2003solutions - 1. (A) (B) (C) (D) (E) (F) (G) In each part...

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Unformatted text preview: 1. (A) (B) (C) (D) (E) (F) (G) In each part of this question circle the number(s) corresponding to all statements that correctly complete the sentence. Note: there may be more than one correct statement in each part. Marks will be deducted for incorrect choices. The kinetic order of an elementary step in a reaction mechanism is... (D always determined by the stoichiometry of the step (2) not necessarily related to the stoichiometry of the step Q) always determined by the molecular-ity of the step (4) not necessarily an integer number (5) always the same as the overall order of the reaction Z A catalyst can alter the... (1} rate of a reaction @ activation energy of the reaction (3) equilibrium position of the reaction 4‘ half-life of the reaction 8 rate constant of the reaction é/i During the isothermal compression of an Ideal Gas using a constant external pressure... 3 The statement “the change in enthalpy of the system is the heat gained or lost at constant pressure” is... ® always true (if only PV work) (2) true only at constant T (3) true only at constant T & P / (4) true only for an irreversible process (5) true only for reversible processes (5) a reversible process takes place For the reversible vaporization of a liquid at its normal boiling point AH = p .h . y ' ‘7 ‘F gao<ii 1,: aft/1L (3) as =nCpln(T2/T1) .. ‘ a W; (4) 13:0 , Z, 539;; @:H=Tas w / flflwl I: 9 I -- ,1 .et. 2/ T 5v] 5 .j'fl’ 1' ;‘95-1‘ " The equation ASS” + AS”, = 0 for a process is (1) always true k (2) true only at constant T / (3) true only at constant T & P (4) true only for an ideal gas Q; true only for reversible processes The osmotic pressure (H) for a solvent is... ,r G) a colligative property (2) an enthalpic effect 69 driven by the solvent attempting to equalize its free energy on both sides of a semipermeable membrane (4) dependent upon the presence of a membrane permeable to all solute and solvent @approximately equal to the quantity... CRT. .. for a dilute solution sw_________.---av / Q 2 w r z. . - f a “ 1 225M Wfid 2. a) Derive (using the definitiOns of work and emIOPY, the ideal gas law, and the laws of thermodynamics) the following equation for the isothermal entropy change of an ideal gas: 7—. If 7- ” aft/7 fps/V M 7’" : 0 7" 1'7 f F 0/ 1/ WV x 2. b) Two moles of a monatomic ideal gas are expanded isothermally and reversibly from 22.4L to 44.8L at 273K. Calculate q, w, AE, AH, ASS”, ASSN, and ASH.“v for this process. Is this process spontaneous? Explain your answer and show all your work. lib is ,s biz Va/ ”:3' V‘UvZZ-VL > V:§/¥.XA Tazv‘b’K 7“: 27—3/< sign number units w : {em #7242:— E V/ E: - = *2X53/7X2fiA43—e;= 5 *— —~ 7 7/ 3W7 was fl : 2/ aime- ASWB ASuniv': MIN/77:7 D E spontaneity w _ w We F—- -/ A : ” Alf =5 flag: 47w N " 3. in important biochemical reaction that is used to do work (on muscle, or in transport of chemical ' r ' species, or in driving biosynthesis) involves AdenosineTriPhosphate (ATP) and AdenosineDiPhOSphatc (ADP) and can be written as: ATP + H20 '9 ADP + Pi‘ + H+ AG°= +9.2 kJ/mol where Pi" is inorganic phosphate. In biological systems this reaction is, to an excellent appoximation, carried out at constant pressure (1 atrn) and constant temperature . a) Is this reaction spontaneous when carried out with all reactants and products present at standard state thermodynamic conditions? Explain your answer. W fl/a til/#5.: (45:27, > O ’ b) Calculate AG for this reaction at 25° C and the typical physiological conditions: pH = 7 [ATP] = 10‘4 M {ADP] = 10“1 M I [Pi‘] = 10‘4 M 9 Is the reaction spontaneous under these conditions? Explain your answer. .: 72%;?” +fti/t‘éz7d'7’g” [HM / a / 7 :- 72yz772‘ 53/5/6276642 fig) 2 . AG : amt/“~74 7M7 ‘* ‘9 .1 J fikfldagflflj 7/7109 4 ‘4. At 37°C the concentration of Sr2+ inside a cell is 0.050 M and outside is 0.045 M . The cell membrane is permeable to Sr2+. a) What potential difference in volts would have to exist across the membrane for Sr2+ to be in equilibrium at the stated conditions? £=6°+£7gnir f; M7, fiaz .05 = 0 7" f‘j/fX-g/‘D 4,4 ~01“? : d . can! Mai/715. .ZX f; 5294: .415 b) The only ions present in addition to S + are Cl‘ and a protein ( Prfi" ) inside the cell. The protein holds a single positive or negative charge. The C1“ is at equilibrium across the membrane while the protein is inside the cell and cannot permeate the membrane. What are the concentrations of [Cl—Lrl , [Cl—km and of [Pr+ f‘ Ln? Is the protein positively or negatively charged? M's, 2/: molar Jr film/73 baa/awn: fluvial: c292! urban;ng 2% 59-050 1" »—-g.¢93>— 2 43 ® : “$.91‘Ié wt ,', Mtfi-CLALV‘fc on P” @ c) What is the osmotic pressure associated with this cell? 7M=AC T A : ,py9“74..&? "6,54,93,74... 4" Z R C ( Jaflf “chap/2‘4) ; .,._ F/ 7;» :: (9.0! 5‘68; 1519K) ) ,p, 5 AQW S. For a reaction, A + B + 2C —> P , the following initial rates of reaction (R) for different initial molar concentrations are given below at 0°C. RUN [A0] [B0] [co] Rt (M s“) 1 0.40 0.40 0.20 24 2 0.40 0.20 0.10 3 3 0.80 0.20 0.10 3 4 0.80 0.10 0.20 6 a) Determine the kinetic order (ie. the value of x,y,and z) for each reactant where Rate = k [A]x [B]y [C]1 b) Determine k at 0°C 57. 3/15": éfO-Zfljffl-lfijl ’ [é __ 5/1754 aawaz/‘f‘a sign number units "2 c) Given that the activation energy for this reaction is 100 kJ mol‘l, calculate the rate constant at 100°C -fy ,.. .. E - 4 A? / V 7" fl —- C ’ é; : fl 8. ’9 4 Emma; 2’52: zkfeéyiz. 2&4 £2- 3 f ’ / H" ' , x? 7" 7;. E s_igg number units A l .. 4% e ref/fl '7? 5%)] .—- ‘l I 3,, : /52& J“ _ L 2.02265U0 6 “I” [mm/.5153 ( 22* 3K 371)] ‘ )6. The high-temperature gas phase reaction , 2No(g> + 2mg) a mg) + 21‘120(g) W goes essentially to completion and obeys the kinetic rate law, M/ +d[N2]/dt = k[NO]2 [H2] at 820°C. may be used in your derivation. 2N0 # (NO); fast equil. ch=k1/k_] (NO)2 +H2 —) N20 + H20 810W N20 + H2 -> N2 + H20 fast (k3) 0/01/12] __ J H; ¢Aa M.¢ 1/230/ 4% _ éflwagyfl Joggdaé/JMVQ/Zflwéa I; [wait] = Kg [w c/[A/J: i 7. a) Give the mechanism of an enzymatic reaction that leads to the following rate equation. Explain the term [E], in the equation. gig} z kztE],[S] " k i d; k_l+l'c2 . ' / k1 5e? e7 55 rte—E”@ —/ [Eff .- 5 7L5; : éz/a/mz/u-WC @ . a ' w b) Show that when substrate concentrations [8} are large, the rate of formation of product/6, becomes zeroth order in substrate and likewise when [S] is small the rate with respect to substrate becomes first order. 49/2314 [5] IAS 42‘. [5] 7) 373/; .915 ; exam] : éfl; 14,” d? _ its} 23 flféfi‘fl' M [2‘7 wém [5] /% 5944M @ >2 [5] £23- c/PI baggy ~/; profit/HMS] 8. Explain how you could differentiate between the following pairs of molecules using the spectrosc0pic technique specified: 3) Using NMR: b) Using IR: #3}! c) Using any one of the spectroscopic methods discussed in CHEM 205: 'x" We??? W . if“ p (I . g f \ CH3CHZCH25§$w onscwc'ECHzczH3 ‘ n {2 e 5 2f - t K J Mi- ’ "h E r? I" ’7 4f 4‘ y l I / ,r l y? I 4 5M1- [jfiff 1: 4a H/W/f-flff’f ff” figs, /, (f? In {A L f“ “I I c” 'f‘ a: C’ If If f Eff} W 5;; g s 4929‘ fii/HPW* [email protected] ‘ 9‘ Refering to the spectra below, solve the structure. Provide a short analysis of the spectra {full credit will not be given for the correct structure without some analysis). Structure: 7“? . . iR Spectrum (mute film) 4000 3000 2000 1 1600 1200 300 V (cm' ) + . 100 | 4: EC!) : Cfi’c’é Mass Spectrum 80 g /I M .- 6 y- 50 E rqu No significant UV g I: M+l= 200mm“ absorption above 220 nm 40 E 20 1 I r‘ ; I CHHfiBr2 40 80 120 160 200 240 230 m/ e “C NMR Spectrum {100 0 MHz CDCIasolutron} DEPT cHzt CH31‘ CH? proton decoupled 200 160 120 80 40 0 5 (Wm) 1H NMR Spectrum two MHz. (inc:3 sotufion) BY (1; expansions ...
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This note was uploaded on 01/31/2012 for the course CHEM 205 taught by Professor Burnell during the Spring '07 term at The University of British Columbia.

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2003solutions - 1. (A) (B) (C) (D) (E) (F) (G) In each part...

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