Q1: A 21.3g sample of poly(hexametyhlene adipamide) is found to contain 2.

50x10-3 mol of carboxyl

groups by both titration with base and infrared spectroscopy. From these data, the polymer is calculated
to have a number average molecular weight of 8520. What assumption is made in the calculation?

Q2: Neglecting the contribution of end-groups to polymer molar mass, calculate the percentage
conversion of functional groups required to obtain a polyester with a number average molar mass of
24,000 g mol-1 from the monomer HO(CH2)14COOH.

Q3: The following data were obtained during the condesation of 12-hydroxy stearic acid at 433.5 K in the
molten state by sampling the rxn mixture at various times. [COOH] was determined for each sample by
titrating with ethanolic sodium hydroxide.

t (h) [COOH] (mol dm-3)

0 3.10

0.5 1.30

1.0 0.83

1.5 0.61

2.0 0.48

2.5 0.40

3.0 0.34

Determine the rate constant for the rxn under these conditions and the order of the rxn. Also suggest
whether or not a catalyst was used. What would be the extent of rxn after 1h and 5 hours?

Q4: A polyamide was prepared by bulk polymerization of hexamethylene diamine (9.22 g) with adipic acid
(11.68 g) at 280°C. Analysis of the whole rxn product showed that it contained 2.6x10-3 mol of carboxylic
acid groups. Evaluate the number average molar mass of the polyamide.

Q5: Discuss the possibility of cyclization in the polymerization of

a. H2N (CH2)m CO2H
b. HO (CH2)2 OH + HO2C (CH2)m CO2H
for the cases where m has values from 2 to 10? At what stage(s) in the reaction is cyclization possible?
What factors determine whether cyclization or linear polymerization is the predominant reaction?