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    26 views19 pages

    Atkins, Physical Chemistry - Chapter1

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    Gwanyun Jeong
    Chapter1 solution

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    of 19
    l The properties of gases p12 Dus E110) Anewere to disoussion questions ‘The partial pressure of a gasin a mixture af gases is the pressure the gas would exert if if ocen alone the same container as the mixture at the same temperature. Dalton’s law is a limiting law because it holds exactly only under conditions where the gases have no effect on 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 cxactly 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 vapour phases disappears. We usually describe tis situation by saying that above the critical temperature the liquid phase cannot be produced by the application of pressure alone. The liquid and vapour phases can no longer cosa, although supercritical fluids have both iquid and vapour characteristics ‘The van der Waals equation is a cubie equation in the volume, V: Every cubic equation has some values of the coefficients for which the number of real roots passes from three to one. In fact, any equation of state of odd degree m > I can in principle account for critical behaviour because for equations of odd degree in V there are necessarily some values of temperature and pressure for ‘which the number of real 1ovts of ¥ passes fiom 1 to 1. That is the multiple values uf F converge from m to 1 as the temperature approaches the critical temperature. This mathematical result is consistent with passing from a two-phase region (more than one volume for a given T and p) to a ‘one-phase region (only one ¥fora given Tand p), aud this cossesponi to the ubserved experimental result as the critical point is reached. Solutions to exercises (a) The perfect gas aw (1.8) is pV=nRT implying thatthe pressure would be RT. E120) 1.246) E1Aib) ‘All quantities on the right are given to us except n, which can be computed from the given mass of Ar 288 39.95 5 mol 0.626 mot (0.628 mo) x 6.3110 *dm? bar K mek) x(30+273K) _ 16 F pq] 15am poses] not 2.0 har (b). The van der Waals equation [1.21] is (G31 x 107 dun? bar Kt mol“) x 0+ 273) K (1.5 den'/0.626 mol) ~ 3.20 x 10 dm mol (1.337 dmé atm mol) x (1.013 bar atm) (5 dm5/0.626 mol)? (a) Boyle’ law [1.5] applies. pV =constant so p= pV, This equation can be solved for either initial or final pressure, hence pel _ 0.97 bat) x(2.14dm") K (2.14 + 1.80) dm? 07 bar] (b) The original pressure in Torr is p,~(1.07 bar) x{ —18_),.{ 700 Tor) _ Feo Fore Tors bar )“(> Vatm The relationship between pressure and temperature at constant volume can be derived from the pertect gaslaw, pV =nRT (1.8) so peT and Bak mill) TT The final pressure, then, ought to be ‘pT, _ 02S kPa) x(11+273) K t (23+ 273) K i 120 kPa| Bs According to the perfect gas aw [1.8], one can compute the amount of gas from pressure, tempera ture, and volume pV enRT PY _(.00atm) x (1.013 10! Pa atm!) x (4,00 x 10m) aT (3145) K mol) x (204273) K = 1.66 x 10° mol 1.5(b) 51.60) E170) ‘Once this is done, the mass of the gas can be computed from the amount and the molar mass sn = (1.65 x 10° mal) x (16.04 g mal!) = 2.67 x 10*g = [2.67 x10 kg] Use the equation for hydrostatic pressure [1.3],p=p.+ gh. Letp., be the pressure atthe top of the strave and p is the pressure on the surface of the liquid (atmoepheric pressure). Thus, the pressure difference is Ug {ten me (EB) ~earmeyxc015m P~ Pa pgh= (LO gen = [£50 a] =1.5 x10-%atm, The pressure iu the apparatus is given by P~ Poot pBh [13] hese pa,= 760 Torr = 1 ate 13x 10° Pa, and pgh=13.55 gom-x| 1) < 10's Lom i0?m ) xoat0mx3s00ms*=139.10'F (P= 1013 10" Pa + 1.33 x10" Pa = 1.146 x 10° Pa = [115 kPal BY _ PY or T Rearrange the perfect gas equation [1.8] to give. All gases are perfect in the limit of zero pressure. Therefore, the value of pV Textrapolated to 7er0 presaure will give the beat valuc of R. ‘The molar mass can be introduced through w= WRT = 5 RT mR _ RT which on rearrangement gives a = vp Pe ‘The best value of Ais obtained from an extrapolation of plp versus p to zero pressure; the intercept is MIRE Draw up the following table: plat (p¥ gl TyKdue atm K mol") (piped? aten *) 0.750000 0.082,0014 1.428 39 0.500000 0,0820227 1.42822 0.250000 _0.0820414 1.42790 (02067 dnd ate KT mol From Figure 1.1(a), (4) ply) P=-7.99 x 10% + 0082082 aw Fosse P 5 | oexco | — 4 O01 02 03 04 08 06 oe isa Figure 1.1(a) 142887 pip = UO01SF88p + 1.92798 1486: 3 14284 joss 18278: { 14276: ac 14274 or 02 Ws ve oy 08 plan Figae 110) From Figure se,(2) 1.42755 gam" aun", wn (0.082062 dan’ atm K~ mol") x (273.15 K) x (142755 ¢dm”atm™) 31,9988 g me ‘The value ohtained for R deviates from the accepted value by 0.005%, better than can be expected from a linear extrapolation from three data points 1.8) The massdensity ois related to the molar volume ¥., bv VV mM nm np E19) 1.1006) where Mis the molar mass. Putting this relationship into the perfect yas law [18] yields p¥a=RT so PM T 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, Tp _ (8.3145 Pa m' mol) x {(100 +273) K] x (0.6388 ke m”) ? 1.6010" Pa = 0.124 kg mot ‘The number of atoms per molecule is 24 mol! suggesting a formula of [P,] Use the perfect gas equation {1.8} to compute the amount; then convert to mass: py Ven nate p¥=nRT so n= 2 ‘We neod the partial pressure of water, which is $3% of the equilibrium vapour pressure atthe given temperature and standard pressure. (We must look it up in 2 handbook like the CRC Handbook of Chemistry and Physics or another resource such as the NIST Chemistry WebBook.) p=(0.53) x (2.81 x 10*Pa) = 1.49 x10" Pa (1.49 x 10°Pa) x (250 m) G3145 TK mol") x 23+ 27K 72x10 g= [2.72 ks 80 =151 mol and m=(I51 mol) x (18.0 g mol (@) 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) RT m v We have the pressure of neon, so we focus on it 3821.13 x10 mol ‘mol! _ L113 10 mol 8.3145 Pa m? Kot 300 K B87 10°Pa 7 = 3.14107 m?=[5.14 dm (©). The total pressure is determined from the total amount of gas, 1'= Neu + Mu + ne 03208 16.04 g mol = (1.993 + 0.438 + 1.113) x 10 mol = 3.55 x 10? mol Poe 1.995 x10 mol 38 x10" mol 3.55 x 10 mol x 8.3145 Pa m?K! mot! x 300 K 3.14107 ane po Eg = [Baron - Pazera E1.14(0) This si to Exercise .11(a) with the exception that the density must first be calculated: Mz oAE (exercise 8¢a)) Bsxit’e, (Won 230 em? SSF )-o0steae (0.134 g dm) x (62,36 dm Lore KI mol") x (298 K) _ = 152 Torr 164g mol E112(0) This exercise is similar to Exercise 1.12(a) in that it uses the definition of absolute zero as that tem- perature 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 that the volume isa near function of the Celsius temperature: V=Vq+a0, where Vq=20.00dm? and a= 0.0741 dm?°C* Atabsolute zero, V=0= Va 20.00 dm? a 007éidm°C Vi+a6 so 6(abs zero) = Which is close to the accepted value of -273°C. ART E119) (@) p= 0.8) 0 mol) x (0.08206 dm? atm mol! K-!) x (273.15 K) 0 ee a [Eat Gy po G2 mol > (0.08006 do asm mel) (800K) _ rea sie gues EER eer eee. emer Cece nRT__ an? ©) p= PAE - Fenty From Table (1.6) for HS, a= 4.484 dm atm mol" and b= 0.0434 dtm? mol" jy p= dda x 0.08206 den’ atm mol K-9) 273.15 K) (P7244 dm? (1.0 mol) x 4.34% 107 dm mol) (4.484 dm* atm mol”) x (1.0 mol)? — (484 dm atm mol) <(.0 mol’ _ 95a @alsem'y (pass) £0 mol) x (0.08206 dm atm mol-!K-!) x ($00 K) 10.150 den? (1.0 mol) x (4.34 x 10-* drm? mol") __ (4484 dom atm mol") > (1.0 mol)? _ (0.150 am"? wp 90 atm] (sig. figures) ‘The conversions needed are as follows: 1 atm= 1,013 x 10" Pa, 1 Pa=1 kg mrs, 1 dm*=(10~' m)*= 10m, 1 dm?= 10 m* Therefore, a =1.32atm dm mot? x L013 x 1kg ws, Lome atm dm = [1.34107 kg m? s? mol) 10° m* and b=0.0426 dm* mal 26x10 mmol dim ‘The compression factor is (@) Because V, 2.+0.12V5=(1.12)¥ 3, we have Z =[112] [Repulsive] forces dominate. (b) The molar volume is veqinrz=d 1ayx( 82) P ¥~isyx{ Qokenbee am mer) 50K) = 27 dm mot" Tain @) ve RE_ 63145) K-!mol) (298.15) a (200 bar) x (10° Pa bar=!) = 124x104? mot'=(0.128dn mor] (b). The van der Waals equation is a cubic equation in V,. The most direct way of obtaining the molar volume would be to solve the cubic analytically. However, this approach js cumbersome, so ‘we proceed as in Example 1.4. The van der Waals equation is rearranged to the cubic form robe spn Bon wo fett fl with x= V,/(dm’ mor’. E4470) 1.1810) ‘The coefficients in the equation are (0.08206 dm’ atm mot! K-!) x (298.15 K) (200 bar) x (1.013 atm bar) 0.1527 dm? mol” 5D -cs9s10°am ery» = (3.19 x 107+ 0.1208) dm! mol @___1.364dméatm mol? Braraeee QOD bar) x (L013 atm barsy 7673 10° dt mot ab _ (1.364 dati mol?) x (3.19 «10 dm? mol) _ 5 145 19-<4mn? mol? P (200 bar) x (LO13atm bar“) Seer ‘Thus, the equation to be solved is x°— 0.152722 + (6.73 x 10°)x ~ (2.148 x 10~) Calculators and computer software for the solution of polynomials are readily available. In this case we find x=0.109 and Va=[0,109 den! m ‘The difference is about 15%, ‘The molar volume is obtained by solving Mo P¥o (1.17), for Va, which yields Zar U1 Th for Van which yi ZRT _ (0.86) x (0.08206 dm? atm mo!” K~!) x (300K) > spam 08 dm* mot" (@) Then, V = n¥q= (8.2 X10~ mol) x (1.08 dan’ mot) =8.7 x 10-+dm*= [87 em (©) Anapproximate value of B can be obtained from eqn I.19b by truncation of the series expan- sion after the second term, B/¥, inthe series Then, | .08 dn mol) x 0.86~ 1) = [£0.15 dint mor Vax(Z-0 (2) Mole fractions are yp agje 25001 —25mel___ 19g ot G54 15 mol OS Similarly, x= [0.37] (©) According to the perfect gas law Poa =touiRT —_MaarRT _ (4.0 mol) x (0.08206 dm’ atm mol! K) x (273.15 K) 8p dm (®) The partial pressures are Po = XPuc™ (0.63) x (4.0 atm) =[2-5 atm] and p_=(0.37) x (4.0 atm) =[1 Sain] 11.19(0) The critical volume of a van der Waals gasis ¥.= 35 $(148 cm? mol-!)= 49.3 cm? mol"'= {0.0493 dm’ mo! Dy interpreting b asthe excluded volume of a mole of spherical molecules, we ean obtain an esti- mate of molecular size The centres of spherical paricies are excluded from a sphere whose radius isthe diameter of thoxe spherical particles (twice their radius): that volume times the Avogadro constant is the molar excluded volume _ y (amare rotf_3)P sem(S52) » (ze) 1f_x493em*mok) Yo 4. ge x Br a The critical pressures p.= 3S 80. a= 27p.b*= 27(48.20 atm) x (0.0493 dm* mol}! = [3.16 dm atm mor But this problem is overdetermined. We have another pieve of information: 8a 27RD According to the constants we have already determined, 1, should be 8(3.16dm°atm mol?) FI(O0R206 den? atm enol KI) w (0.0493 den mol) 1K However, the reported T, is 305.4 K, suggesting that our computed a/b is about 25% lower than it should be, (a) The Boyle temperature is the temperature at which Jim lim Saray Vasishes. According to the van der Waals equation (7 BV Rr a __(oz) ( aq a0iY,) Vy)” (Sarr). (%)- val dv _ Vib a “Uo RT E4216) 1.220) In the limit of lazge molar volume, we have (0.08206 atm moi" K~) x (0.0434 dia’ mol") (©) Asin Excreise 1.1%b) Aa w (222) uy 7 1 30.0434 don’ mol!) 4(6.022 > 10 moi) 9 x10 °dm = 1.29 x10 m =(0.129 am] States that have the same reduced pressure, temperatuse, and volume arc said to cortespond. The reduced pressure and temperature tor Nat 1.0.atm and 25° are 10am T_(5+27)K -2. 0.030 and 7, = 2 = SLIDE 9561.24, aie 1.3 P73 Shoe 713K C | The corresponding states are (@) Forks P= Bebe= (0030) x 88.3 atm) ~ [2.6 ata T=T,T,= (2.36) x (373.2 K) = [881K] (Critical constants of H,S obtained from CRC Handbook of Chemistry and Physics.) (b). For CO, P~ P= (0.030) x (72.85 atm) = [2.2 atm] T= TT, (2.36) x (304.2K)=[718K| (© PorAr = p.pe= (0.030) x (48.00 atm) = [4 au T =.= (2.36) x (150.72 K) = [356K] ‘The van der Waals equation is RT # p.2ib) which can be solved for b be vg-—BE = 400 x 1o-n mor - —@-3145 1K" mot!) 288K) = doc tme eat) rn G00xi0 a mor yr = [13x104m mol 2 ‘The compression factor is (4.010 Pa) (4.00 10mm? mol”) _ Pha 7) er 171°" @ 31457 K\mol)x@88K) Solutions to problems Solutions to numerical problems Solving forn trom the perfect gas equation [1.8] yields x. From the definition of molar mass 2, nease p— % —MP. Reacrangement yields relationship, name! PE vemep 7 MP. Rearangement ils the desiedratonship, namely Therefore. fr idea gases 2 = SF and M = EF. For rel gases find the zero-presure limit of £ by plotting it against p. Draw up the following table, Bear in mind that 1 kPa= 10° kgm! s% itkPa) 12.223 25.20 36.97 3785.23 1013 ite 3) 0s 0.456 0.664 1.062 1.468 174 ple 543 $53 58.7 568 58.1 584 10 Fis plotted in Pigure 12. A straight ine fits the dato rather well The extrapolation top = Oyiclds an intoreopt of $4.0% 10° ms, Then, Ma BP___ (6.3145 1 K- mol) (298.15 K) Saux 10 ms SAO x1 ms = 0.0459 kg mot” =[45.9 g m¢ 594 pip 0.0K +540 58 fossnnnnnsnnninn eo ¢ 2% z Bx st 3 * 0 >» © @ OO pops) Figure 12 Pia pis. COMMENT, This method of the determination cf the molar masses of gaseous cempounds is due to ‘Cannizairo, whto presented it atthe Kersrune conterence of 1860, which had been called to esolve the problem ofthe determination of the molar masses of atoms and molecules and the molecular forms of ‘compounds. ‘The mass of displaced gas is pV, where Vis the volume of the bulb and pis the density of the gas. ‘The balance condition for the two gases is (bulb) = pY(bulb, m (bulb) = ff M(oulb) s Because [Problem 1.2] p= 2M, the balance condition is pM=7'M", which ‘which implies that ich implies that a implies that M’= 2 x af. ’ This relationship is valid in the limit of zero pressure (for a gas behaving perfectly) In experiment 1, p = 423.22 Torr, p’ = 327.10 Tore. Hence, 423.22 Torr 327.10 Torr 70.014 g mol"'= 90.59 g mol“! In experiment 2, p=427.22 Torr, p’= 293.22 Tom hence, 427.22 Torr a = REZ TOF 79.014 g mol" 293.22 Tor : In a proper series of experiments one should reduce the pressure (eg. by adjusting the belanced ‘weight). Experiment 2is closer to zero pressure than experiment 1,80 itis more likely to be close to the true value: 102.0 g mol" [M’ = 102 g mol ‘The molecules CH,ECF, and CHF,CHF; have molar mass of 102 g mot" ‘COMMENT, The substantial dference in molar masa betwoon the two exporiments ought lo make us wary ‘of confidenty accepting the result of Exzerment 2, even fits the more tkely estimate, ‘We assume that no H, remains after the reaction has gone to completion. The balanced equation is, N,+3H,2.NH,. Wecan draw up the following table: ™ H, NH, Total Initial amount v0 nen Finalamount oo n-ty’0Bt ned Specifically 0.33mol —0——1.33mol_—_ 1.66 mol Molefraction 0.20 0080 1.00 18 naz TR (008206 eon’ atm mol" K-) x(Z/3.19K)) _ EET 1-0 nays oem as AFL) = a(Ht)p =[9] PAIN, = x(N;)p = 0.20 x 1.66 atm =|0.33 atm) PANE) = (Np =0 80x 1.66 m= [13am From the definition of Z {1.17} and the virial equation [1 19b], Z may he expressed in virial form as EE, hence on substitution and dropping terms Since V,= 22 assumption of perfect gas . A Rr beyond the second power af 4 ze aE) E) Zale Ta 102dnemat9 100 wit (0.08206 dix aim mol K7) x 273K), 100 atm } Seer were xO Z =1- (0.0968) + (0.0239) = [0.927] raeosrnx| 2 ) scons ooetantamac sat} x091) 100 aim Wan ‘Question. What is the value of Z obtained from the next approximation using the value of V, just calculated? Which value of Zs likely to be more accurate? Since #'(T4)=0 atthe Boyle temperature [Section | 3b], B'(y)=a + be™74=0 i i “1K 01936 yl (0.7002 bar ) (aay ey Ss jekds( 22% GR} Ay be solved for from the expression Forze and vite 2 } 50x10) Solving tor Ty: 2) (20) From tases 77.=(2)x( 34), P16 mm eli) GI) 210K] By interpreting b as the excluded volume of a mole of spherical molecules, we can obtain an esti- mate of molecular size. The centres of spherical particles are excluded from a sphere whose radius is the diameter of those spherical particles (i. twice their radius); that volume times the Avogadro constant is the molar excluded volume b v3 paw, {3820 1f_3 ant se rsa lar, (x9 J renter 2\ 4x(6022 x10? mo) 0138 an] igen avetoten- Solutions to theorctical problems ‘Substitute the van der Waals equation [1.21] into the definition of the compression factor [1.17] ar Beets 12000) mdoncapasiomot {1 ele ME) ‘We note thar all erms beyond the sevoud ate necessarily postive, so only if tf) RIV, Vn Yn) 6 can Z beless than one. If we igaore terms beyond 7, the conditions are simply stated as Zei when Ze>b Z>1 when ge 1 when size effects (short-range repulsions) predominate, ‘The Dieterici equation is RT [Table 1.7] 18, Atthe critical point the derivative of p with respect to ¥, equal zero along the isotherm defined by TT. This means that (@p!@V..)r = 0 and (@2p/@V 2)-=0 at the critical point a) _ fuvanab~ RIV We) R= DRD | (-2aV 3+ 4 ,ab + RTV3=2ab%) Wy (3) (#) {see eem ne I, A VV RTI WE), (Wale | 0a-XRT) Setting the Dieterici equation equal tothe critical pressure and making the two derivatives vanish at the critical point yields three equations: _ Riles Vnb ~2aV 2+ AV.ab + REV }~2ab?= & . uF, = ab REV 2=0 Solving the middle equation for T., substitution of the result into the last equation, and solving for ¥, yields the result Vin2b or b= V2 (The solution V,= 6 is rejected because there isa singularity in the Dieterici equation at the point ¥._=6.) Substitution of ¥,= 2b nto the middle equation and solving for 7, gives the result MOR or a=2RT.V, Substitution of ¥,=26 and 7, /AbR into the first equation gives ¥, ‘The equations for ¥, T,, p. are substituted into the equation for the eritical compression factor 11.23) t0 give 2e*= 0.2707 ‘This is significantly lower than the critical compression factor that is predicted by the van der Waals equation, Z,(vdW) =p, VJRT, = 3/8 = 0.3750. Experimental values for Z.are summarized in Table 1.5, where it is seen that the Dieterici equation prediction is often better. He <4 Bp eCipt [194 i aa BE Bi a VR [L19b Thus, B+ Cpe Multiply through by V,, replace pV, by RT{1 + (BIV,) + --},and equate coefficients of powers of UV 4.20 pr2z DBRT + CRT? v BRT Hence, B’RT'= B, implying that Also, BB'RT + CRT? = C= B+ CR: 2, implying that| Write V=/(7.p), then dV, ( oe) are| (3) « Restricting the variations of T’and p to those that leave V, constant, that is d¥,~ 0, we obtain (2)-A G2, ‘From the equation of state = (B)-# Substituting Ven) | va | KYate RYE My af), (WyRT Mat OT) VE)” VyRT +2087) From the equation of state, a+ 67 = TV 5 m ( OF RVR4 BV OT)” WRT +2pVi- 2RIV Fan where V5, = the molar volume uf a perfect gas From the gen eguationof state noe BE pany 2 10h, we have 10b= b+, so V2, = 96, 105 fio Then, 2 = 10? 2/9 1 WZm gy alg Hl P12 ‘The virial equation is a= are =t a 19] or ae Vo {@) If we assume that the series may be truncated after the 2 term, then a plot of have Rasits slope and 1 asits IMPs Fa/(dm' mol) —_(1/¥M(mol dm) 0.4000 6.2208 0.1608 0.5000 4.9736 0.2011 0.6000 4.1423 0.2414 0.8000 3.1031 0.3223 1,000 2.4795 0.4033, 1,500 1.6483 0.6067 2.000 1.2328 0.8112 2500 0.98357 1.017 3.000 0.81746 1.223 4.000 0.60998 1.639 intercept. Transforming the data gives DVa/RT 0.9976 0.9970 0.9964 0.9952 0.9941 0,912 0.9885 0.9858 0.9832 82 DigiRE=-0O1324Vq 0.99308 | 0.995. 7 Josef Of A & i B 0985 fons oss. 7 oars. 002 04 06 a8 1 12 ‘4 16 19 (Vp Man0t a0) Figure 130) Tuedata are plotted in Figure 1.3(a). The data fia straight live wasonably well, nd he yi is very close to 1. The regression yields 2 ~[-1.324x107dm? mol". wept (b) A quadratic function fits the data somewhat etter (Figure 1 3(h)) with a slightly hetter cor- ‘elation coefficient and a y-intercept closer to 1, This ft implies that truncation of the virial series aller the term with Cis more accurate than atter just the B term. The regression then yields 1 BY alRT = 0.001060, 0015037, 0.99996 Pat : avs 98 fosnegunsn 7 ors: 0 02 04 06 o8 1 19 14 48 18 (uve am) Figure 1.3(6) B=[1503x10%dm* mort] and C= [1.06 x 10%dm’mol* Solutions to applications ‘The perfect eas law is p= mRT a iil RT At mic-latitudes p~ {0 atm) x {(1.00 dm?) (250 x 10° emy/10 em a ~ [1232107 mol] (0.08206 dm?atm Ki mol-!) x 73K) In the ozone hole (1,00 atm) x {(1.00 dm?) > (100 » 10 em)/10 em dime i (0.08206 dm? atm K"' mol) x (273K) [4.46 x10 mol] The corresponding concentrations are a 1.1210" mol ¥ > (00 den*) = (40> 10m) ¥ (10 dn ma) 4.46 x 10-4mol ¥ ~ (Loodm) x (40 x 107m) x lodm m+) 8x10? mel dma 1.1510? mol am>| and respectively P1238 i } = 113 m?= volume of balloon F P= J

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