High-pressure phase equilibria for chlorosilane + carbon dioxide mixtures

Eduardo Vyhmeister, Anthony J Muscat, David Suleiman, L. Antonio Estévez

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Fluid-phase equilibria, including dew points, bubble points, and critical points were measured for four binary systems composed of a chlorosilane and carbon dioxide. The measurements were carried out in a constant-composition, variable-volume cell equipped with a sapphire window, which allowed visual observation of the phases in the cell. A syringe pump was used to inject the CO2 into the cell and to control its pressure. Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and diethyldichlorosilane up to about 0.14 mol fraction were studied in this apparatus and a total of 243 phase-boundary points were obtained. Displacements in the critical point with respect to pure CO2 of up to 11.81 MPa and 348.05 K were observed. Modeling of the fluid-phase equilibria for three of the four binary systems was done using the Peng-Robinson equation of state, standard van der Waals mixing rules with two binary interaction parameters, and a φ-φ formulation of the equilibrium. The binary interaction parameters were obtained by fitting the model to the experimental data. The model produced excellent agreement between computed and experimental data. Graphical representations of the modeling results are presented and compared to experimental results. The results indicate that the largest chlorosilane (diethyldichlorosilane) produced the largest shift in critical pressure and critical temperature with respect to pure CO2.

Original languageEnglish (US)
Pages (from-to)121-128
Number of pages8
JournalFluid Phase Equilibria
Volume270
Issue number1-2
DOIs
StatePublished - Aug 25 2008

Fingerprint

chlorosilanes
Carbon Dioxide
Phase equilibria
carbon dioxide
Carbon dioxide
Syringes
Fluids
Pressure control
Aluminum Oxide
critical point
Phase boundaries
cells
Equations of state
Sapphire
dew point
syringes
visual observation
critical pressure
fluids
Pumps

Keywords

  • Chlorosilane
  • Critical locus
  • Diethyldichlorosilane
  • Dimethyldichlorosilane
  • Fluid-phase equilibrium
  • Methyltrichlorosilane
  • Mixture critical point
  • Supercritical carbon dioxide
  • Trimethylchlorosilane

ASJC Scopus subject areas

  • Fluid Flow and Transfer Processes
  • Physical and Theoretical Chemistry

Cite this

High-pressure phase equilibria for chlorosilane + carbon dioxide mixtures. / Vyhmeister, Eduardo; Muscat, Anthony J; Suleiman, David; Estévez, L. Antonio.

In: Fluid Phase Equilibria, Vol. 270, No. 1-2, 25.08.2008, p. 121-128.

Research output: Contribution to journalArticle

Vyhmeister, Eduardo ; Muscat, Anthony J ; Suleiman, David ; Estévez, L. Antonio. / High-pressure phase equilibria for chlorosilane + carbon dioxide mixtures. In: Fluid Phase Equilibria. 2008 ; Vol. 270, No. 1-2. pp. 121-128.
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AB - Fluid-phase equilibria, including dew points, bubble points, and critical points were measured for four binary systems composed of a chlorosilane and carbon dioxide. The measurements were carried out in a constant-composition, variable-volume cell equipped with a sapphire window, which allowed visual observation of the phases in the cell. A syringe pump was used to inject the CO2 into the cell and to control its pressure. Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and diethyldichlorosilane up to about 0.14 mol fraction were studied in this apparatus and a total of 243 phase-boundary points were obtained. Displacements in the critical point with respect to pure CO2 of up to 11.81 MPa and 348.05 K were observed. Modeling of the fluid-phase equilibria for three of the four binary systems was done using the Peng-Robinson equation of state, standard van der Waals mixing rules with two binary interaction parameters, and a φ-φ formulation of the equilibrium. The binary interaction parameters were obtained by fitting the model to the experimental data. The model produced excellent agreement between computed and experimental data. Graphical representations of the modeling results are presented and compared to experimental results. The results indicate that the largest chlorosilane (diethyldichlorosilane) produced the largest shift in critical pressure and critical temperature with respect to pure CO2.

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