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Importance of Surface Reactions in Pyrolysis Units. In Albright, L. F., Crynes, B. L., Corcoan, W. H., Eds.; Academic: New York
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33847533557
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Laboratory Reactors for Pyrolysis Reactions. In Albright, L. F., Crynes, B. L., Corcoan, W. H., Eds.; Academic: New York
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Cooney, M.J.1
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0000879246
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Trahanovsky, W. S.; Ong, C. C.; Lawson, J. A. J. Am. Chem Soc. 1968, 90, 2839.
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Trahanovsky, W.S.1
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41
-
-
33847555839
-
-
At 600 C, thé conversion of PPE was 46.8%, and the mass balance was 99.6%. The pyrolysis products included phenol (56.2 mol %), styrène (40.1 mol %), benzène (1.5 mol %), benzaldehyde (0.7 mol %), toluène (0.6 mol %), ethylbenzene (0.35 mol %), bibenzyl (0.2 mol %), and o-(2-phenylethyl)phenol (0.1 mol %) and p-(2-phenylethyl)phenol (0.1 mol %).
-
At 600 C, thé conversion of PPE was 46.8%, and the mass balance was 99.6%. The pyrolysis products included phenol (56.2 mol %), styrène (40.1 mol %), benzène (1.5 mol %), benzaldehyde (0.7 mol %), toluène (0.6 mol %), ethylbenzene (0.35 mol %), bibenzyl (0.2 mol %), and o-(2-phenylethyl)phenol (0.1 mol %) and p-(2-phenylethyl)phenol (0.1 mol %).
-
-
-
-
42
-
-
33847545034
-
-
8737
-
f°(PhO), = 11.2 ±1.5. Therefore, BDE (C-O) in PPE is increased to 64.7 kcal mol'1.
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J. Am. Chem. Soc.
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Wayner, D.D.M.1
Lusztyk, E.2
Page, D.3
Ingold, K.U.4
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Aldrich, H.S.7
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44
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0001321916
-
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Arends, I. W. C. E.; Louw, R.; Mulder, P. J. Phys. Chem. 1993, 97, 7914.
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Arends, I.W.C.E.1
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45
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-
0024302933
-
-
(a) Mackie, J. C.; Doolan, K. R.; Nelson, P. F. J. Phys. Chem. 1989, 93, 664.
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, pp. 664
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Mackie, J.C.1
Doolan, K.R.2
Nelson, P.F.3
-
48
-
-
0025402426
-
-
and references therein.
-
(b) Poutsma, M. L. Energy Fuels 1990, 4, 113 and references therein.
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(1990)
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, vol.4
, pp. 113
-
-
Poutsma, M.L.1
-
51
-
-
33847556525
-
-
-1.34
-
-1.34
-
-
-
-
56
-
-
33847533106
-
-
31
-
31
-
-
-
-
58
-
-
33847558486
-
-
note
-
+ and the slope, p, was -1.36 (at 335 °C) indicating that moderate carbocationic character developed on the carbon containing the leaving group in the transition state,
-
-
-
-
59
-
-
0011056413
-
-
and references therein
-
(a) Maccoll, A. Chem. Rev. 1969, 69, 33 and references therein,
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Chem. Rev.
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-
-
Maccoll, A.1
-
62
-
-
33847570661
-
-
2 and PPE is 0.55 ±0.08% and 0.71 ±0.2%, respectively.
-
2 and PPE is 0.55 ±0.08% and 0.71 ±0.2%, respectively.
-
-
-
-
63
-
-
84986791355
-
-
-1. Colussi, A. J.; Zabel, F.; Benson, S. W. Int. J. Chem. Kinet. 1977, 9, 161.
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, vol.9
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-
Colussi, A.J.1
Zabel, F.2
Benson, S.W.3
-
64
-
-
33847552946
-
-
This ratio can also be calculated by the yield of benzyl fragments (i.e., toluene plus 2 × bibenzyl), but toluene and o-cresol (0.45 ±0.05 mol %) are also formed by C-C homolysis of o-(2-phenylethyl)phenol.
-
This ratio can also be calculated by the yield of benzyl fragments (i.e., toluene plus 2 × bibenzyl), but toluene and o-cresol (0.45 ±0.05 mol %) are also formed by C-C homolysis of o-(2-phenylethyl)phenol.
-
-
-
-
65
-
-
84970559179
-
-
Mulcahy, M. F. R.; Tucker, B. G.; Williams, D. J.; Wilrashurst J. R. Aust. J. Chem. 1967, 20, 1155.
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, pp. 1155
-
-
Mulcahy, M.F.R.1
Tucker, B.G.2
Williams, D.J.3
Wilrashurst, J.R.4
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66
-
-
84985399709
-
-
Brezinsky, K.; Litzinger, T. A.; Glassman, I. Int. J. Chem. Kinet. 1984, 16, 1053.
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Int. J. Chem. Kinet.
, vol.16
, pp. 1053
-
-
Brezinsky, K.1
Litzinger, T.A.2
Glassman, I.3
-
67
-
-
33847539826
-
-
note
-
-1 11
-
-
-
-
69
-
-
84986746862
-
-
(a) Martin, G.; Martinez, H.; Ascanio, J. Int. J. Chem. Kinet. 1989, 21, 193.
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Int. J. Chem. Kinet.
, vol.21
, pp. 193
-
-
Martin, G.1
Martinez, H.2
Ascanio, J.3
-
70
-
-
33847550977
-
-
(b) Martin, G.; Martinez, H.; Ascanio, J. Int. J. Chem. Kinet. 1990, 22, 1136.
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(1990)
Int. J. Chem. Kinet.
, vol.22
, pp. 1136
-
-
Martin, G.1
Martinez, H.2
Ascanio, J.3
-
71
-
-
0003520123
-
-
National Institute of Standards and Technology, Gaithersburg, MD
-
Mirokhin, Y.; Mallard, G.; Westly, F.; Herren, J.; Frizzell, D.; Hampson, R. NIST Chemical Kinetics Database; National Institute of Standards and Technology, Gaithersburg, MD, 1998.
-
(1998)
NIST Chemical Kinetics Database
-
-
Mirokhin, Y.1
Mallard, G.2
Westly, F.3
Herren, J.4
Frizzell, D.5
Hampson, R.6
-
72
-
-
33847551409
-
-
note
-
5 - 62.7/θ. At 500 °C, the ratio of the rate constants is 3.98:1.
-
-
-
-
73
-
-
33847544131
-
-
note
-
+ and σ, respectively, indicating that in the anisoles, direct conjugation with the aromatic ring is not important,
-
-
-
-
75
-
-
0342420287
-
-
(b) Sakurai, H.; Hosomi, A.; Kumada, M. J. Org. Chem. 1970,35, 993.
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J. Org. Chem.
, vol.35
, pp. 993
-
-
Sakurai, H.1
Hosomi, A.2
Kumada, M.3
-
77
-
-
33847565167
-
-
Phenoxy radicals abstract hydrogen atoms slightly faster (16-fold at 375 °C) than benzyl radicals
-
Phenoxy radicals abstract hydrogen atoms slightly faster (16-fold at 375 °C) than benzyl radicals,
-
-
-
-
78
-
-
0022285463
-
-
Schlosberg, R., Ed.; Plenum: New York
-
(a) Stein, S. E. In Chemistry of Coal Conversion; Schlosberg, R., Ed.; Plenum: New York, 1985; p 13.
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(1985)
Chemistry of Coal Conversion
, pp. 13
-
-
In, S.S.E.1
-
79
-
-
33845374222
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(b) Franz, J. A.; Alnajjar, M. S.; Barrows, R. D.; Kaisaki, D. L.; Camaioni, D. M.; Suleman, N. K. J. Org. Chem. 1986, 51, 1446.
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-
Franz, J.A.1
Alnajjar, M.S.2
Barrows, R.D.3
Kaisaki, D.L.4
Camaioni, D.M.5
Suleman, N.K.6
-
80
-
-
0021120664
-
-
Bockrath, B.; Bittner, E.; McGrew, J. J. Am. Chem. Soc. 1984, 706, 135.
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J. Am. Chem. Soc.
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Bockrath, B.1
Bittner, E.2
McGrew, J.3
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84
-
-
0001033850
-
-
Koski, A. A.; Price, S. J. W.; Trudell, B. C. Can. J. Chem. 1976,54, 482.
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(1976)
Can. J. Chem.
, vol.54
, pp. 482
-
-
Koski, A.A.1
Price, S.J.W.2
Trudell, B.C.3
-
85
-
-
0001765358
-
-
(e) Zhang, H.-X.; Ahonkhai, S. I.; Back, M. H. Can. J. Chem. 1989, 67, 1541.
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Zhang, H.-X.1
Ahonkhai, S.I.2
Back, M.H.3
-
86
-
-
33847556285
-
-
note
-
-1) = 8.6-21.8/0. Assuming no polar effects in the hydrogen transfer reaction, the Evans-Polanyi correlation (E = αAWnn) + C) can be used with a = 0.5, i.e., a symmetrical transition state, and C is determined from the base reaction. To construct the hypothetical thermoneutral reaction for reaction between aliphatic and benzylic centers, C = EtîK - 0.5(Aff°base).
-
-
-
-
87
-
-
33847552945
-
-
note
-
34-57 Another method to estimate this number uses the O-H BDE of guaiacol, (ABDE 3.9 kcal mol"1, relative to phenol in solution)64 estimated as 83.1 kcal mol"1 in the gas phase,26 and the ΔH°t (guaiacol) = -58 kcal mol'1.27 The A/T298 of o-CH3OC6H4O' is estimated as -27.0 kcal mol"1. The A//°29a of o-'CH2OC6H40H is estimated as -17.1 kcal mol-J from ΔH°298 of C6H5OCH2- (25 kcal mol-1)11 and group additivity (~CB-H + CB-O + O-CaH). Another method to estimate this number uses the BDE of the OCHz-H bond as 93.3 kcal mol"1, which is assumed to be similar to that of dimethyl ether.11 The tf°29s of o-'CHzOCeHtOH is estimated as -16.8 kcal mol"1 by this procedure. An average value for the 1,5hydogen shift (8.9 kcal mol'1) will be used.
-
-
-
-
89
-
-
84985380097
-
-
and references therein. The rate constant for the 1,5hydrogen shift from 1-hexyl to 2-hexyl radical has been measured as log (s-1) = 9.5-11.6/0.
-
Dôbé, S.; Berces, T.; Réti, F.; Màrta, F. Int. J. Chem. Kinet. 1987, 19, 895 and references therein. The rate constant for the 1,5hydrogen shift from 1-hexyl to 2-hexyl radical has been measured as log (s-1) = 9.5-11.6/0.
-
(1987)
Int. J. Chem. Kinet.
, vol.19
, pp. 895
-
-
Dôbé, S.1
Berces, T.2
Réti, F.3
Màrta, F.4
-
90
-
-
0001681791
-
-
For recent examples, see: (a) Chung, G.; Kwon, O.; Kwon, T. J. Phys. Chem. A 1998,102, 2381.
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J. Phys. Chem. a
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Chung, G.1
Kwon, O.2
Kwon, T.3
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91
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-
0033095009
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-
(b) Fujimaki, E.; Fujii, A.; Ebata, T.; Mikami, N. J. Chem. Phys. 1999, 110, 4238.
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Fujimaki, E.1
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92
-
-
0031236851
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