chapter one the estimation of physical properties

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PURE COMPONENT CONSTANTS 2.30 CHAPTER TWO Pair # Atom/Group Pair N k N k tbbk 149 OH 131 141 H CH 10 133 131 H H 134 131 CH 10 3 3 10 131 133 134 141 149 — —CH3 & C [r] —CH[ ] [r] & C[ ] [r] CH— [r] & CH— [r] CH— [r] & C [r] C [r] & C [r] C [r] & —OH 7 k1 N k F k 2 3 1 1 1 1 — 291.12 873.45 285.07 237.22 180.07 456.25 2323.18 The estimate using Eq. (2-4.5) is T 122.167 b 0.404 (2323.18) 156.00 489.49 K The Appendix A value is T b 484.09 K. Thus the difference is T Difference 484.09 489.49 5.40 K or 1.1% b Example 2-14 Estimate T b for five cycloalkanes with formula C 7 H 14 using Marrero and Pardillo’s method. solution The group pairs for the cycloalkanes are: Pair # Atom / Group Pair cycloheptane methyl cyclohexane ethyl cyclopentane cis-1,3- dimethyl cyclopentane trans-1,3- dimethyl cyclopentane 2 CH 3 — & —CH 2 — 0 0 1 0 0 8 CH 3 — & CH— [r] 0 1 0 2 2 35 —CH 2 — & CH— [r] 0 0 1 0 0 112 —CH 2 — [r] & —CH 2 — [r] 7 4 3 1 1 113 —CH 2 — [r] & CH— [r] 0 2 2 4 4 Using values of bond contributions from Table 2-5 and experimental values from Appendix A, the results are: T b , K cycloheptane methyl cyclohexane ethyl cyclopentane cis-1,3- dimethyl cyclopentane trans-1,3- dimethyl cyclopentane Experimental 391.95 374.09 376.59 364.71 363.90 Calculated 377.52 375.84 384.47 374.16 374.16 Abs. percent Err. 3.68 0.47 2.09 2.59 2.54 These errors are a little above this method’s average. A summary of the comparisons between estimations from the Marrero and Pardillo method and experimental Appendix A values for T b are shown along with those from other estimation methods in Table 2-10. Other Methods for Normal Boiling and Normal Freezing Points. There are several other group/bond/atom and molecular descriptor methods that have been applied for estimating T ƒp and T b . Most of the former are restricted to individual Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
PURE COMPONENT CONSTANTS PURE COMPONENT CONSTANTS 2.31 classes of substances such as hydrocarbons or complex substances such as triglycerides (Zeberg-Mikkelsen and Stenby, 1999). The molecular descriptor techniques are based on properties of the molecules of interest which are not normally measurable. As described in Sec. 2-2, these ‘‘Quantitative structure-property relationships (QSPR)’’ are usually obtained from on-line computation from quantum mechanical methods. Thus, in most of these methods, there is no tabulation of descriptor values. Katritzky, et al. (1998) summarize the literature for such methods applied to T b . Egolf, et al. (1994), Turner, et al. (1998), and St. Cholokov, et al. (1999) also give useful descriptions of the procedures involved. We present here comparisons with T fp and T b data of Appendix A for some recent methods. The method of Yalkowsky (Yalkowsky, et al., 1994; Krzyzaniak, et al., 1995; Zhao and Yalkowsky, 1999) for both properties is a hybrid of group contributions and molecular descriptors; direct comparisons are possible for T ƒp . We also examine the more extensive results for T b published for full molecular descriptor methods of Katrizky, et al. (1996) and Wessel and Jurs (1995). The early method of Grigoras (1990) described above is not as bad for T b as for the critical properties, but is not as good as the others shown here. Finally, in Sec. 2-5, we comment on how these techniques compare with the group/bond/atom methods. Method of Yalkowsky for T ƒp and T b . Yalkowsky and coworkers (Yalkowsky, et al., 1994; Krzyzaniak, et al., 1995; Zhao and Yalkowsky, 1999) have explored connections between T ƒp and T b as well as have proposed correlations for T ƒp . This is part of an extensive program to correlate many pure component and mixture properties of complex substances (Yalkowsky, et al., 1994). The method consists of both group contributions which are additive and molecular descriptors which are not additive. The main properties of the latter are the symmetry number, , and the flexibility number, . The former is similar to that used for ideal gas properties (see Sec. 3-5 and Wei, 1999) and the latter is strictly defined as the inverse of the probability that a molecule will be in the conformation of the solid crystalline phase of interest. It is argued that flexibility affects both melting and boiling while symmetry affects only melting. The methodology has been to determine easily accessible molecular properties to estimate the flexibility contribution while values of are to be obtained directly from molecular structure such as described in Sec. 3-4 for the Benson group method for ideal gas properties. Thus, Krzyzanaik, et al. (1995) and Zhao and Yalkowsky (1999) use k T N (b )/(86 0.4) (2-4.6) b k k T N (m )/(56.5 19.2 log 9.2) (2-4.7) ƒp k k 10 k where b k and m k are selected from among 61 group contribution terms and 9 molecular correction terms that they tabulate. The value of is estimated by SP3 0.5SP2 0.5RING 1 (2-4.8) Here, SP3 is the number of ‘‘non-ring, nonterminal sp 3 atoms,’’ SP2 is the number of ‘‘non-ring, nonterminal sp 2 atoms,’’ and RING is the number of ‘‘monocyclic fused ring systems in the molecule.’’ Examples of the appropriate assignments are given in the original papers. Though no detailed comparisons have been made with this method for T b , the authors report their average deviations were 14.5 K compared to an average of 21.0 for Joback’s method, Eq. (2-4.2). Table 2-9 below shows about 17 K as our average Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
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Page 4 and 5: THE ESTIMATION OF PHYSICAL PROPERTI
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