THE UNIVERSITY OF THE WEST INDIES Semester! ] semester it C] supplementavSummer Schoot [1] Examinations of December JApriv/May (‘July 0) 2009 Origneting Campus: cavern =] Mone St Auguetine Mode: Ooncampus Mt _By Distance Course Code and Title: CHEM1901 - INTRODUCTORY CHEMISTRY A Date: December 17, 2009 Time: 9:00-11:00a.m. Duration: 2 Hours. Paper No: 2 jaterals ‘Answer booklet: Normal O Special W Not required Calculator: Programmable [] Non Programmable i (where applicable) Multiple Choice answer sheets: numerical alphabetical O 120 0 140 0 Aunliary/Other materials) ~ Please specity: CHEMISTRY ANSWER BOOKLET ‘Candidates are permitted to bring the following items to thelr desk Instructions to Candidates: This paperhas_4 pages & 6 questions. (Candidates are reminded that the examiners shall take into account the proper use of the English Language in determining the mark for each response. This paper has TWO sections. ‘You are required to answer FOUR questions in total TWO questions from EACH section, Answer each SECTION in a separate booklet ‘The numbers in brackets on the right hand side of the paper are the marks allocated.Section A INORGANIC CHEMISTRY (Answer any TWO (2) questions) « (@) Briefly outline how Linus Pauling determined the electronegativity values (zz) of various elements in his scale of electronegativities. Refer to any assumptions he made and/or equations that he used. a () Calculate the effective nuclear charge (Z*) for a 2p electron in N, O and F. Are the calculated values of Z* consistent with the relative sizes of these atoms? 6) (®) Using VSEPR, explain why the CI-N-Cl bond angle in NCI is 107° while the F-N-F bond angle in NF3 is 102°. 6) (d) List all the symmetry elements of NCI and show that BF has a $3 but NCh does not. @&) . (a) Differentiate between molecular orbital (MO) theory and valence bond (VB) theory. «@ (b) i) Using a MO energy level diagram, determine how bond lengths AND bond dissociation energies will vary for the series of diatomics, B2, Bz” and By”. o ii) Draw a Lewis structure for By and compare the magnetic properties of Ba predicted from the MO diagram above with the magnetic behavior predicted from its Lewis structure. ©) (© Sketch the sigma (6) bonding MO that results from positive overlap of the following orbitals on separate atoms: Take the internuclear axis as the z axis. i) sands ii) pzand p, iii) sandp, (2x3) . (@) Distinguish between hexagonal and cubic close-packing. ® (b) For each of the following ionic crystals, NaCl, CsCl and TiO i) describe the packing of both anions and cations, © i) sketch the structure of the unit cell, © iii) state the coordination number and geometry of the cation. @ (© Show that the ideal :"/ ratio for cation-anion and anion-anion contact for an octahedral arrangement of anions around a cation is 0.414. ©Section B ORGANIC CHEMISTRY (Answer any TWO (2) questions) ‘The examiners will attach importance to carefully drawn structures in which charges, if any, are clearly labeled. 4. Answer ALL parts. (a) With the use of appropriate examples, define the following terms: @ constitutional isomers, Q) }) geometric isomers, @) Gil) conformational isomers (conformers) @) (b) When 2-methylpropane, ((CH3);CH), is reacted with chlorine in the presence of ultraviolet light, two monohalogenated products are formed. (Propose structures for these two compounds and name them. @ (ii) Indicate which is the major product and show mechanistically how it is formed. © (© Ahydrocarbon, A, (CsHs) (pK, = 25) is treated with sodium amide (NaNH2) followed by methyl iodide (CHs1) and produces B (CsHg). When B is treated with hydrogen in the presence of Lindlar's catalyst, C (CsHj9) is formed. C is oxidized with ozone (03) followed by reductive work-up (Znvacetic acid) to give D (C2H,O) and E (CsH0). Deduce the structures of A-E. aM 5. Answer ALL parts. (a) Draw structures for compounds G-L formed in the scheme below. e G HBr 1 NtBHe on Kx _HHg(Ae)y, THE-H0 ie HBr, peroxides, ee ee oH, (1) 0805 Cla HQ, (ii) NaHSO3, (b) Write mechanisms for the reactions leading to compounds G, H and K above. (12) (c) Devise a reaction sequence for achieving the conversion: OH 1 CHy-CH-CH; ——————» _ CH;-CH,—CH,-OH Give reagents and conditions and draw the structures of the intermediate compounds formed. Reaction mechanisms are not required. @ ‘Semester 1 2009/20106. Answer ALL parts. (a) Provide IUPAC names for the following compounds (Indicate stereochemistry where appropriate) CHSCH; e Q a 6-ctiy CHECH See ii i. HyC-C—CH,-CH=CH), cr ‘CH3 Br CH; CH CH, a iv, HxC-C~C==C-CHCH; —v. HyCACHCH; CH; Br (10) (b) Give a mechanistic explanation for the formation of the three products obtained when 1,2-dimethyl-1-propanol (F) is dehydrated under the conditions shown. O) CH3 CH3 CHa HPO, HyC—CH—CH—OH = 7 ———*HyC —CH—CH= City iH CH; CH; HyC==C—CH—CH; (©) Give the mechanisms for the following transformations. @) 7 ee i, (CH3)3CCl + CH;CH,ONa ———* — (CH3),C==CH oO 7 _HgSOs HSOs@Q Bites END OF QUESTION PAPER