Scribd Logo
Upload

Welcome to Scribd!

  • CH 13 PDF

    Uploaded by

    khan
    309 views8 pages

    Original Title

    Ch 13.pdf

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Report this Document

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    309 views8 pages

    CH 13 PDF

    Uploaded by

    khan

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 8
    13 Estimating Physical Properties 181 Solution As a starting point, students should review the material in Section 8.4 on ideal-gas state heat ‘capacities. For the most general eas ofa polyatomic molecule, a molecular interpretation of C2 is expressed using Eg. (8-94) : 30) e960 a se i al [ewe - 1] were 6, =! spect molecules vibrational chance Getededevasty 2} 2000 ® * a [even q Ss jeefecnes(ip] otal = i 7) [exp ja/D - Defining a dimensionless temperature Oy 6) o Estimating Physicl Properties Chapter 13 api 0/27 T 2 Coma ka gk kl aR OD) o ‘This is mathematically consistent with an expression ofthe form eel Colter] ® The third term on the righ-hand side ofthe Aly-Lee formulation arises through consideration of the electronic energy of the molecule ‘The electronic energy contribution to the heat capacity is [McQuarrie (1976)] 2 D,|Semerpi-ayen | Saw exn-oen o ie Lmeocatn | Lweweasan | Cre xa slglying spun, hls onion ws nes ath teem at 40) expl0/7) 3 paket eg. a9) si oT) [exwo= 17 e — Dz = round sate leon enersy level 5 om i dearasc mang) irl out eeyehie peter UT The summations may once again be simplified; by taking the ground state energy level, a, as zero and stimming only tom=2 since generally Aa, >> KT, each series is reduced toterms containing a ay + ch wsexpon/KD)_ [ayn exnay/¥T) + apm expla eT wp eanaiED rmgespasiN) | wyexpea/iDwgexpay/al | | 7 -o _Jaba extn /*D) [en 20-Gnu/KT)} | De ne [Teemptea ED [eH tma/AD | | TE Estimating Physical Properties Chapter 13. 133 2, dao an P+ xp -Guo/KDE ‘The exponentials may be manipulated using the substation (2) a3) aay a! as) ‘Adding Eg (15) othe earlier expression for Cf that ony included the translational rotational and vibrational contributions we Dera fl Se pg aie =f ' inp k tg kek + kl rg 7an| + P| cosh (a,,/2KD, ney Eq, (16) is mathematically consistent with Eg (13-15) in the text. Quulitativly, he group contribution and Aly-Lee formulations for Cy will provide predictions with essentially the same accuracy because both formulations involve a number of adjustable Parameters four in the group contsibution formulation and five inthe Aly-Lee formulation) which should allow the temperature behavior of G;to be captured reasonably accurately, In addition, the terms neglected inthe derivation of the Aly-Lee formulation (the higher characteristic temperatures and electronic levels) should not contribute significantly for small molecules such as methylene chloride and toluene. In addition, de sinh () and cosh () unction ofthe exponential equivalent can bbe expanded in appropriate power series. For example, as calculated in Example 12.4, C for toluene is given by 31.38 + 0.58097 3.88 107" 49.80 x 10°17 Estimating Physical Properties Chapter 13 cy c = cosh (67D) 171233 K/300K J ‘i [_783938x/300k = 108.5 Hmol K 182 Solution ‘or propylene CH, = CH ~ CH, we have non-ring groups. Using Tables 13.4 and 13.5, with the molecular groups selected as follows: Table 1 Group ae be 4, =cH- 1 00129-0006 = 24.26 Hy Hl oo1s’ 00028 18:18, “CH. Hl oo) = 00012 23.58, Estimating Physicel Properties Chapter 13. 135 e Table 2 on 4, 4, A A =CH- t 80 105x107 963x107 3.56% 10 =CH; i 236x10' 31x10? 172% 10 -1.03x 107 “CH 1 195% 10" -go8x 10 153x104 -967x 10% Using Bq, (13-6) 7,=198+ vay, = 198+ (24.264 18.18 23.58) =264K which is very inaccurate compared to the experimental value of 225.5 K, Using Bg. (13-5) 1, aan, osseroses Exp, -(E% Ar) vA, =w0129 +00113+00141 0088s - 7 [4262 K using 7, = 264K © 0.584 + 0965(0.0383) —(0.0385)7 = [set cane Tp) = 228 5K pee a 8113+ 0.0032.,- Ev Bp l , Sivy4,, =-0.0006-0.0028-00012 = -0.0046 and n,=9 Sulina io113 + 0029)+ 0.006) T/T,_) P. 80 Fars [aa 9 ro o=3{{ 255/364), (46.65))_ Now for iP), using Ba, (13°14) and summing the terms in Fable 2, we Bet: Dy, 46.66 bar Using Eg. (13.9), = 0.1606 8423.64 195=35.1 381 107-808 x 107 = 0.0888 136 Estimating Physical Properties Chapter 13 Sy, 4,= 3:56 x 10 — 1.03 x 109.67 x 10 = 1.64% 107 (5.1 -37.93) + (0.0588 + 0.210)7 + (2.29 x 103.91 x 10°) +16 107+ 2.06% 107)" Maxi eedaxoee 4883 Soon Using Table 13.4 with phenylene oxide dissected into groups: Group y Ay pa taal be CH, (oon-ting) 2 ooist 00012 6s, ~O-(non-ring) 2 0.0168 0.0015 18 242 ® =CH- (ring) 6 0.0082 0011 41 2673 Tyr, = 200141) +2(00168) + 6(00082)=0.1110 TvAr,=2010012) + 20.0015) + 660.001) = 00072 Lvs, Diva, =223.58) +202242) + 626.73) 2(65) +2(18) + 6(41) =412.0 38 ‘Using Eq, (13-6): + 3 vy, = 198+ 252.38 = 45038 K o Using a, (13-5) 7-—____™. (0584+ 096500.1 0.1107 =663.50K @ Estimating Physical Poperties Chapter 19 ‘Using Eq. (13-18) for vapor pressure: e In|? =A" @ & } sg it My a asim i=. Sobstuing into (5) and earanging iP, 16 } 447) tU 194 Solution Start with Joback’s method for estimating critical properties. Dividing caffeine into molecular e™ Gow yy or 4 by 4s, -CH, 3 cout 00012 6 23.58 >C=0 (cing) 2 0.0284 0.0028 55 9497 CH (ring) 0.0082 0011 4 26.73 2 0.0143 0.0008 2 3L0L 1 0.0085 0.0076 4 5735, 2) 3 0.016 o.007s 2 174 Tv ots oss a7 442.2 (number of atoms) 4 (molecular weight) ‘Using Equations (13-5) and (13-6) forthe Joback method T,= 198 + 442.2=640K @ 190 Estimating Physical Properties Chapter 19 Vi= 17. = 488.5 em'/mal @) P,= 10.113 + 0.00: ‘Tocstimate vapor pressure, use Eq (13-18) wi 0.0345)? = 41.46 bar and P, estimates substituted appropriately 6) ' iain | ml aang io 6 =f, Maa IF 2 (24 OMA SIAR OOM

    You might also like