BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE-PILANI,
Hyderabad CAMPUS
Mid Semester TEST FIRST SEMESTER 2018-2019 Date: 09/10/2018
Time: 90 minutes Max. Marks – 70 Weightage 35%
Closed Book Time: 09.00am -10.30 a.m.
COURSE NO: CHEM F325 COURSE TITLE: POLYMER CHEMISTRY
There are four questions, printed in two pages. Answer all questions. All parts of
the question should be answered together. Start a new question from a fresh page .
Q.1 (a) (i) Draw the stereochemical structures of poly(propylene). Indicate which form is
the most stable in solution and which would have the lowest melting point? Very briefly
explain your answer. (ii) Draw various conformations of poly(propylene) and indicate
the most stable and unstable conformation. (Drawings should be presented neatly)
[6+4=10M].
(b) Among PS, PVC and PMMA what would be a suitable thermoplastic for use as
glazing for a bus shelter? Why? [1+3=4M]
(c) A polymer consisting of highly rigid aromatic back bone was found to possess
crystalline melting temperature at 750K, what would the range of its glass transition
temperature? [2M]
Q2. (a) A polydisperse sample of poly(decanediol adipate) is prepared by mixing three
monodisperse samples in the following way: 10 g of A (40,000 m.w) ; 5 g of B (100,000
m.w) and 3 g of C (200,000 m.w). Calculate the number average, weight average
molecular weight and polydispersity index of the mixture. [5M]
(b) Ethylene may be polymerized by using sulfuric acid. Write down the reaction scheme
(mechanism) for this particular process. [5M]
(c) A 1M solution of styrene in benzene was polymerized by a free-radical mechanism,
using an initiator concentration of 0.05M. The steady state propagation rate was 1.510-7
mol L-1s-1. (i) Calculate the propagation rate for a monomer concentration of 2M, given
that the other conditions are same as above. (ii) Also, calculate the rate of propagation for
an initiator concentration of 0.1M, again under the same conditions as above. [4M]
(Hint: Rp= {kp(f kd[I]) / kt)1/2[M]}
(d) (i) Given the Q-e values for styrene (Q = 1.00, e = -0.8) and 4-chlorostyrene (Q =
1.03, e = -0.33), Calculate the reactivity ratios for styrene and 4-chlorostyrene (ii) What
do you infer from the values obtained. [4M]
1
Q.3 (a) What are Zeigler–Natta catalysts? What is the significance of using metallocene
catalysts for polymerization. Consider two entities i.e. a growing chain bound to metal
and a monomer, show the mechanism of a coordination polymerization through insertion
in just three steps. [5M]
(b) Write four types of polymerization techniques that are used most
commonly/industrially and the concept (just about 2-3 sentences) utilized in each of these
techniques. [6M]
(c) Calculate the contour length and the root mean square end-to-end distance for
polyethylene chain with molecular weight of 280 kg/mol. Assume that the length of a C-
C bond is 154 pm. [3M]
(d) Which physical parameter governs the miscibility of polymer and solvent? Draw the
representative phase diagram of polymer solution with proper labelling of the axis and
indicate all the salient features as well the phase transitions. [4M]
Q4. (a) A polymer with molecular weight 300,000 obeys Mark-Howink-Sakurada
equation with mark-howink parameters as 0.80 and 1×10-4. Consider Huggins constant as
0.33. What would be the relative viscosity at a concentration of 0.30 g/dL. [5M]
(b) The osmotic pressure of a solution of PVC in cyclohexane at 298 K is given below:
concentration 2g/ L and height 0.71 cm. The density of polymer solution is 0.980 g/cm3.
Determine the molecular weight of the polymer. [3M]
(c) (i) What is the free energy of mixing polystyrene with benzene at 35 °C in order to
make a 10% solution by volume, if the number of polystyrene molecules are 6.831018
and benzene molecules are 5.21021? Consider the interaction parameter as 0.40. (ii)
Which experimental technique is most commonly used to determine interaction
parameter? [4M]
(d) What is meant by swelling of polymer chain? Determine the solubility parameter in
(MPa)1/2 for poly(vinyl acetate), by the method of Small. Density of the polymer was
reported as 1.23 g cm-3. The molar-attraction constant for the repeating unit of poly (vinyl
acetate) are: CH3: 438; CH2: 272; COO (ester): 634; >C<: -190. [3M]
(e) Assume that you are given a plastic sheet of 0.01inch thick which is stiff and also
transparent. It does burn slowly with a smell of vinegar. It also dissolves completely in
acetone. By the features mentioned above identify the polymer? (write either name or
molecular structure). [3M]
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