CHEM3116/3916 Polymer Assignment 2015

This assignment is to be submitted on e-Learning by 11pm Monday 7th September.

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a) The hydrodynamic radius, RH, of polystyrene polymers in a cyclohexane solution is

given as a function of average molecular weight and temperature in the following
table.
Molecular Weight (gmol-1)
Hydrodynamic radius ()
T = 25 C
T = 40 C
7
2.610
505
1450
1.3107
401
1025
0.7107
326
752
7
0.210
215
402
Determine the scaling relationship between RH and N at each temperature, and briefly
comment on the geometrical arrangement of the polymers at each temperature. What
does this data indicate about the strength of interactions between the polymer and
solvent?

b)
i) Using the Flory-Huggins theory, calculate the critical volume fraction cA and critical
temperature c-1 of polymer A made of XA=700 monomers when mixed with a short chain
molecule B consisting of XB=4 monomers. What is the value of the mole fraction of A
corresponding to your calculated value of cA?
ii) Based on your answer to part i) of this question, describe qualitatively what you would
expect to see as you cooled a mixture of molecules A and B at a volume fraction A = 0.5
from above the critical temperature. Include in your answer any trends in composition of
phases during the cooling.

c) Explain how you could use condensation polymerization involving only ester bonds to
produce polymers with the following sequence of monomers:
i) ... ABABABABAB ...
ii) .... BBBBBBBB ...
iii) .... AABAABAAABA ... (i.e. ABA units separated by sections of AA
A of random length)

d) A polymer has 7,000 monomers, each with a length of 2.3 nm.

i) Calculate the dimension of the polymer as a random coil and when fully extended.
ii) Calculate the force required to extend the random coil by 12% of its original dimension at
300K.

e) Consider a short oligomer chain made up of N rigid bonds connected by flexible joints.
There is a bond angle force constant with the result that there is a tendency for bonds to be
aligned. This tendency is expressed by the relation

ri ri + n = 0.8 n b 2

where ri is the vector lying along bond i, bonds i and i+n are separated by n bonds, is
the average over chain configurations, and b=0.45 nm.
First, determine the mean squared end-to-end distance <Rend2> for N=2, N=4, N=8, N=16,
N=32, N=64, N=128, N=256, N=512, N=1024. Show some working and the tabulated results.

Next, plot your results on a log-log plot, and comment on the meaning of the observed
relationship.
Normal Question (Only for students doing Chem3116)
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f1) Consider the attractive interaction energy between two argon atoms in a vacuum. The
Lennard-Jones and Buckingham potentials have been fitted for argon, obtaining the following
expressions:

12 6
Lennard-Jones:
V (r ) = 4
r
r
with = 125.7 K k B and = 0.3345 nm
C
Buckingham:
V (r ) = A exp( Br ) 6
r
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with A = 1.69 10 J , B = 3.663 1010 m -1 , and C = 1.02 10 77 Jm 6
First, for each model, determine the equilibrium distance and interaction energy between two
otherwise isolated atoms.
Next, consider the solid argon crystal. The argon crystal has the cubic closest-packed
structure, in which each atom is surrounded by twelve others. By considering only the
nearest-neighbour interactions, and assuming that each of these interactions matches the gasphase equilibrium previously calculated, calculate an estimate of the molar heat of
sublimation of argon.

Advanced Question (Only for students doing Chem3916)

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f2) We showed in lecture 8 that the Gibbs free energy of mixing a polymer of length X with a
similar solvent of length 1 can be approximated as:

Gmix H mix
S
ln p
=
T mix = k BT s p sp + s ln s +
M
M
M
X

For a long chain polymer with large X, the final term becomes negligible. Consider a longchain polymer in a monomer solvent, at an effective temperature of -1=0.6. Determine the
volume fraction of long chain polymer in the polymer-rich phase of the equilibrium twophase system.