INSTRUCTOR'S SOLUTIONS MANUAL TO ACCOMPANY ‘ — 7 —> - A ATKINS’ PHYSICAL CHEMISTRY 220: 200 PETER ATRINS « CHARLES TRAPP MARSHALL GAD = CARIMEN GUINTA,INSTRUCTOR'S SOLUTIONS MANUAL TO ACCOMPANY ATKINS’ PHYSICAL _ CHEMISTRY . - Eighth Edition P. W. Atkins Professor of Chemistry, University of Oxford and Fellow of Lincaln College C. A. Trapp Professor of Chemistry, University of Louisville, Louisville, Kentucky, USA M. P. Cady Professor af Chemistry, Indiana University Southeast, New Albany, Indiana, USA C. Giunta Professor of Chemistry, Le Mayne College, Syracuse, NY, USA OXFORD UNIVERSITY PRESSOXFORD UNIVERSITY PRESS Great Clarendon Street, Oxford OX2 6DP Oxford University Press is a department of the University of Oxford. It furthers the University’s objective of excellence in research, scholarship, and education by publishing worldwide in Oxford New York Auckland CapeTown Dares Salaam Hong Kong Karachi KualaLumpur Madrid Melboume Mexico City Nairobi New Delhi Shanghai Taipei Toronto With offices in Argentina Austria Brazil Chile Czech Republic France Greece Guatemala Hungary Italy Japan Poland Portugal Singapore South Korea Switzerland Thailand Turkey Ukraine Vietnam Oxford is a registered wade mark of Oxford University Press in the UK and in cerdain other countries Published in the United States by W.H. Freeman and Company, New York © Oxford University Press, 2006 The moral rights of the authors have been asserted Database right Oxford University Press (maker) First published 2006 All rights reserved. No part of this publication may be reproduced, stored in a retricval system, or transmitted, in any form or by any means, without the prior permission in writing of Oxford University Press, or as expressly permitted by law, or under terms agreed with the appropriate reprographics rights organization. Enquiries concerning reproduction outside the scope of the above should be sent to the Rights Department, Oxford University Press, at the address above You must not circulate this book in any other binding or cover and you must impose the same condition on any acquirer British Library Cataloguing in Publication Data Data available Library of Congress Cataloging in Publication Data Data available Typeset by Newgcn Imaging Systems (P) Lid., Chennai, India Printed in Great Britain on acid-free paper by Ashford Colour Press Ltd, Gosport, Hampshire ISBN 0-19-928857-7 978-0-19-928857-1 13579 108642Preface This manual provides detailed solutions to all the end-of-chapter (b) Exercises, and to the even-numbered Discussion Questions and Problems. Solutions to Exercises and Problems carried over from previous editions have been reworked, modified, or corrected when needed. The solutions to the Problems in this edition rely more heavily on the mathematical and molecular modeling software that is now generally accessible to physical chemistry students, and this is particularly true for many of the new Problems which request the use of such software for their solutions. But almost all of the Exercises and many of the Problems can still be solved with a modern hand-held scientific calculator. When a quantum chemical calculation or molecular modeling process has been called for, we have usually provided the solution with PC Spartan Pro™ because of its common availability. In general, we have adhered rigorously to the rules for significant figures in displaying the final answers. However, when intermediate answers are shown, they are often given with one more figure than would be justified by the data. These excess digits are indicated with an overline. We have carefully cross-checked the solutions for errors and expect that most have been eliminated. We would be grateful to any readers who bring any remaining errors to our attention. We wanrmly thank our publishers for their patience in guiding this complex, detailed project to completion. P.W. A. C. A. T. M.P.C. C.GContents PART 1. Equilibrium 1 The properties of gases Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 2 The First Law Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 3 The Second Law Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 4 Physical transformations of pure substances Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 21 21 21 32 32 38 42 47 47 49 56 56 62 69 73 73 73 76 76 80 82 5 Simple mixtures Answers to discussion questions Solutions to exercises Solutions to problems Solutions te numerical problems Solutions to theoretical problems Solutions to applications 6 Phase diagrams Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 7 Chemical equilibrium Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical! problems Solutions to theoretical problems Solutions to applications PART 2 Structure 8 Quantum theory: introduction and principles Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 84 84 84 91 91 97 98 102 102 103 109 109 114 114 118 118 119 128 128 138 139 145 147 147 148 152 152 154 159viii INSTRUCTOR'S SOLUTIONS MANUAL 9 Quantum theory: techniques and applications 161 Answers to discussion questions 161 Solutions to exercises 162 Salutions to problems 169 Solutions to numerical problems 169 Solutions to theoretical problems 170 Solutions to applications 180 10 Atomic structure and atomic spectra 184 Answers to discussion questions 184 Solutions to exercises 185 Solutions te problems 192 Solutions to numerical problems 192 Solutions to theoretical problems 194 Solutions to applications 199 11 Molecular structure 203 Answers to discussion questions 203 Solutions to exercises 204 Solutions to problems 207 Solutions to numerical problems 207 Solutions to theoretical problems 220 Solutions to applications 221 12 Molecular symmetry 226 Answers to discussion questions 226 Solutions to exercises 226 Solutions to problems 230 Solutions to applications 236 13 Spectroscopy 1: rotational and vibrational spectroscopy 239 Answers to discussion questions 239 Solutions to exercises 239 Solutions to problems 249 Solutions to numerical problems Solutions to theoretical problems Solutions to applications 14 Spectroscopy 2: electronic transitions Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 15 Spectroscopy 3: magnetic resonance Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 16 Statistical thermodynamics 1: the concepts Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 17 Statistical thermodynamics 2: applications Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 249 258 260 268 268 269 273 273 275 276 278 278 279 286 286 290 29) 294 310 310 311 317 317 321 32618 Molecular interactions Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 19 Materials 1: macromolecules and aggregates Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications - 20 Materials 2: the solid state Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications PART 3 Change 21 Molecules in motion Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems 330 330 331 334 334 336 339 342 342 344 347 347 350 353 361 361 362 37] 371 378 382 387 389 389 390 400 400 Contents Solutions to theoretical problems Solutions to application 22 The rates of chemical reactions Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 23 The kinetics of complex reactions Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 24 Molecular reaction dynamics Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications 25 Processes at solid surfaces Answers to discussion questions Solutions to exercises Solutions to problems Solutions to numerical problems Solutions to theoretical problems Solutions to applications ix 406 410 413 413 414 42] 42] 428 432 439 439 440 443 443 446 449 455 455 456 463 463 468 472 475 475 AT7 487 487 497 499PART 1 EquilioriumDi.4 D1.6 E1.1(b) The properties of gases Answers to discussion questions The partia! pressure of a gas in a mixture of gases is the pressure the gas would exert if il occupied alone the same container as the mixture at the same temperature. It is a limiting law because it holds exactly only under conditions where the gases have no effect upon each other. This can only be true in the limit of zero pressure where the molecules of the gas are very far apart. Hence, Dalton’s law holds exactly only for a mixture of perfect gases; for real gases, the law is only an approximation. The critical constants represent the state of a system at which the distinction between the liquid and vapor phases disappears. We usually describe this situation by saying that above the critical temperature the liquid phase cannot be produced by the application of pressure alone. The liquid and vapor phases can no longer coexist, though fluids in the so-called supercritical region have both liquid and vapor characteristics. (See /mpacr 1.4.1 for a more thorough discussion of the supercritical state.) The van der Waals equation is a cubic equation in the volume, V. Any cubic equation has certain properties, one of which is that there are some values of the coefficients of the variable where the number of reai roots passes from three to one. In fact, any equation of state of odd degree higher than I] can in principle account for critical behavior because for equations of odd degree in V there are necessarily some values of temperature and pressure for which the number of real roots of V passes from #1 (odd) to |. That is, the multiple values of V converge from # to 1 as T — T,. This mathematical result is consistent with passing from a two phase region (more than one volume for a given T and )9) to a one phase region (only one V for a given T and p and this corresponds to the observed experimental result as the critical point is reached. Solutions to exercises (a) The perfect gas law is pV = nrkT implying that the pressure would beE1.2(b) E1.3(b) E1.4(b) 4° INSTRUCTOR'S SOLUTIONS MANUAL All quantities on the right are given to us except n, which can be computed from the given mass of Ar. 2 - n= _— 28 = 0.626 mol 39.95 g mol! 0.626 mol) x (8.31 x 1072 dm? bar K7! mol! 273 K = sop= mol) x ¢ x — mol” ') x (30+ 27 )_ 10.5 bar dm not 2.0 bar. (b) The van der Waals equation is LRT a Vm -b V2 _ (8.31 x 107? dm? bar K7™' mol!) x (30 + 273) K P= “G53 dm? /0.626 mol) — 3.20 x 10-2 dm? mol (1.337 dm®atm mol~?) x (1.013 bar atm7!) —oaeeeree Or =| 10.4 bat (1.5 dm? /0.626 mol)? P= (a) Boyle’s law applies: pV =constant so prV¥r = piv; and pe¥p (1.97 bar) x (2.14 dm?) (= = _—— =| 1.07 bar PTV (2.14 + 1.80) dm3 [1.07 bar] (b) The original pressure in bar is 1 atm 760 Torr p, = (1.07 bar) x (aes) x (a) =| 803 Torr 1 atm The relation between pressure and temperature at constant volume can be derived from the perfect gas law Pj Pf V =aART so «xT and — = — P Pp T, T; The final pressure, then, ought to be pitt (125kPa) x (11+ 273) K = A = So =| 120 kPa | PE Tj (23 + 273) K [120 kPa] According to the perfect gas law, one can compute the amount of gas from pressure, temperature, and volume. Once this is done, the mass of the gas can be computed from the amount and the molar mass using pV =nrkT pV (1.00 atm) x (1.013 x 10° Pa atm™’) x (4.00 x 107 m3) RT (8.3145 J K—'mol7!) x (20 + 273) K and m = (1.66 x 10° mol) x (16.04 g mol~!) = 2.67 x 10°g =| 2.67 x 10? k g = |.66 x 10°molE1.5(b) E1.6(b) E1.7(b) THE PROPERTIES OF GASES 5 Identifying pex in the equation p = pex + egh [1.3] as the pressure at the top of the straw and p as the atmospheric pressure on the liquid, the pressure difference is P — Pex = ogh = (1.0 x 10° kg m7?) x (9.81 ms~) x (0.15 m) =| 1.5 x 10? Pa} (= 1.5 x 107? atm) The pressure in the apparatus is given by P = Pam + gh [1.3] Pam = 760 Torr = 1 atm = 1.013 x 10° Pa Lk 6 3 pgh = 13.55 gem-3 x (LKB), (IPE) x o.100m x 9.806 ms7? = 1.33 x 10° Pa 103 g m? p= 1.013 x 10° Pa + 1.33 x 107 Pa = 1.146 x 10° Pa =| 115 kPa All gases are perfect in the limit of zero pressure. Therefore the extrapolated value of pV,/T will give the best value of R. The molar mass is obtained from pV = ART = ght RT RT which upon rearrangement gives M = ass p— V p P The best value of © is obtained from an extrapolation of p/p versus p to p = 0; the intercept is M/KT. Draw up the following table p/atm (pVmn/T)/(am* atm K-!mol~!) (p/p)/(dm7 atm!) 0.750 000 0.082 0014 1.428 59 0.500 000 0.082 0227 1.428 22 0.250 000 0.082 0414 1.427 90 Y From Figure 1.1(a), (Ce) —| 0.082 061 5 dm? atm K~! mol7! p=0 /(dm? atm K~! mol ! 2 pV a 107 eH Figure 1.1(a)E1.8(b) 6 INSTRUCTOR'S SOLUTIONS MANUAL From Figure 1.1(b), (2) = 1.42755 gdm? atm-! p=0 Figure 1.1(b) M =RT (2) = (0.082 061 5 dm? atm mol~! K~') x (273.15 K) x (1.42755 g dm~2atm7!) p=0 = | 31.9987 g mol™! The value obtained for R deviates from the accepted value by 0.005 percent. The error results from the fact that only three data points are available and that a linear extrapolation was employed. The molar mass, however, agrees exactly with the accepted value, probably because of compensating plotting errors. The mass density p is related to the molar volume V,, by where M is the molar mass. Putting this relation into the perfect gas law yields M pVm =RT so -—=RT p Rearranging this result gives an expression for M; once we know the molar mass, we can divide by the molar mass of phosphorus atoms to determine the number of atoms per gas molecule RTp _ (8.314 Pam? mol7!) x [(100 + 273) K] x (0.6388 kg m~*) po 1.60 x 104 Pa = 0.124 kg mol7! = 124 g mol7! The number of atoms per molecule is 124g mol7! ———— . = 4.00 31,0 ¢ mol! suggesting a formula ofTHE PROPERTIES OF GASES 7 E1.9(b) Use the perfect gas equation to compute the amount; then convert to mass. _ pv V = nRT iO => P n sO on RT We need the partial pressure of water, which is 53 percent of the equilibrium vapor pressure at the given temperature and standard pressure. p = (0.53) x (2.69 x 10° Pa) = 1.43 x 10° Pa (1.43 x 10° Pa) x (250m*) (= (8.3145) K7! mol~!) x (23 + 273) K or mt = (1.45 x 10° mol) x (18.0g mol7!) = 2.61 x 10° 2 =| 2.61 kg E1.10(b) (a) The volume occupied by each gas is the same, since each completely fills the container. Thus solving for V we have (assuming a perfect gas) S07 = 1.45 x 10% mol nyRT 0.225 2g VY = — "ne iN =“ Py 20.18 g mol7! = 1.115 x 107? mol, pne =8.87kPa, T = 300K ve (1.115 x 107? mol) x (8.314 dm? kPa K~! mol7') x 300 K) 8.87 kPa = (b) The total pressure is determined from the total amount of gas, 7 = wen, + Mar + Ne. = 3.137dm? 0.320 g - 0.175 g RCH, = ————_ = 1.995 x 10-7? mol wap = ———*=— = 4.38 x 107? mol 16.04 ¢ mol~ 39.95 g mol™ n= (1.995 + 0.438 + 1.115) x 1072mol = 3.548 x 1072mol nT 8) (3.548 x 1072 mol) x (8.314 dm? kPa K~! mol7!) x (300 K) y= — |. SO I V 3.137 dm? - [a E1.11(b) This is similar to Exercise 1.1 1(a) with the exception that the density is first calculated. RT M — p—— [Exercise |.8(a)] p _ 33.5mg ? = 350cm! py = C1840 8 dm™) x (62.36 dm’ Torn KR mol) * 298K) _ 116 14.9 mol! 152 Torr E1.12(b) This exercise is similar to Exercise [.12(a) in thal it uses the definition of absolute zero as that temperature at which the volume of a sample of gas would become zero if the substance remained a gas at low temperatures. The solution uses the experimental fact thal the volume is a linear function of the Celsius temperature. = 0.13402 dm~?, p=152Torr, FT = 298K8 INSTRUCTOR'S SOLUTIONS MANUAL Thus V = Vo + aVo@ = Vo +60, b =aVp At absolute zero, V = 0, or 0 = 20.00 dm? + 0.0741 dm? °C7! x @(abs. zero) 20.00 dm? @ (abs. zero) = — > = | —270°C | ( ) 0.0741 dm? oc! [-270°C] which is close to the accepted value of —273 °C, HRT E1.13(b} (a) p= Vv n= 1.0mol T = (i) 273.15 K; Gai) 500K V = (i) 22.414 dm’; (ii) 150cm? @ (1.0 mol) x (8.206 x 107? dm? atm K7! mol7!) x (273.15 K) p=-2 rr? v\vVv''" 22.414dm° - [10am] (ib _ (0 mol) x (8.206 x 107? dm? atm K7’ mol7!) x (500 K) pe 0.150dm3 = (2 significant figures) (b) From Table (1.6) for H2S a = 4.484 dm® atm mol”! b = 4.34 x 1072 dm? mol! _ net an ~~ Vonb ¥2 w _ (1.0 mol) x (8.206 x 107? dm? atm K7! mol7!) x (273.15 K) - 22.414 dm? — (1.0 mol) x (4.34 x 10-2 dm? mol7!) (4.484 dm® atm mol7!) x (1.0 mol)? (22.414 dm3)° = Gi (1.0 mol) x (8.206 x 1072 dm? atm K~! mol7') x (500K) i me 0.150dm? — (1.0 mol) x (4.34 x 10-2 dm? mol7!) (4.484dm%atm mol”) x (1.0 mol)? (0.150 dm?) = 185.6atm * (2 significant figures). E1,14(b) The conversions needed are as follows: latm = 1.013 x 10° Pa; | Pa=Ikgm7!s7*; 1dm®=10-%m°, Idm? =107? m*THE PROPERTIES OF GASES 9 Therefore, a = 1.32 atmdm® mol~ becomes, after substitution of the conversions a =} 1.34 x 107! kg m°s~?mol-? |, and b = 0.0436 dm? mol! becomes b =14.36 x 1075 m3mol7! E1.15(b) The compression factor is 7= PVm _ Vn RT ve (a) Because Vm = V2, + 0.12 V2 = (1.12) V9, we have Z = forces dominate. (b) The molar volume is V = (1.12)¥9, = (1.12) x (=) 0.08206 dm? atm K~! mol7!) x (350K V = (1.12) x (ce | =[2.7 4m? mol"! 12 atm RT — (8.314) K~' mol™!) x (298.15 K) p (200 bar) x (105 Pa bar!) = 1.24 x 1074 m3 mol~! =| 0.124 dm? mol! (b) The van der Waals equation is a cubic equation in Vn. The most direct way of obtaining the molar volume would be to solve the cubic analytically. However, this approach is cumbersome, so we proceed as in Example 1.4. The van der Waals equation is rearranged to the cubic form RT b RT b va (b+) va+(2) w- 2 =0 or o- (642) 24(2)x-2 <0 p p p p p p with x = Vin/ (dm? mol~!). The coefficients in the equation are evaluated as E1.16(b) (a) yo = m (8.206 x 1072 dm? mol™!) x (298.15 K) R b+ = (3.183 x 107? dm? mol!) + Bp (200 bar) x (1.013 atm bar—") = (3.183 x 1077 + 0.1208) dm? mot! = 0.1526 dm*mol7! 6 -2 a 1.360 dm® atm mol — = 6.71 x 10-3(dm? mot~!)2 P = (200 bar) x (1.013 atm bar™") ab (1.360 dm® atm mol~*) x (3.183 x 1072dm? mol!) = 2.137 x 1074(dm? mol7!)* (200 bar) x (1.013 atm bar") Thus, the equation to be solved is x° — 0.1526x? + (6.71 x 1074)x — (2.137 x 1074) = O.10 INSTRUCTOR'S SOLUTIONS MANUAL Calculators and computer software for the solution of polynomials are readily available. In this case we find x=0.112 or Vg =|]0.112dm) mol™! The difference is about 15 percent. E1.17(b) The molar volume is obtained by solving 2 = pVm/AT [1.17], for Vm, which yields ZRT __ (0.86) x (0.08206 dm? atm K~! mot!) x (300K) = 1.059 dm? mo!7! p 20 atm mn — (a) Then, V = nVm = (8.2 x 10-3 mol) x (1.059 dm? mol~!) = 8.7 x 10-3 dm? =[8.7 om? | (b} An approximate value of B can be obtained from eqn 1.19 by truncation of the series expansion after the second term, 8/V,), in the series. Then, V B= Vm (SP = 1) = Vn x Z— 1 = (1.059 dm? mol!) x (0.86 — 1) =| —0.15 dm3 mol! E1.18(b) (a) Mole fractions are Nn 2.5 mol = — = ————_ = 0.63 NT nol (25+ 1.5) mol Similarly, xy = (b) According to the perfect gas law Piotal ¥ = Mora RT MoalRT Y (4.0 mol) x (0.08206 dm? atm mol~! K~!) x (273.15 K) 22.4dm> SO Pigul = (c) The partial pressures are PN = XNPtor = (0.63) x (4.0atm) = and py = (0.37) x (4.0atm) = E1.19(b} The critical volume of a van der Waals gas is Vo = 3b sob= iVe = (148 cm? mol!) = 49.3cm3 mol~! =| 0.0493 dm? mol™! By interpreting b as the excluded volume of a mole of spherical molecules, we can obtain an estimate of molecular size. The centers of spherical particles are excluded from a sphere whose radius is theTHE PROPERTIES OF GASES = 11 diameter of those spherical particles (i.e. twice their radius); that volume times the Avogadro constant is the molar excluded volume 5 4 3 b \'8 pam (222) wo rad (4) 1/3 l 3(49.3 cm? mol! =~ ae sen ne = 1.94 x 1078 cm =] 1.94 x 107! m 2 \ 47(6.022 x 1023 mol!) The critical pressure is _ a 276? so d = 27p.b? = 27(48.20 atm) x (0.0493 dm? mol~!)? =| 3.16 dm® atm mol7? But this problem is overdetermined. We have another piece of information Pe _ 8a ~ 27Rb6 c According to the constants we have already determined, 7, should be 8(3.16 dm® atm mol~*) Te = 57(0,08206 dm? amK-! mol-) x (0.0493daP mols) 27(0.08206 dm° atm K~ mol™') x (0.0493 dm" mol”) However, the reported 7, 1s 305.4 K, suggesting our computed a/b is about 25 percent lower than it should be. E1.20(b) (a) The Boyle temperature is the temperature at which limy,od2/(d(1/Vm)) vanishes. According to the van der Waals equation RT a —— - — | Va P¥im _ Vm —5 Va _ Vin a RT RT Va—-b VaRT dZ (<2) ( dVin o —-—- = | -—- | x | ——__— d(1/Vin} dVin dd/Vin) dZ >f -Vm a = _y2 —__ =-V- SE ———_. —— m (a) m (a — be Va b ae) _ Vb a (Vn — 6)? ORT Z= 5 In the jimit of large molar volume, we have dz lim —“ =p-4 =9 gs “4 =p Vm 700 d(1/Vin) RT RT 4 (4.484 dm® atm mol?) and T= — = —[1259K Rb (0.08206 dm? atm K7! mol—!} x (0.0434 dm? mol—')12. INSTRUCTOR'S SOLUTIONS MANUAL (b) By interpreting 6 as the excluded volume of a mole of spherical molecules, we can obtain an estimate of molecular size. The centres of spherical particles are excluded from a sphere whose radius is the diameter of those spherical particles (i.e. twice their radius); the Avogadro constant times the volume is the molar excluded volume & 4n(2r)> lf 3b \'8 b= Na 3 0 T= 3 GaN 1/3 1 { 3(0.0434dm° mol~’) _9 10 r= - (eee) 1.286 x 10-8 dm = 1.29 x 107! m = [0.129 nm| 2 (aac x 1073 mol!) E1.21(b) States that have the same reduced pressure, temperature, and volume are said to correspond. The reduced pressure and temperature for Nz at 1.0 atm and 25 °C are 1.Oat T (25+273)K P atm _ 9.030 and T= Ea Ot? _ 156 Pe 33.54aim Ty 126.3K The corresponding states are (a) For H2S P = PrPc = (0.030) x (88.3 atm) = T = 7,;T, = (2.36) x (373.2K) =| 881K (Critical constants of HzS obtained from Handbook of Chemistry and Physics.) (b) For CO? P = Pec = (0.030) x (72.85 atm) = T = T,Te = (2.36) x (304.2K) =[718 K {c} For Ar P = PrPc = (0.030) x (48.00.atm) = T = TT; = (2.36) x (150.72 K) =| 356 K E1.22(b) The van der Waals equation ts RT a P= which can be solved for 5 RT a = 4.00 x 107* m? mol! — ye 40 108+ ( =| 1.3 x 10-4 m3 mol! (8.31453 K7!mol7!) x (288K) 0.76 m® Pa mol~2 (4.00 x 10-4 m3 mol7!)? b=Van —-P1.2 THE PROPERTIES OF GASES 13 The compression factor is V, 4.0 x 10° Pa) x (4.00 x 1074 m3 mol! _ P¥m _ (40 x 10"Fy x CO ne _ RT (8.31453 K—! mol7!) x (288 K) Solutions to problems Solutions to numerical problems Solving for n from the perfect gas equation [1.8] yields n = pV/RT and n = m/M, hence p = in/V = . . . RT p RT RT Mp/RT. Rearrangement yields the desired relation, that is| p = o—— |, or — = —_, and M = —— M p M P/p Draw up the following table and then plot p/p versus p to find the zero pressure limit of p/p where all gases behave ideally. p/(gdm7*) = p/(kg m*); 1 atm 1.013 x 10° Pa | Torr = (1 Torr) x x | —————— } = 133.3Pa 760 Torr | atm p/Torr 91.74 188.98 277.3 452.8 639.3 760.0 p/(104 Pa) 1.223 2.519 3.696 6.036 8.522 10.132 p/(ke m73) 0.225 0.456 0.664 1.062 1.468 1.734 (p/p) (104 m2 s~*) 5.44 5.52 5.56 5.68 5.81 5.84 P is plotted in Figure 1.2. A straight line fits the data rather well. The extrapolation to p = 0 yields an p intercept of 5.40 x 104 m*s~*. Then _ RT _ (8.314) Ku! mol!) x (298.15K) ~ 5.40 x 104m? s-? 5.40 x 104m? s~? = 0.0459 kg mol~! =| 45.9 g mol! (pip)! 104m s-!) pi(10" Pa) Figure 1.2P1.4 P1.6 14. INSTRUCTOR’S SOLUTIONS MANUAL COMMENT. This method of the determination of the molar masses of gaseous compounds is due to Can- nizarro who presented it at the Karlsruhe conference of 1860 which had been called to resolve the problem of the determination of the molar masses of atoms and molecules and the molecular formulas of compounds. The mass of displaced gas is oV, where V is the volume of the buib and a is the density of the gas. The balance condition for the two gases is #(bulb) = pV (bulb), m(bulb) = o’V (bulb) which implies that 9 = 9’. Because [Problem 1.2] p = pM/RT the balance condition is pM = p'’M’ which implies that M’ = 2 x M p This relation is valid in the limit of zero pressure (for a gas behaving perfectly). In experiment 1, p = 423.22 Torr, p’ = 327.10 Tor; hence , 423.22 Torr — =e 70.014 1-' = 90.59 ! 327.10Ton ~ gmo &mo In experiment 2, p = 427.22 Tor, p’ = 293.10 Torr; hence , _ 427.22 Torr = x 70.014 I~! = 102. 17! 293.10 Ton * emo Ogmo In a proper series of experiments one should reduce the pressure (e.g. by adjusting the balanced weight). Experiment 2 is closer to zero pressure than experiment 1; it may be safe to conclude that M = 102 g mol7! |. The molecules | CH2FCF3 | or| CHF2CHF |have M * 102g mol7!, We assume that no H2 remains after the reaction has gone to completion. The balanced equation is No + 3H: — 2NH3 We can draw up the following table No H> NH, Total Initial amount n nv 0 n+n Finalamount »— su 0 inl n+ sa Specifically 0.33 mel 0 1.33 mol 1.66 mol Mole fraction 0.20 0 0.80 1.00 RT 8.206 x 107% dm? atm K~! mol7! 273.15K eS a - [166 am] 22.4dm4 p(H) = x(H2)p = [0] p(N2) = x(No)p = (0.20 x (1.66atm)) = p(NH3) = x(NH3)p = (0.80) x (1.66 atm) =