Based upon a mass balance of the oleic acid and ozone versus
the observed products, 73.15% of mass was accounted for by
pelargonic acid and azelaic acid. The unaccounted mass could
be due to volatile aldehydes that were swept out of the reaction
system by the exiting ozone + oxygen stream. The traditional
ozonolysis reaction was zero-order with a reaction rate constant
of (0.077 0.002) mol s-1 m-3. Based upon the apparent order
of the reaction, the ozonolysis of oleic acid was mass-transfer
limited. No reaction was observed for the ozonolysis of oleic
acid in supercritical carbon dioxide. This was due to the lack of
sufficient ozone for reaction.
10 M. S. Macsai, M. J. Mannis, and A. C. Huntley, Acne Rosacea, In Eye
and Skin Disease: Part X. Acneiform, Diseases, Dermatology Online
Journal, 1996, 1, no. 2, Chapter 41, http://dermatology.cdlib.org/
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12 Pelargonic Acid, 1996, The Merck Index, 12th Ed., Merck & Co., Inc.,
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13 H. Kroha, Industrial Biotechnology Provides Opportunities for
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14 H. V. Smith, Oleochemicals in the Plastics Industry, JAOCS, 1985,
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15 J. O. Metzger and U. Bornscheuer, Lipids as Renewable Resources:
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16 J. C. Reynolds, D. J. Last, M. McGillen, A. Nijs, A. B. Horn, C.
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17 C. G. Goebel, A. C. Brown, H. F. Oehlschlaeger and R. P. Rolfes,
Method of Making Azelaic Acid, US Pat., 2 813 113, 1957.
18 S. G. Kadesch, Fat-Based Dibasic Acids, JAOCS, 1979, 56, 845A–
849A.
19 J. F. Brennecke, Chapter 16: Spectroscopic Investigations of Re-
actions in Supercritical Fluids, in Supercritical Fluid Engineering
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Brennecke, American Chemical Society, Washington, D. C., 1993,
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Notation
a
order of reaction in Eq. 3
COA
COA0
E
concentration of oleic acid in Eqs. 3 and 5 (mol m-3)
initial concentration of oleic acid in Eq. 5 (mol m-3)
activation energy in Eq. 4 (kJ mol-1)
reaction rate constant in Eqs. 3 and 4 (m2.25 s-1 mol-0.75),
5 and 6 (mol s-1 m-3)
k
R
rOA
t
gas constant in Eq. 4 (kJ mol-1 K-1)
reaction rate of oleic acid in Eqs. 3 and 6 (mol s-1 m-3)
time in Eqs. 3 and 5 (s)
20 M. Zou, Z. R. Yu, P. Kashulines and S. S. H. Rizvi, Fluid-Liquid
Phase Equilibria of Fatty Acid Methyl Esters in Supercritical Carbon
Dioxide, The Journal of Supercritical Fluids, 1990, 3, 23–28.
21 N. R. Foster, S. L. J. Yun and S. S. T. Ting, Solubility of Oleic Acid
in Supercritical Carbon Dioxide, The Journal of Supercritical Fluids,
1991, 4, 127–130.
22 W. B. Nilsson, E. J. Gauglitz and J. K. Hudson, Solubilities of Methyl
Oleate, Oleic Acid, Oleyl Glycerols, and Oleyl Glycerol Mixtures in
Supercritical Carbon Dioxide, JAOCS, 1991, 68, 87–91.
23 P. Maheshwari, Z. L. Nikolov, T. M. White and R. Hartel, Solubility
of Fatty Acids in Supercritical Carbon Dioxide, JAOCS, 1992, 69,
1069–1076.
T
temperature in Eq. 4 (K)
Acknowledgements
This research was supported by the United States Department of
Energy (Grant DE-FG36-04GO14251). The authors would like
to thank Bill Holmes and Dr. Earl Alley of the Mississippi State
Chemical Laboratory as well as John Slay and Jason McEwen
of the Dave C. Swalm School of Chemical Engineering for their
tremendous help with this project.
24 Z. Yu and S. S. H. Rizvi, Phase Equilibria of Oleic Acid, Methyl
Oleate, and Anhydrous Milk Fat in Supercritical Carbon Dioxide,
The Journal of Supercritical Fluids, 1992, 5, 114–122.
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