School of Chemical and Biomedical Engineering

CH4220 Special Topics in Green Chemistry and Engineering

Yoel Sasson

Assignment No. 1 (5 questions)

August 29th 2017. To be submitted by September 10th 2017

Solution of this assignment contributes 4% to the final course grade.

Question 1
The following is a literature procedure for the laboratory scale synthesis of 2-DMAP
[2-(dimethylamino)pyrimidine]. Based on this procedure you were asked to design a
pilot scale process (100 kg scale) for this product. Assume complete conversion of
2-chloropyrimidine and stoichiometric amount of dimethylamine fed.

[a] Write a complete stoichiometric equation for the reaction and calculate the atom
yield.

[b] Draw a batch process flowchart based on 100 kg of 2-DMAP and check the overall
mass balance. Describe which streams you would recycle and which you would consider
as waste.

[c] Calculate the atom yield, the mass intensity and the mass productivity, the mass
efficiency, the E-factor and the Environmental Index (out)
 Procedure: In a 250-ml. three-necked flask equipped with a reflux condenser and
a gas-inlet tube are placed 45.6 g. (0.4 mole) of 2-chloropyrimidine and 150 ml. of
absolute ethanol. The mixture is refluxed for 6 hours while anhydrous dimethylamine
gas is bubbled into the solution. The solution is cooled, and 100 ml. of ethanol is
removed by distillation using a water aspirator. The residue is chilled in an ice
bath for 1 hour, and 75 ml. of ether is added to cause precipitation of dimethylamine
hydrochloride. After the removal of dimethylamine hydrochloride (by filtration)and
solvent, the residue is distilled at reduced pressure. The fraction boiling at 85
86/28 mm. is collected; yield 4042.5 g. (8186%),

Additional data:
MW (2-chloropyrimidine) = 114.53 gr/mol
MW (dimethylamine) = 45.08 gr/mol
MW [2-(dimethylamino)pyrimidine] = 123.16 gr/mol
MW (dimethylamine hydrochloride) = 81.54 gr/mol
bp (2-chloropyrimidine) = 76 C @10mmHg
bp (dimethylamine) = 8 C
D (ethanol) = 0.789 g/ml
D (diethylether) = 0.7134 g/ml

Question 2
Chlorobenzene is an important solvent and intermediate in the production of numerous
chemicals. It is produced by bubbling chlorine gas through liquid benzene in the presence
of ferric chloride catalyst. In an undesired side reaction the product is further chlorinated
to dichlorobenzene and in a third reaction the dichlorobenzene is chlorinated to
trichlorobenzene.

The feed to a chlorination reactor consist of pure benzene and chlorine. The liquid output
from the reactor contains 65 wt% benzene, 32 wt% C6H5Cl, 2.5 wt% C6H4Cl2 and 0.5
wt% C6H3Cl3. The gas output contains only HCl.

[a] Write down stoichiometric equations for the reactions taking place in this process .

[b] Determine: the E-factor (assume benzene can be recycled), conversion of benzene,
yield of chlorobenzene and selectivity to the desired product vs. all undesired products.
Question 3
The following multiple reaction is carried out in a continuous flow reactor in steady
state:

C2H6 C2H4 + H2

C2H6 + H2 2CH4

The desired product is ethylene. The incoming feed is composed of 85 mol% ethane
(C2H6) and 15 mol% inert nitrogen. The conversion of ethane in the reactor is 0.501 and
the yield of ethylene is 0.939.

a. Calculate the composition of the product stream. Base your calculation on a 100
mol of incoming stream.
b. What is the selectivity of ethylene (C2H4) vs. methane (CH4).
c. Check the mole balance of the process (mol H and mol C in and out).

Question 4
Consider the following system of gas phase reactions:

Sketch the instantaneous selectivities SB/X SB/Y and SB/XY as function of the concentration of A.

Question 5
In the following multiple parallel reaction with the given rate equations the desired
product is D:

A+CD rD = 800e-2000/TCA0.5CC
A+CU rU= 10e-300/TCACC
What type of reactor would you select and at what temperature would you recommend to
work (high or low) to maximize the selectivity to D vs. U.