Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry

Chambreau, Steven D.; Koh, Christine J.; Popolan-Vaida, Denisia M.; Gallegos, Christopher J.; Hooper, Justin B.; Bedrov, Dmitry; Vaghjiani, Ghanshyam L.; Leone, Stephen R.

doi:10.1021/acs.jpca.6b06289

Title: Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry

Full Record
Other Related Research

Abstract

The unusually high heats of vaporization of room-temperature ionic liquids (RTILs) complicate the utilization of thermal evaporation to study ionic liquid reactivity. Although effusion of RTILs into a reaction flow-tube or mass spectrometer is possible, competition between vaporization and thermal decomposition of the RTIL can greatly increase the complexity of the observed reaction products. In this paper, in order to investigate the reaction kinetics of a hypergolic RTIL, 1-butyl-3-methylimidazolium dicyanamide (BMIM⁺DCA^–) was aerosolized and reacted with gaseous nitric acid, and the products were monitored via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Reaction product formation at m/z 42, 43, 44, 67, 85, 126, and higher masses was observed as a function of HNO₃ exposure. The identities of the product species were assigned to the masses on the basis of their ionization energies. The observed exposure profile of the m/z 67 signal suggests that the excess gaseous HNO₃ initiates rapid reactions near the surface of the RTIL aerosol. Nonreactive molecular dynamics simulations support this observation, suggesting that diffusion within the particle may be a limiting step. Finally, the mechanism is consistent with previous reports that nitric acid forms protonated dicyanamidemore »« less

Authors:

Chambreau, Steven D. ^[1]; Koh, Christine J. ^[2]; Popolan-Vaida, Denisia M. ^[3]; Gallegos, Christopher J. ^[4]; Hooper, Justin B. ^[5]; Bedrov, Dmitry ^[5]; Vaghjiani, Ghanshyam L. ^[4]; Leone, Stephen R. ^[3]

ERC, Inc., Edwards AFB, CA (United States)
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Physics
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Air Force Research Lab. (AFRL), Edwards AFB, CA (United States). Aerospace Systems Directorate. Rocket Propulsion Division. Propellants Branch
Univ. of Utah, Salt Lake City, UT (United States). Dept. of Materials Science and Engineering; Wasatch Molecular Inc., Salt Lake City, UT (United States)

Publication Date:: Thu Sep 22 00:00:00 EDT 2016

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR)

Contributing Org.:: Univ. of Utah, Salt Lake City, UT (United States); Wasatch Molecular Inc., Salt Lake City, UT (United States)

OSTI Identifier:: 1377547

Grant/Contract Number:: AC02-05CH11231; FA9550-10-1-0163; FA9550-14-0154; FA9300-06-C-0023

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 120; Journal Issue: 41; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Chambreau, Steven D., Koh, Christine J., Popolan-Vaida, Denisia M., Gallegos, Christopher J., Hooper, Justin B., Bedrov, Dmitry, Vaghjiani, Ghanshyam L., and Leone, Stephen R. Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.jpca.6b06289.

Copy to clipboard


                    Chambreau, Steven D., Koh, Christine J., Popolan-Vaida, Denisia M., Gallegos, Christopher J., Hooper, Justin B., Bedrov, Dmitry, Vaghjiani, Ghanshyam L., & Leone, Stephen R. Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry.  United States.  https://doi.org/10.1021/acs.jpca.6b06289

Copy to clipboard


                    Chambreau, Steven D., Koh, Christine J., Popolan-Vaida, Denisia M., Gallegos, Christopher J., Hooper, Justin B., Bedrov, Dmitry, Vaghjiani, Ghanshyam L., and Leone, Stephen R. Thu .  
"Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry".  United States.  https://doi.org/10.1021/acs.jpca.6b06289.  https://www.osti.gov/servlets/purl/1377547.

Copy to clipboard


                    
@article{osti_1377547,

  title        = {Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry},

  author       = {Chambreau, Steven D. and Koh, Christine J. and Popolan-Vaida, Denisia M. and Gallegos, Christopher J. and Hooper, Justin B. and Bedrov, Dmitry and Vaghjiani, Ghanshyam L. and Leone, Stephen R.},

  abstractNote = {The unusually high heats of vaporization of room-temperature ionic liquids (RTILs) complicate the utilization of thermal evaporation to study ionic liquid reactivity. Although effusion of RTILs into a reaction flow-tube or mass spectrometer is possible, competition between vaporization and thermal decomposition of the RTIL can greatly increase the complexity of the observed reaction products. In this paper, in order to investigate the reaction kinetics of a hypergolic RTIL, 1-butyl-3-methylimidazolium dicyanamide (BMIM+DCA–) was aerosolized and reacted with gaseous nitric acid, and the products were monitored via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Reaction product formation at m/z 42, 43, 44, 67, 85, 126, and higher masses was observed as a function of HNO3 exposure. The identities of the product species were assigned to the masses on the basis of their ionization energies. The observed exposure profile of the m/z 67 signal suggests that the excess gaseous HNO3 initiates rapid reactions near the surface of the RTIL aerosol. Nonreactive molecular dynamics simulations support this observation, suggesting that diffusion within the particle may be a limiting step. Finally, the mechanism is consistent with previous reports that nitric acid forms protonated dicyanamide species in the first step of the reaction.},

  doi          = {10.1021/acs.jpca.6b06289},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 41,

  volume       = 120,

  place        = {United States},

  year         = {Thu Sep 22 00:00:00 EDT 2016},

  month        = {Thu Sep 22 00:00:00 EDT 2016}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpca.6b06289

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 25 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Soft Ionization of Thermally Evaporated Hypergolic Ionic Liquid Aerosols

Journal Article Koh, Christine J. ; Liu, Chen-Lin ; Harmon, Christopher W. ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf₂N–]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca–]), are generated by vaporizing ionic liquid submicrometer aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim⁺ and Bmim⁺, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Also, hotoionization efficiency curves in the near threshold ionizationmore »« less
https://doi.org/10.1021/jp200633b

Full Text Available
Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

Journal Article University of California ; ERC, Incorporated, Edwards Air Force Base ; Air Force Research Laboratory, Edwards Air Force Base ; ... - J. Phys. Chem. A

Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization regionmore »« less
Full Text Available
Thermal and Catalytic Decomposition of 2-Hydroxyethylhydrazine and 2-Hydroxyethylhydrazinium Nitrate Ionic Liquid

Journal Article Chambreau, Steven D. ; Popolan-Vaida, Denisia M. ; Kostko, Oleg ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

To develop chemical kinetics models for the combustion of ionic liquid-based monopropellants, identification of the elementary steps in the thermal and catalytic decomposition of components such as 2-hydroxyethylhydrazinium nitrate (HEHN) is needed but is currently not well understood. The first decomposition step in protic ionic liquids such as HEHN is typically the proton transfer from the cation to the anion, resulting in the formation of 2-hydroxyethylhydrazine (HEH) and HNO₃. In the first part of this investigation, the high-temperature thermal decomposition of HEH is probed with flash pyrolysis (<1400 K) and vacuum ultraviolet (10.45 eV) photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS). Next,more »« less
https://doi.org/10.1021/acs.jpca.1c07408

Full Text Available
Molecular simulation study of dynamical properties of room temperature ionic liquids with carbon pieces

Journal Article Feng, Guang ; Zhao, Wei ; Cummings, Peter T. ; ... - Science China Chemistry

Room temperature ionic liquids (RTILs) with dispersed carbon pieces exhibit distinctive physiochemical properties. In order to explore the molecular mechanism, RTILs/carbon pieces mixture we investigated it by molecular dynamics (MD) simulation in this work. Rigid and flexible carbon pieces in the form of graphene with different thicknesses and carbon nanotubes in different sizes were dispersed in a representative RTIL 1-butyl-3-methyl-imidazolium dicyanamide ([Bmim][DCA]). Our study demonstrated that the diffusion coefficients of RTILs in the presence of flexible carbons are similar to those of bulk RTILs at varying temperatures, which is in contrast to the decreased diffusion of RTILs in the presencemore »« less
Cited by 2
https://doi.org/10.1007/s11426-016-5580-5

Full Text Available
Forcing Dicyanamide Coordination to f-Elements by Dissolution in Dicyanamide-Based Ionic Liquids

Journal Article Tang, Si-Fu ; Smetana, Volodymyr ; Mishra, Manish Kumar ; ... - Inorganic Chemistry

A robust general route to lanthanide dicyanamide (DCA^–) complexes has been developed where f-element salts are dissolved in DCA^–-based ionic liquids (ILs) directly or formed in situ, forcing coordination of these normally weakly coordinating soft N-donor anions, even in an ambient, non-moisture-excluding environment. A series of lanthanide complexes [C₂mim][Ln(DCA)₄(H₂O)₄] (C₂mim = 1-ethyl-3-methylimidazolium; Ln = La, Nd, Eu, Tb, Dy, and Yb) and [C₂mim]_3n[La(OH₂)₄(μ²-DCA)₄]_n[La(OH₂)₂(μ³-DCA)₃(μ²-DCA)₄]_2n(Cl)_4n were crystallized under a variety of conditions using this methodology and structurally characterized using single crystal X-ray diffraction. Although not all examples were isostructural, the dominant feature across the series was the presence of [Ln(DCA)₄(H₂O)₄]^- anionic nodesmore »« less
Cited by 17
https://doi.org/10.1021/acs.inorgchem.0c00667

Similar Records