Alkaline hydrolysis of methyl benzoate to benzoic acid and monitoring by TLC

Aim: Alkaline hydrolysis of methyl benzoate to benzoic acid and monitoring by TLC

Chemicals and Apparatus required:

1) Methyl benzoate 2) Sodium hydroxide (20 %) 3) Conc. HCl

4) 150 ml R. B. flask 5) Reflux condenser 6) Boiling chip

7) Hot plate 8) Suction filtering apparatus 9) Crystalline dish

10) Thermometer 11) TLC Plate 12) Silica gel

13) DCM

Theory:
Esters are hydrolysed either by an acid or a base. Alkaline hydrolysis of ester is irreversible while
acid hydrolysis of ester is a reversible reaction. Acid hydrolysis of esters can occur by more than
one type of mechanism, the common mechanism is the alkaline hydrolysis, which occurs through
a nucleophilic acyl substitution. Here OH ion of sodium hydroxide act as a nucleophile. Methyl
benzoate react faster with aq. NaOH to give sodium benzoate and methanol. This process is called
saponification. Sodium benzoate is non-volatile, so remain in solution. On treating this solution
with HCl, we get benzoic acid which can be recrystallized to get white crystalline solid.
The progress of this reaction can be monitored using thin layer chromatography. Thin layer
chromatography is a highly efficient technique used to identify number of components in a mixture
as well as to monitor the progress of a reaction. By this method, sharper separation and detection
of very small quantity of components can be achieved in a short time. In thin layer chromatography,
the stationary phase silica gel or alumina mixed with a binder like CuSO 4 is mixed with a solvent
to form slurry and is then applied on a glass or plastic plate to make a coating. The prepared thin
layer on glass is called a chromoplate. A small capillary tube is dipped inside the mixture and then
taken out. A spot is made, at one end of the chromoplate, with the mixture remaining inside the
capillary tube. The chromoplate is then placed inside a chamber containing the solvent. The solvent
(eluent) moves up along the chromoplate, by capillary action through the spot. Solvent used for
this purpose should be low boiling so that plate can dry quickly after moving from the chamber.
The use of TLC and the calculation of the retention factor (R f) allows to determine how pure the
final product is and therefore whether or not all the methyl benzoate was removed.

Reactions:

Procedure:

Place 2 ml of methyl benzoate and 20 ml of 20 % sodium hydroxide solution in a 150 ml round-

bottomed flask equipped with a reflux condenser. Add some boiling chips. Boil the mixture under
reflux for 30 minutes or until the ester layer disappears. Cool and acidify with conc. HCl and then
allow to stand at room temperature. Filter the crude benzoic acid under suction, wash with cold
water and drain well. Recrystallize the crude acid from hot water. Pure benzoic acid separates as
colorless crystals. Check the melting point of the product. Calculate the yield and percent yield of
the product.

Thin Layer Chromatography:

Take a TLC plate and with a pencil, rule a faint line (1cm) from one end. Draw three dots for
starting material(SM), Compound(C), Product(P). Place a spot using a capillary of the pre-made
mixture on the dot SM and C. Spot using a capillary the collected solution of DCM after filtration
onto dot P and C. Add 20mL of DCM into a TLC Jar. Place the TLC plate in the jar. When the
solvent has reached 2cm from the top, take the plate out of the jar and mark the solvent layer with
a pencil and let the solvent evaporate. Examine the plate under ultraviolent light and mark the spots
by drawing pencil circles around them on the plate. Record what you see. Calculate the retention
factor by measuring the distance travelled by the compound and the distance travelled by the
solvent front.
Calculation:
Molecular formula of methyl benzoate = C8H8O2
Molecular formula of benzoic acid = C7H6O2
Weight of methyl benzoate = ……….. g/mole
Weight of benzoic acid = ………. g/mol
Theoretical yield:
136.15 g of methyl benzoate gives 112 g of benzoic acid
2g of methyl benzoate gives benzoic acid = ……………… g
Experimental yield = ………g
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
% yield = × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

Thin layer chromatography:

Distance travelled by Compound

Rf = Distance travelled by solvent front.

Calculation of Retention Factor: Rf = ……………. cm

Result: The melting point of the product formed __________
The yield of the product formed _________
The percent yield of the product formed _________
Calculation of Retention Factor_________
 Experiment: 2

1.Name of the experiment: Determination of two acids in a mixture by conductometric

titrations.

2.Chemical used: Given acid mixture solution, N/10 NaOH solution, Oxalic acid salt.

3.Glassware and apparatus: measuring cylinder, volumetric flask, burette (25 mL), beaker

(100 mL and 250 mL), magnetic stirrer, conductivity cell and conductivity meter

4.Theory: When a mixture of strong acid and weak acid is taken, the strong acid exists
almost completely in the ionic form as shown below

HCl + H2O H3O + + Cl ¯

The weak acid like acetic acid exists in the un-dissociated molecular form. In the presence
of the strong acid, due to common ion effect, the dissociation is further suppressed and the
molecule almost exists in the undissociated molecular form.

CH3COOH + H2O H3O + + CH3COO¯

Therefore, the initial conductivity of a mixture of strong acid and weak acid is only due to
the ions of the strong acid and is also high, due to the high mobility and abundance of H +
ions in solution. When NaOH is added during the titration, these H + ions are replaced with
less mobile Na+ ions resulting in a rapid decrease of conductance. This continues until all
the strong acid is neutralized. Further addition of NaOH results in the formation of sodium
acetate due to the neutralization of acetic acid. As CH3COONa exists in ionic form, its
formation raises the conductance of the solution slightly due to the low ionic mobilities of
both Na+ (50.1mhos.cm2. mol-1) and CH3COO¯ (40.9 mhos.cm2. mol-1) ions. This continues
until all the CH3COOH is neutralized. The excess NaOH added above this again raises the
conductance due to relatively high mobility of OH¯ ions. The titration curve contains three
linear portions with two intersection points. The first intersection point ‘x’ corresponds to
the neutralization of the HCl and second at ‘y’ corresponds to the total of strong & weak
acids. From the values of ‘x’ & ‘y’ the concentrations of both strong & weak acids in a
mixture can be determined.
5.Procedure:

Preparation of solutions

1. Sodium hydroxide solution: Prepare 250 ml of approximately 1.0 N Sodium hydroxide by

dissolving 10gms of analytical grade sodium hydroxide (gm. equivalent weight = 40.0) in
carbon dioxide free distilled / deionized / conductivity water.

2. Acetic acid (17 N) solution: Prepare100 ml of 1.0 N acetic acid solution by diluting 5.88
(6) ml of concentrated acetic acid in distilled water and make it up to the mark.

3. Hydrochloric acid solution (11.4N): Prepare 100 ml of approximately 1.0 N hydrochloric

acid stock solution by diluting 8.83 (9) ml of concentrated hydrochloric acid in distilled water
and make it up to the mark.

Determination of strength of acids:

Standardize sodium hydroxide solution using standard oxalic acid solution with
phenolphthalein as indicator

 Prepare 0.1 N solutions of both hydrochloric and acetic acid by exact dilution of the stock
solutions (10 ml 1N solution diluted to 100 ml with distilled water each separately).
 Switch on the conductivity meter for at least one hour before taking any measurements.
Standardize the conductivity meter using internal standard.
 Clean the conductivity cell thoroughly with distilled water and then with conductivity
water. Prepare the experimental solution by taking 25.0 ml each of 0.1N hydrochloric
acid and 0.1N acetic acid with a burette in to a 100 ml beaker.
 Mix the contents of the beakers thoroughly with a glass rod. Insert the conductivity cell
in to the experimental solution and note down the meter reading after selecting an
appropriate range using the range switch of the meter.
 Fill the burette with the standardized solution of sodium hydroxide and titrate the
experimental solution by adding 0.2-0.5 ml portions.
 Note down the meter readings each time after thoroughly stirring the contents of the
beaker.
 Concentration of the titrant (NaOH) = 1N;
 Volume of titrant added = vt ml Total initial volume of the Analyte solution, V = 50 ml
(25 ml HCl + 25 ml CH3COOH)
6.Observations:

Serial No Volume of NaOH Observed Conductance Actual Conductivity =

added (ml) (milli mhos) Observed Cond x [(vt + V
) / V]
1 0.0
2 1.0
3 2.0
4 2.4
5 2.8
6 3.0
7 3.5
8 4.0
9 4.4
10 4.8
11 5.0
12 5.5
13 6.0
14 6.4
15 6.8
16 7.0
17 7.4
18 7.8
19 8.0
20 9.0
21 10.0
7. Graph: Draw a graph of corrected conductance versus volume of sodium hydroxide
added. Join the points in the three portions of the curve linearly and extend them to get the
intersection points. Note down the volumes of the sodium hydroxide ‘x’ and ‘y’
corresponding to the intersection points.

Calculations:

Calculate the strengths of the strong acid and weak acid in the mixture as follows:

[𝑁𝑎𝑂𝐻]
Strength of Strong acid = 𝑥 × =x First equivalence point from graph.
25

[𝑁𝑎𝑂𝐻]
Strength of Weak acid = (𝑦 − 𝑥 ) × =y Second equivalence point from graph.
25

Results

Acid Strength Equivalent point

HCl
CH3COOH
 Estimation of Cu (II) in given Solution
Aim: To determine the amount of Cu (II) in a given solution.
Requirements: (a) Apparatus: Burette, pipette, conical flask, stand.
(b) Chemicals: Cu (II) solution, Na2CO3 solution, Na2S2O3
solution, dil. acetic acid, KI solution, starch solution, K2Cr2O7 solution.

Theory: This experiment comes under the category of Iodometry. Iodometry

means the titration of liberated iodine with a standard solution of sodium
thiosulfate. Sodium thiosulfate (Na2S2O3, 5H2O) is not a primary standard
substance because its crystals are efflorescent, its aqueous solution is unstable and
on standing turns turbid due to the separation of colloidal sulfar, which is caused
by atmospheric CO2, or by bright sunlight and by bacteria. So, first the thiosulfate
solution is required to be standardized by a primary standard solution.

So, the experiment involves double titration. In the first titration the exact
normality of a given thiosulfate solution is calculated by titrating against a given
standard (known strength) solution of K2Cr2O7. Then this thiosulfate solution of
known normality is used in the second titration for calculating the normality of the
given sample of Cu (II) of unknown strength.

First Titration: Standardization of thiosulfate

In acid medium, Cr2O72- quantitatively oxidizes I- to I2 and the liberated I2 is

titrated with thiosulfate solution using starch as indicator (End Point: Blue to
Green)
Second Titration: Estimation of the strength of Cu (II) solution

Cu (II) reacts with iodide and the liberated I2 is titrated with thiosulfate solution
using starch as indicator (End Point: Blue to White)

From the above equation, it is evident

Eq. Wt. of Cu2+ = (2 x 63.5)/2 = 63.5

From the normality equation, normality of Cu2+ and hence the strength of Cu2+ in
hydrated CuSO4 crystals is determined.

Procedure: (a) Determination of strength of thiosulfate solution: Fill the

burette with thiosulfate solution. Pipette out 5 ml (N/20) K2Cr2O7 solution in a
conical flask. Add 1/3 test tube of dil.H2SO4 to it. Then add 5-6 drops of KI
solution, cork the flask and leave in dark for 2-5 min. The solution in the titration
flask will now become dark brown and is titrated against Na 2S2O3 till a pale brown
colour is obtained. Add 2 drop starch. The solution turns blue. Now titrate it further
to get the end point. Repeat and get the concordant reading.

(b) Determination of strength of Cu(II) solution: Pipette out 5ml Cu(II) solution
in a clean conical flask. Neutralise any free acid present by adding Na 2CO3
solution drop by drop till a faint permanent precipitate remains even on shaking.
Add dil. Acetic acid drop wise until the precipitate just dissolves. Then add 10-15
drop of KI solution. Cork the flask and leave in dark for 2-5 min. The solution in
the titration flask will now become dark brown and is titrated against Na 2S2O3 till a
pale brown colour is obtained. Add 2 drop starch. The solution turns blue. Now
titrate it further to get the end point. Repeat and get the concordant reading.
Observation:
Table 1 for Procedure (a)

No. of Obs. Vol. of Burette Reading Concordant Vol. Of

K2Cr2O7 Reading thiosulfate
(ml) Initial Final Difference (ml)

Table 2 for procedure (b)

No. of Obs. Vol. of Burette Reading Concordant Vol. Of

Cu(II) Reading thiosulfate
Solution Initial Final Difference (ml)
(ml)

Calculation: From Table 1: N1V1 of K2Cr2O7 = N2V2 of Na2S2O3

N2 =
From Table 2: N1V1 of Cu(II) solution = N2V2 of Na2S2O3
N1 =

Result: Strength of Cu(II) solution = N1 X 63.5 gm/L = ………..gm/L

 Estimation of Fe (Ⅱ) in given solution
Aim: To determine the amount of Fe(Ⅱ) in a given solution
Requirements:(a) Apparatus: Burette, pipette, conical flask, stand
(b) Chemicals: Fe(Ⅱ) solution, KMnO4, Oxalic acid, H2SO4
Theory: KMnO4 is a secondary standard since it contains traces of MnO2 as
impurity; therefore, a solution of approximate normality is obtained when a
definite weight of it is dissolved in definite volume of water. It is an oxidising
agent and the exact strength of it can be calculated by titrating against oxalic acid
solution of definite strength.
Reaction involved:

Indicator: KMnO4 acts as self-indicator. End Point: Colourless to light pink

By knowing the strength of KMnO4, the strength of Fe(Ⅱ) solution can be
calculated by redox titration between Fe(Ⅱ) solution and KMnO4.

Reaction involved:

Indicator: KMnO4 acts as self-indicator. End Point: Colourless to light pink

Procedure:
(a) Standardization of KMnO4 by oxalic acid: Fill the burette with KMnO4
solution. Pipette out 5 ml (N/20) oxalic acid solution in a conical flask. Add
1/3 test tube of dil. H2SO4 to it and gently heat the solution to about 60-
800C. Then titrate this heated mixture against KMnO4 to get the end point.
Repeat and get the concordant reading.
(b) Standardization of Fe(Ⅱ) solution by KMnO4: Pipette out 5ml Fe(Ⅱ)
solution in a conical flask. Add 1/3 test tube of dil. H2SO4 and 4-5 drops of
H3PO4 to it and titrate (at room temperature) against KMnO4 taken in a
burette to get the end point. Repeat and get the concordant reading.
Observation:
Table 1 for procedure (a)
No. Vol. Of Burette Reading Concordant Vol. Of
Of oxalic Reading KMnO4(ml)
Initial Final Difference
Obs. acid(ml)

Table 2 for procedure (b)

No. Vol. Of Burette Reading Concordant Vol. Of
Of Fe(Ⅱ) Reading KMnO4(ml)
Initial Final Difference
Obs. soln (ml)

Calculation: From Table 1: N1V1 of oxalic acid = N2V2 of KMnO4

N2 = ………………
From Table 2: N1V1 of Fe(Ⅱ) soln = N2V2 of KMnO4
N1 = ………………

Result: Strength of Fe(Ⅱ) solution = N1×56 gm/L = …………… gm/L

 Estimation of Hardness of water
Aim: To determine the hardness of given water sample by EDTA method
Requirements:
(a)Apparatus: Burette, pipette, conical flask, stand
(b)Chemicals: CaCl2 solutions, buffer solution, tap water, Erichrome Black-
T(EBT) indicator, EDTA solution

Theory:
EDTA is ethylene diamine tetra acetic acid. Since pure EDTA is not dissolved in water.
Disodium salt of EDTA is taken for this experiment. It is a well-known complexing agent. It
is used to estimate the hardness of given hard water containing the Ca2+ and Mg2+ ions. When
the EDTA is added to hard water, it reacts with the calcium and magnesium present in hard
water to form stable EDTA metal complexes. From the volume of EDTA consumed the
hardness can be calculated. Erichrome Black-T is used as an indicator. The indicator forms a
weak complex with the metal ions present in hard water and gives wine red colour.

When the EDTA is added into the hard water, the metal ions form a stable complex with EDTA
by leaving the indicator. When all the metal ions are taken by EDTA from the indicator metal
ion complex, the wine-red colour changes into steel blue, which denotes the end point. The
metal EDTA complex is stable at 8-10. This pH range can be maintained by adding buffer
solution (NH4Cl +NH4OH).

Procedure
(a) Standardization of EDTA solution by CaCl2 solution: Fill the burette with EDTA
solution. Pipette out 5ml (M/20) CaCl2 solution in a conical flask. Add ½ test tube
of buffer solution and 2 drops of EBT indicator to it. Titrate against EDTA solution
to get the end point (wine red to blue colour). Repeat and get the concordant reading.
 (b) Standardization of tap water by EDTA solution: Pipette out 25ml tap water in a
conical flask. Add ½ test tube of buffer solution and 2 drops of EBT indicator to it.
Titrate against EDTA solution to get the end point (wine red to blue colour). Repeat
and get the concordant reading.

Observation: Table 1 for procedure (a)

No. of Vol. of Burette Reading Concordant Vol. of
obs. CaCl2 Reading EDTA
solution solution
(ml) Initial Final Difference (ml)

V1 V1

Table 2 for procedure (b)

No. of Vol. of tap Burette Reading Concordant Vol. of
obs. water Reading EDTA
(ml) solution
Initial Final Difference (ml)

V2 V2

Calculation: From table 1:

V1 ml EDTA = 5 ml (M/20) CaCl2
= 5ml (M/20) CaCO3 = (100×5×1/20)/1000 g = 1/40g = 25mg CaCO3

1ml EDTA = 25/V1 mg CaCO3

*W= (Mol. Wt. ×Vol.× Strength in molarity)/1000
From table 2:
25 ml tap water = V2 ml EDTA = V2×25/ V1 mg CaCO3
1000 ml tap water = V2×25/ V1×1000/25 mg CaCO3=………. ppm CaCO3

Result: Hardness of given water sample is ……... ppm.

 Experiment no. 8

Aim: Preparation of 1-nitronaphthalene by nitration

Chemicals and Apparatus required:

1) Naphthalene 2) Glacial Acetic acid 3) Conc. HNO3

4) Ethanol 5) 100 ml 24/29 Joint Conical flask 6) Air condenser

7) Boiling chip 8) Suction filtering apparatus 9) Hot plate

10) Crystalline dish 11) Thermometer

Procedure:
Dissolve 2 g of naphthalene in 10 ml glacial acetic acid by warming in a 100 ml conical
flask. Cool the solution and add dropwise 2 ml of concentrated nitric acid keeping the
temperature of the reaction mixture below 40oC. Heat the reaction mixture on a hot water
bath at ~45oC - 50oC for 10 minutes. Pour the solution on to ~ 20 g crushed ice with stirring.
When ice has melted, filter the solid under suction and wash thoroughly with cold water.
Recrystallize the crude product from ethanol. 1-Nitronaphthalene separates as, pale yellow
needles. Check the melting point of the product. Calculate the yield and percent yield of the
product.

Reactions Involved:

Inference: The melting point of the product formed __________

The yield of the product formed _________
The percent yield of the product formed _________
 Experiment no. 1

Aim: Preparation of dibenzalacetone by aldol condensation reaction

Chemicals and Apparatus required:

1) Benzaldehyde 2) A.R. Acetone 3) Sodium hydroxide

4) Ethanol 5) Rectified spirit 6) 250 ml Conical flask

7) Test tube 8) Suction filtering apparatus 9) Thermometer

Procedure:
Prepare a cold solution of 2.5 g of sodium hydroxide in 25 ml of water and 20 ml of ethanol
in a 250 ml conical flask. In a dry test tube, prepare a mixture of 2.5 ml of benzaldehyde and
1 ml of A. R. acetone. Add the mixture from the test tube into the cold solution in the
conical flask. Shake frequently and keep the temperature at 20oC-25oC for 15 minutes by
immersing the flask in a bath of ice-cold water. Collect the precipitated dibenzalacetone by
filtration at the pump, wash with cold water to remove the alkali and dry the solid at room
temperature upon the filter paper. Recrystallize the crude product from hot rectified spirit.
Dibenzalacetone appears as pale yellow crystalline needles. Check the melting point of the
product. Calculate the yield and percent yield of the product.

Reactions Involved:

Inference: The melting point of the product formed __________

The yield of the product formed _________
The percent yield of the product formed _________
 PREPARATION OF p-IODONITROBENZENE
Aim: -To synthesize p-Iodonitrobenzene by using a diazotization reaction.

Requirements:

(a) Apparatus: 25 ml Erlenmeyer flask, Buchner funnel, Filter paper, Water bath,
Hot plate, 400 ml beaker (2)

(b) Chemicals: p-Nitroaniline, Sodium nitrite, Sodium thiosulphate, Concentrated

H2SO4, Potassium iodide, Deionized water.

Theory: Benzenediazonium salts are very useful for the synthesis of compounds,
such as iodoarenes (ArI) and arenenitriles (ArCN) that are not easily available from
electrophilic aromatic substitution reactions. The diazonio group (N 2+) is a super
leaving group that makes the attached carbon very electrophilic and susceptible to
nucleophilic attack. Thus, benzenediazonium salts can undergo a variety of
nucleophilic aromatic substitution reactions by nucleophiles such as iodide ion. The
outer nitrogen atom of the diazonium salt is also an electrophilic site and can serve
as the electrophilic atom of the aromatic substitution reactions on activated benzene
rings such as anilines. The diazonium salt is prepared using sodium nitrite and
sulphuric acid from the corresponding aromatic amine in a process termed
“diazotization”.
In this experiment diazotization of p-nitroaniline was carried out the resulting p-
nitrobenzenediazonium salt solution was reacted with aqueous potassium iodide to
form p-iodonitrobenzene.

Experimental procedure

Place 2 g of p-nitroaniline, 12 ml of water and 1.7 ml Conc. Sulphuric acid in a 100

ml beaker. Stir for 20 minutes. Place a thermometer in the beaker and cool the
reaction mixture to 0-5oC (ice-salt bath). Add dropwise with stirring a solution of 1
g of NaNO2 in 3 ml of water keeping the temperature below 5oC. Filter the cold
solution and add the filtrate with stirring to a solution of 4 g of KI in 12 ml of water
taken in a 100 ml beaker. Collect the precipitated solid by filtration under suction
and then shake it with sodium thiosulphate solution to remove the excess of iodine.
Filter off the product, wash with water, drain well and dry by suction, then
recrystallize from ethanol. Check the melting point of the product. Calculate the
yield and percent yield of the product.

Results and analysis

Product Weight:

Weight of watch glass alone……………………………….

Weight of filter paper………………………………………

Weight of watch glass, filter paper and product…………...

• Final weight of product………………………...

Melting point:

Melting point of product………………..............................

Theoretical Yield:

% yield = (Actual/ Theoretical yield) ×100

The melting point was recorded and the percentage yield of the product was
obtained.
 Proximate analysis of coal
Aim: To determine moisture, volatile matter and ash content of a given sample of coal

Apparatus: Silica crucible with vented lid, electric oven, Muffle furnace, spatula, desiccator,
pair of tongs, weighing balance, long legged tongs, etc.

Chemicals: Powdered coal sample

Theory:
Coal is a primary, solid, fossil fuel. Coal sample has to be analysed before using it in any
field/industry to find out its quality and suitability. Moisture, volatile matter and ash content of
coal are determined under proximate analysis. This method is simple and quick and is used
primarily to determine the suitability of coal for cooking, power generation or for iron ore
smelting in the manufacture of steel.
Moisture: Moisture held within the coal itself is known as inherent moisture and is analysed.
Moisture reduces the calorific value of coal and considerable amount of heat is wasted in
evaporating it during combustion. Moisture content should be as low as possible.

Volatile matter: Volatile matter is usually a mixture of short and long chain hydrocarbons,
aromatic hydrocarbons and some sulphur. Volatile matter of the coal is related to the length of
the flame, smoke formation and ignition characteristics. High volatile matter coal gives long
flame, high smoke and relatively low heating values. Volatile matter content should be low but
minimum 20% is required for the ignition of coal.

Ash: Ash content of coal is the non- combustible residue left after coal is burnt. It consists of
inorganic matter like silica, alumina, iron oxide, lime, magnesia etc. Ash reduces the heating
value of coal, reduces air supply in furnaces and also requires labour (extra cost) for its regular
disposal. Therefore, ash content of coal should be as low as possible.

Fixed carbon: The fixed carbon content of the coal is the carbon found in material which is
left after volatile materials are drive off. More the fixed carbon content, higher will be the
calorific value of coal.
Procedure:

A. Determination of Inherent Moisture

Transfer about 1g (known quantity) of powdered air-dried coal sample into a previously
weighed silica crucible. Place the open crucible with sample in an electric oven and heat it at
about 105-110°C for an hour. Take out the crucible after one hour from the oven and cool it in
a desiccator. Then weigh the crucible with sample and repeat the process of heating, cooling
and weighing till constant weights obtained. Calculate the loss in weight.

B. Determination of Volatile matter

The dried sample of coal after determining moisture content is closed with a vented lid. The
closed crucible is then heated in a Muffle furnace-maintained T 925 ± 20°C for exactly 7
minutes. The crucible is taken out from Muffle furnace carefully with the help of long-legged
tongs. It is first cooled in air and then in desiccator. When the crucible attains room temperature
it is weighed. Calculate the loss in weight.

C. Determination of Ash

Transfer about 1g (known quantity) of powdered air-dried coal sample into a previously
weighed silica crucible. Place the open crucible with sample in Muffle furnace maintained at
725 ± 25°C for about 40 minutes or till constant weight is obtained. Coal burns in open and the
residue left is ash. Take out the crucible from muffle furnace carefully using long legged tongs.
Cool the hot crucible first in air and then in desiccator. Weigh the crucible and find out the
amount of unburnt residue left(ash).

D. Determination of fixed carbon

The percentage of fixed carbon is determined indirectly by subtracting the sum total
percentages of moisture, volatile matter and ash from 100.

Observations and calculations:

A. For moisture

1) Weight of empty crucible (W1) = g.

2) Weight of crucible + Coal sample (W2) = g.
3) Weight of coal sample before heating (W3) = W2-W1 = g.
4) Weight of crucible + Sample after heating for 1h at 105-110 °C (W4) = g.
 5) Weight of coal sample after heating (W5) = W4-W1 = g.
6) Loss in weight of sample due to moisture (WM) = W3-W5 OR W2-W4 = g
(where WM = weight of moisture)
7) % Of moisture in coal = Weight of moisture = %
weight of coal before heating (W3)

B. For Volatile matter

1) Weight of empty crucible (W1) (W1 from part A) = g.

2) Weight of crucible + moisture free coal sample (W2) (W4 from part A) = g.
3) Weight of moisture free sample (before heating)(W3) (W5 from part A) = W2 – W1
=______g.
4) Weight of crucible + Sample after heating for 7 mins. at 925 ± 20o C (W4) = g.
5) Weight of Sample after heating (W5) = W4 – W1 = g.
6) Loss in weight of sample due to volatile matter (WVM) = W3 – W5 = g.
7) % Of volatile matter in coal = Weight of volatile matter
x 100 = %
Weight of coal (before heating) W3

C. For Ash
1) Weight of empty crucible (W1) = g.
2) Weight of crucible + Coal sample (W2) (W4 from part B) = ___________g.
3) Weight of Coal sample (before heating) (W3) (W5 from part B) = W2 – W1 = g.
4) Weight of crucible + Sample after heating for 40 mins. at 725 ± 25o C (W4) = g.
5) Weight of Ash formed (WA) = W4 – W1 g.
6) % Of Ash in coal = Weight of Ash
x 100 = %
Weight of coal (before heating) W3

D. For Fixed carbon (FC)

% Of Fixed Carbon = 100 – (% Moisture + % Volatile matter + % Ash) = %
Results:
The coal sample contains: Moisture = %
Volatile matter = %
Ash = %
Fixed Carbon = %

Conclusion:

Quality of coal is good /Poor.

 Synthesis and Characterization of
Tris(acetylacetonato)Manganese(III)

Aim: To synthesize Tris(acetylacetonato)Manganese(III) and characterization by

determining melting point.

Requirement: Apparatus: 100 mL beaker, Buchner funnel setup, watch glass, 5

mL measuring cylinder, dropper, Spatula, Glass rod Capillary tube, Wash bottle,
thermos meter, melting point apparatus, filter paper. Chemicals: KMnO4, Acetyl
acetone.

Theory: The complex Tris(acetylacetonato)Manganese(III) or

Manganesetris(acetylacetonato) is synthesized by reacting KMnO 4 with
acetylacetone.

The reaction is based on electron transfer between Mn(VII) and acacH. No any
buffer is required. The compound is obtained as dark brown-black crystals. The
Mn(acac)3 is monomeric in nature. The oxidation state of Mn in the compound is
determined iodometrically by reduction of a known amount of the compound with
acidified potassium iodide solution followed by titration of liberated iodine with
standard sodium thiosulphate solution. The redox titration can be also used for
quantitative determination of Mn content in the compound.
Procedure: Take fine powdered of KMnO4 (0.5g. 3.2 mmol) in 5mL of distilled
water into a 100 mL beaker. Dissolve it by slightly warming on water bath. To this
solution add acetylacetone (2.3 mL, 22 mmol) in dropwise and swirl time to time.
Stir the reaction mixture for 5 min. Keep it again on water-bath until dark brown-
black shiny crystals appear from the reaction mixture. Take out the reaction
mixture from water-bath and allow mixture to cool for 20 min. Filter the reaction
mixture with suction on Buchner funnel and wash the solid material with small
amount of cold acetyl acetone water mixture (1:1 v/v). Collect the dark brown
black crystal and dry in vacuum oven. Weigh the solid material and calculate its
yield. Find out the melting point of compound.

Observation: Weight of compound prepared: -

Melting point of the compound: -

Calculation: Calculate the theoretical yield and find out percentage yield of
product.

Results:

Percentage yield ……………………….

Melting Point ………………………..