Department of Chemical & Process Engineering

Faculty of Engineering
University of Peradeniya
CP 518: Polymer Science & Engineering
Assignment 05

(100 Marks)

Registration Number

Answer ALL questions Write your answers in the spaces provided.

Submit your answers on or before 2020.11.09
Refer Lecture notes (Lecture 04 & 05), Examples and Videos Provided- FEELS

Q1)
Identify the product (repeating units) of following reactions (28 Marks)

a)

b)

c)
d)

e)

f)

Q2 (24 M)
Polyurea, Polyurethane, Nylon 6,6 formation are indicated below. If the number average degree
of polymerization is 100 for each case, find the number average molecular weight of the polymer
((N=14, H=1, C=12, O=16)

a)
b)
c)

Q3) (48 M)

W.H Carothers, the pioneer of step-growth reactions, proposed a simple equation relating x́ n to a
quantity p describing the extent of the reaction for linear polycondensations or polyadditions.

If N0 is the original number of molecules present in an A-B monomer system and N is the
number of all molecules remaining after time t, then the total numbers of functional groups of
either A or B that have reacted is (N0-N). At that time t, the extent of reaction p is given by

N o−N
P= N0

No
Degree of polymerization x́ n can be expressed as x́ n = (N0= initial concentration of
N
molecules and N is current concentration of molecule)

1
a) Show that x́ n= (5 M)
1−P
A polymer sample usually contains a distribution of chains with different degrees of
polymerization; x́ n. Therefore, an average value must be taken when determining the x́ n. The
degree of polymerization can be calculated by using the following relationship if a molecular
weight of a polymer molecule is known.
Mn= x́ n M0;
Mn is the number average molecular weight of the polymer, and x́ n is the average degree of
polymerization
M0 is the formula weight or average weight of the repeating unit.
A precisely controlled stoichiometric imbalance of the reactants in the mixture can provide the
desired result. For example, an excess of diamine over an acid chloride would eventually
produce a polyamide with two amine end groups incapable of further growth when the acid
chloride was totally consumed.
b) Starting from first principle, expressed the extended Carothers equation as follows

(1+r )
x́ n=
(1+r −2rp )

NA
where r is the ratio of the number of molecules of the reactant; r = and p is the extent of
NB
reaction.

1
c) Show that extended Carothers equation can be used to deduce x́ n= when diamine
1−P
and an acid chloride initial molar ratio is 1:1. (4 M)
 1+ P
The weight-average molecular weight can be expressed as Mw= x́ w M0 where x́ w=
1− p
Number of X-mers (Nx) in terms of the initial amount of monomers and the extent of
reaction is given by following equation

The weight fraction, Wx, of X-mers is obtained by following equation

Polyester fibers for “lace” material can, in principle, be produced from ω = hydroxycaproic
acid as shown below.

d) If the initial n moles of the hydroxyacid are reduced to 0.03 n moles after 10 h reaction
time, calculate:
i. If the extent of the reaction is 0.95, Calculate the value of n (4 M)
 ii. x́ n and x́ w (5 M)

iii. The number average molecular weight <Mn> (5 M)

iv. The weight average molecular weight <Mw> (5 M)

v. The probability that the reaction mixture contains heptamers (5 M)

vi. The weight fraction of pentamers. (5 M)

As a result of extraneous reactions of the hydroxyl groups, a 6% excess of the carboxylic acid
is present in the reaction mixture.
e) Calculate the ratio of the number of molecules (r) of the reactant (5 M)

f) Calculate the number-average molecular weight when the extent of reaction is 0.97. (5
M)