Mechanism of Sulfation of Alcohols<sup>1,2</sup>

Deno, N. C.; Newman, Melvin S.

doi:10.1021/ja01165a005

Cited by 64 publications

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“…3b, it is obvious that the slope of the log k !Ho line di!ers from those obtained in the other studies, which may indicate that the reaction occurs via an other reaction mechanism. The slope of the log(k )!Ho plot (+0.75) agrees with the results of Deno and Newman (1950) for the rate of sulfation of 1-and 2-butanol, where a corresponding value of 0.8 is found. Although it is uncertain if the same slope should be expected for the hydrolysis of alkylsulfates.…”

Section: Discussionsupporting

confidence: 85%

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Gas–liquid–liquid reaction engineering: the Koch synthesis of pivalic acid from iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase

Brilman

Swaaij

Versteeg

1999

Chemical Engineering Science

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. Gas-liquid-liquid reaction engineering: the Koch synthesis of pivalic acid from iso-and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase. Chemical Engineering Science, 54(21), 4801-4809. https://doi.org/10.1016/S0009-2509(99)00197-9 Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. AbstractIn gas}liquid}liquid reaction systems with fast parallel and consecutive reactions the e!ects of mass transfer and mixing on the product yield can be signi"cant. The Koch synthesis of pivalic acid, using sulfuric acid as catalyst, was chosen to study these e!ects. Reaction kinetics and the e!ect of the catalyst-phase composition have been investigated by using isobutanol as reactant. For studying the e!ect of an immiscible liquid phase on the reaction products obtained, the more reactive tert-butanol was used. Pivalic acid can be produced from isobutanol using sulfuric acid as a catalyst solution with 2-methylbutanoic acid as main byproduct, if gas}liquid mass transfer limitations are excluded. The selectivity towards 2-methylbutanoic acid is generally less than 20% and decreases strongly with decreasing acidity. The reaction is "rst order in isobutanol and dehydration is likely to be rate determining. The presence of pivalic acid and isobutanol strongly reduces the apparent reaction rate constant by decreasing the solution acidity (Ho). For the industrially applied backmixed reactors in the Koch synthesis, this may imply that these operate at much lower values for Ho. On addition of an immiscible heptane phase, the reaction products are extracted to some extent and this adds to maintaining a high catalyst solution acidity. Using tert-butanol, the yield and pivalic acid selectivity was found to depend strongly on CO transport to the reaction zone through gas}liquid mass transfer and mixing. The presence of an immiscible heptane phase increased the product yield and selectivity towards pivalic acid signi"cantly.

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Section: Discussionsupporting

confidence: 85%

“…Esters of isobutanol with sulfuric acid were found to disappear rapidly in excess sulfuric acid (Deno and Newman, 1950;Tian, 1950). Due to the excess sulfuric acid used, esteri"cation is probably of minor importance.…”

Section: Other Reactionsmentioning

confidence: 99%

Gas–liquid–liquid reaction engineering: the Koch synthesis of pivalic acid from iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase

Brilman

Swaaij

Versteeg

1999

Chemical Engineering Science

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“…45,46 Butanol may also form butyl hydrogen sulfate and sulfate anions (BuOSO 3 H and BuOSO 3 -), 47 48,49 On the basis of their analysis, we estimate that less than 10% of the butanol in our experiments is converted to BuOSO 3 D and BuOSO 3 -, leaving 90% or more as BuOD and BuOD 2 + .…”

Section: Properties Of Pure and Butanol-doped Sulfuric Acid Solutionsmentioning

confidence: 91%

Evaporation of Water through Butanol Films at the Surface of Supercooled Sulfuric Acid

2005

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The evaporation of water was monitored from 60, 64, and 68 wt % D(2)SO(4) at 213 K containing 0-0.18 M 1-butanol. Measurements were performed in vacuum using a mass spectrometer to record the velocities and relative fluxes of the desorbing D(2)O. In addition, the surface activity of butanol in the acid was characterized by hyperthermal argon atom scattering in conjunction with surface tension and butanol evaporation measurements. The segregated butyl species reach surface concentrations of approximately 4 x 10(14) cm(-2) (approximately 80% surface coverage) at 0.18 M bulk concentration. We find that the butyl films do not impede the evaporation of D(2)O from the acid to within the 5% uncertainty of the measurements. This result implies that small, soluble surfactants such as butanol form porous films that will not alter the growth or shrinkage of supercooled sulfuric acid droplets in the atmosphere.

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“…Mechanistically, a Markownikoff product is obtained. H 2 SO 4 also sulfates saturated monohydric alcohols, although the formation of water in the reaction results in only 65% yield of the sulfate ester from equimolar concentrations of acid and alcohol 39. Addition of excess acid, the removal of water through a Deans-Stark distillation unit and CCl 4 , adding boron sulfate (a dehydrating chemical) and sulfation in vacuo have been attempted to enhance yields 38…”

Section: Chemical Sulfation Approachesmentioning

confidence: 99%

Chemical sulfation of small molecules—advances and challenges

2010

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Mechanism of Sulfation of Alcohols^1,2

Cited by 64 publications

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Gas–liquid–liquid reaction engineering: the Koch synthesis of pivalic acid from iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase

Gas–liquid–liquid reaction engineering: the Koch synthesis of pivalic acid from iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase

Evaporation of Water through Butanol Films at the Surface of Supercooled Sulfuric Acid

Chemical sulfation of small molecules—advances and challenges

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Mechanism of Sulfation of Alcohols1,2

Cited by 64 publications

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Gas–liquid–liquid reaction engineering: the Koch synthesis of pivalic acid from iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase

Gas–liquid–liquid reaction engineering: the Koch synthesis of pivalic acid from iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase

Evaporation of Water through Butanol Films at the Surface of Supercooled Sulfuric Acid

Chemical sulfation of small molecules—advances and challenges

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Mechanism of Sulfation of Alcohols^1,2