Indian Institute of Technology Guwahati

Department of Chemistry
End-Semester Examination

PART-B

Course Name- Green Chemistry and Technology

Course No: CH-426
Date: 25.11.2023 Duration:2:40 p.m.-5:00 p.m.

Total Marks: 40

All questions are compulsory. Mark is given in the right hand side of each question.

1. The greener synthesis of the pesticide, carbaryl (C), from -naphthol is given below. Find out the
reactants A, B, and the final product C. 2

Ans: A = Dimethyl carbonate (CH3O)2CO; B = Methyl amine (CH3NH2); (0.5 x 2)

(01)

2. Among the four structures, which one is the correct structure of the nonsteroidal anti-inflammatory
drug, ketoprofen? 2

Ans: A (02)

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3. Due to the changes in the dielectric constant of water at high temperatures and pressures, it behaves
like some organic solvent. Match between the two columns. 2
Water-Temperature Water behaves like an organic solvent
I. 150 oC A. Acetone (H3CCOCH3)
o
II. 175 C B. Acetonitrile (CH3CN)
III. 200 oC C. Dimethyl sulfoxide (H3CSOCH3)
o
IV. 300 C D. N,N-Dimethyl formamide ((CH3)2N-CHO)

Ans: I = C; II = D; III = B; IV = A (0.5 x 4)

4. Dimethyl sulfoxide (DMSO) boils at 189 ºC at 760 mm of Hg. DMSO was distilled at the reduced
pressure of 1 mm of Hg and the boiling point was 39.1 ºC. Which equation is required to calculate
the value of the final boiling point at the reduced temperature and write the equation? 2
Ans: Clausius Clapeyron Equation: (01 + 01)
𝑃2 ΔH 1 1
𝑙𝑛 = ( − )
𝑃1 R T1 T2

5. Show the direction of the equilibrium shift while (1) increasing and (2) decreasing the pressure for
the following equilibrium gas reaction. 2

Ans: I. 2 moles give 1 mole : (1) to the right; (2) to the left

II. 7 moles give 8 moles : (1) to the left; (2) to the right

III. 2 moles give 2 moles : No change in both the cases while increasing or decreasing pressure

IV. 3 moles give 2 moles : (1) to the right; (2) to the left. (0.5 x 4)

6. Give the three tenets for sustainability. Compare the C2C approach with the 12 principles of Green
Engineering. Specifically, comment on the goal of tenet 2 of C2C and the 12th principle of Green
Engineering. 2
Ans: 1) The natural step; 2) biomimicry; 3) cradle to cradle (C2C) (0.33 x 3)

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 Tenet 2 recommends the use of solar energy, which is also a goal of principle 12 according to
which energy should be renewable. (01)

7. The solvent-less synthesis of terpyridine is carried out in the first two steps. What reagents (A, B,
and C) are required for the three steps? Give the reaction’s names for the first two steps. 3

Ans: A = NaOH, grinding, Aldol condensation (01 x 3)

B = NaOH, grinding, Michael Reaction [For A & B, 01= 0.5 x 2]
C = NH4OAc in acetic acid
8. For the preparation of n-tetrabutylammonium tribromide (TBATB, M.W- 482), 2.75 mmol of V2O5
(M = 181) was dissolved in 44.1 mmol 30% H2O2 (w/v) with continuous stirring at 0-5 ºC. To this
clear red solution, 11 mmol of n-tetrabutylammonium bromide, TBAB (Bu4NBr, M = 322) was added
to obtain 3.66 g TBATB. Find out how much mL of 30% H2O2 is required for 44.1 mmol, and
calculate the percentage of yield for the formation of TBATB. Can you justify whether the procedure
is green or not? 3
Ans) 11 mmol TBAB = 0.322 x 11 = 3.542 g
322 g TBAB gives = 482 g TBATB
So, 3.542 g TBAB gives = (482 x 3.542)/322 = 5.302 g (Expected yield)
% yield = (Observed yield x 100)/Expected yield = (3.66 x 100)/5.30 = 69% (01)

100 mL 30% H2O2 solution contains 30 gm H2O2

1 mL H2O2 solution contains 0.3 gm H2O2
MW of H2O2 = 34
44.1 mmol = 44.1 x 0.034 = 1.499 g H2O2
Amount of H2O2 requires = 1.499/0.3 = 5 mL (01)

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 For making TBATB, the quaternary ammonium salt is lost for compensation of the bromide anion.
That is why the procedure is not green. If we add KBr, or any bromide anion source then the yield
will be higher. (01)

9. Asymmetric reduction of 2-butanone with sodium borohydride in the presence of enzyme Lipase
gives S-enantiomer in an excess amount. Pure S-2-butanol has a specific rotation [α]D of +13.52
degrees. The observed specific rotation [α]D of the reduction product is +6.76. Calculate the optical
purity and enantiomeric excess (ee). Find out how much (S)-2-butanol and (R)-2-butanol are
obtained from the reaction. 3
Ans: Optical purity = Observed specific rotation/Actual specific rotation of S isomer (01 x 3)
= +6.76/(+ 13.52) = 0.5 = 50% pure S isomer = 50% racemic
 Total S isomer = 75% and R isomer = 25%
 Enantiomeric excess (ee) = 50%

10. The Passerini reaction is shown below.

When the reaction is carried out in dichloromethane at 25 oC for 18 hours, how much percentage
conversion and yield? When the temperature was increased from 25 oC to 50 oC how much % of the
reaction rate was decreased? When the temperature was lowered from 25 oC to 4 oC how much % of
the reaction rate was increased? Which reactants are the source of O1 and O2 respectively? 4
Ans: 50% conversion, 45% yield (01 x 4)
 44% decreased
 Increased by 11%
 O1 from aldehyde and O2 from carboxylic acid

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11. If 107 g of benzylamine converts to 82.4 g of benzonitrile in the presence of 1 μM catalyst at 95 oC
for 25 hours. Calculate the percentage yield of the product, and also find out the Turn Over Number
(TON) and Turn Over Frequency (TOF) of the reaction. 4

Ans: Number of moles of product = Weight of the product/Molecular weight of the product
= 82.4/103 = 0.8 M
Number of moles of Reactant = Weight of the reactant/Molecular weight of the reactant
= 107/107 = 1.0 M
 % yield of the product = (Number of moles of product/ Number of moles of reactant) × 100
%
= (0.8/1.0) × 100 % = 80 % (01)
Number of moles of Catalyst = 1 μM = 1 × 10 M -6

 Turn Over Number (TON) = Number of moles of product/ Number of moles of Catalyst
= 0.8 M/1 × 10-6 M = 800000 (02)
 Turn Over Frequency (TOF) = TON/time = 800000/25 h =32000 h-1 (01)

12. Write down a concise simplified version of 12 Principles of Green Engineering. Between 12
principles of Green Chemistry and Green Engineering, which principles are similar? 5

Ans: 1) Inherent rather than circumstantial; 2) Prevention instead of treatment; 3) Design for
separation; 4) Maximize efficiency; 5) Output-pulled vs input-push; 6) Conserve complexity; 7)
Durability rather than immortality; 8) Meet need, minimize excess; 9) Minimize material
diversity; 10) Integrate local material and energy flows; 11) Design for commercial after life;
12) Renewable rather than depleting. (03)

 Green chemistry principle 1 and green engineering principle 2 both focuses on waste
prevention; Green chemistry principle 7 and green engineering principle 12 both cover a
need for renewable resources; Green chemistry principle 3 and green engineering principle
1 both state goal for non-hazourdous processes; Green chemistry principle 10 calls for
design for degredation so that product do not persist in the environment and this goal is

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 embedded also in green engineering principle 7, which calls for durability rather than
immortality. (02)

13. Can you draw a simplified phase diagram of CO2? Mention the temperature and pressure in the
diagram for the triple point and the critical point of CO2. Give four important uses of supercritical
carbon dioxide. 6
Ans:

(02)
 Tripple point = -56.6 oC and pressure = 5.2 bar or 5.1 atm; (01)
 Critical point = 31.1 oC and pressure = 56.5 bar or 55.8 atm. (01)
 Importance: 1) Extraction of coffee from coffee bean; 2) as a reaction solvent; 3)
cleaning of clothes; 3) coating of paints (02)