Kinetic study of the reaction of dimethyl carbonate with trialkylamines

Duane E. Weisshaar, Gary W. Earl, Eric Villa, Jessica L. Zierke, Christopher J. Fry, Kara L. Becvar, Shik Ki Li, Matthew C. Schafer

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.

Original languageEnglish
Pages (from-to)221-225
Number of pages5
JournalInternational Journal of Chemical Kinetics
Volume42
Issue number4
DOIs
StatePublished - Apr 2010
Externally publishedYes

Fingerprint

carbonates
asphalt
Chain length
Kinetics
Anions
reagents
kinetics
ammonium compounds
Quaternary Ammonium Compounds
anions
Ionic Liquids
Alkylating Agents
metathesis
Amines
amines
Carbon
formulations
Temperature
carbon
liquids

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Biochemistry

Cite this

Weisshaar, D. E., Earl, G. W., Villa, E., Zierke, J. L., Fry, C. J., Becvar, K. L., ... Schafer, M. C. (2010). Kinetic study of the reaction of dimethyl carbonate with trialkylamines. International Journal of Chemical Kinetics, 42(4), 221-225. https://doi.org/10.1002/kin.20476

Kinetic study of the reaction of dimethyl carbonate with trialkylamines. / Weisshaar, Duane E.; Earl, Gary W.; Villa, Eric; Zierke, Jessica L.; Fry, Christopher J.; Becvar, Kara L.; Li, Shik Ki; Schafer, Matthew C.

In: International Journal of Chemical Kinetics, Vol. 42, No. 4, 04.2010, p. 221-225.

Research output: Contribution to journalArticle

Weisshaar, DE, Earl, GW, Villa, E, Zierke, JL, Fry, CJ, Becvar, KL, Li, SK & Schafer, MC 2010, 'Kinetic study of the reaction of dimethyl carbonate with trialkylamines', International Journal of Chemical Kinetics, vol. 42, no. 4, pp. 221-225. https://doi.org/10.1002/kin.20476
Weisshaar, Duane E. ; Earl, Gary W. ; Villa, Eric ; Zierke, Jessica L. ; Fry, Christopher J. ; Becvar, Kara L. ; Li, Shik Ki ; Schafer, Matthew C. / Kinetic study of the reaction of dimethyl carbonate with trialkylamines. In: International Journal of Chemical Kinetics. 2010 ; Vol. 42, No. 4. pp. 221-225.
@article{5a087d97862d46e29f672c68ad75d192,
title = "Kinetic study of the reaction of dimethyl carbonate with trialkylamines",
abstract = "Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.",
author = "Weisshaar, {Duane E.} and Earl, {Gary W.} and Eric Villa and Zierke, {Jessica L.} and Fry, {Christopher J.} and Becvar, {Kara L.} and Li, {Shik Ki} and Schafer, {Matthew C.}",
year = "2010",
month = "4",
doi = "10.1002/kin.20476",
language = "English",
volume = "42",
pages = "221--225",
journal = "International Journal of Chemical Kinetics",
issn = "0538-8066",
publisher = "John Wiley and Sons Inc.",
number = "4",

}

TY - JOUR

T1 - Kinetic study of the reaction of dimethyl carbonate with trialkylamines

AU - Weisshaar, Duane E.

AU - Earl, Gary W.

AU - Villa, Eric

AU - Zierke, Jessica L.

AU - Fry, Christopher J.

AU - Becvar, Kara L.

AU - Li, Shik Ki

AU - Schafer, Matthew C.

PY - 2010/4

Y1 - 2010/4

N2 - Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.

AB - Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.

UR - http://www.scopus.com/inward/record.url?scp=77949864268&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77949864268&partnerID=8YFLogxK

U2 - 10.1002/kin.20476

DO - 10.1002/kin.20476

M3 - Article

VL - 42

SP - 221

EP - 225

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

SN - 0538-8066

IS - 4

ER -