UNIT PROCESS LAB MANUAL

Shazir Abbas 2022-CH-11

Submitted To : Mam Anum Saeed

Chemical Engineering Session 2022

LABORATORY SAFETY RULES
 Always wear a lab coat
 Identify safety equipment
 Wear appropriate PPE ( Personal protective equipment)
 Know emergency exit routes
 No smoking in the laboratory
 Handle lab equipment carefully
 Know locations of laboratory safety showers, eyewash stations,
and fire extinguishers. The safety equipment may be located in
the hallway near the laboratory entrance.
 Avoid skin and eye contact with chemicals
 Never leave containers of chemicals open.
 Wash exposed areas of the skin prior to leaving the laboratory
 Determine the potential hazards and appropriate safety
precautions before beginning any work.
 Label all containers and process equipment
 LAYOUT FOR UNIT PROCESSES LAB

6 2

7 3

8 4

1- Oxidation
2- Nitration
3- Sulphonation
4- Esterification
5- Nitration
6- Polymerization
7- Oxidation
8- Halogenation
 Introduction to Nitration

• Nitration is a chemical process that involves the introduction of a nitro group (-NO2) into a
chemical compound.
• This reaction is often employed to synthesize a variety of nitroaromatic compounds, which find
applications in the production of dyes, pharmaceuticals, and explosives. The nitration reaction
typically utilizes a mixture of nitric acid (HNO3) and a strong acid, such as sulfuric acid (H2SO4), as
the nitrating agent.

• The nitration mechanism involves the generation of nitronium ions (NO2+), which act as the
electrophile in the reaction.

• The electrophile attacks the electron-rich regions of the substrate, leading to the substitution of
hydrogen atoms with nitro groups.

• The overall reaction can be represented as follows:

• R-H + HNO3/H2SO4 → R-NO2 + H2O + H2SO4

• In this equation, R represents the organic substrate undergoing nitration. The reaction conditions,
such as the concentration of nitric acid, reaction temperature, and reaction time, play crucial roles
in determining the yield and selectivity of the nitration process.

• It is essential to exercise caution during nitration experiments due to the potentially hazardous
nature of the reagents involved.

• Safety precautions, including proper protective equipment and adherence to laboratory

protocols, must be followed to minimize risks.

• In this experiment, we will explore the nitration of a specific aromatic compound, closely
monitoring the reaction parameters to achieve the desired product with high purity and yield. By
understanding the underlying theory and mechanisms of nitration, we aim to gain insights into
the practical application of this important synthetic method in organic chemistry.

Electrophilic Aromatic Substitution (EAS):

Nitration is a classic example of electrophilic aromatic substitution, a fundamental reaction in

organic chemistry. EAS involves the replacement of a hydrogen atom on an aromatic ring with an
electrophile, in this case, the nitronium ion.

Reaction Mechanism:

The nitration mechanism comprises several steps, starting with the protonation of nitric acid by
sulfuric acid to generate the nitronium ion. The nitronium ion then attacks the aromatic ring,
leading to the formation of an intermediate, which ultimately undergoes deprotonation to yield
the final nitroaromatic product.
Regioselectivity:

The regioselectivity of nitration is influenced by the directing effects of substituents on the

aromatic ring. Electron-donating groups typically direct the nitration to the ortho and para
positions, while electron-withdrawing groups favor substitution at the meta position.

Temperature Control:

The reaction temperature is critical in nitration experiments. Higher temperatures can lead to
multiple substitutions and side reactions, while lower temperatures may result in incomplete
reactions. Optimizing the temperature is essential for achieving the desired regioselectivity and
yield.

Yield and Purity Considerations:

Monitoring the reaction progress and controlling the reaction conditions are crucial for obtaining
high yields and pure products. Techniques such as thin-layer chromatography (TLC) and column
chromatography may be employed to assess reaction completion and isolate the final product.

Safety Precautions:

Nitration reactions involve corrosive and potentially explosive reagents. Proper safety measures,
including the use of personal protective equipment (PPE), ventilation, and adherence to
laboratory safety protocols, must be strictly followed to ensure the well-being of researchers.

Application in Synthesis:

Nitration is a versatile method widely used in organic synthesis to introduce nitro groups into
aromatic compounds. The resulting nitroaromatic products serve as key intermediates for the
synthesis of various valuable chemicals, including pharmaceuticals, agrochemicals, and industrial
materials.
 Experiment No: 01
Objective
Production of Picric acid by Phenol, Sulfuric acid, and Nitric acid.

Unit Process
The unit process involved is the nitration of phenol sulphonic acid obtained by
heating phenol with concentrated sulfuric acid.

Chemical Required
• Phenol (solid form)
• Nitric Acid (Conc)
• Sulfuric Acid (Conc)
Apparatus
• Glass beakers
• Hot plate
• Weighing balance
• Mearing cylinder
• Glass stirring rod
• Glass funnel with filter paper
• Conical flask
• Chilling bath
Chemical reaction
Reactions:

C6H5OH(s)+ H2SO4 C6H6O4S + H2O

C6H6O4S + 3HNO3 C6H3N3O7 + 2H2O + H2SO4

Overall reaction:
H2SO4
C6H5OH + 3HNO3 C6H3N3O7 + 3H2O (Sulfuric acid used as catalyst)

Procedure
• Taken 7ml sulfuric acid and 4grams of phenol
• Stirrer both to 30C - 40C for 10 -15 minutes
• Then mix both till colorless to slightly colored
• A slightly colored mixture of sulfuric acid and phenol is formed.
• Then keep the mixture in a cooling bath and add Nitric acid slowly
• After adding nitric acid a dark red color is formed
• Then stir and heat the above mixture to 40C for 2 Hours
• After that the dark red color is changed to light yellow.
• Then Added 30ml of distilled water to precipitate picric acid
• Then the mixture by using filter paper to collect the product (picric acid) in crystal
form.
• After that we dried the filter paper in the oven @ 100 °C for 15 minutes.
• Finally, we took the final weight of the filter paper and performed the calculations as
given below.
 Observation and Calculation

Theoretical yield
Based on limiting reactant
Moles of Phenol
Mass of Phenol =4g
Molecular mass of Phenol =94.11g/mole
Number of moles =mass/molecular mass
=(4g)/(94.11g/mole)
=0.042 gmol
Moles of Nitric acid
Volume of Nitric acid =25ml
Density of Nitric acid =1.42g/ml
Mass of Nitric acid =(volume)(Density)
=(25ml) (1.42g/ml)
=35.5g
The molecular mass of Nitric acid =63g/mole
Number of moles =mass/molecular mass
=(35.5g)/(63g/mole)
=0.563 gmol
Moles of Sulfuric acid
Volume of Sulfuric acid =7ml
Density of Sulfuric acid =1.92g/ml
Mass of Sulfuric acid =(volume)(Density)
=(7ml) (1.92g/ml)
=13.44g
The molecular mass of Sulfuric acid =98.07g/mole
Number of moles =mass/molecular mass
=(13.44g)/(98.07g/mole)

=0.137 gmol
The limiting reactant is Phenol.

Mole balance
Phenol : Picric acid
1:1
0.042 : (1) (0.042)
=0.042 gmol
Molecular mass of Picric acid =229.1g/mole
Number of moles =mass/molecular mass
Mass of Picric acid = (Number of moles) (Molecular mass)
 =(0.042gmol) (229g/gmol)
=9.6 grams
Theoretical yield is 9.6 grams.
Actual yield
Weight of filter paper = w1 =1.579g
Weight of filter paper with crystals = w2 =5.588g
Weight of crystals = w = w2 - w1
=5.588g-1.579g
Mass of Picric acid =4.009 grams
Actual yield is 4.009 grams.

Percentage yield
Percentage yield = (Actual yield/Theoretical yield) (100)
=(4.009 grams/9.6 grams) (100)
=41.76 %

Result
The amount of product is 5.588 g and the percentage yield is 41.76 %.

Conclusion
The amount of actual yield is less than theoretical yield because some amount of nitric acid and
phenol is converted to water and NO2 (gas). The desired product of this experiment is picric acid but
water and NO2 are formed as by-products. So, the amount of product is deceased.
 Introduction to Sulphonation
Sulphonation is a chemical process that involves the introduction of a sulfonic acid group (-SO3H)
into an organic compound. This reaction is commonly used in the synthesis of detergents, dyes, and
pharmaceuticals. Sulphonation, similar to nitration, is an electrophilic aromatic substitution (EAS)
reaction and typically employs sulfuric acid (H2SO4) as the sulfonating agent.

Reaction Mechanism:
The sulphonation mechanism follows the EAS pathway. Sulfuric acid acts as a strong acid and a
dehydrating agent, promoting the formation of a sulfonium ion. This ion acts as the electrophile,
attacking the electron-rich aromatic ring to form an intermediate, which eventually undergoes
deprotonation to yield the sulfonated product:

R−H+H2SO4→R−SO3H+H2O

Regioselectivity:
Similar to nitration, the regioselectivity of sulphonation is influenced by substituents on the
aromatic ring. Electron-donating groups direct sulphonation to the ortho and para positions, while
electron-withdrawing groups favor substitution at the meta position.

Temperature Control:
Controlling the reaction temperature is crucial in sulphonation. Elevated temperatures may lead to
over-sulphonation and side reactions, whereas lower temperatures can result in incomplete
reactions. Optimizing the temperature is essential for achieving the desired regioselectivity and
yield.

Yield and Purity Considerations:

Monitoring the reaction progress and ensuring appropriate reaction conditions are vital for
obtaining high yields and pure sulphonated products. Techniques such as chromatography may be
employed to assess reaction completion and isolate the final product.

Safety Precautions:
Sulphonation reactions often involve the use of concentrated sulfuric acid, which is highly corrosive.
Safety measures, including the use of protective equipment, proper ventilation, and adherence to
laboratory safety protocols, must be strictly followed to mitigate risks.

Application in Synthesis:
Sulphonation is a valuable method in organic synthesis, enabling the introduction of sulfonic acid
groups into aromatic compounds. The resulting sulfonated products serve as versatile intermediates
for the production of various industrial chemicals, including surfactants, dyes, and pharmaceuticals.
 EXPERIMENT NO: 2

Objective
Preparation of Sodium Sulphate from Sodium Chloride and Sulfuric acid.

Unit Process
Sulphonation

Reagents
• Sodium Chloride 12 g
• Sulfuric Acid 6 ml

Apparatus
• Glass beakers
• Mearing cylinder
• Glass funnel with filter paper
• Conical Flask
• Glass stirring rod

Chemical reaction
2NaCl + H2SO4 Na2SO4 + 2HCl
Procedure
• Measure 12 grams sodium chloride with measuring balance and 6ml sulfuric acid with
measuring cylinder.
• Then, add measured sodium chloride in beaker and pour measured sulfuric acid in it
• After that Shake and stir it well.
• After about 10minutes, filter the solution. Sodium Sulphate remains on filter paper while
hydrochloricacid collects in the conical flask.
• After collection of sodium sulfate dry and measure the filter paper.
• After measuring subtract the initial weight of the filter paper.

Product name

Sodium Sulphate
Confirmatory test for sodium sulphate

• On adding BaCl2 solution to SO42− salt aqueous solution BaSO4 is formed as a

white precipitate, which confirms the presence of the anion.
y
 Observation and Calculation

Theoretical yield
• Based on limiting reactant

Moles of Sulfuric Acid

Volume of Sulfuric acid

=6ml Density of Sulfuric

acid =1.92g/ml

Mass of Sulfuric acid =(volume) × (Density)

=(6ml) × (1.92g/ml)

=11.92g

Molecular mass of Sulfuric acid =98.07g/mole

Number of moles = Mass(gram)

Molecular mass(g/mole)
= 11.92g

98.07g/mole

=0.1215gmol

Moles of Sodium Chloride

Mass of Sodium Chloride =10grams

The molecular mass of Sodium Chloride =58.5g/mole
Mass (gram)
Number of moles
molecular mass (g/mole)
12 g
=
58.5g/mole
=0.2051gmol

Limiting reactant is Sulfuric acid.

Moles balance Sulfuric acid :

Sodium Sulphate 1 : 1
0.1215: (1) (0.1215)
= 0.1215gmol
 Molecular mass of Sodium Sulphat=142.04g/mole

Mass of Sodium Sulphate = (Number of moles) × (Molecular mass)

= (0.1215gmol) × (142.04g/mole) =17.25grams

Theoretical yield is 17.25grams.

Actual yield
Weight of filter paper = w1 =2.11g

Weight of filter paper with crystals = w2

=18.55gWeight of crystals = w = w2 - w1
=18.55g-02.11g
Mass of sodium sulphate =16.44grams

Actual yield is 16.44grams.

Percentage yield
Percentage yield = Actual yield ×100
Theoretical yield

= 16.44g ×100
17.25g
= 95.30%

Result
The amount of product is 16.44grams and the percentage yield is 95.30%.

Conclusion
The desire product of this experiment is sodium sulphate. The actual yield of
theproduct is less than the theoretical yield because hydrochloric acid produced
as byproduct. So, some of reactant converted to hydrochloric acid, resulting
decrease in percentage yield.
 Introduction To Esterification
Esterification is a chemical process that involves the synthesis of esters by the reaction between a
carboxylic acid and an alcohol. Esters find widespread applications in the fragrance, flavor, and
pharmaceutical industries, making esterification a crucial reaction in organic chemistry. The general
reaction equation for esterification is as follows:

Carboxylic acid + Alcohol Acid catalyst Ester +Water

Reaction Mechanism:

Esterification typically proceeds via a nucleophilic acyl substitution mechanism. The acid catalyst (often a
strong mineral acid like sulfuric acid) facilitates the protonation of the carbonyl oxygen, enhancing the
electrophilicity of the carbonyl carbon. The alcohol then acts as a nucleophile, attacking the carbonyl
carbon to form an intermediate, which undergoes subsequent proton transfer and elimination to yield
the ester and water.

Acid Catalysis:

The acid catalyst plays a dual role in esterification. It not only protonates the carbonyl oxygen to enhance
reactivity but also serves as a source of the nucleophilic hydronium ion (H3O+), which participates in the
final steps of the reaction.

Equilibrium Reaction:

Esterification reactions are often reversible and reach equilibrium. Le Chatelier's principle can be applied
to shift the equilibrium towards the formation of the ester by using excess reactants or removing the
water formed during the reaction.

Yield and Purity Considerations:

Monitoring the reaction progress, controlling reaction conditions, and choosing appropriate reaction
times are critical for obtaining high yields and pure ester products. Purification techniques such as
distillation or extraction may be employed to isolate the final ester.

Safety Considerations:

While esterification reactions are generally safe, precautions should be taken when handling strong acids.
Proper personal protective equipment, such as gloves and goggles, should be used to ensure safety.

Application in Synthesis:

Esterification is a versatile synthetic tool used to produce a wide range of ester compounds. These
compounds serve as important building blocks for the synthesis of various products, including perfumes,
flavors, plasticizers, and pharmaceuticals.
 Experiment No 3

Objective
Preparation of Ethyl Acetate from Acetic acid and n-butyal Alcohol.

Unit Process
Esterification

Chemical Required
• Acetic acid 25 ml
• n-butyal alcohol 25 ml
• Sulfuric acid 7 ml
• Sodium Carbonate 12.5 ml

Apparatus
• Glass beakers
• Hot plate
• Mearing cylinder
• Total Reflux Condenser
• Separating funnel
• Distillation flask (round bottom flask)

Chemical reaction
H2SO4
C2H5OH + CH3COOH CH3COOC2H5 + H2O

Procedure
• Measure 25ml n-butyal alcohol, 25ml acetic acid and 7ml sulfuric acid.
• Add measured ethyl alcohol and acetic acid in distillation flask.
• Slowly, add measured sulfuric acid to the mixture of ethyl alcohol and acetic acid.
• Heat the solution for about 50 minutes at total reflux condenser at temperature of 50-
100°C. (Initially heat at 100°C then reduce the temperature to 60°C).
• Heat (distillate) the solution until 2/3rd of the solution obtained. Pour distillate (mixture of
product ethyl acetate and water) in the separation funnel.
• Prepare 20% solution of sodium carbonate (by add 20g sodium carbonate in 100ml distilled
water).
• Add prepared solution of sodium carbonate in separation funnel. (contained mixture of
ethyl acetate and water)
• Two layers are formed; top layer is ethyl acetate. Separate it by drain off the bottom liquid

Product name:
Ethyl Acetate
 Observation and Calculation

Reaction
H2SO4
C2H5OH + CH3COOH CH3COOC2H5 + H2O

Theoretical yield
Based on limiting reactant

Moles of Acetic Acid

Volume of Acetic acid =25ml
Density of Acetic acid =1.05g/ml
Mass of Acetic Acid = Volume × Density
= 25ml × 1.05 g/ml
= 26.25 g
Molecular mass of Acetic acid =60.05g/mole
No of Moles = Mass/ M.Wt
= 26.25/60.05
= 0.4371 gmoles
Moles of Ethanol
Volume of Ethanol =25ml
Density of Ethanol =0.789g/ml
Mass of Ethanol =(volume) ×(Density)
=(25ml) × (0.789g /ml)
=19.72g
Molecular mass of Ethanol =46g/mole
No of Moles = Mass/ M.Wt
= 19.72/46
= 0.428 gmoles

Limiting reactant is Ethanol.

Moles balance

Ethanol : Ethyl Acetate

1 : 1

0.428 : (1) (0.428)

=0.428gmol

Theoretical yield is 0.428gmol.

Actual yield
Volume of Ethyl Acetate =24ml
Density of Ethyl Acetate=0.902g/ml
Mass of Ethyl Acetate =(volume)×(Density)
=(24ml) × (0.902g /ml)
=21.64g
Molecular mass of Ethyl Acetate =88.11g/mole
No of Moles = Mass/ M.Wt
= 21.64/88.11
= 0 .245 gmoles

Percentage yield
Percentage yield = (Actual Yield/ Theoretical Yield) × 100
= (0.245/0.428) × 100
= 57.40%
Result
The amount of product is 24ml and the percentage yield is 57.40%.

Conclusion
The amount of actual yield is less than theoretical yield because some amount of ethanol and
acetic acid converted to water. The desire product of this experiment is ethyl acetate but
water is formed as by product. So, the amount of product is deceased. However, the
percentage yield is greater than 50%, it means more than 50% reactant converted to
product.
 Experiment No 04

Objective:
Preparation of Oxalic acid with Sugar and Nitric acid.
Unit Process:
Oxidation
Reagents:
Sugar (Sucrose) 05gm
Nitric acid 30ml

Apparatus:
Beakers
Hot plate
Stirring rod
Weighing balance
Measuring cylinder

Chemical reaction:

C12H22O11 + 36HNO3 6(COOH)2 + 36NO2 + 23H2O

Procedure:

• Firstly, wash all glassware and dried them.

• Measure 5gram sugar with weighing balance and 25ml nitric acid with measuring cylinder.
• Then, take sugar in glass beaker and pour nitric acid in it.
• Then, heat the solution of sugar and nitric acid in Hot plate at 60°C.
• Heat the solution until the evolution of reddish-brown gas. When brown gas started to evolve,
add remaining 5 ml volume of nitric acid in the beaker and heat continuous until the volume
of solution dropped to about 4 ml.
• When volume dropped to 4ml, remove the beaker and wait for 5 minutes.
• Then, dip the beaker in chilled water for about 15-20 minutes.
• The colorless (white) crystals of oxalic acid are formed.

Product name:

• Oxalic acid
 Observation & Calculation:
Theoretical yield:
Firstly, we find limiting reactant.
C12H22O11 + 36HNO3 6(COOH)2 + 36NO2 + 23H2O
Moles of Nitric acid:
Mass of sugar =5 gm
Molar mass of sugar =342 g/gmol
Number of moles =mass/molecular mass
= (5g)/ (342 g/gmol)
=0.0146 gmol
Moles of Nitric acid:
Density of nitric acid =1.42 g/ml
Volume of nitric acid =30 ml
Mass of nitric acid = (density) (volume)
= (1.42 g/ml) (30 ml) =42.6 g
Molar mass of nitric =63g/gmol
Number of moles =mass/molecular mass
= (42.6 g)/ (63 g/gmol)
=0.676 gmol
Limiting reactant is sugar.
Mole balance:
Sugar: Oxalic acid
1: 6
0.0146: (6) (0.0146)=0.0876 gmol
Theoretical yield is 0.0876 gmol

Actual yield:

Initial Weight of filter Paper = w1 =0.788gm

Weight of filter paper with crystals = w2 =2.039 gm
Weight of crystals = w =w2 - w1= 2.039 – 0.788
Mass of Oxalic = 1.251 gm
Molar mass of oxalic acid = 90.03 g/gmol
Number of mole= mass/molecular mass= (1.251 g)/ (90.03g/gmol) = 0.0138gmol

Percentage yield:
Percentage yield =
(Actual yield/Theoretical yield) × (100)
= (0.0138 gmol / 0.0876) (100) =15.75 %
Result:
The amount of product is 1.251gm and percentage yield are 15.75 %.

Conclusion:
The amount of actual yield is less than theoretical yield because some amount of sugar
and nitric acid converted to water and nitrogen dioxide.
 Oxalic Acid

Oxalic acid is a naturally occurring organic compound with the chemical formula H2C2O4. It is a
dicarboxylic acid found in many plants, including certain vegetables like spinach, rhubarb, and beet
greens, as well as in some fruits and nuts. Oxalic acid is also found in some household products like
rust removers and cleaners due to its ability to dissolve various substances, including metals like
calcium and iron.

Oxalic acid, also known as ethanedioic acid, has several notable properties:

Chemical Formula:

The chemical formula of oxalic acid is H2C2O4, indicating that it contains two carboxyl groups (COOH)
and two carbon atoms.

Physical State:

At room temperature, oxalic acid exists as a colorless, odorless, crystalline solid.

Solubility:

Oxalic acid is highly soluble in water and other polar solvents.

Acidity:

It is a strong organic acid, readily donating protons (H+) in aqueous solutions, making it acidic.

Toxicity:

In its pure form, oxalic acid is toxic when ingested in large quantities. It can cause severe damage to
the kidneys and other organs. However, in smaller amounts, it is metabolized harmlessly by the
body.

Occurrence:

Oxalic acid is found in many plants, particularly in foods such as spinach, rhubarb, and beet greens. It
serves various purposes in plants, including defense against herbivores.

Industrial Uses:

Oxalic acid has several industrial applications, including as a bleaching agent for textiles and wood, a
rust remover, and a component in certain chemical processes.

Chemical Reactivity:

Oxalic acid can react with metals to form metal oxalates, which are often insoluble in water. It also
participates in various chemical reactions due to its acidic nature