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- Q1. (a) In each of the following cases (I. to III.) identify which polymer in each pair has the greatest Tg and then explain your selection in terms of molecular structures. Assume that molecular weight differences are insignificant. Note: PMV = pendant molar volume/ cm³/mol Pair I Section A Answer ALL questions in this Section Pair II Pair III Polymer 1 H₂ +²2² 0+. Repeat unit A ht Polymer 3 (PMV=92.3) 3 Polymer 5 (PMV-60.1) tyt OC-CH₂ Polymer 2 | to-0²-0-0 H₂ + -ot Polymer 4 (143.9) (b) Consider the following repeat units A and B, state which polymer is likely to be amorphous and which is likely to be semi-crystalline then explain why in terms of the structure of the repeating units. to *** Polymer 6 (PMV=70.3) Repeat unit B tA solution (1 dm3) of styrene (H2C=CHPh, 1 mol dm–3) in tetrahydrofuran was polymerised by addition of 5 cm3 of a 0.1 mol dm–3solution of n-butyllithium in tetrahydrofuran with rigorous exclusion of air and water at room temperature. Calculate the expected number average relative molar mass (Mn) of the final polymer at complete monomer conversion. Type your answer as a dimensionless number (no units), in normal (not scientific) notation, with no spaces but WITH comma separators for thousands.a) Calculate the concentration of benzoyl peroxide required to prepare polystyrene with a number-average molar mass of 750 kg mol-¹ by bulk polymerization at 60 °C. Assume: (i) the initiator is 60% efficient; (ii) the rate coefficients for initiator dissociation, propagation and termination are, respectively, 2x 10-6 s-¹, 341 dm³ mol-¹ s-¹ and 4x 107 dm³ mol s¹; (iii) the density of styrene at the polymerization temperature is 0.88 g cm3; and (iv) that ter- mination by disproportionation, and chain transfer to initiator and monomer, are negligible. 4
- (h) Describe a chromatographic technique that could be suitable for studying the molecular weight distribution of poly(phenylenevinylene) derivatives that are soluble in organic solvents. Explain the physical basis on which separation could occur and suggest how the polymers could be detected after elution.11. (8pts) how can silica gel F2s4 TLC plates can be visualized ( give two methods? :Explaining the following polymer size fractions in a polymer sample: Fraction Molecular Weight Number of Chains 1 3,250 400 5,000 500 3 500,000 4 а. Calculate the number-average molecular weight of the polymer. b. Calculate the weight-average molecular weight of the polymer. c. Which average molecular weight did the 4 chains of molecular weight of 500,000 most significantly affect? why ? d. Calculate the polydispersity index (PI = (Mw/Mn) of the polymer.
- Arrange the following compounds in order of decreasing ease of elution from a column of silica gel: (a) 2-octanol; (b) 1,3-dichlorobenzene; (c) tert-butylcyclo hexane; (d) benzoic acid.If 9 grams of polymer A with molecular weight of 30,000 Dalton is mixed with 5 grams of polymer B with molecular weight of 50,000 Dalton, calculate the number average molecular weight, weight average molecular weight and polydispersity index of the polymer mixture.(b) An aqueous solution of propanone (acetone, 1) of total volume 0.120 mL was analysed by quantitative 1H NMR, using the CH protons of (E)-butenedioic acid (fumaric acid, 2) to provide an internal standard. A stock solution of 2 with concentration = 10.00 x 10-3 mol L-1 was prepared by dissolving pure solid 2 in deuterium oxide (D₂O). The solution of 1 was mixed with a 0.400 mL aliquot of the stock solution of 2 and the 400 MHz 1H NMR spectrum of the mixture was recorded (see Table 2 below). H³C || CH3 1 HO₂C H C=C H CO₂H 2 SH (D2O, 400 MHz) Multiplicity Relative peak area (integration) Assignment 2.22 4.80 singlet broad singlet 4.50 6.53 singlet not determined 1.00 CH3 groups of 1 OH from HOD CH groups of 2 Table 2. ¹H NMR data for the mixture of aqueous propanone (1) and the internal standard (2). (i) Calculate the mass of propanone (1) contained in the original aqueous solution.
- Explaining the following polymer size fractions in a polymer sample: Fraction Molecular Weight Number of Chains 1 3,250 400 2 5,000 500 3 500,000 4 a. Calculate the number-average molecular weight of the polymer. b. Calculate the weight-average molecular weight of the polymer. c. Which average molecular weight did the 4 chains of molecular weight of 500,000 most significantly affect? why ? d. Calculate the polydispersity index (PI = (Mw/Mn) of the polymer.22-30. (a) The mean free path is the average distance a molecule travels before colliding with another molecule. The mean free path, A, is given by A = kT/(V20P), where k is Boltzmann’s constant, T is temperature (K), P is pressure (Pa), and o is the collision cross section. For a molecule with a diameter d, the col- lision cross section is nd. The collision cross section is the area swept out by the molecule within which it will strike any other molecule it encounters. The magnetic sector mass spectrometer is maintained at a pressure of ~103 Pa so that ions do not collide with (and deflect) one another as they travel through the mass analyzer. What is the mean free path of a molecule with a diam- eter of 1 nm at 300 K in the mass analyzer?With reference to the polymerisation mechanisms explain why the polydispersities of the two samples are so different.
