TY - JOUR
T1 - Mechanisms of decarboxylation of phenylacetic acids and their sodium salts in water at high temperature and pressure
AU - Glein, Christopher R.
AU - Gould, Ian R.
AU - Lorance, Edward D.
AU - Hartnett, Hilairy E.
AU - Shock, Everett L.
N1 - Funding Information:
The research reported above represents part of the first author’s Ph.D. dissertation at Arizona State University. It is also a product of the research program in Hydrothermal Organic Geochemistry (HOG) at ASU, which the late John Holloway helped to catalyze into existence in part by teaching C.R.G. the art of experimental geochemistry. We are grateful to Lynda Williams, Jessie Shipp, Ziming Yang, Kris Fecteau, Kristin Johnson, Kirt Robinson, Jeff Dick, Christa Bockisch, Charlene Estrada, and other members of the HOG group for many enlightening discussions. C.R.G. is indebted to George Cody for his mentorship and generosity, and for many helpful and enjoyable discussions that enriched his knowledge of organic reactions on Earth and in the solar system. An earlier version of this paper benefited greatly from clarifying remarks and suggestions from Laurent Richard and Alex Sessions. The critical comments of two anonymous reviewers also helped to improve this paper. Funding for this work was provided by National Science Foundation Grants OCE-0826588 and OCE-1357243 . C.R.G. dedicates this paper to J.L.W.G. for her unwavering support. Appendix A
Publisher Copyright:
© 2019
PY - 2020/1/15
Y1 - 2020/1/15
N2 - Mechanistic interpretations of how organic reactions happen can enhance the predictive capacity of models for geochemical transformations built on thermodynamic and kinetic relations. In this study, the mechanisms of hydrothermal carboxylic acid decarboxylation reactions are explored using aqueous solutions of the model compound phenylacetic acid, its ring-substituted derivatives, and their sodium salts. Time-series experiments in gold capsules are performed at 300 °C and 1034 bar, and analyzed using gas chromatography. The decarboxylation products are the appropriately substituted toluene and CO2 or HCO3 − depending on the pH. It is found that the decarboxylation reaction is irreversible at the studied conditions, consistent with the expectation of a strong thermodynamic drive at elevated temperatures. Decarboxylation of both the acid and anion forms of phenylacetic acid follow first-order kinetics, with apparent rate constants of 0.044 ± 0.005 h−1 ([1.2 ± 0.14] × 10−5 s−1) and 0.145 ± 0.02 h−1 ([4.0 ± 0.56] × 10−5 s−1), respectively. However, trends in the reaction rate with changes in the electronic properties of methyl and fluoro substituents reveal that the two forms of phenylacetic acid decarboxylate via two different mechanisms. It is inferred that the associated phenylacetic acid molecule decarboxylates by the formation of a ring-protonated zwitterion, whereas the acid anion directly decarboxylates to a benzyl anion. Zwitterionic mechanisms of activation to decarboxylation may be applicable to other aromatic acids (e.g., benzoic acid) having unsaturation that is alpha- or beta- to the carboxyl group, as well as to aliphatic acids that can be converted to α,β- or β,γ-unsaturated acids in natural hydrothermal systems. For acids lacking suitable unsaturation (e.g., acetic acid) or at higher pH, carbanion mechanisms may predominate in hydrothermal fluids. In these cases, there is potential to predict decarboxylation rates from the pKa of the hydrocarbon product. The finding of speciation-dependent reaction mechanisms implies that host rocks of aqueous fluids are key to determining decarboxylation rates, as a consequence of water-rock reactions that control fluid pH.
AB - Mechanistic interpretations of how organic reactions happen can enhance the predictive capacity of models for geochemical transformations built on thermodynamic and kinetic relations. In this study, the mechanisms of hydrothermal carboxylic acid decarboxylation reactions are explored using aqueous solutions of the model compound phenylacetic acid, its ring-substituted derivatives, and their sodium salts. Time-series experiments in gold capsules are performed at 300 °C and 1034 bar, and analyzed using gas chromatography. The decarboxylation products are the appropriately substituted toluene and CO2 or HCO3 − depending on the pH. It is found that the decarboxylation reaction is irreversible at the studied conditions, consistent with the expectation of a strong thermodynamic drive at elevated temperatures. Decarboxylation of both the acid and anion forms of phenylacetic acid follow first-order kinetics, with apparent rate constants of 0.044 ± 0.005 h−1 ([1.2 ± 0.14] × 10−5 s−1) and 0.145 ± 0.02 h−1 ([4.0 ± 0.56] × 10−5 s−1), respectively. However, trends in the reaction rate with changes in the electronic properties of methyl and fluoro substituents reveal that the two forms of phenylacetic acid decarboxylate via two different mechanisms. It is inferred that the associated phenylacetic acid molecule decarboxylates by the formation of a ring-protonated zwitterion, whereas the acid anion directly decarboxylates to a benzyl anion. Zwitterionic mechanisms of activation to decarboxylation may be applicable to other aromatic acids (e.g., benzoic acid) having unsaturation that is alpha- or beta- to the carboxyl group, as well as to aliphatic acids that can be converted to α,β- or β,γ-unsaturated acids in natural hydrothermal systems. For acids lacking suitable unsaturation (e.g., acetic acid) or at higher pH, carbanion mechanisms may predominate in hydrothermal fluids. In these cases, there is potential to predict decarboxylation rates from the pKa of the hydrocarbon product. The finding of speciation-dependent reaction mechanisms implies that host rocks of aqueous fluids are key to determining decarboxylation rates, as a consequence of water-rock reactions that control fluid pH.
KW - Decarboxylation
KW - Hydrothermal organic transformations
KW - Reaction mechanisms
KW - Reaction rates
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U2 - 10.1016/j.gca.2019.11.003
DO - 10.1016/j.gca.2019.11.003
M3 - Article
AN - SCOPUS:85075547460
SN - 0016-7037
VL - 269
SP - 597
EP - 621
JO - Geochimica et Cosmochimica Acta
JF - Geochimica et Cosmochimica Acta
ER -