Name: a Date: Exam A Chem 401 Unit 1 Exam: Thermodynamics & Kinetics (Nuss: Fall 2012) Mattiple Choice Identify the choice that best completes the statement or answers the question. (3 pts each) 1. Which of the following statements regarding spontaneous changes is false? a. Spontaneity is favored when heat is released. b. Spontaneity is favored when the dispersal of matter is increased, ©. Spontaneous changes occur at a given state without any outside influence. d.__Iee melting at 25°C is spontaneous primarily due to the increase in molecular disorder (dispersal of matter). 2. Which one of the following reactions has a positive entropy change? pacer BF3(g) + NH3(g) > FsBNHx(s) 2S0,(g) + Ox(g) + 2SOx(2) Nz — 2NHx INH, NOss) > 2N(@) + 4H,0(8) + Ox@) a Foto ons mal porticles 9 # mal particles 3. Consider the conversion of a substance from soli to liqui. Solid <> Liquid tone atmosphere pressure and at the melting point of the substance, 0 for the process AS = 0 for the process AB=Ofortheproeess true during equilibrium includling phase changes both AiT=0 and AE=0 for the process process cannot be spontaneous (product fvored) if ie Serpe eae tae ae ie it is endothermic, and there is an increase in disorder it is exothermic, and there is a decrease in disorder a ainapy oft waves Gees papge> 5. Which of the following expressions does not represent a proper expression for the rate ofthis reaction? ad: 2A +3B > F+2G ~alA] alr] -a[Al *( Bat rang & Fat =A[B] ALG] Sat “ 2At6. 10. 1D: A AB} In the following reaction the rate of change of reactant B, overall rate of the reaction at this time? A+3B— AB; a b. ©. -0.30 mol/L+s d. 2.7 mol/Les ©. 0.22 mol/Les A hypothetical reaction X + 2Y —> Products is found to be first order in X and second order in Y, What are the units of k, the specific rate constant, if reaction rate is expressed in units of moles per liter per second? di Ms! ec Mls Which statement is incorrect? a. The reaction rate for a zero-order reaction is independent of concentrations. b. Che specific rate constant for a second-order reaction is independent of temp ©. The half-life fora first-order reaction is independent of initial concentrations, 4. The rate law expression relates rate and concentration, e. The integrated rate equation relates time and concentration, ure, Which idea listed below is not a part of the collision theory of reaction rates? a. Molecules must be properly oriented when they collide to react. b. Molecules must collide to react. c. Molecules must collide with enough kinetic energy to overcome the potential energy stabilization of the bonds. Effective collisions result in a chemical reaction. : Consider the hypothetical reaction shown below. 2A+G > AC+C ‘Assume that the following proposed mechanism is consistent with the rate data, A + G—-ACHC slow AC + A>AC fast DAE C= WALCLEG! overall Which one of the following statements must be true? The reaction is___. Ne ata ‘b, second order in C; é d. second order in C;, zero order in A’ e. second order in A and first order in C2Name: u 13, 4 WD: A ‘A reaction has an activation energy of 40 ki/mol and an overall energy change of reaction of -100 k/mol. In euch of the following potential energy diagrams, the horizontal axis is the reaction coordinate and the vertical axis is pofential energy in kJ. Which potential energy diagram best describes this reaction? 100 0 “0 b, a Which of the following statements regarding the rate constant in the rate law expression is incorrect? fa, Its value increases with increasing temperature. . Its value is independent of initial concentration at a given temperature. Its units depend on the overall order of reaction. : b. larger molecules collide more frequently c. the energy of the transition state is lowered d. the activation energy is decreased ce. (@greater fraction of molecules possess the activation energy when they collide A student analyzed a first-order reaction and obtained the graph below. Unfortunately the student forgot to label the axes. What are the correct labels for the X and Y axes? ~~, a. m b. K=time, Y= WAT ©. X=time, Y= In(/[AD a. X=Iime, Y= [A] e X=Nam ____ 15, Given the following mechanism: 16. 17. 18, AYC>AC step 1 BHAC>AB+C step? A+B AB overall ACisa: a. catalyst ¢. transition state complex b. Cfeaction intermediate) d. coordination compound ‘The rate constant for the first order reaction A > B+ C is k=3.3 x 10? min at $7 K, What is the half-life for this reaction at 57 K? a. 21min for Ist order reactions b. 30min ec Up tnd, 0.92 ~ almin ©. 1200 min fe 3.3.x 10 Yin Given the following data for the NH," + NO» —> Nz + 2H;0 reaction Trial___ (NEL) (NOs) Rate T0010M 0.020 0.020 is, 2 0.020M 0.020 =— 0.040 Mis By 0.010. M 0.010. 0.005 Mis ‘The rate law forthe reaction is T#alé Wwo2 InmytSdoubleS 5 ig order ‘a, rate = K{INH,"][NO2] rate doubles rate = KINH,*}[NO>] Tals Ive 3 CNDZ] doubles > gad order b. d. “rate = MINH,"P[NOy rode PYX ‘e. None of the above Evaluate AS” for the reaction below at 25°C and 1 atm, 3NOg) + H,O(6) > 2HNOs(aq) + —NO(g) S°(Jimol*K) 240 69.91 146 210.7 2 4137x108 UK AS * [Ded (NUT nd KY + mal (AIOAT/nal-K) | — 8 oe [Beal (240 Tonal: ES + lool (1.91 T/mod KY] Ke = S024 T/k - 439.9) T/k 4Name: IDA 19. For the following reaction at 25°C, AHP = -26.88 kJ and AS® = 11.2 J/K, Caleulate AG? for the reaction at 25°C inkilojoules. §— 25"C % AS+atB= AIWKelvin k@+CH > 2) AEs AY-TAS a. 307K 7-26.88 ks -|(aIBkYo.011aKs/K), b. +506 KF 8 k ra x re] 30.22 KF 4-26. 8BKI- 3.3376 KT 27.1645 ___ 20. Evaluate the specific rate constant for this reaction at 800°C. The rate-law expression is rate = A[ NOP[Ha} (Choose the closest answer.) + 2NOg) + 2Hs(g) > (8) + 2H.0(@) using His Experiment Initial [NO] Initial [H,] __Initial Rate of Reaction (Mss) pee ma\aee) T 0.0010M 0.0000M 7.9% 107 a 2 0.0040M —0.0060M = 1.2.x 105 and ann 3 0.0040. M 0.0030 M 64x 104 expert meat: a 22M%st ZX used experiment #1 b cone, F.9X107 M/s =e (0.0010m)~ (0.0060m) 6 0.82.M2s1 Bax 10? Wis > R(G.0x10 7m?) ; eg = fear ve e. 0.024 Miss Bee B9x107 m/s yyy zeigt y Lexis Goxigt ms ‘Completion (2 pts each) Complete each statement 21 2 23 24, pathway or ‘A catalyst works by changing the oct vation energy. for a reaction. ‘A reaction whose rate law can be written directly from the stoichiometric coefficients of the reaction must be an) _elementory reaction. ‘The third law of thermodynamics states that at zero Kelvin, the entropy of a pure cyrstal equals 2¢ro . A(n) Cx nee reaction is a spontaneous reaction.Name: ‘True/False (2pts each) Indicate whether the statement is true or false, F__ 25. Foratypical substance, AS of fusion (melting) is expected to be greater than AS of vaporization. F__ 26. Anclementary step involving a colission between two particles is a dimolecular step. T_ 27. The entropy at standard states is greater for CHsCH,CH; than it is for CHy, Short Answer 7 sat! 54 28. ‘The reaction SF, -» SF; + Fzhas the following rate law: rate = 0.011 mol ISP. paced How many minutes will it take for the concentration of SF1o be reduced frafn 2.5.M to 0.25 a (4 pts) om ee oe (o.onyey + = ead y= (o.0nXe) fee 3.62 (6.01 Ltd be ae — 2 3B secant x dala. S.lis4S nn >]5.5minl aca Celsivs 29, Estimate the boiling point®f tin(IV) chloride, SnCl, at one atmosphere pressure: (4pts) SnCl,() ‘SnCl(g) For SnCl,(1), AH® = -511.3 ki/mol, S° = 258.6 I/molK, and for SnCl,(g), AH? = -471.5 ki/mol, S* = 366 J/molK at 298 K. ac briling point ASvap? Seq - Seay 7 366 ASB.6 107.4 T/mol- D Hye * AH Ca) ~ DW ee—y? (HHS )C-SI-3)* +39-B KT/mo! Tyap= AHvap 2 34.8 ¥T/mo! =B7BGK BSvap 0.10744 KT /mal-K 370.UK -293.15 = 934 9ID: A 30, Fora particular reaction at 25°C, AHP = -297 ki/mol, and AS” = -113.3 Jimol*K. a) At w hob temperature, would the reaction switch between being spontaneous and nonspontaneous’ (3 pts) b) Would it be spontaneous above or below that temperature? (1pts) a) set 8670 7DH-TAS &) Sece AH is OD Gena aB KT pulse and SISO a oe The reaction would bE usat lower 297 cae = (TY ous fe xs Spontaneous at |e temperatures. cae an0eat| *OUalk 0.1133 KS/mdl alz.uzx10*k 31, Calculate AG? at 298 K for the reaction below. (5 pts) Fe0s) + 13CO() > 2Fe(CO)(g) + 3COx(g) AE? (S/o) 824.2 “110.5 “733.8 393.5 S (imolK) 874 197.6 445.2 213.6 - 2648.4 dMHee 2] Smol(-3435 ES /mol) + anal (7433.3 k3/mal)] > L leno) (-Ba4.a lex fmol + 1S mol (“110.5 FT nell] = 387.4 KT ~AQwOt 4D Spon >] 3rol(ais.s/mal-e) + Amol (YYS-2 T/mat-K)\ — 1. tenet (93.49 fmol: ke) # 13 mol (197-6 T/mal: KD) BG= OH-TOS = -BB2 YRS — (adekYA-lasog /K) > “B8RUKS + 835. askr Sl aSoalsika >Esaxs|Name: 32 Based on the data below, what are the average rates of change of [02] and [NO>] over the interval 285 to 1175 seconds for the reaction 2NO(g) + Ox(g) > 2NO3(g)? (4pts) Time(s) | [NO] [02] [NO] 0 0.1000 M_| 0.01000M | 0.0000 M 285 | 0.0090M | 0.0095M | 0.0010M 1175 | 0.00070M | 0.0085M | 0.0030M 33. Extra Credit (5pts) 34. “4s -S0o— Men Paes) -6.0 5 ‘Average Rate of Change of 0; = (0.0085 M~ 0.0095’) (1175s -A853)~ 0.00/09 ~) 115 S905 3 Average Rate of Change of NO: = (0.0030m= 0.00 10 mY(i17Ss- ABSS> 79020 sg axiHtnp (Cor =2 rate 2), ‘The specific rate constant, k, for a reaction is 0.44 s at 298 K, and the activation energy is 245.kJ/mol. Calculate k at 398 K. (5 pts) 1 ~ee sorties ene, hk) El Eas Ao Ba An (0.44) = -C245 000T/mst) [+ eral (8.3113 /mat-k) Bek oe fates - (-0.821) = ~ ag%08 K (0.002573 K' -0.003356K") 7729468 K (-0.c00843K"'D ay seca Anke 7 ABS -— 0.82) = 24.02 e,* oe .[aa x10 Ss A student measured the rate constant of a reaction at two different temperatures. At 30°C k = 0.00150M"s" AL78°C k= 0,00674M"'s1, Sketch an Arthenius plot for this data set,and estimate Fo SO free) frees = Ge) & [ene _Bv_|303 |0.00330 |e. 001sv |-@.sd | #8 _|397 |o-ov0a3s 0.0 ety | -S.00 i i x-axis axis aeeil soaea a slope eee Ea/R a Ew = (8333(8.314) = ItF!/ BI/mol (CK 7 23KT/mol ovag 00.29 0030 +0033, po33