) HCl
10 𝑥 1.05 𝑁
Normality of the water sample (with respect to OH- content) = =0.0021 N
100 𝑥 50

Concentration in gms/litre = normality x eq. wt. of OH-

= 0.0021 x 17 gms/ litre in terms of OH-

= 0.0357 gms/ litre in terms of OH-

Concentration in gms/ litre in terms of CaCO3 = normality x eq. wt. of CaCO3

= 0.0021 x 50 gms/ litre in terms of CaCO3

= 0.0021 x 50 x 1000 mg/ litre in terms of CaCO3

= 105 mg/ litre in terms of CaCO3

= 105 ppm

3
 105 0
= Clark
14.3

= 7.34 0Clark

Note: In engineering works, it is a general practice to express alkalinity in terms of CaCO 3 as parts per
million and 0Clark

14.3 ppm = 10Clark

Alkalinity due to CO3- - ions:

The volume of the standard HCl acid equivalent to CO3- - ions in 100 ml of water sample = 2(y - x)

= 2(14 - 12) = 4 ml
𝑁
That is, 100 ml of the water sample = 4 ml of 50
( f= 1.05) HCl
4 𝑥 1.05 𝑁
Normality of the water sample (with respect to CO3- - content) = =0.00084 N
100 𝑥 50

Concentration in gms/litre in terms of CO3- - = normality x eq. wt. of CO3- -

= 0.00084 x 30 gms/ litre in terms of CO3- -

= 0.0252 gms/ litre in terms of CO3- -

Concentration in gms/ litre in terms of CaCO3 = normality x eq. wt. of CaCO3

= 0.00084 x 50 gms/ litre in terms of CaCO3

= 0.00084 x 50 x 1000 mg/ litre in terms of CaCO3

= 42 mg/ litre in terms of CaCO3

= 42 ppm
42 0
= Clark
14.3

= 2.94 0Clark

Conclusion:

Precautions:

4
Experiment no. 2

TO DETERMINE THE ALKALINITY OF THE GIVEN WATER SAMPLE B

Requirements

1. Standard HCl solution of N/50

2. Phenolphthalein indicator

3. Methyl orange indicator

4. Water sample

5. Arrangement for titration with 100 ml pipette

Theory:

The alkalinity of a natural sample of water may be due to the presence of

a. Soluble hydroxides only

b. Soluble carbonates only

c. Soluble bicarbonates only

d. a mixture of soluble hydroxides and carbonate

e. a mixture of soluble carbonates and bicarbonates.

The type and degree of alkalinity of a water sample ar usually determined by titration with a double
indicator. A fixed volume of the water is titrated with a standard acid first to the phenolphthalein
endpoint, and then continuing the titration to the methyl orange endpoint.

The reactions taking place in the first half i.e. up to the phenolphthalein endpoint are

OH- + H+ → H2O ................1

CO3- - + H+ →HCO3- .............2

That means, the volume of the acid used up to the phenolphthalein endpoint corresponds the complete
neutralization of hydroxide ions (OH-) and only half neutralization of CO3- - ions to HCO3- ions.

After that, we add methyl orange and continue the titration up to the methyl orange endpoint. The
reaction taking place in the second half i.e. after the phenolphthalein endpoint is

HCO3- + H+ → H2 CO3 ..........3

That means, the volume of the acid used after the phenolphthalein endpoint corresponds to the
neutralization of all HCO3- to carbonic acid H2 CO3.

Let x = volume of acid required up to phenolphthalein endpoint

y = volume of acid required from beginning to methyl orange endpoint

5
Note: y corresponds to the total alkalinity and represents thecompletion of all neutralization reactions
from 1 to 3

Hence, the results can be summarized as follows:

Summary of results

Hydroxide(OH-) Carbonate (CO3- -) Bicarbonate (HCO3-)

Conditions
If x = 0 nil nil y
If x = y y nil nil
1 nil 2x nil
if x = 𝑦
2
1 2x - y 2 (y - x) nil
If x > 𝑦
2
1 nil 2x y-2x
If x < 𝑦
2

Procedure:

1. 100 ml of the given water sample in the 250 ml conical flask and add 2 drops of phenolphthalein
indicator.

2. Titrate the water sample against the standard HCl acid from the burette until the pink colour is just
discharged. Note the burette reading as the phenolphthalein endpoint (x)

3. Now, add 2 drops of methyl orange indicator to the same solution and continue the titration until the
colour changes from yellow to just orange. Note the whole titre value from the beginning to the end as
the methyl orange endpoint ( y ).

4. Repeate the whole process until concurrent reading is obtained.

Observation:

Volume of water sample (A) taken for each titration = 100 ml

Indicator used = Phenolphthalein and then methyl orange

Normality of standard HCl acid = N/50 (f = 1.05)

Burette reading

No. of obs. Initial Phenolphthalein Methyl orange endpoint (y) Concurrent x Concurrent y
endpoint (x) ml ml
1 0.0 6.4 19.0 6.2 18.8
2 0.0 6.2 18.9
3 0.0 6.2 18.8
4 0.0 6.2 18.8
Calculations:

Here x = 6.2 ml of N/50 (f = 1.05) HCl and y = 18.8 ml of N/50 (f = 1.05)

6
 1
Since x < 2 𝑦 , the water sample contains only CO3- - and HCO3-ions and no ions. OH- is absent in the sample.

Alkalinity due to CO3- - ions:

The volume of the standard HCl acid equivalent to OH- ions in 100 ml of the water sample = 2x

= 2 x 6.2 = 12.4 ml
𝑁
That is, 100 ml of water sample = 12.4 ml of 50
( f= 1.05) HCl
12.4 𝑥 1.05 𝑁
Normality of the water sample (with respect to OH- content) = = 0.0026 N
100 𝑥 50

Concentration in gms/litre in terms of CO3- - = normality x eq. wt. of CO3- -

= 0.0026 x 30 gms/ litre in terms of CO3- -

= 0.078 gms/ litre in terms of CO3- -

Concentration in gms/ litre in terms of CaCO3 = normality x eq. wt. of CaCO3

= 0.0026 x 50 gms/ litre in terms of CaCO3

= 0.0026 x 50 x 1000 mg/ litre in terms of CaCO3

= 130 mg/ litre in terms of CaCO3

= 130 ppm
130
=14.3 0Clark

= 9.09 0Clark

Alkalinity due to HCO3 - ions:

The volume of the standard HCl acid equivalent to HCO3 - ions in 100 ml of water sample = y - 2x

=18.8 - 2 x 6.2 = 6.4 ml

𝑁
That is, 100 ml of the water sample = 6.4 ml of 50
( f= 1.05) HCl
6.4 𝑥 1.05 𝑁
Normality of the water sample (with respect to HCO3 -content) = =1.344 x 10-3 N
100 𝑥 50

Concentration in gms/litre in terms of HCO3 - = normality x eq. wt. of HCO3 -

= x 61 gms/ litre in terms of HCO3 -

= 81.984 x 10-3 gms/ litre in terms of HCO3 -

Concentration in gms/ litre in terms of CaCO3 = normality x eq. wt. of CaCO3

= 1.344 x 10-3 x 50 gms/ litre in terms of CaCO3

= 1.344 x 10-3 x 50 x 1000 mg/ litre in terms of CaCO3

7
= 67.2 mg/ litre in terms of CaCO3

= 67.2 ppm
67.2
=14.3 0Clark

= 24.70 0Clark

Results:

Conclusion:

Precautions:

Explanation of summary table

Soluble hydroxides, carbonates and bicarbonates of metal ions or other cations are present in alkaline
water. There might be indivual presence or presence of carbonates along with hydroxide or with
bicarbonates. If we add a strong acid solution in the sample, hydroxide will react first forming water. If
hydroxide is completely neutralized, acid will find carbonates and react to produce bicarbonate. When
carbonates are completely half neutralized, the colour of phenolphthalein will changed to colourless.
Bicarbonates finds acid to reactwith below the pH range of phenolphthalein.

Complete neutralization of hydroxide, OH- + H+ →H2O

Complete half neutralization of carbonates to bicarbonates, CO32- + H+ →HCO3-

Phenolphthalein end point

Complete half neutralization of carbonates to bicarbonates, HCO3- + H+ →H2CO3

Methyl orange end point

Case I : When water sample contains only soluble hydroxides

If water sample contains only soluble hydroxide ions as a factor of alkalinity, when phenolphthalein
indicator is added, it gives pink color. The whole reaction after adding acid from burette is OH- + H+ →H2O.
Phenolphthalein indicator turns colourless when all the OH- ions get neutralized. Since there is no other
alkaline components in water when we add methyl orange indicator it directly changes to red and
yellow colour is not seen. So here volume of acid up to methyl orange end point is equal to that upto
phenolphthalein end point (y = x). And all the acid consumed is due to OH- ions.
So, if y = x, only hydroxide is present and carbonates and bicarbonates are absent.

8
volume of acid consumed corresponds to hydroxide is y or x (which are equal)
Condition appeared: y = x
Volume of acid consumed by carbonates: x or y

x
Complete neutralization of hydroxide,
y
OH- + H+ →H2O

Phenolphthalein end point Methyl orange end point

Condition: x = y
Volume of acid consumed by hydroxide = x = y

Case II: When water sample contains only carbonates

If water sample contains only carbonate ions, then pink colour appears when phenophthalein indicator
is added. Half neutralization(CO32- + H+ →HCO3-) will be completed on addition of acid from burette up to
the phenolphthalein end point. Equal amount of acid is required to react with the produced
bicarbonate. So, x = y/2. All acid is consumed by carbonates. So volume of acid consumed by carbonates
is 2x or y
Condition appeared: x = y/2
Volume of acid consumed by carbonates: 2x or y

Complete half neutralization of carbonates to bicarbonates,

x
CO32- + H+ →HCO3-
y
Phenolphthalein end point

Complete half neutralization of carbonates to bicarbonates,

x
HCO3- + H+ →H2CO3

Methyl orange end point

Condition: x = y/2
Volume of acid consumed by carbonates = x + x = 2x = y

Case III: When water sample contains only bicarbonates

If water sample contains only bicarbonates, no pink colour will appear on addition of phenolphthalein
indicator. So volume of acid consumed upto phenolphthalein end point is zero. Methyl orange indicator

9
gives yellow colour due to bicarbonate alkalinity. The total volume of acid consumed up to methyl
orange end point corresponds to the volume of acid consumed by bicarbonates (HCO3- + H+ →H2CO3).
Condition appeared: x = 0,
volume of acid consumed by bicarbonates: y

Phenolphthalein end point

Complete half neutralization of carbonates to bicarbonates,

y/2
CO32- + H+ →HCO3-
y

Complete half neutralization of carbonates to bicarbonates,

y/2
HCO3- + H+ →H2CO3

Methyl orange end point

Condition: x = 0
Volume of acid consumed = y/2 + y/2 = y

Case IV: When water sample contains carbonates and hydroxide

If water sample contains carbonates only, equal amount of acid will be consumed up to phenolphthalein
end point and after it to methyl orange end point. Since hydroxide reacts with acid before carbonate
reacts with acid, volume of acid up to phenolphthalein end point exceeds half of total volume of acid
consumed by both alkaline components.

Due to the presence of hydroxide and carbonates, water sample appears pink when phenolphthalein
indicator is added. On addition of acid from burette first hydroxide reacts with it (OH- + H+ →H2O). Even
after the completion of this reaction, end point will not be observed as the solution still contains
carbonates. End point of phenolphthalein will be reached after completion of half neutralization of all
carbonates (CO32- + H+ → HCO3-). After phenolphthalein end point when methyl orange indicator is added
yellow colour appears due to the bicarbonates formed from carbonates. The volume of acid consumed
(HCO3- + H+ →H2CO3) up to methyl orange end point after phenolphthalein end point (y - x) is the half
amount of acid consumed by carbonates. so, volume of acid consumed by carbonates is 2(y -x) and
remaining volume of acid consumed ( y - 2( y - x ) ) or ( 2x - y ) is the volume of acid consumed
hydroxide.

Condition appeared: x > y/2

volume of acid consumed by hydroxide = ( 2x - y )

volume of acid consumed by carbonate = 2 ( y - x )

10
 y-2( y - x ) = 2x - y

x
Complete half neutralization of carbonates to bicarbonates,
(y-x)
y CO32- + H+ →HCO3-
Phenolphthalein end point
Complete half neutralization of carbonates to bicarbonates,
(y-x) HCO3- + H+ →H2CO3

Methyl orange end point

Condition: x > y/2

volume of acid consumed by OH- = 2x - y
volume of acid consumed bu CO32- = 2(y-x)

Case V: When carbonate is present along with bicarbonate.

If water sample contains carbonates only, equal amount of acid will be consumed up to phenolphthalein
end point and after it to methyl orange end point. Since there is some more bicarbonates in the sample,
the later part of the titration consumes more acid. So here x < y/2

Due to the presence of carbonates, water turns pink on addition of phenolphthalein indicator. Half
neutralization of carbonates (CO32- + H+ → HCO3-) completes up to phenolphthalein end point ( x ). Same
amount of acid will be consumed for the complete reaction of it (HCO3- + H+ →H2CO3) after addition of
methyl orange i.e. 2x. But the solution does not change to red because there are extra bicarbonates. The
extra volume of acid consumed up to total end point or methyl orange end point is the volume
consumed by bicarbonates.

Condition appeared: x < y/2

Volume of acid consumed by carbonate = 2x

Volume of acid consumed by bicarbonate = y - 2x

11
 Complete half neutralization of carbonates to bicarbonates,
x CO32- + H+ → HCO3-
Phenolphthalein end point
y remaining neutralization of carbonates to carbonic acid
xx HCO3- + H+ →H2CO3

neutralization of bicarbonates to carbonic acid

y - 2x
HCO3- + H+ →H2CO3
Methyl orange end point

Condition: x < y/2

volume of acid consumed bu CO32- = 2x
Volume of acid consumed by HCO3- = y - 2x

12
Experiment no. 3

TO DETERMINE THE TOTAL HARDNESS OF THE WATER SAMPLE

Requirements
𝑀
Standard 100 EDTA disodium salt solution

Eriochrome black T indicator

NH3-NH4Cl buffer of pH 10

Theory:

Hardness of water can be defined as the consumption of soap by the water due to the presence of calcium
and magnesium ions which react with soap to form insoluble precipitate. Other metal ions such as iron,
barium, strontium, manganese and aluminium ions also can react with soap in the same way, but these
metal ions are present in natural water only in trace amounts. Hence, the degree of hardness is, in
practice, determined only by the amount of calcium and magnesium ions present. Hardness is of two
types:

il Temporary hardness and

ii. Permanent hardness

Temporary hardness is caused by the presence of bicarbonates of calcium and magnesium, and it can be
removed by boiling.

Ca(HCO3)2  CaCO3 + CO2 + H2O

Mg(HCO3)2 MgCO3 + CO2 + H2O

Permanent hardness is caused by the presence of soluble salts of calcium and magnesium other than the
bicarbonates i.e. chlorides, sulphates and nitrates.

EDTA (ethylene diamine tetra acetic acid) is a very good complexing agent that easily forms complexes
with calcium and magnesium ions. The acid is normally used in the form of its disodium salt.

HOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COOH

Structure of EDTA

13
 HOOCH2C CH2COOH
N CH2 CH2 N
+-
Na OOCH2C CH2COO- Na+

Structure of EDTA disodium salt

The large anion of this salt complexes the calcium and magnesium ions as follows.

Structure of EDTA complex with a divalent metal cation

When all the calcium and magnesium ions have reacted with the EDTA, a suitable indicator changes
colour.

The disodium salt of EDTA may be represented as Na2H2A which ionises in the aqueous solution to give
the complexing anion H2A- -

Na2H2A  2Na+ + H2A- -

The complexing anion H2A- - can react with various metal ions (divalent or higher valent cations) in a 1:1
mole ratio. The reaction with a divalent cation (Ca+ + or Mg+ +) can be represented as

M+ + + H2A- -  MA- - + 2H+ .....1

1mol 1mol
The EDTA complexes of divalent cations (i.e. MA- -) are stable in alkaline or slightly acidic medium.

Indicators for EDT titration:

Metal ion indicators are usually used in EDTA titrations. Eriochrome black T is one of the metal ion
indicators used in EDTA titrations. It is an organic dye stuff which is also a complexing agent like EDTA

14
itself. For simplicity, its sodium salt can be represented as NaH2X and the anion can function as an acid-
base indicator with two colour changes as follows:

In pH range 8 - 10, the blue form of the indicator (HX- -) is predominant, and reacts with Mg+ + ions to give
a wine red complex.

Mg+ + + HX- -  MgX- + H+

Blue wine red

So, when a few drops of the indicator are added to the sample of hard water containing Mg+ + ions, the
solution first turns wine red due to the formation of the metal indicator complex MgX-. Now, if EDTA is
added to such a solution, Mg+ + preferentially complexes with EDTA because the metal-EDTA complex is
more stable than the metal indicator coomplex. As a result, the free indicator is liberated back at the
endpoint, thereby producing a sharp colour change from wine red to blue. The reactions occurring during
EDTA titrations may be summed up as follows.

Mg+ + + HX- -  MgX- + H+

Blue wine red

H2A- - + Ca+ +  CaA- - + 2 H+

EDTA

H2A- - + Mg+ +  MgA- - + 2 H+

H2A- - + MgX-  MgA- - ++ HX- - + 2 H+

Note:

a. When Eriochrome black T is used as the indicator in EDTA titrations, Mg+ + ions must be essentially
present in the hard water sample.

b. The medium should be definitely alkaline. A pH of 10 is most satisfactory. Hence NH3 - NH4Cl buffer of
pH 10 must be added to the sample water before the addition of the indicator.

c. The solution should be clear blue at the endpoint.

d. The titration should be done slowly near the endpoint.

Procedure:

1. Take 50 ml of the hard water sample into a conical flask. Add 2ml of NH3 - NH4Cl buffer and three drops
of Eriochrome black T indicator.

15
 𝑀
2. Titrate against the standard 100EDTA solution from the burette until the colour changes from wine red
to clear blue at the endpoint. Perform the titration slowly near the endpoint. Repeat the titrations till you
get two concurrent readings. The titre value corresponds to the total hardness of the water sample.

Observation

Water sample taken for each titration = 50 ml

𝑀
Concentration of EDTA taken in the burette = 100 (𝑓 = 1.08)

Indicator used = Eriochrome black T in buffer of pH 10

Endpoint = from wine red to clear blue

Burette reading for total hardness

No. of obs. Burette reading Vol of EDTA consumed Concurrent

Initial Final (Final - Initial) ml reading
1 0.0 10.7 10.7 10.5 ml
2 0.0 10.5 10.5
3 0.0 10.5 10.5
Calculation:

Calculation for total hardness:

Since EDTA reacts with the metal ions in the ratio 1:1 by moles, (reaction 1)

1 mol of EDTA ≡ 1 mol of Ca+ + ≡ 1 mol of CaCO3

or 1000 ml of 1M EDTA ≡ 40 gm of Ca+ + ≡ 100 gm of CaCO3

100
or 1 ml of 1M EDTA ≡ 1000 gm of CaCO3

or 1 ml of 1M EDTA ≡ 100 mg of CaCO3

𝑀 100 𝑥 10.5 𝑥1.08
or 10.5 ml of 100 (f = 1.08) EDTA ≡ 100
mg of CaCO3

= 11.34 mg CaCO3 = total hardness present in 50 ml water sample

11.34 𝑥 1000
Hardness in 1 litre of water sample = 50
= 226.8 mg CaCO3 per liter
226.8
 Total hardness = 226.88 mg/l = 226.8 ppm = 14.3 0Clark = 15.86 0Clark

Results:

Conclusion:

Precautions:

16
Experiment no. 4

TO DETERMINE THE PERMANENT HARDNESS OF THE WATER SAMPLE

Requirements
𝑀
Standard 100 EDTA disodium salt solution

Eriochrome black T indicator

NH3-NH4Cl buffer of pH 10

Theory:

Hardness of water can be defined as the consumption of soap by the water due to the presence of calcium
and magnesium ions which react with soap to form insoluble precipitate. Other metal ions such as iron,
barium, strontium, manganese and aluminium ions also can react with soap in the same way, but these
metal ions are present in natural water only in trace amounts. Hence, the degree of hardness is, in
practice, determined only by the amount of calcium and magnesium ions present. Hardness is of two
types:

i. Temporary hardness and

ii. Permanent hardness

Temporary hardness is caused by the presence of bicarbonates of calcium and magnesium, and it can be
removed by boiling.

Ca(HCO3)2  CaCO3 + CO2 + H2O

Mg(HCO3)2  MgCO3 + CO2 + H2O

Permanent hardness is caused by the presence of soluble salts of calcium and magnesium other than the
bicarbonates i.e. chlorides, sulphates and nitrates.

EDTA (ethylene diamine tetra acetic acid) is a very good complexing agent that easily forms complexes
with calcium and magnesium ions. The acid is normally used in the form of its disodium salt.

HOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COOH

Structure of EDTA

17
 HOOCH2C CH2COOH
N CH2 CH2 N
+-
Na OOCH2C CH2COO- Na+

Structure of EDTA disodium salt

The large anion of this salt complexes the calcium and magnesium ions as follows.

Structure of EDTA complex with a bivalent metal cation

When all the calcium and magnesium ions have reacted with the EDTA, a suitable indicator changes
colour.

The disodium salt of EDTA may be represented as Na2H2A which ionises in the aqueous solution to give
the complexing anion H2A- -

Na2H2A  2Na+ + H2A- -

The complexing anion H2A- - can react with various metal ions (divalent or higher valent cations) in a 1:1
mole ratio. The reaction with a divalent cation (Ca+ + or Mg+ +) can be represented as

M+ + + H2A- -  MA- - + 2H+ .....1

1mol 1mol
The EDTA complexes of divalent cations (i.e. MA- -) are stable in alkaline or slightly acidic medium.

Indicators for EDT titration:

Metal ion indicators are usually used in EDTA titrations. Eriochrome black T is one of the metal ion
indicators used in EDTA titrations. It is an organic dye stuff which is also a complexing agent like EDTA

18
itself. For simplicity, its sodium salt can be represented as NaH2X and the anion can function as an acid-
base indicator with two colour changes as follows:

In pH range 8 - 10, the blue form of the indicator (HX- -) is predominant, and reacts with Mg+ + ions to give
a wine red complex.

Mg+ + + HX- - → MgX- + H+

Blue wine red

So, when a few drops of the indicator are added to the sample of hard water containing Mg+ + ions, the
solution first turns wine red due to the formation of the metal indicator complex MgX-. Now, if EDTA is
added to such a solution, Mg+ + preferentially complexes with EDTA because the metal-EDTA complex is
more stable than the metal indicator coomplex. As a result, the free indicator is liberated back at the
endpoint, thereby producing a sharp colour change from wine red to blue. The reactions occurring during
EDTA titrations may be summed up as follows.

Mg+ + + HX- -  MgX- + H+

Blue wine red

H2A- - + Ca+ +  CaA- - + 2 H+

EDTA

H2A- - + Mg+ +  MgA- - + 2 H+

H2A- - + MgX-  MgA- - + HX- - + H+

Wine red blue

Note:

a. When Eriochrome black T is used as the indicator in EDTA titrations, Mg+ + ions must be essentially
present in the hard water sample.

b. The medium should be definitely alkaline. A pH of 10 is most satisfactory. Hence NH3 - NH4Cl buffer of
pH 10 must be added to the sample water before the addition of the indicator.

c. The solution should be clear blue at the endpoint.

d. The titration should be done slowly near the endpoint.

Procedure:

1. Take 250 ml of the water sample in a 500 ml beaker, Boil gently for until the volume of sample water
reduced to half and then cool it. Filter the solution into a 250 ml volumetric flask. Make up the volume up
to the mark with distilled water, and shake to make it homogeneous.

19
2. Pipette out 50 ml of this solution into a conical flask. Add 2ml of NH3 - NH4Cl buffer and three drops of
Eriochrome black T indicator. Titrate against EDTA solution till the colour changes from wine red to clear
blue. Repeat the titrations till you get two concurrent readings. This titre value corresponds to the
permanent hardness of the water sample.

Observation

Water sample taken for each titration = 50 ml

𝑀
Concentration of EDTA taken in the burette = 100 (𝑓 = 1.08)

Indicator used = Eriochrome black T in buffer of pH 10

Endpoint = from wine red to clear blue

No. of obs. Burette reading Vol of EDTA consumed Concurrent

Initial Final (Final - Initial) ml reading
1 0.0 4.7 4.7 4.5 ml
2 0.0 4.5 4.5
3 0.0 4.5 4.5

Calculation:

Calculation for permanent hardness

1 ml of 1M EDTA ≡ 100 mg of CaCO3

𝑀 100 𝑥 4.5 𝑥1.08
or 4.5 ml of 100 (f = 1.08) EDTA ≡ 100
mg of CaCO3

= 4.86 mg CaCO3 = permanent hardness present in 50 ml water sample

4.86 𝑥 1000
Permanent hardness in 1 litre of water sample = = 97.2 mg CaCO3 per liter
50
97.2
 Permanent hardness = 97.2 mg/l = 97.2 ppm =14.3 0Clark = 6.8 0Clark

Results:

Conclusion:

Precautions:

20
Experiment no. 5

TO DETERMINE THE AMOUNT OF RESIDUAL CHLORINE IN THE GIVEN

SAMPLE OF WATER
Requirements:
𝑁
1. Standard 20 potassium dichromate

2. Potassium iodide solution (10%)

3. Concentrated hydrochloric acid

4. Sodium Hydrogen carbonate (NaHCO3)

𝑁
5. 20 Sodium thiosulphate solution

6. Starch solution as indicator

Theory

The surface water may, very often, contain various kinds of undesirable algae, fungi and harmful bacteria.
The presence of these microorganisms in water may lead to serious health hazards. The drinking water
should, therefore, be properly sterilized and disinfected before domestic supply.

The most common method of sterilization is chlorination. In practice, chlorination is done by the use of
bleaching powder or chlorine or chloramines. chlorine ( which is liberated from bleaching powder or the
one which is direclty used) reachs with water to form hydrochloric acid (HCl) which is fully ionized and
hypochlorous acid (HOCl) which ionizes only to a small extent.

Ca(OCl)Cl + H2O  Ca(OH)2 + Cl2

Cl2 + H2O  H+ + Cl- +HOCl

HOCl H+ + OCl-

It is generally believed that it is the undissociated HOCl acid which is the active species in the sterilizing
action.

Sometimes, another type of chlorine containing compounds called chloramines are added to sterilize
water. The chloramines decompose slowly in water to yield the active hypochlorous acid.

NH2Cl + H2O NH3 + HOCl

The chloramines thus act as a reserve of HOCl which can kill organisms.

However, excess of free chlorine in drinking water is undesirable, and must be removed. Because too high
concentration imparts both odour and colour to the water and is harmful to human metabolism also.
Hence, the amount of free chlorine in municipal water is usually estimated prior to the domestic supply.

21
The principle of estimation fo free chlorine in water is based on the fact that the free chlorine present in
water can liberate iodine from iodide. The liberated iodine can be estimated by titration against a standard
sodium thiosulphate (hypo) solution.

Cl2 + 2KI 2KCl + I2

Free chlorine

I2 + 2Na2S2O3  2NaI + Na2S4O6

Hypo solution Sodium tetrathionate
Hypo solution (sodium thiosulphate) is a secondary standard solution, which can be standardized against
standard potassium dichromate solution by iodometric titration.

K2Cr2O7 + 14 HCl + 6 KI  8KCl + 2 CrCl3 + 3I2 + 7 H2O

Procedure:

Standardisation of hypo solution

1. Take 100 ml of distilled water in a conical flask. Add about 1 gm KI and about 1 gm NaHCO3 and shake
slowly till the salts are dissolved. Add 5 ml of conc. HCl slowly. Now, add 25 ml of standard potassium
dichromate solution, close the conical flask and keep it in darkness for 5 minutes.

2. Titrate the liberated iodine against the sodium thiosulphate (hypo solution) from the burette. When
the solution assumes a greenish yellow colour, add starch solution as indicator. The solution turns blue
because of the formation of blue starch iodide.

3. Continue the titration carefully dropwise until with a last single drop, the blue colour changes to light
green.

4. Repeat the titration till you get the concurrent readings.

Estimation of residual chlorine in water sample

1. Take 100 ml of the water sample in a conical flask, and add 10 ml of 10% KI solution in it. Close the
conical flask, shake well and keep it in darkness for 5 minutes.

2. Titrate against the standard sodium thiosulphate solution till the colour turns pale yellow. Now add
starch solution as indicator and continue tiration dropwise till the blue colour is just discharged.

3. Repeat the titrations till you get concurrent readings.

Observation:

Standardization of hypo solution

Solution taken in the burette = hypo solution

N
Solution taken for each titration = 25 ml of 20 (f = 1.10) K2Cr2O7

Indicator used = starch solution

22
Endpoint : blue to light green

Burette reading

No. of obs Burette reading Concurrent

Initial Final Vol of hypo soln (ml)

1 0.0 20.4 20.4 20.3 ml

2 0.0 20.3 20.3

3 0.0 20.3 20.3

Estimation of free chlorine in water sample

Solution taken in the burette = hypo solution

Volume of water sample taken for each titration = 100 ml

Indicator used = Starch solution

Endpoint = Blue to colourless

Burette reading

No. of obs Burette reading Concurrent

Initial Final Vol of hypo soln (ml)

1 0.0 3.5 3.5 3.4 ml

2 3.5 6.9 3.4

3 6.9 10.3 3.4

Calculation

Standardization of hypo solution

25 𝑥 𝑁 𝑥 1.10 𝑁
Concentration of hypo solution = 20.3 𝑥 20
= 20 (𝑓 = 1.3546)

Estimation of free chlorine in water sample:

𝑁
Free chlorine present in 100 ml of the water sample = 3.4 ml of 20 (𝑓 = 1.3546)hypo
3.4 𝑥 𝑁 𝑥 1.3546
Concentration of free chlorine in the watr sample = = 2.303 x 10- 3 N
100 𝑥 20

Concentration in gms/litre = 2.303 x 10- 3 x 35.46 gm/l

=2.303 x 35.46 mg/l

23
= 81.664 mg/l = 81.664 ppm

Result:

Conclusion:

Precautions:

24
Experiment no. 6

TO DETERMINE THE AMOUNT OF IRON IN MOHR’S SALT SOLUTION.

Requirements

1. Burette

2. Conical flask

3. Pipette (10 ml)

4. Beakers

5. KMnO4 solution

6. Standard oxalic acid N/10 (f=....)

7. Mohr's salt solution

8. Bench sulphuric acid

Theory:

The estimation of amount of iron in Mohr's salt by titration against standard KMnO 4 is an example of
redox titration. In redox titration, a reducing agent is titrated against an oxidizing agent or vice versa. The
oxidation and reduction are complementary to one another and takes place simultaneously. Potassium
permanganate is not primary standard substance. So it should be standardized by titration against
standard oxalic acid in acidic medium and reaction involved is represented as

2KMnO4 + 5 H2C2O4 + 3 H2SO4  K2SO4+ 2MnSO4 +10 CO2 + 8 H2O

Hydrated ferrous ammonium sulphate[FeSO4(NH4)2SO4.6H2O] is commonly known as Mohr's salt in

which active species is FeSO4. It is a double salt and is more stable than FeSO4 so generally used in
qualitative analysis as reducing agent. The estimation of iron in Mohr's salt can be determined by titration
against standard KMnO4 solution in acidic medium. During redox titration Fe +2 ions of Mohr's salt are
oxidized to Fe +3 ions by KMnO4 and itself reduces to colourless manganous sulphate. The reaction
involved is represented by following equation.

2KMnO4 + 10 FeSO4 + 8 H2SO4  K2SO4 + 2 MnSO4 + 5Fe2(SO4)3 + 8 H2O

In this titration, KMnO4, the oxidizing agent is the self indicatyor as it is strongly colored (Purple) and
decolorizes after reduction. Potassium permanganate is purple in its oxidized form (MnO4-) but colorless
in its reduced form (Mn2+).

As the titration proceeds, the MnO4- will be reduced to Mn2+ and simultaneously Fe2+ will be oxidized to
Fe3+. When whole of the reducing agent (Fe2+) will be consumed, the oxidizzing agent (MnO4-) cannot be
reduced, then the addition of even one drop of KMnO4 solution gives light pink color to the solution. This
(light pink) indicates the endpoint of the titration.

25
The equivalent weight of an oxidizing and reducing agent can be obtained by dividing molecular weight of
the compound by the total number of electrons that are gained or lost in a reaction per molecule of the
substance.

Procedure

Step I : Standardization of KMnO4 solution by titration against standard oxalic acid (N/10)

1. Prepare N/10 oxalic acid solution

2. Rinse the burette with KMnO4 and fill upto zero mark and note the upper meniscus as KMnO4 is
translucent.

3. Pipette out 10 ml of 0.1 N oxalic acid into 250 ml conical flask.

4. Add about 10 ml of bench sulphuric acid and then heat it at 60 - 70ᵒ Celsius.

5. Titrate while hot slowly with continuous shaking.

6. Continue the adding of potassium permanganate till a last single drop makes the solution light
pink (endpoint).

7. Repeat the whole process to get concurrent readings.

Step II: Estimation of iron in Mohr's salt solution by titration against standard potassium permanganate

1. Take 10 ml of Mohr's salt solution into 250 ml conical flask with the help of 10 ml pipette

2. Add one test tube of bench sulphuric acid. Then titrate it with standard potassium permanganate
solution till light pink color persists (endpoint).

3. Repeat the titration to get concurrent readings.

Observation:

Vol. of oxalic acid taken in each titration = 10 ml

Bench H2SO4 = 10 ml

indicator: KMnO4 as self indicator

Endpoint : light pink from colourless

I. Standardisation of KMnO4

No. of Obs Burette Reading Concurrent Reading (ml)

Initial Final Difference (ml)
1
2
3
Calculation:

26
v1 = Vol. of oxalic acid = 10 ml

S1 = Strenght of oxalic acid = N/10 (f=.....)

V2 = Vol. of KMnO4 = (concurrent reading)

S2 = Strenght of KMnO4 = ?

S2 = V1 x S 1 / V2

Estimation of Iron in Mohr's salt solution

Vol. of Mohr's salt solution in each titration = 10 ml

Vol . of Bench sulphuric acid = 20 ml

Indicator : KMnO4 self indicator

endpoint : colourless to light pink

No. of Obs Burette Reading Concurrent Reading (ml)

Initial Final Difference (ml)
1
2
3
Calculation

v1 = volume of KMnO4 = concurrent burette reading

s1 = strength of KMnO4 = obtained from previous calculation

v2 = volume of mohr's salt solution

s2 = strength of mohr's salt solution = ?

s2 = v1 x s1 / v2 (obtained in N)

= .... x 392 (gm/l) mohrs salt [392 is eq. wt of Mohr's salt]

= a (let suppose)(gm/l) mohrs salt

392 gm of Mohr's salt contains 56 gm of iron [ at. wt of Fe = 56]

a gm of mohr's salt contain 56 x a / 392 gm of iron.

Result:

Conclusion:

Precautions:

27
Experiment no. 7

TO DETERMINE THE pH OF THE UNKNOWN ACIDIC BUFFERS BY USING

STANDARD ACIDIC BUFFER SOLUTIONS
Requirements
1. 100 ml. volumetric flasks
2. Test tubes and test tube stand
3. Beakers
4. Pipette
5. Burette
6. Conical flask
7. Funnel
8. Glacial acetic acid
9. standard NaOH
10. Pure AR sodium acetate
11. Universal indicator
12. phenolphthalein indicator

Theory

Theory:

A buffer solution is such a solution which has a constant pH value, and resists the change in pH even on
the addition of small amounts of acids or bases.

The pH of a buffer consisting of a weak acid and its soluble ionic salt can be calculated by using the
following Henderson equation.
[𝑠𝑎𝑙𝑡]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔10 [𝑎𝑐𝑖𝑑]..................................1

Where, 𝑝𝐾𝑎 = - log𝐾𝑎 of weak acid

[salt] = molar concentration of the soluble salt

[acid]= molar concentration of the weak acid

Buffer solution made from the mixture of acetic acid and sodium acetate can resist the change in pH upon
addition of small amount of acid or base as follows:

28
The pH of an unknown solution can be accurately determined by using a pH meter. But its approximate
value can be determined by using a universal indicator.

Universal indicators are mixtures of several indicators which can show several colour changes over a wide
range of the pH values.

Procedure
The process involves the following steps-

Step I: Preparation of 100 ml approx. 0.4 M acetic acid from glacial acetic acid
Prepare 100 ml of an acetic acid solution of approx. 0.4 M by calculating the required volume of acetic
acid using normality equation. (Strength of glacial acetic acid = 16 M)

V1 S1 = V2 S2

V1 = 100 ml, S1 = 0.4 M, V2 = ?, S2 = 16 M

V2 = 0.4 x 100/ 16 = 2.5 ml

Take 2.5 ml of glacial acetic acid from the burette into 100 ml volumetric flask. Add distilled water upto
the mark and shake well.

Step II: Standardization of the approx 0.4 M acetic acid against standard NaOH.
Pipette out 10 ml of standard NaOH in 250 ml conical flask and add a drop of phenolphthalein. Titrate it
with prepared acetic acid from the burette, till colorless (endpoint). the titration table is given in
observation.

The strength of acid is calculated by normality equation.

VA SA = VBSB

VA = 2.3 ml (suppose), SA = ?

VB = 10 ml, SB = M/10

SA = ((10)/(10 x 2.3))M = 0.43 M

Step III: Preparation of exactly 0.2M acetic acid from above prepared standardized acetic acid

Calculate the volume of standardized acetic acid prepared, required to prepare of strength 0.2M, 100 ml
by using normality equation for dilution.

V1 S1 = V2 S2
𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑡𝑜 𝑏𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑒𝑑 x Volume to be prepared
or, Volume of acid to be taken =
exact strength of the acetic acid

V1 = 100 ml, S1 = 0.2 M, V2 = ?, S2 = 0.43 M (use your value here)

V2 = 0.2 x 100/ 0.43 = 46.5 ml

Take 46.5 ml of acetic acid from the burette into 100 ml volumetric flask. Add distilled water upto the
mark and shake well. The resulting solution is 0.2M acetic acid.

29
Step IV: Preparation of 100 ml solution of exactly 0.2M

Prepare 100 mo of exact 0.2 M sodium acetate solution by dissolving the calculaged amount of pure dry
AR sodium acetate.

If the molecular weight of sodium acetate is 82 (only for anhydrous salt)

Gram molecular weight of sodium acetate = 82

Dissolving 82 gm of sodium acetate in 1000 ml makes 1M sodium acetate solution.

to prepare 100 ml of 0.2M sodium acetate solution needs 82x0.2x100/1000 gm of acetic acid = 1.64
gm.of acetic acid

Weigh exactly 1.64 gm of sodium acetate and transfer into 100 ml volumetric flask. Add distilled water
up to the mark and shake well.

Step V: Preparation of standard acidic buffer solutions by mixing 0.2 M acetic acid and 0.2M sodium
acetate solutions

Take 9 test tubes and mark 1, 2, 3, 4,...., 9 and prepare a standard acidic buffer solutions by mixing 0.2M
sodium acetate and 0.2M acetic acid in each test tube in different rations as shown in the table. the
total volume in each test tube should be equal to 10 ml.

Test tube no. 1 2 3 4 5 6 7 8 9

vol of sodium acetate 1 2 3 4 5 6 7 8 9
vol of acetic acid 9 8 7 6 5 4 3 2 1

Then add 5 drops of the universal indicator in each test tube and shake well.

Finally, take 10 ml of the provided unknown buffer solutions in three clean test tubes and mark A1, A2
and A3. Add 5 drops of universal indicator in each test tube and shake well.

Calculate the pH of all the standard buffer solutions using Henderson equation.

Determine the pH of the unknown acidic buffer solutions by matching the color against the standard
buffer solutions.

Observation

No. of obs Vol of NaOH Burette reading Concurrent

(ml) initial final difference reading
1 10
2 10
3 10
The strength of acid is calculated by normality equation

VASA = VBSB

30
SA = VBSB/VA

Therefore the exact strength of the prepared acetic acid is ......M.

pKa of acetic acid = 4.74

Test Vol of 0.2M Vol of 0.2M sodium pH = pKa + log([salt]/[acid]) pH of unknown buffer solutions
tube no. acetic acid (ml) acetate (ml)
1 9 1
2 8 2
3 7 3
4 6 4
5 5 5
6 4 6
7 3 7
8 2 8
9 1 9
Calculation

Calculation of pH of different standard buffer solutions

pH of standard buffer solution in test tube no. 1

pH = 4.74 + log((( 1/10)x0.2)/ (( 9/10)x0.2)) = 3.78

..... calculate the pH of all standard buffer solutions from test tubes.

Result:

The pH of unknown buffer solutions A1, A2 and A3 are found to be ......., ...... and ...... respectively.

Conclusion:

The pH of unknown buffer solutions can be determined by matching the colour with that of standard
fuffer solutions.

Precautions

 The same number of drops of universal indicator should be added.

 Glacial acetic acid must be closed after taking required amount.
 Matching the colour of the solutions in test tubes should be done carefully.
 While carrying test tube stand, support should be provided at base.

31
Experiment no. 8

TO DETERMINE THE pH OF THE UNKNOWN BASIC BUFFERS BY USING

STANDARD BASIC BUFFER SOLUTIONS
Requirements
1. 100 ml. volumetric flasks
2. Test tubes and test tube stand
3. Beakers
4. Pipette
5. Burette
6. Conical flask
7. Funnel
8. Ammonia solution
9. standard HCl
10. Methyl orange indicator
11. Pure AR ammonium chloride
12. Universal indicator

Theory:

A buffer solution is such a solution which has a constant pH value, and resists the change in pH even on
the addition of small amounts of acids or bases.

If the pH of the given unknown solution happens to be in the alkaline range (above pH 7), then its pH value
can be approximately determined by preparing a series of standard buffer solutions consisting of
ammonia and ammonium chloride, and then by using the universal indicator.

The pH of a buffer consisting of a weak base and its soluble ionic salt can be calculated by using the
following Henderson equation.
[𝑠𝑎𝑙𝑡]
𝑝𝑂𝐻 = 𝑝𝐾𝑏 + 𝑙𝑜𝑔10 [𝑏𝑎𝑠𝑒]..................................1

𝑝𝐻 + 𝑝𝑂𝐻 = 14.................................................2

Where, 𝑝𝐾𝑏 = - log𝐾𝑏 of weak base

[salt] = molar concentration of the soluble salt

[base]= molar concentration of the weak base

Buffer solution made from the mixture of ammonium hydroxide and ammonium chloride can resist
the change in pH upon addition of small amount of acid or base as follows:

32
Procedure:

1. Prepare approximately100 ml of 0.4 M ammonium hydroxide solution from provided concentrated

ammonia solution (it's approximate strength is 14M)

Standardise prepared ammonia solution (approximately 0.4 M) against standard (N/10) HCl solution
using methyl orange as an indicator. (Note: take acid in burette and 10 ml of NH4OH in conical flask.)

2. Using the exact strength of the given HCl solution, calculate the volume of the ammonia to be taken
to dilute it to prepare 100 ml of exactly 0.2 M ammonium hydroxide solution.
𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑡𝑜 𝑏𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑒𝑑 x Volume to be prepared
Volume of base to be taken = exact strength of the provided ammonium hydroxide

3. Prepare 100 ml of exactly 0.2 M ammonium hydroxide by taking the required volume and by diluting
upto the mark in volumetric flask by addition of water.

4. Calculate the weight of ammonium chloride to be taken to prepare 100 ml of exactly 0.2 M
ammonium chloride solution.

Weight of ammonium chloride to be taken

molecular weight of ammonium chloride x molarity to be prepared x volume to be prepared in ml
= gm
1000

5. Prepare 100 ml of exactly 0.2 M ammonium chloride solution by dissolving calculated amount of it
accurately weighed out.

6. Prepare a series of 9 standard buffer solutions by mixing 0.2 M ammonium hydroxide and 0.2M
ammonium chloride in different proportions as given in buffer solution table. and arrange it in series
in test tube stand.

7. Put 5 drops of universal indicator in each of them and shake well.

8. Now, take 10 ml of the given unknown solution in another test tube and add 5 drops of the universal
indicator in it. Determine the pH of it by matching the colour against the standard buffers.

Observation and Calculation:

Standardization of ammonium hydroxide

volume of ammonium hydroxide taken in conical flask = 10 ml

N
Strength of hydrochloric acid = 10 (f = 1.00)

33
Indicator used = methyl orange (endpoint-> yellow to orange)

No. Vol of Burette reading Consumed HCl Concurrent

of NH4OH Initial Final (Final - Initial) reading
obs. (ml) (ml)
1 10 0.0 40.3 40.3 40.0 ml
2 10 0.0 40.0 40.0
3 10 0.0 40.0 40.0

strength of HCl x volume of HCl N x 40.0 x 1.00

strength of ammonium hydroxide = volume of ammonium hydroxide = 10 x 10
= 0.4 𝑁

Dilution of ammonium hydroxide

𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑡𝑜 𝑏𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑒𝑑 x Volume to be prepared 0.2 x 100
Volume of base to be taken = exact strength of the ammonium hydroxide
= 0.4 = 50 𝑚𝑙

Preparation of ammonium chloride

Chemical taken =ammonium chloride = NH4Cl

Molecular weight = 53.5

Weight of NH4Cl to be taken

molecular weight of ammonium chloride x molarity to be prepared x volume to be prepared in ml 53.5 x 0.2x100
= 1000
= 1000
= 1.07
gm

Buffer solutions

Test tube Vol. of 0.2 Vol. of pOH pH pH of the

No. NH4Cl 0.2M unknown
NH4OH solution

1 1 9
2 2 8
3 3 7
4 4 6
5 5 5
6 6 4
7 7 3
8 8 2
9 9 1

Calculation of the pH of the buffer solutions:

𝑝𝐾𝑏 of weak base = 4.74

34
For buffer of test tube no. 1
1
[𝑠𝑎𝑙𝑡] x 0.2M 1
10
𝑝𝑂𝐻 = 𝑝𝐾𝑏 + 𝑙𝑜𝑔10 [𝑏𝑎𝑠𝑒] = 4.74 + 𝑙𝑜𝑔10 9 =4.72 + 𝑙𝑜𝑔10 9
= 3.78
x 0.2M
10

𝑝𝐻 = 14 − 𝑝𝑂𝐻 = 14 − 3.78 = 10.22

....similarly calculate the pH values of other buffer solutions.

Conclulsion:

Precaution:

35
Experiment no. 9

TO DETERMINE THE pH OF SOIL SAMPLES

Requirements

1. pH meter
2. weighing balance
3. beaker
4. distilled water

Theory

Soil is source of nutrients and habitat for plants. It is also a construction site and a construction material.
Soil pH has a direct impact on physicochemical and biological soil parameters. It can affect soil
compactness and soil shear strength parameters through its action on soil water retention and is strongly
related to nutrient availability and microbial activity.

Approximate pH of soil samples can be measured by using universal indicator and standard buffer
solutions. pH meter is considered as more reliable method to measure hydrogen-ion activity (acidity or
alkalinity) in solution. Fundamentally, a pH meter consists of a voltmeter attached to a pH-responsive
electrode and a reference (unvarying) electrode. The pH-responsive electrode is usually glass, and the
reference is usually a silver–silver chloride electrode, although a mercury-mercurous chloride (calomel)
electrode is sometimes used. When the two electrodes are immersed in a solution, they act as a battery.
The glass electrode develops an electric potential (charge) that is directly related to the hydrogen-ion
activity in the solution (59.2 millivolts per pH unit at 25°C), and the voltmeter measures the potential
difference between the glass and reference electrodes.

Procedure

 Weigh 10 g of air dried soil samples (<2 mm) in 100 ml beaker.

 Add 25 ml of distilled water.
 Shake for about 1 minute. and leave for about an hour.
 The soil water suspension is stirred well with a glass rod just before immersing the electrode.
 The pH of soil water suspension is then measured with the calibrated pH meter.

Observation

Results

Conclusion

Precautions

36
Experiment no. 10

TO ESTIMATE THE AMOUNT OF BARIUM IN THE GIVEN SAMPLE OF

BARIUM CHLORIDE SOLUTION

Theory :-
To a solution of barium chloride, excess of K2SO4 solution is added. The precipitated insoluble
BaSO4 is weighed out.

K2SO4+BaCl2 → 2KCl + BaSO4

Procedure:-
1. Weigh out accurately 0.5 gm of pure K2SO4 and dissolve in 50 ml of distilled water in a
500 ml beaker with a stirrer and cover with it a watchglass.
2. Add 2 ml of cone HCl and dilute to 150 ml with distilled water.
3. Heat it nearly to boiling. A test-tube of 5% BaCl2, solution diluted with about 40 ml of
water is also heated to boiling.
4. Add this solution slowly with stirring to the hot solution of sulphate in the beaker till the
precipitation is complete.
5. Allow to settle the precipitate.
6. Add a drop of BaCl2 solution on the supernatant liquid to see whether drop proceipitation
is complete i. e. add BaCl2, solution if necessary.
7. Cover the beaker and warm (but do not boil) then cool and allow to setle for an hour or
so.
8. Decant the supernant liquid through the quantitative filter paper whatman No-40.
9. Wash the precipitate with hot distilled water as usual.
10. Ultimately transfer the precipitate into the filter paper with the help of rubber tipped glass
rod.
11. Wash the precipitate again with hot distilled water. Test the last drop of filtrate with
AgNO3 for chloride
12. Wash it until it is free from chloride.
13. Dry the precipitate along with the funnel covered with a filter paper in an air oven.
14. Take out very carefully the precipitate in a small piece of glazed paper over a big one.
Cover it with a funnel.
15. Fold the filter paper and ignite it over a heated crucible which is already weighed to
constant weight.
16. The precipitate in the glazed paper is also then transfered into the crucible with the help
of a camel hair brush.
17. Heat the contents in the crucible with lid very strongly.
18. Cool it and add a drop of cone H₂SO4 to convert reduced BaS to BaSO4, again.
19. Allow it to cool & keep it in a dessicator when luck warm for 15 minutes & weigh.
20. Repeat the process of heating, cooling and weighing till the final weight is constant.

Calculation:
BaSO4, contains Ba
233gm 137 gm
X gm 137x X/233 gm

37
N.B.
This very principle may be used to estimate Ba or Pb in BaCl2, or Pb(NO3)2, respectively by
using excess of sulphate solution etc.

Requirements

Theory

Procedure

Observation

Results

Conclusion

Precautions

38
Experiment no. 11

TO ESTIMATE THE AMOUNT OF SULPHATE IN GIVEN COPPER SULPHATE

SOLUTION.
Requirements

Theory

Copper is precipitated out as copper hydroxide by using a known excess of standard sodium hydroxide
solution. Unused amount of sodium hydroxide is determined with the help of a standard sulphuric acid.
The volume of standard sodium hydroxide solution consumed by the copper sulphate solution is then
calculated.

CuSO4 + 2NaOH  Cu(OH)2 + Na2SO4

Procedure

1. Take 50 ml of copper sulphate solution.

2. Warm the solution and add 25 ml of bench sodium hydroxide solution.
3. Stir the mixture and heat to boiling when the bluish white precipitate of copper hydroxide gets
converted into black of copper (CuO).
4. Cover the beaker with a watchglass and allow to stand for a while, when the precipitate gets
settled.
5. Filter the supernatant liquid through a whatman No. 40 filter paper.
6. Wash the precipitate several times with warm water (avoid excess of water).
7. Test for free alkali with litmus and collect all the filtrate into a beaker.
8. Cool and transfer into a 250 ml volumetric flask.
9. Make up the volume with thorough shaking.
10. Titrate this alkali 10 ml at a time with standard N/10 acid in the burette.
11. Use phenolphthalein or Methyl orange as indicator.
12. Try to get at least two concurrent readings.

Observation

Weight out accurately 0.5 gm of copper sulphate erystals by difference in a weighing tube.
Dissolve it in about 100 cc of distilled water in 400 c. c. beaker.
Warm it and add 25 c. c. of bench NaOH solution with contant stirring.
Heat it carefully till the precipitated copper hydroxide gets converted to black mass of cupric
oxide.
Allow it to settle and see that the precipitation is complete with a drop or two of bench NaOH
solution.
When no precipitation occurs be sure that whole of copper has been converted into hydroxide
first and then into oxide. Filter through a quantitative ter paper whatman No. 40 by decantation.
Wash the precipitate several (3 or 4) time with minimum quantity of hot water in the beaker itself
till the last washing is free from alkali.

Ultimately transfer the precipitate into the Biter paper very carefully. See that the last drop of
filtrate is free from alkali. Dry the precipitate in the funnel covering with a piece of paper in an air

39
oven. Transfer the precipitate in a small incinerate (ignite) it carefully with a Bunsen Burner over
a already weighed Crucible. Transfer the precipitate. Heati again. Add a drop of conc. HNO, to
exidise any reduced copper oxide. Cool it and weigh. Repeat the process of healing cooling and
weighing till constant weight.

(132)

Calculation:-

contains

CuO

79 gm

63 gm (63 x 1)/79=.07973 gm

Suppose 1 gm 1. e. final weight of copper oxide multiplied by 0.798 g the weight of copper
sulphate crystals.

Results

Conclusion

Precautions

40
Experiment No. 12: Extra experiment for ECA Program

TO ETCH PCB CIRCUIT BOARD USING IRON(3) CHLORIDE

Requirements

1. PCB circuit board

2. Permanent marker
3. Trough or plastic container
4. Latex gloves and other safety wearings
5. FeCl3

Theory
Plating on a PCB refers to the electrochemical process by which a metal is deposited onto the
surface of the circuit board, and inside the plated through-holes. The most common plated
metal in PCB fabrication is copper. Copper plating serves two purposes, it increases the copper
thickness of the surface pads and conductors as well as providing a robust copper connection
from layer to layer through the plated through-holes.
A solution of FeCl3 dissolves copper metal fairly quickly. hydrated form, FeCl3.6H2O is used
as PCB etchant in electronics.
FeCl3 can act as an etchant, because of two reasons:
1. Fe3+ is a fairly strong oxidizer.
2. Cl- is a strong complexing agent for copper (II) ions.
The reaction in solution often is written as
2Fe3+ + Cu → 2Fe2+ + Cu2+
This, however, is a too strong simplification. If you put copper in a solution of iron (III) sulfate
then it does not dissolve. The chloride plays an essential role:
2Fe3+ + Cu + 4Cl- → 2Fe2+ + CuCl42-
In reality even this is simplified, because iron also is present as complex with chloride. So, a
slightly better description of the reaction may be
2FeCl4- + Cu → 2Fe2+ + CuCl42- + 4Cl-
When all iron (III) is converted to iron (II), then the CuCl42- ion in turn also oxidizes copper
metal quite well, where copper (I) species are formed:
CuCl42- + Cu → 2CuCl2-
These copper (I) species form very dark-colored mixed oxidation-state species with copper
(II) species, when all iron (III) is used up. This causes the PCB-etchant liquid to turn very dark,
when it is near exhausted.

You cannot simply say that copper is more noble than iron and so the reaction cannot
proceed. This only is true for Fe(2+) and Cu. Fe(3+) is a more oxidizing ionic form of iron. With
chloride ions present, the nobleness of copper is reduced, due to complex formation, as
described above, and that effect makes Fe(3+) a sufficiently strong oxidizer to dissolve copper.

41
Procedure:

1. Draw circuit in PCB board with permanent marker.

2. Prepare 10% FeCl3 solution in hot water.
3. Use plastic container to itch PCB board and pour FeCl3 solution over the PCB board.
4. Agetate them by rocking the container back and forth for about 10 minutes.
5. Inspect the board and if no copper is visible, remove the board while wearing a latex glove.
6. Wash the board with water to remove all ferric chloride from the board.
7. Rinse the board with acetone that will make quick work of the marker ink to reveal your
unharmed traces.

42
VIVA-VOCE QUESTIONS AND SOME HINTS TO FACE VIVA-VOCE

Alkalinity

1. What is alkalinity of water?

2. What are the possible sources of alkalinity in natural water?
3. What are the main causes of alkalinity of water?
4. Is the alkalinity of water caused by the simultaneous presence of OH- and HCO3-?
5. How is the alkalinity of water determined?
6. What is the double indicator titration?
7. Why are two indicators used for determining alkalinity of water?
8. What are the disadvantages of alkalinity of water?
9. Can methyl orange indicator be used first?
10. Why does CaCO3, not cause alkalinity in water?
11. How do carbonate ions make water alkaline when dissolved in water?
12. Why hydrochloric acid of N/50 is used instead of N/10?
13. Why is 100 ml water sample taken rather than 10 or 25 ml?
14. Why is alkalinity of water expressed in terms of CaCO3 equivalent?
15. What will be the color of phenolphthalein and methyl orange indicator in alkaline medium?
16. What will be the color of the solution containing HCO3- ion, on adding phenolphthalein indicator?
17. If you are asked to use only one indicator, which indicator is suitable to determine the alkalinity of
water?
18. Why is methyl orange end point twice the phenolphthalein end point if water sample contain only
carbonate ion?
19. What type of alkalinity is present if phenolphthalein end point is more than half the methyl orange
end point?
20. Which ions are responsible for alkalinity of water if phenolphthalein end point is less than the half
the methyl orange end point?
21. What are the units of alkalinity?
22. What is meant by degree Clark?
23. Point out the pH range of phenolphthalein and methyl orange indicators.

Some hints to face viva-voce

 If no color develops on addition of phenolphthalein to water sample, it means that,
phenolphthalein alkalinity is zero. Hence do not titrate the sample for phenolphthalein alkalinity.
 Methyl orange end point would be the volume of acid upto phenolphthalein end point plus the
volume of acid used upto methyl orange end point.
 Since phenolphthalein and methyl orange indicators are used in determination of alkalinity, the
end point of the titration should be observed carefully.
 There should not be any red tinge in phenolphthalein end point otherwise orange color is
developed on addition of methyl orange without titration.
 It is better to use N/50, H2SO4, since H₂SO4 is nonvolatile acid.
 HNO3 cannot be used since it is an oxidizing acid and oxidizes the components present in water.

43
Hardness

1. What do you understand when someone says the water is hard?

2. What is hardness of water?
3. Distinguish between hard and soft water.
4. What are the causes of hardness of water?
5. For which purpose do you use hard water and soft water?
6. Why is it not advised to use hard water for domestic and industrial purposes?
7. Name the soluble salts responsible for temporary and permanent hardness of water.
8. What happens when hard water is boiled?
9. Draw structures of EDTA, EDTA-disodium salt and metal-EDTA complex.
10. What is complexometric titration?
11. What indicator is suitable in complexometric titration?
12. What type of indicator EBT is?
13. Why is disodium salt of EDTA used in complexometric titration?
14. Mention the role of EDTA in complexometric titration.
15. Explain the reason behind the use of buffer (pH = 10) in EDTA titration.
16. Which is more stable: EDTA-metal complex or EBT-metal complex? Why?
Hint: EDTA is a hexadentate ligand, so it forms a chelating complex which is more stable than normal
complex.
17. Give the application of EDTA titration.
18. State the colours of EBT indicator at different conditions.
19. Why does the wine red color obtain when EBT is added to Hard water sample?
20. Why does the colour of the solution change from wine red to blue at the end point?
21. If buffer is not used, what will be the colour of the solution at the end point?

Residual Chlorine

1. What do you mean by the residual chlorine?

2. Why is starch solution used as an indicator in iodometric titration?
3. Why is starch solution added only at the end of titration?
4. What reactions are involved in standardization of thiosulphate against potassium dichromate?
5. Why is water chlorinated?
6. Name three substances used for the sterilization of water.
7. Why is the estimation of residual chlorine done indirectly?
8. Which concept is used in iodometric titration to estimate the amount of residual chlorine in water
sample?
9. What is chemical species used to sterilize water before domestic supply?
10. What is selective indicator used for the iodometric titration? Why?
11. What is the role of KI in the estimation of residual chlorine in water?
12. Why are the contents of the iodine flask kept in dark during the standardization of hypo solution?
13. Why is Chlorine conveted into iodine?
14. Why is this titration called iodometric titration?
15. What is the role of sodium thiosulphate in the titration?
16. Why are chloramines better than chlorine for sterilization of water?

44
17. What is the effect of excess of residual chlorine in water?
18. What is hypo solution? Why is it not used as primary standard?
19. Why is sodium bicarbonate added before addition of potassium iodide?
20. What is the role of sodium bicarbonate in the estimation of residual chlorine in
21. What compound is formed when starch solution is added to greenish yellow during titration?

Some clues to face viva-voce

 The WHO guideline value for free residual chlorine in drinking water is 0.5 ppm and the accepted
level for free residual chlorine of swimming pool water is 1.0 -1.5 ppm.
 At the end point, the blue or violet color of starch iodide disappears due to change of iodine to
iodide.
 In many cases residual chlorine is very low and starch needs to be added before starting up the
titration.
 After liberation of iodine, titration should be done fast because if not titrated immediately the
liberated I2 will escape out.
 The mixture is kept in dark to avoid any side reaction since iodine liberated is ligh sensitive.
 The possible source of error in iodometric titration is the air oxidation of acid- iodide solution. It
can be eliminated by adding an excess of sodium bicarbonate to the mixture. In addition to this it
also supports for the mixing of the solution.

Permanganometric titration

1. Why is bench sulphuric acid added to oxalic acid in the conical flask during titration?
2. What is the indicator used in this titration?
3. Why should the addition of KMnO be done slowly during titration?
4. Can HNO3, or HCI be used in place of bench H2S04?
5. Can conc. H2SO4 be used instead of dil. H2SO4?
6. Why is oxalic acid used as a primary standard solution in redox titration?
7. Why is KMnO4 not used as the primary standard?
8. Why is ferrous sulphate not used instead of ferrous ammonium sulphate?
9. What is the nature of ferrous ammonium sulphate in this titration?
10. Why is FeSO4 only written in the equation even the salt contains FeSO4, and (NH4)2SO4?
11. What type of salt is ferrous ammonium sulphate?
12. Why is H₂SO, added in the preparation of solution of ferrous ammonium sulphate?
13. Why is heating of the solution needed before titration of KMnO4 Vs Oxalic acid?
14. Why is heating of the solution not needed during titration of KMnO4, and Mohr's Salt?

Some hints to face viva-voce

 Potassium permanganate (KMnO4) is a strong oxidizing agent in acid medium.
 Among three mineral acids available only suphuric acid is suitable as it has no action on
permanganate in dilute solution.
 As the titration proceeds the MnO4- will be converted to Mn2+ and simultaneously Fe2+ will be
converted to Fe3+. When whole of the reducing agent (Fe2+) is consumed, the oxidizing agent
(MnO4-) cannot be reduced, then the addition of even one drop of KMnO4 solution gives light pink
color to the solution.

45
 The reaction of oxalic acid with potassium permanganate is very slow therefore the solution should
be heated to 60-70 °C before titration.
 Once the reaction has started the reaction rate increases due to the formation of manganous
sulphate which catalyzes the reaction.
 The active species in Mohr's salt is ferrous sulphate. Ammonioum sulphate does not take part in
the reaction.

Buffer Solution

1. Define buffer solution and name the types of buffer solution.

2. Give the two examples of acidic and 2 examples of basic buffers.
3. Mention the applications of buffer solution.
4. What are meant by pH and pH scale?
5. Why are the buffer solutions that you prepared, called standard buffers?
6. Write the Henderson equations.
7. What are pKa and pKb?
8. What are the pH range of Methyl orange and Phenolphthalein?
9. Why is the measured pH approximate but not the exact?
10. What is the pH of pure water and rain water?
11. How do you increase or decrease the pH of pure water?
12. What is a universal indicator? What is its advantage?
13. What is the effect in pH of buffer of acetic acid and sodium acetate when diluted 10 times?
14. Which indicator should be used for titration of weak base and strong acid?
15. Which indicator should be used for titration of weak acid and strong base?
16. What is relation between pKa, and pKb values? [where Ka and Kb are ionization constant of acid
and its conjugate base respectively]
[Hint: pKa + pKb = pKw-14 = pKw = -log14]
17. Why does aqueous solution of ammonium acetate act as a buffer? [Hints-It is the salt formed by
acetic acid (weak acid) and ammonium hydroxide (weak base).

Some hints to face viva-voce

 Water for domestic use has pH between 6.5 and 8.5.
 Acidic/alkaline water cannot be used for construction purposes.
 The mixture of strong acid and its corresponding salt does not form buffer because both the
solutions are highly ionized.
 During titration, the acidic / basic medium is maintained by the addition of acidic/basic buffer.
 pH of buffer changes with temperature because Kw changes. pH decreases with increase of
temperature.
 Buffer capacity or buffer index is the no. of moles of acid or base required to be added to one litre
of the buffer solution so as to change its pH by one unit.
Buffer capacity = No. of moles acid or base added to 1 litre of the buffer
Change in pH

46
 When the concentration of the weak acid and its salt or weak base and its salt are equal, buffer
capacity is maximum. [pH = pKa or pOH = pKb].
 Blood is a buffer of carbonic acid and bicarbonate ions. Small amount of acid and base produced
from the spicy food do not alter its pH.

47