‘Chem 444B Homework Set #1 - Solutions DUE: Friday, January 30, 2009 1) (MeQ&S 16-3) P= phg Ee ragee Lme- I2in | 2.54em) cm P=(100 So 9 fi SOT P=1.01x10° 8. om 5 k atm P=1.01%10° “8_ =1.01%10° Pax ms? Tp1x10"Pa P=1.00atm 2) (McQ&S 16-11) In the ideal-gas equation, all the variables except n are constant. Therefore, the number of moles of N, must equal the number of moles of the unknown. 0.3625g N, x M2! Na ~ 9,01295mol N, 28g N, For the unknown. -_0.917Sgunknown _ 4 2 0.01295mol unknown mol ‘The only homonuclear diatomic with this molar mass is Cl, 3) (MeQ&S 16-16) i =0.09416 P 10,6201 mo dm dm? bar 0.083145 400K) ( ‘mol K iG ) '=353bar 0.094162 mol Problem Set #1 olede P dm? bar (roo (400K) 9.301920" bar Seer 0.094162 0.090494" (9 994160". mol mol P= ar 1059 bar P = 8013 bar dm? bar 0.083145 400K" ( mol K eae) P= ooni62™ —on623™ mol =——— mol 183.0240" bat moPK2 (400x)2 (0 oosi6 lo oss +0. oem | P=1058 bar—619 bar P £439 bar a) err. a TET V+ B)+B(7-A) loa Serie} ossi4s 2” =i je) o.osai6& 0.056329 = dnt bar 9.6938 mol’ i _, Py (c.oste)(005416+0.0s630) “Ys o0sey ome o0sen2) P=879 bar ~595 bar P= 284 bar Problem Set #1 oeHL aoe 4) Compare the pressure predicted by a)the ideal-gas equation and b)the van der Waals equation for 1.00 mol of -octane confined to 20.0 dm’ at 200 °C. Use a = 37.81 dm® bar mol and b = 0.2368 dm’ mot. Why does the van der ‘Waals equation give a reasonable answer for this problem but not for the previous problem? a) dm? es (imot)| 0.083145 (473K) pare fobs Se) v 0a P=1.97 bar b) RT v-5 Vv dm’ bar Satan 0.083145 (473K) 3781 P= K = mol* ane in? es ry 20.04.9368 i nol So (200%) P=1.99 bar—0.095 bar P=1.90 bar The van der Waals equation works well for this problem because we're using very low pressures. In the previous problem, we were using higher pressures and higher densities, which as shown in Figure 16.5 causes large deviations in the pressure predicted by the van der Waals equation. 5) Calculate the van der Waals constants a and b for (C:Hz):S using T. = 557.0 Kand P.=39.6 bar From Eq, 16.17, we know a and b in terms of the critical values: dm? bar se gx) 2 3145 SPA 557.0, 2(Rr 27(o08 145 Tg 87 | AP, (64 (39.6 bar) af22,3 bar mol dm’ bar Rr, _ 0.083145 Tg x5570K 8(39.6 bar) Problem Set #16) (McQ&s 16-30) Begin with the Redlich-Kwong equation given in Eq. 16.7: ‘and substitute this into the equation for Z —B TV (7 +B) ee RT? (7 +B) ‘Now substitute for A and B using Eq. 16.18 0.42748R°7? R 0.086640RT, Pp 0.42748R°T> v (0.086640R7 P. 7 i Lame { Te~0259 1217, 40.2500) 4. cert an Ae 702922)1? (McQ&S 16-37) Eq. 16.23 expresses Z as a polynomial in P. If we ignore any terms of O(P*) or higher then Z will be linear in P, and we can solve for Bae by graphing (Z-1) versus P and finding the slope. y= 0.0015x+ 4£-06 4.2006-03 _ . . 1.0006-08 8.0006-04 Wi 6000604 ‘4.0006-04 2.0006-04 0.000600 000 010 020 030 040 060 060 070 080 P (bar) ‘The slope of this line, and therefore the value of Bzp, is 0.0015 bar 8) (MeQ&S 16-39) Eq, 16.29 gives the Lennard-Jones potential: u(r) = (2) 2) | ‘The minimum value of r occurs at r,,, =r’ =2°a (see Example 16-9) Substitute this equation for into the Lennard-Jones potential: }{e] E36] Problem Set #19) (MeQ&S 16-41) Use the values of € and o from Table 16.7 to plot Eq. 16.29 for Hz and O2 2 tk (K) ‘o (pm) He 37 293 o 118 358 ‘ule (K) (pm) H Os 150 448423.40 —16035666.46 175 6855507 _2501010.90 200 © 13001.68 «49518869 225 © 2797.79 116606.27 250 610.48, 31025.99 275 100.22 '8885.24 300 “16.97 2573.20 325, -36.80 663.17 350 133.41 78.50 375 "26.01 86.82 400 “19.33 “117.91 425 nat8 "108.38 450 “10.42 “89.33, 475 “7.70 “70.68 500 “575 “55.03, 525, 14.34 42.68 550 °331 “33.17 575 255 25.89 600 “1.98 20.34 625 21155 “16.08 650 123 “12.81 Lennard-Jones potentials ‘800.00 600.00 | @ 400.00 - oH 2-02 ek (K) on * oOo? ee 1 oogesssssees! rn F (om) You may have chosen to change the units of € to J by multiplying by ke or to kJ/mol by multiplying by ky and then converting J->ki/mol. In either case, the graph should look the same as the one shown here, with different values along the y-axis. Problem Set #110) (MeQ&S 16-55) Begin with the Redlich-Kwong equation shown on pages 672-673 fen in Eq, 16.7 and follow the logic Rr. rv (+B) Put each fraction in the form ck, with a(S v #l B Group the terms based on their power of V: yar Jovem r Ty a Muliply by 7 to wrt it in tems of : 7 fe goteabte gts) RT? : - Compare to Eq. 16.22 to solve for Byy (7) and Byy(T) : A By (1) =B-— RT? by (T) = Bt AB. RT? Problem Set #1