Mid-year Examinations, 2017 Mopet CHEMt11-1781 (C) ANSWERS Family Name First Name ‘Student Number Venue ‘Seat Number No electronic/communication devices are permitted. No exam materials may be removed from the exam room. Chemistry EXAMINATION Mid-year Examinations, 2017 CHEM111-17S1 (C) Chemical Principles and Processes Examination Duration: 150 minutes Exam Conditions: Closed-book exam: Students may not bring in anything apart from writing instruments and calculators. ‘Any scientific/graphics/basic calculator is permitted Materials Permitted in the Exam Venue: None Materials to be Supplied to Students: 4x Write-on question paperfanswer book 4 x Scantron multi-choice sheet ‘This exam has one attachment: physical chemistry formula and periodic table Instructions to Students: Attempt all questions. This test paper is divided into two parts: PART A contains 50 multiple-choice questions, which are answered UC®8 UNIVERSITY OF CANTERBURY Te Whare Wananga 0 Waitaha Ginrsronunen New ZtAtanD For Examiner Use Only ‘Question Mark A B1 B2 B3 B4 BS Total by filling in the appropriate circle on the provided answer sheet IN PENCIL. Rough working can be done of Mee beck of the opposite sheet in the question book. Each multiple-choice question is worth 1 mark. PART B contains questions worth 75 marks. Answers are to be entered in the spaces provided in the question book (and continue on the back of the opposite sheet if necessary). Page 1 of 22Mid-year Examinations, 2017 CHEMI 11-1754 (C) BEFORE YOU ANSWER ANY QUESTIONS YOU MUST READ AND IMPLEMENT THE FOLLOWING INSTRUCTIONS: Step 1: Write your name and subject (CHEM111) at the top right of the multi-choice answer sheet. Step 2: Read the instructions about filling in your answers. POCHOOD Eta joosceseoo loo 0a e000 aes 902590000 Siaese Fr] |scesvoeons BH 719088000005 HEE 2099000 2804098 One ae oo oe {oes do] weoeoo] saeooe reeees| Jocese] goocee R29 HSGS) T19HOBO JO GOGH) BOoHHEE! ©6090] we oO @ &| 1G GOGO] WOHOHHB) HWOHOHS pie®@eaeoo® 10 6060| o006G] goeooo| waeeo0 196900] 9 GSE 0] go See O| 1/0 9 0 e 2 198008] BOGE HO B® HOGS) Be HOO 199660| 09000) Hooooe a[aecoo| Jo eee 0) woooOo) Haoeee u]a 9 @ oo} Step 3: Fillin your student ID number as both a column of digits and by filling circles, as instructed here. Page 2 of 22‘Mid-year Examinations, 2017 CHEM111-1781 (C) PARTA For each question, indicate your choice for the single correct answer by filling in the appropriate circle on the provided answer sheet. Each question is worth 1 mark. ‘The figures above illustrate four items of chemical laboratory equipment used by a student to dexrmine the molar mass of CaCOs according to the following steps. The equipment and the laboratory steps are the subject of questions Al ~ A10. @ A101 g sample of solid CaCOs was carefully transferred to vessel A. | (i) A solution of 0.1000 M HCI was carefully added to vessel A, causing the evolution of a gas, ‘which ceased after several minutes. ‘This solution was then made up to precisely 50. 00 mL by the addition of further 0,100 M HCI solution, and was then thoroughly mixed by shaking. (ii) 10.00 mL of the solution from vessel A was transferred to vessel C using device B. (iv) The excess HCL in vessel C was then titrated with 0.0250 M NaOH solution from D returning an average NaOH titre of 24.00 ml. from three concordant titrations. | Al, What is the name of item A? a) Burette b) Beaker (GYotumetre flask d) Conical flask. ‘A2, What is the name of item D? b) Pipette °) Measuring flask — d) Measuring tube 'A3, What was the gas evolved when the CaCOs and aqueous acid solution were mixed (step(ii))? a) HC] b) Ch oie Jo Page 3 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) |A4, The balanced equation for the reaction of HCI(aq) with CaCOx(s) (step (ti) is: a) HCI(aq) + CaCOx(s) > CaCl(aq) + HCO3(aq) (B)2 Hetaa) + CaCO18) > CaCh(aq) + COx(e) + H200) © 2HCI(aq) + CaCOs(s) > Cha(g) + CaHCOx(aq) 4) 2HClaq) + CaCOs(s) > CaClo(aq) + Ha(g) + COs(aa) |S, ‘The balanced equation for the reaction of HCI(ag) with NaOH(aq) (step (iv) is: @® HCI(aq) + NaOH(aq) > NaCl(aq) + H20() b)_2HCI(aq) + NaOH (aq) > NaCh(aq) + H20() c) 2 HCl(ag) + NaOH(aq) > NaCl(aq) + Ch(g) + #2001) @) 2 HCI(aq) + NaOH (aq) > NaCla(aq) + Ha(g) + OH@a) 'A6. How many moles of Hare there in 50 ml of 0.1 M HCl(aq)? 005 mol; b) 0.025 mol; c) 0.100 mol; 4) 0.002 mol AZ. According to the result of step (iv), how many moles of excess HI” were there in vessel C before the titration? a) 0.025 mol b) 0.125 mol ) 0.024 mol (@poovs mol [AS By what factor would you multiply your answer in A7 to determine the mumber of moles of in vessel A after step (ii)? a) 50 b) 1/50 ous (oy ‘Ad, Assuming that the number of moles of CaCOs was determined fo be 9.923 10 mol, what nould be the student's result (to four significant figures) for the molar mass of CaCOs? a) 99.1. g mol! ) 100.1 g mol" CO) 9 gmot? 4) 109.0 gmol" |A10, What isthe accepted value (to four significant figures) of the molar mass of CaCOs? a) 99.1 gmolt (oo 1 gmot! ©) 100.9 gmol 4) 109.0 gmol AIL, Fora reaction A(e) +2B(g) —> C(g) + D(e), which of the following expressions forthe reaction rate is definitely correct?” ate = df AVt (b) Rate =-a[Cyde (©) Rate = MATIB? (d) All of (a) to (€) above are definitely correct Page 4 of 22Mid-year Examinations, 2017 (CHEM111-1781 (C) ‘Al2. For three reactions occurring at 7’ = 300 K with the following thermodynamic parameters, which of the following statements is correct? Reaction AAP AS AG? A 300 kJ molt 200 Jmol! K™ 360 KJ mol B ~450 kJ mot -400 J mol! K7 330 kJ mol! Cc 350 kJ mol 400 J mot! Kt 230 kJ mol" (a) Reaction A has the greatest rate because it has the largest decrease of Gibbs energy. (b) Reaction B has the greatest rate because it is the most exothermic. (c) Reaction C has the greatest rate because it causes the largest increase of entropy. he listed thermodynamic data do not permit a decision as to which reaction is the fastest. ‘13, Which of the following is correct concerning the units of a rate coefficient? (a) no units (b) st (©) mol Ls @Yevends on the order of reaction |Al4, The first-order reaction A > P has a half-life of fi = 2.35 s. If [A]o = 0.1000 mol! L*, what will be the concentration of A after 6.43 s? (a) 0.0500 mol L!—(b) 0.0250 mol L* ©} 0150 mol L* (@) 0.0125 mol L* 2k{AP[B]. Which of the ‘AIS, Areaction 2A +B — Chas an empirical rate law given by d[AJ/dt following statements is most reasonable? (a) The reaction is definitely elementary. (b) The reaction is probably, but not definitely, elementary. (ne reaction is probably, but not definitely, complex. (a) The reaction is definitely complex. 'A16, Which of the following statements is typically correct for the rates of gas-phase reactions? (2) they increase with temperature; (b) they are much slower than the rates of collision between reactant molecules; (c) they increase with temperature much faster than collision rates; @m of the above. Page 5 of 22Mid-year Examinations, 2017 (CHEM111-1781 (C) Questions A17— A20 refer to a reaction that occurs in two elementary steps given below: Stepl1 A+B>C+D Step2. D+E>B AIT. For the overall reaction, which of the following reaction components is a reactant? ()B (wc (@D A18. For the overall reaction, which of the following reaction components js a product? @A ()B @r @D A19, For the overall reaction, which of the following reaction components is an intermediate? @A )B wc ‘A20. For the overall reaction, which of the following reaction components is a catalyst? (@A (b), (Cc @D A21, An exothermic reaction with A,S > 0 is: @atways spontaneous; (b) never spontaneous; (©) spontaneous only at low temperatures; (@ spontaneous only at high temperatures. A22, An exothermic reaction with ArS'<0 is: (@) always spontaneous; (b) never spontaneous; © @ spontaneous only at high temperatures. ontaneous only at low temperatures; ‘23, An endothermic reaction with A,S> 0 ist (a) always spontaneous; (b) never spontaneous; (©) spontaneous only at low temperatures; ©Ppontancous only at high temperatures. Page 6 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) A24, A25. A26. A27. A28. A29. ‘An endothermic reaction with Acs <0 is: (a) always spontaneous; never spontaneous; © spontaneous only at low temperatures; @ spontaneous only at high temperatures. ‘As temperature increases, the value of the Gibbs energy change for a reacti (a) increases; (b) decreases; (©) stays approximately constant; (@)my either increase or decrease. ‘The change of thermodynamic equilibrium constant, X, with temperature, 7, is given by: (@)ine van’t Hoff equation; (b) Kirehhof?’s law; (0) the Arthenius equation; (@) a van Gogh masterpiece. The slope of a plot of InK versus T' may be used to determine: the reaction enthalpy change, A:H; (b) the reaction entropy change, AcS; (©) the activation energy of reaction, Fs; (@) the frequency factor of reaction, A. ‘The intercept of a plot of InK versus 7"! may be used to determine: (@) the reaction enthalpy change, Ail ]@Yve reaction entropy change, Acs; (6) the activat energy of reaction, Ea; (d) the frequeney factor of reaction, A. For the reaction 2HI(g) —> Ha(e) + I(g) carried out at 298 K, the sign of the entropy change is: (a) positive; (b) zero; (©) negative; @Poor-zer0 but cannot be determined from the given information. Page 7 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) Question A30 — A34 relate to the following reaction system at equilibrium: Haq) + 402(g) = Hb(O2)a(aq) This represents the binding of oxygen to the protein haemoglobin, Hb, in red blood cells. 30, How does the system respond if Ar(g) is added at constant temperature and volume? (a) There is a net shift in the direction of the forward reaction. (b) Phere is no net change. (©) There is a net shift in the direction of the reverse reaction. (@) This cannot be decided without further information being given. A31. How does the system respond if Hb(aq) is removed at constant temperature and volume (of 0)? (a) There is a net shift in the direction of the forward reaction. (b) There is no net change. (c) Where is a net shift in the direction of the reverse reaction. (@ This cannot be decided without further information being given. ‘A32, How does the system respond if volume is increased at constant temperature and mass? (@) There is a net shift in the direction of the forward reaction. (b) There is no net change. (c) Where is a net shift in the direction of the reverse reaction. (d) This cannot be decided without further information being given. A33. How does the system respond if pressure is increased by adding Ox(g) at constant volume and temperature? @ here is a net shift in the direction of the forward reaction. (b) There is no net change. (©) There is a net shift in the direction of the reverse reaction. (@) This cannot be decided without further information being given. A34, How does the system respond if temperature is increased at constant pressure? (a) There is a net shift in the direction of the forward reaction, (b) There is no net change. ‘There is a net shift in the direction of the reverse reaction, ()ni cannot be decided without further information being given. Page 8 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) A35. A36, Which of the following is a correct statement of the third law of thermodynamics? (@) The entropy of a compound at zero kelvin is zero. (b) The entropy of a crystal at zero kelvin is zero. © rhe entropy of a perfect crystal at zero kelvin (@ The entropy of a perfect crystal is zero. Which of the following statements is both correct and related to the second law of thermodynamics? (a) The energy of an isolated system is constant. () The entropy of an isolated system is constant, @Oenerwy cannot, of itself, pass as heat from a colder to a hotter body. (@ None of the above Questions A37— A40 relate to a phase change (“pe”) for which Apel7 = +100 kJ mol and Tye = 100 K (under standard thermodynamic conditions). A37. A38, A39. Ad0. For the phase change at 100 K, what is the value, in J K' mo", of the entropy change of the system? @y1000 (+H (1 (@)-1000 For the phase change at 100 K, what is the value, in J K mot", of the entropy change of the surroundings? (a) positive (b) zero Oyezative (@) cannot say. For the phase change at 100 K, the Gibbs energy change of the system is: (a) positive; @rs; (c) negative; (@) cannot say. For the phase change above 100 K, the Gibbs energy change of the system is: (@) positive; (b) zero; Opezstives (@ cannot say. Page 9 of 22Mid-year Examinations, 2017 CHEM141-1781 (C) AAI. The chloride-water hydrogen bond is stronger than the water—water hydrogen bond because: (a) chloride has mote lone pairs of electrons than water; ion-dipole forces are stronger than dipole-dipole forces; (©) chloride ions are larger than water molecules; (@) chlorine atoms ate less electronegative than oxygen atoms A42. Which statement is true? (a) A colloid will quickly settle under gravity. Light is dispersed when passed through a colloid. (A suspension will completely pass through filter paper. (@ A solution contains larger particles than a colloid or suspension. A43, Which of the following statements is true? (a) The hydroxide salt of Mg” has greater aqueous solubility than the Ca** and Ba”* hydroxides. (b) The sulfate salt of Ba has greater aqueous solubility than the Mg” and Ca” sulfates, (re sulfate salt of Ba®* has lower aqueous solubility than the Mg”* and Ca** sulfates. (@) The hydroxide salt of Ba”* has lower aqueous solubility than the Ca®* and Mg™ hydroxides. A44, Which of the following correctly orders intermolecular interactions from the strongest to the weakest? (@) ion-induced dipole; ion — ion; ion — dipole. (b) ion induced dipole; ion — dipole; ion — ion. (c) ion—ion; ion — induced dipole; ion — dipole. (@)ion Bion ion — dipole; ion — induced dipole Ad5, Which of the following statements is correct? (a)_lon —ion interactions increase with increasing size of the ions. @ Ynduced dipole — induced dipole forces increase with increasing size of the molecules. (©) Ion ~ dipole forces decrease with increasing charge of the ion, (@ Anion cannot have an induced dipole. Page 10 of 22,Mid-year Examinations, 2017 CHEM111-1781 (C) Questions A46 — A50 relate to the titration curve below, which was obtained when a 50.0 mL sample ‘of a monoprotic acid HA, of unknown molarity, was titrated with 0.100 M NaOH solution, The pH of the resultant solution was measured with a pH meter and graphed as a function of the volume of NaOH solution added, pH VERSUS VOLUME TITRANT ADDED 14- 12; 10: iu 1 is T 12: 8 %, 4 2 0. 0.0 20.0 40.0 60.0 80.0 100. ‘Volume 0.100 M NaOH Added (mL) A46, At point T in the titration, which of the following species has the highest concentration? (HA (© Ho" (on ‘A47. Which of the following is the best representation of the species (other than H20) that are present in significant concentrations in the solution at point R in the titration? () () ® © le_ © © e| © © © @ 6) © @ A48. At which point on the titration curve is [A“] the same as [HA]? @R ©T @u Page 11 of 22Mid-year Examinations, 2017 CHEM111-17814 (C) A49, A student carries out the same titration but uses an indicator instead of a pH meter. If the indicator changes colour slightly past the equivalence point, what will the student obtain for the calculated concentration of the acid? (@) Slightly less than 0.080 M @: iightly more than 0.080 M (©) Slightly less than 0.125 M (@) Slightly more than 0.125 M A50. Which of the indicators listed below would be the best choice for this titration? Indicator pH range @ Thymol blue 12-28 ® Bromophenol blue 3.0-4.6 © Methyl red 42-63 | (a) resol red 72-88 | . | Page 12 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) PART B Answers are to be entered in the spaces provided (continue on the back of the opposite sheet if necessary). Question B1. (15 marks) A series of three experiments gave the following data for the reaction A(g) + 2B(g) > P at T= 298.2 K. Experiment | _[AJo (mol L™) [Bo (mol L) [Aho (molL) | -AfAyar — os ee 1 0.1000 0.1000 0.0997 [BO xl0"S mol L's“! 7 ged 2 0.1000 0.2000 oof Ie 2 10 mol LS : cen 3 0.2000 0.2000 0.1976 | Qe KID mol LS (a) [Aho is the concentration of reactant A after the reaction has proceeded for 10 s. What is represented by the parameter [B]o? (1 mark) | The cementation a) rea emt Bo at Ine beginnic 4 ot he yeachon — he. at tO (b) Calculate the values (including their units) of -A[AVAF over the period of the first 10 seconds of ‘each experiment and write those values into the right-hand column of the table above. (3 marks) Bip 1 ATA/At = — (0:0979=0-1000) mol L'a oy 107 10s poles — ATAV/AE = L200 x 107% mol b's-? Eph 2 Expt 3 CAEAD/BL = 240 K1* ool 9! (©) In what way do these -A[AJ/Af values relate to the rate of reaction? (1 mark) They veprerend (near echwedea ol Ine inihad | toler ah Tro veachons Page 13 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) (d) Determine the values of the following: (i) The order of the reaction with ee toA; (2:marks) Gace. Ke(caoecen | ioe ml Bales ~ Ye( 0.200)" (2007 = Duxore ~ > ore) (ii) The order of the reaction with respect to B; (2 marks) Raed _ Xe (10 F' (0.1009 _ (4)F Poni) Qakz ~ AK (o108% (0200)F pele u = p-2 (iii) The overall order of the reaction; (1 mark) wt B= 3 +hivel ovclow (iv) The value of the rate coefficient of oe reaction Gnctning i its units). (2 marks) Bale 1 = hlo-1000)* (01000)* mol? L-* hx 1O-Emol® Loe = 3-0 x10" S mot i s7 b= BOxID 10? LPmol se“! © B-Dx IO L? woh 5” > (©) When the temperature was increased from 298.2 K to 300.8 K, the rate coefficient of the reaction ‘was found to double. What is the activation energy of the reaction? (3 marks) | paws | _ Ea } . Se liscnw) ~ RK Czo0e~ ~ 299-2 loge (4) . owe (-2-294x107 #7) ad D> Ea * = Joge (Me) x BY Tool ° = 2. 24 IO” S = | = 4aS x 10> T mat Ses ey Page 14 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) Question B2. (15 marks) @ (>) onsider the following equilibrium: (5 marks) CaCOx(s) = CaO(s) + CO2x(g) (i) Write an expression for the thermodynamic equilibrium constant of this reaction, X, in terms of the equilibrium activities of the reaction components. (@ca059)! core)! G@eacoas))? K (ii) Write an expression for K in terms of the equilibrium concentrations and/or partial pressures, as appropriate, of the reaction components. PNesats TDA Desa t oF Tbar ‘This is since'w= 1 for (pure) Solids, The “1 bar must be ineluded to make clear the units of pcos! (iii) At 800 °C the above system is at equilibrium, The (partial) pressure of COs is 0.236 atm, What is the value of K? 236 aim x (1.013 bar/I atm) = 0,239 bar 239 bar/T bar = 0.239, Peoue) = Hence K NB. The inforination for atm to bar is on the “Physical Chemistry Formulae” sheet! ‘The following information refers to the indicated equilibria at a temperature of 25 °C. Na(e) + 40r(2) = N20(@) Ki=4.21 x10" Nal) + Ox(g) + NOx(e) Kr= 154 x 10% Use this information to calculate K for 2Nz0(g) + 302(g) # 4NO2() at 25 °C (4 marks) Reverse equilibrium (1) and multiply iby 2N20(g) = 2Ne(g) + Ox(@) Kr’ = (IIR) 5164 10% Multiply’ equilibritin (2) by 42 2Nx(e) + 402g) = 4NOx(e) Ka! = (Ka)* = 5.62% 104 ‘Add these up to obtain, as desired) 2N20(g) + 302(g) & 4NO2(@).-K= Ki? x Ka’ = (Ko) M(Ki)? = 3.17 10% ‘This is all using rules from lectures for manipulating K values! Page 15 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) (©) Ha(g), No(g) and NHs(g) are placed in a reactor at a particular temperature so that their partial pressures are initially 220, 140 and 20 bar respectively. ‘The equilibrium. 3Ha(g) + No(g) = 2NH3(e) is established at this temperature, at which point the partial pressure of hydrogen is measured to be 100 bar. Calculate the value of K, the thermodynamic equilibrium constant, at this temperature, (6 marks) Let x be the unit change in p in reaching equilibrium, Then: “Species Initial | Bqullibiuimp | Equilibrium p (bar) (bar) (bar) Tae) 220, P20= 3% 100 Nixa) 140 140-9 100 Nw) [20 20-28 100 ‘The third column follows from reaction stoichiometty! For Ha(g) at equilibrium: 100 bar = 220 — 31) bar = x= 40, ‘The final Goluinn of the table follows froin the third with x= 40 (see above)! For the given equilibrium’ K= (ns)? / [(ain)! Cans)! = (ene ll bar)? / [pu/l bar)? x (px! bar)! Using equilibrium p in this expression = K= (100)°/ [(100)* x (100)] = 1007 = 1 x 104 Comment: From the value of K il looks like equilibrium should lie a long way towards reactants. But in fact in this case there is production of NH, as desired, and the equilibrium is an even mixture of reactants and products. ‘This is because of the high pressures (consider Le Chatelier’s principle) and the mathematical nature of the expression for K. Note that this problem has used realistic values of p and K (See Page 16 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) Question B3, (15 marks) ‘A table of thermodynamic data is given below. All symbols have their usual meaning. Use this information in answering the following questions for the reaction (diamond) -> C(graphite) ‘Compound AdPae ‘Same _ (kJ mol! (JK mor!) C(graphite) 0 57 (diamond) H9 2.4 (a) Calculate A,S°209, the standard molar entropy change of the reaction at 298 K. (2 marks) ‘AvSP25u = S°20s(C(graphiite)) — S*0x(C(diamond)} 5 (8.7-2.4) JK! mol! = 43.30 Tol (b) Explain the meaning of the sign of your answer in (a) in terms of the structures of graphite and diamond. (2 marks) ‘AiS'is positive, which means that graphite has a less ortlered (or more disordered) structure than diamond, (©) Calculate Ar 1°29, the standard molar enthalpy change of the reaction at 298 K, (2 marks) WiEP2oe = AceP298(C(graphite)) — AcHPa9s(C(diamond)} = Oki mol (41.9 ki mol 19k) mol! (@ Calculate A:G?29e, the standard molar Gibbs energy change of the reaction at 298 K, (3 marks) AGPa9s = Ait? 08 Tx AS?a99 ==1,9 kJ mol! —298 K x (0.0033 kTK! mol 2.9 ki mol! Page 17 of 22Mid-year Examinations, 2017 CHEMI11-1781 (C) (©) _ Inthe light of your answer to (d), is C(diamond) -> C(graphite) spontaneous or nonspontaneous at 25°C? (1 mark) Spontaneous, because AG, <0, (That said, itis welll known from everyday life that diamond transforms into graphite so slowly at 25 °C that essentially “diamonds are forever”!) (f) Caleulate K, the thermodynamic equilibrium constant, for C(diamond) = C(graphite) at 298 K. (3 marks) Ke exp-aG[RT]) = exp(-[-2.8834 x 10° Jmol '/[8.314 J mol! K"! x 298 K]) = exp(l 16) Sa (g) Briefly discuss the state of the C(diamond) = C(graphite) equilibrium at 0K. (2 marks) ‘The process is exothermic, so K increases as T decreases, meaning the equilibrium will favour graphite more and more, ‘ALO K one has AG = Av/f, which is negative and finite, This creates the expectation of K'=1 and finite: But in fact K = exp-A,G°/[RT]), which for AvG° < 0 is positive and infinite at T= 0, and thus the reaction goes completely to graphite ‘The physteal reason for this is that the prevalence of order at 0 K results in a desperate need to create disorder. In the present ease this is achieved by evolving as much heat as possible, which means the system entirely existing as graphite. Inierms of'a van't Holf plot, 75 O means 1/7 Yeo, which means Ini rises to +20] (Comment? One learns from this discussion that a 0 K there iso chemical equifibritim: depending on the sign of Ail, K is either negative or positive infinity, and so a system is either all reactants or all products, respectively, in what will not be a dynamic state, Page 18 of 22Mid-year Examinations, 2017 (CHEM111-1781 (C) Question B4, (15 marks) 0 o1 18.2. 28.2 VraowlmL (a) The figure above shows the titration curve obtained (using a pH meter) when a 25.0 ml. solution of an acid, HA, is titrated with 0.200 M NaOH solution. (i) What is the pKa of HA? (1 mark) When [HA] = [A"], pH = pKa. Therefore, pK. = 5:30 (ii) Calculate the concentration of the original HA solution, (3 marks) Equivalence occurs at 18.2 mL. So, 0.200 Mx 18.2 = [HA] x 25! ‘Therefore, [HA] = 0.146 M iii) Calculate the pH at point A. (marks) [Ht PHA] = Ka iH# = (408 0.146)" 8.55 x 104 pH = —log[H*] = 3.07 Page 19 of 22Mid-year Examinations, 2017 (CHEM111-1781 (C) (iv) Calculate the pH at point D. (3 marks) [OH = (28.2 = 18.2) mL * 0.2 mol/L / (28.2 + 25) mL = 0.0376 M pOH = —log(0.0376) = 1.42 pH= 14-1425 12.58 (v) _Isthe pH at point C less than, greater than, or equal to 7? Explain why. (2 marks) Greater than 7, because the conjugate base (A-) of a weak acid will give a basic solution! (b) Explain what is meant by the term buffer solution. (2 marks) A solution which resists change in pH despite the addition of (small amounts of) acid or base! (© Write an equation for the reaction that occurs when a small amount of NaOH is added to an acetic acid/acetate (CHsCOOH/CH3COO >) buffer solution. (1 mark) CHsCOOH + OH" ——> CH3COO- + HO Page 20 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) Question BS, (15 marks) (@) Explain, using a diagram, why water is more dense than ice. (3 marks) ‘At low temperatures, hydrogen bonding between water molecules constrains them into ‘an open 3D lattice structure that contains a lot of empty space. A typical six-membered ring is shown below: (b) Whats polarizability? (1 mark) The distortion of an electron cloud caused by an electric charge! (© Explain why larger atoms are more polarizable than smaller atoms. (2 marks) The orbitals are larger and so the electrons are further away from the nucleus and so they are more easily influenced by a charge, (® Describe how a non-polar molecule can induce a dipole in another molecule? (2 marks) A non-polar molecule can have a temporary (instantaneous) dipole (as a result of electron motions), This dipole can then polarise.a nearby molecule! Page 21 of 22Mid-year Examinations, 2017 CHEM111-1781 (C) (@) Below isa table of water solubilities for compounds X, Y and Z. Compound | Water solubility ‘Name of compound (gL at 25°C) i x 0.15 Ethylbenzene Y 3.00 Benzoic acid Z Fully miscible | Agetone ‘The names and structures of the compounds are below (not in order): HO. oO A HC’ ‘CH Benzoic acid Acetone Ethylbenzene (i) Identify X, Y and Z by their water solubilities and write their names in the right-most column of the table, 3 marks) (ii) Explain why compound Z is the most water soluble, (2 marks) Bécalise itis Small, polar, and a hydrogen-bond acceptor. ii) Explain why compound Y is much more water soluble than compound X. (2 marks) Because it is able to form many hydrogen bonds with water (both hydrogen bond donor and acceptor) and also forms ionic species (benzoate) which are very polar and are strong hydrogen bond acceptors. o End of Examina Page 22 of 22