Indian Institute of Technology Guwahati

Department of Chemistry
Mid-Semester Examination

Course Name- Green Chemistry and Technology

Course No: CH-426
Date: 25.09.2021 Duration: 2 hours

Total Marks: 40

All questions are compulsory. Mark is givenon the right hand side of each question.Answer paper
should be written by own handwriting and it has to be submitted in the following branch-
wise mail ID: [email protected], [email protected], [email protected]
[email protected] including backlog students. Roll numbers 170121033 and 204107018 are requested
to submit their quiz papers at [email protected] . Do not forget to write your name and Roll
Number. Make Sure that your answer script is readable properly for evaluation.

1. Who introduced the term ‘Environmental Impact Factor’ and which year? 1.0
Answer: Roger A. Sheldon, 1992
2. Who coined the term ‘The Triple Bottom Line’, which is directly tied to the concept of
sustainable development? 1.0
Answer: Management Consultant John Elkington in 1997. The Triple Bottom Line
performance is directly tied with economic, environmental and social.
3. How DDT is prepared and to whom the Nobel Prize in 1948 was awarded for invention of
insecticidal action/properties of DDT? 1.0
Answer: DDT is prepared by heating chloral and chlorobenzene in 1:2 ratio in the
presence of conc. sulphuric acid.
The Nobel Prize in Physiology or Medicine 1948 was awarded to Paul Hermann
Müller "for his discovery of the high efficiency of DDT as a contact poison against several
arthropods."

4. Who gave the concept of atom economy and which journal the same concept is published?
1.0
Answer: Barry M. Trost, Department of Chemistry, Stanford University, Science, 254,
1471-1477, 1991

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5. For the production of sodium carbonate by the Leblanc process, what are the raw materials
utilized for its preparation? Mention the name of the waste products. 1.0
Answer:The raw materials used for preparation of sodium carbonate by the Leblanc
process were rock salt, coal, limestone and sulfuric acid. For the production of one
Na2CO3, 2 mol of HCl, 1 mol of CaS and 4 mol of CO are produced as Waste.
6. Write down the 4th Principles of Green Chemistry given by Anastas & Warner. 1.0
Answer:The 4th Principle of Green Chemistry is Designing Safer Products. The full
description of the principle is given by Anastas and Warner as follows: “Chemical
products should be designed to preserve efficacy of function while reducing toxicity.”
7. Why is thioketal not hydrolyzed by acid and how deprotection is achieved? 1.0
Answer: Sulfur is less basic as compared to oxygen present in ketal. Therefore, it is not
protonated easily and hydrolysis is failure. However, sulfur is better nucleophile and it is
hydrolyzed easily with mercuric chloride in presence of CdCO 3.
8. Name the reagent, which is used for the complex formation during estimation of creatinine
in urine by a flow injection spectrophotometric method. How does this complex degrade
as a greener waste? 1.0
Answer: Sodium salt of 2,4,6-trinitrophenol or Sodium salt of picric acid. The complex is
decomposed by TiO2, H2O2 in presence of UV light.
9. What is Darzens reaction and where it has been used? 1.0
Answer: This is indirect method for the preparation of epoxide from ketone. The reaction
is carried out with ketone or aldehyde, α-chloroester and in the presence of a base such as
sodium ethoxide to give α,β-epoxy ester, which is known as glycosidic ester. It was used in
Boot’s Ibuprofen Synthesis from step 2 to step 3.
10. What is Bechamp reduction and explain with a suitable example. 1.0
Answer: The reduction of aromatic nitro compound to their corresponding aromatic
amines in presence of Fe/HCl is known as Bechamp reduction. The reduction is used for
the industrial preparation of phloroglucinol from 2,4,6-trinitrotoluenene.
11. Name the drug which was withdrawnfrom the market due to birth defects of the new born
baby and give the scientific reason for its withdrawal. 1.0
Answer: Thalidomide. The toxicity was not investigated before launching the drug in the
market.

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12. Fill in the blank with the appropriate words:2.0
i) One of the most widely publicized successful waste minimization programmes was
developed by 3M in 1975. The initiative was called ‘3P-standing for’
, Pollution, Prevention Pays
ii) Degradation of chemical products should give benignend products. Pesticides tend
to accumulate in living organisms especially in the lipid tissues, which is known as
Bioaccumulation.
13. On reaction of 32 g pure benzaldehyde with 29 g of potassium hydroxide in 27 mL of water
produced 13 g of benzyl alcohol and 13.5 g of benzoic acid on acidification using 80 mL
of concentrated hydrochloric acid in 80 mL of water and 100 g crushed ice. Calculate and
show the percentage yield for both the products.3.0
Answer:

It shows:
230 g of reactant can give 108 g of benzyl alcohol
1 g of reactant can give = 108/230 g of benzyl alcohol
32 g of reactant can give = (108/230)*32 g of benzyl alcohol
= 15.02 g

Therefore, % yield of benzyl alcohol = 13/15.02 = 86.55%

Similarly,

230 g of reactant can give 122 g of benzoic acid

1 g of reactant can give = 122/230 g of benzoic acid
32 g of reactant can give = (122/230)*32 g of benzoic acid
= 16.97 g

Therefore, % yield of benzoic acid = 13.5/16.97 = 79.55%

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14. Give three methods for the preparation of dimethyl carbonate. Discuss the merits and
demerits of each method. Mention which method is ‘Greener Synthesis’ and why? 3.0
Answer: Phosgene was reacted with methanol to give dimethylcarbonate and HCl.
Dimethyl carbonate is prepared by the carbonylation reaction of methanol using CuCl 2
catalyst. The waste product is H2O.
Methanol reacts with CO2 in presence of copper catalyst and by-product is H2O.
So, this process is superior to phosgene and CO synthesis. This is a direct method for
fixation of CO2.
15. In Willstaetter’s first tropinone synthesis (1901), what starting material is used?
Write down two merits and two demerits of the synthesis? Why Robinson’s tropinone
synthesis (1917) is considered to be ‘Landmark synthesis’? Justify it. 3.0
Answer: Cycloheptanone
Though it is a long synthesis but it is a creative and elegant. Therefore it is useful to the
student to think a complex problem.
Since it is a multistep synthesis, overall yield is low i.e. less than 1%. To complete the
synthesis large amount of cycloheptanone is required.
Robinson synthesis is landmark because 17 step synthesis is completed in only one step by
choosing 3 reactants such as saccinaldehyde, methyl amine and a salt of (Ca)acetone
dicarboxylic acid. The reaction was carried out in water at neutral PH and overall yield
42%.
16. Give the final product in the reaction given below. Among these three reactant which one
is toxic? Write down the mechanism for the formation of the product.3.0

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17. What would be the product for the three-component reaction shown below? Give the
reactions’ names for the formation of the product. 3.0

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18. Why is it necessary to carry out high boiling liquid to distill at a reduced pressure? Water
boils at 100oC at 760 mm pressure. At what temperature, the water will boil at 10mm
pressure. 4.0
Answer:
Clausius Clapeyron Equation:
𝑃 ΔH 1 1
𝑙𝑛 = −
𝑃 R T T
For a particular liquid;
T1 is initial boiling point at P1 vapour pressure

T2 is final boiling point at P2 vapour pressure

R = 8.314 Jmol-1K-1, the universal gas constant

ΔH is Latent Heat of Vaporisation at T1 boiling point

In case of water, T1 is 100 ℃ or 373K where P1 is 760 mmHg

& ΔH is 2260 KJ/Kg or 40800 J/mole

If,P2 = 10 mm of Hg then T2 = ?

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 From Clausius Clapeyron Equation,
10 40800 1 1
𝑙𝑛 = −
760 8.314 373 T

Or, T2 = 280.38 K
= 7.38 ℃

19. Give the suitable reagent(s)/catalyst in the following transformation: 1.0 x 4=4.0

Answer: a) Dimethyl carbonate, b) Na2WO4, H2O2, KHS4, Alamine 336 c)Ag2O, d)

Zn/CH3COOH
20. Outline for the synthesis of Ibuprofen is given below. Calculate the percentage atom
economy for the synthesis. What is the name of the reagent (Et) 2AlCN? Why is HCN not

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 used for hydrocyanation reaction? 2.0 + 1.0 + 1.0=4

Answer: Molecular weight of C10H14 = 134.22, Molecular weight of C2H3ClO = 78.49,

Molecular weight of (Et)2AlCN = 111.12, Molecular weight of H2O = 18, Molecular
weight of H2 = 2, Molecular weight of C13H18O2 = 206.28
The percentage atom economy for the synthesis of Ibuprofen
= 206/ (134.22+78.49+111.12+36+2) X 100 = 206.28/361.83 X 100 = 0.5701 X 100
= 57.01
The name of the reagent is Nagata’s reagent.
HCN is avoided because it is a poisonous gas and difficult to handle.