Chemical Science and Technology Laboratory IUPAC Ionic Liquids Database - ILThermo 230th American Chemical Society Meeting & Exposition 230th American Chemical Society Meeting & Exposition August 28 August 28 – – September 1, 2005 Washington, DC September 1, 2005 Washington, DC Qian Dong, Chris Muzny, Robert D. Chirico, Vladimir V. Diky, Joseph W. Magee, Jason Widegren, Kenneth N. Marsh*, Michael Frenkel Physical and Chemical Properties Division National Institute of Standards and Technology 325 Broadway, Boulder, Colorado 80305-3328 * Department of Chemical and Process Engineering University of Canterbury, Christchurch, New Zealand
Transcript
Chemical Science and Technology Laboratory
IUPAC Ionic Liquids Database- ILThermo
230th American Chemical Society Meeting & Exposition230th American Chemical Society Meeting & ExpositionAugust 28 August 28 –– September 1, 2005 Washington, DCSeptember 1, 2005 Washington, DC
Qian Dong, Chris Muzny, Robert D. Chirico, Vladimir V. Diky, Joseph W. Magee, Jason Widegren, Kenneth N. Marsh*, Michael Frenkel
Physical and Chemical Properties DivisionNational Institute of Standards and Technology 325 Broadway, Boulder, Colorado 80305-3328
* Department of Chemical and Process EngineeringUniversity of Canterbury, Christchurch, New Zealand
What are Ionic Liquids (ILs) ?What are Ionic Liquids (ILs) ?
N+
NCH3 CH3 P
FF
FF
F F
N+
F BF
FF
Chemical Science and Technology Laboratory
The materials are unique (properties and variety)– Tunability – Negligible vapor pressure – Good thermal stability– Wide liquid range– Electrolytic conductivity
The prospects for ILs applications are vast– Possibility to establish environmentally benign chemical processing
20 million ton VOCs discharged into atmosphere per year2/3 of all industrial emission and 1/3 of VOCs emission nationwide from traditional solventsGlobal climate change, poor urban air quality, and human illness
– Potential to revolutionize the way how solvents are utilizedNew extraction, catalysis, separations , and polymer processesNew chemical synthesisEnhancement of existing processes
– Opportunities to develop task-target performance chemicalsEngineering fluids for machinery and equipmentNew materials in the automotive, textile, construction, oil and gas, and energy industries
Why are ILs a Hot Topic ?Why are ILs a Hot Topic ?
Chemical Science and Technology Laboratory
Dramatic Increase in Research on Ionic LiquidsDramatic Increase in Research on Ionic Liquids
Worldwide Worldwide EscalationEscalation in Number of Ionic in Number of Ionic Liquids Publications (Web of Science)Liquids Publications (Web of Science)
YearYear
Publ
icat
ions
Publ
icat
ions
Total 2421Total 2421
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2000 2000 NATO Advanced Research Workshop – “Green Industrial Applications of Ionic
Liquids” in Heraklion, Crete, Greece with 41 participants
2001 2001 –– 20032003Trilogy of American Chemical Society (ACS) National Meeting Ionic Liquid
Symposia in San Diego, 2001, Boston, 2002, and New York, 2003
2002 Workshop on Ionic Liquids: Properties of Ionic Liquids and their Application in
Chemical Engineering. IACT/IUPAC International Conference on Chemical Thermodynamics, Rostock, Germany
2003 2003 Ionic Liquids Symposium, in Melbourne, Australia
2004 2004 Ionic Liquids Workshop of Background, State-of-the-Art, and Academic/Industrial
Applications in The University of Alabama, Tuscaloosa, AL
2005 2005 1st International Congress on Ionic Liquids in Salzburg, Austria. More than 400
participants from 33 countries and six continents
Workshops and Conferences
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11stst International Congress on Ionic Liquids International Congress on Ionic Liquids
Overall:Overall:
279 presentations
Main Topics:Main Topics:
New ionic liquids – synthesis of ionic liquidsCharacterization and thermodynamic properties and modelingToxicology, persistence and sustainabilityInteresting new applications in synthesis, catalysis, biocatalysis, separation, electrochemistry and analytics
Salzburg, Austria, June 2005Salzburg, Austria, June 2005
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OpportunitiesOpportunities
Storage and delivery of hazardous gases like phosphine or BF3
Detect ethanol by using ILs as solvents for advanced NMR-techniquesILs based electrolytes for dye-sensitized solar-cells and for the deposition of metalsSuitable solvents for the dimerization of olefins
ChallengesChallenges
Cost of ILs and ILs technologyComplexity of coordination, speciation, and extraction in chemical processes when utilizing ILs Limited information and data on structural variations, chemical and physical properties, corrosion and toxicity.
Message from the Salzburg CongressMessage from the Salzburg Congress
Chemical Science and Technology Laboratory
Urgent Call for DataUrgent Call for Data
"A public, free, independently verified, web-based database of physical, thermodynamic, and related data is urgently needed. There is also an immediate need for toxicity, biodegradation, bioaccumulation, and other safety, health, and environmental impact data. New analytical tools are also required for assessing the purity of ionic liquids. In addition, applications-oriented research on ionic liquids should include cost-benefit, economic, and life-cycle analyses.”
Professor Robin D. RogersCenter for Green Manufacturing
The University of Alabama“Green Industrial Applications of Ionic Liquids”
NATO Advanced Research Workshop, April, 2000
Chemical Science and Technology Laboratory
Two IUPAC Task Groups Two IUPAC Task Groups on Ionic Liquids Dataon Ionic Liquids Data
Thermodynamics of ionic liquids, ionic liquid mixtures, and the development of standardized systems at http://www.iupac.org/projects/2002/2002-005-1-100.html, formed in 2002.
– Encourage systematic studies of thermodynamic and thermophysical properties
– Recommend a reference ionic liquid and make reference quality measurements
Ionic liquids database at http://www.iupac.org/projects/2003/2003-020-2-100.html, formed in 2003
− Create a new database of experimental thermodynamic properties for ionic liquids
− Provide a web-based comprehensive data retrieval system with free public access
AimAim– Provide users worldwide with an up-to-date collection of
experimental investigations on ILs
Subject Coverage:Subject Coverage:– Chemical identification of ions and ILs– Chemical systems of pure ILs, binary and ternary mixture
systems containing ILs– Thermodynamic, thermochemical and transport properties– Phase behavior and solvent properties– Sample purity– Metadata (state variables, phases, system constraints, and
measurement technology…)– Reviews and bibliography
Developments and Plans– Develop and maintain at NIST as an ongoing commitment– Provide FREE public access– Anticipated public release for December of 2005
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NISTNIST--SOURCE for ILs Depository and Data EntrySOURCE for ILs Depository and Data Entry
Guided data entryGuided
data entry
In-house Data Entry Facility
NIST-SOURCE data archive
system
NIST-SOURCE data archive
system
Outside Contributors
NISTNIST--SOURCESOURCEDepository of all experimental thermophysical and thermochemical properties reported in the world’s scientific literature
IncludeInclude2,200,000 numerical property values and
their uncertainties17,400 pure compounds24,700 binary and ternary mixture systems4,000 reaction systemsdata entry rate is near 300,000 values per
Molecular compounds: (a) water; (b) alcohols; (c) aliphatic alkanes; (d) cyclohydrocarbons; (e) aromatic hydrocarbons; (f) chloroalkanes; and (g) CO2 and other gases
Examples:- Solubility of oxygen and carbon dioxide in 1-butyl-3-methyl imidazolium
tetrafluoroborate– Apparent molar volume and isentropic compressibility of ionic liquid
1-butyl-3-methylimidazolium bromide in water, methanol, and ethanol
Ternary mixtures containing ionic liquidsExamples:– Conductivities and viscosities of the ionic liquid [bmim][PF6] + water +
ethanol and [bmim][PF6] + water + acetone– Ionic liquids/water distribution ratios of some polycyclic aromatic
hydrocarbons
Chemical Systems of Ionic LiquidsChemical Systems of Ionic Liquids
Chemical Science and Technology Laboratory
Sample Purity Sample Purity
1) Original Source of the SampleStandard reference sample; Commercial source; Synthesizedby author; Isolated from a natural product; not stated
2) Initial Purity of sampleReported at a percentage of mole percent or mass percent; water and halid impurity identified
3) Method of purification21 common methods identified such as adsorption of impurities, crystallization, a chemical reagent, fractional distillation …
4) Final purity of sample
5) Method of Purity Analysis13 methods identified such as chemical analysis, density, differential scanning calorimeter, mass spectrometry, NMR …
Chemical Science and Technology Laboratory
Data TypeStrict application of the Gibbs Phase Rule (GPR) forms the basis for organizing numerical data in the database. The number of independent variables, called degree of freedom of the system given by GPR, is a fundamental criteria used to classify all types of physicochemical properties as:- Constants (critical temperature and pressure)- with one state variable (heat capacity – Temperature T)- with two state variables (solubility – T, Composition X)- with three state variables (viscosity – T, X and Pressure P)
Data SetEach data set / data point in the database consists of two parts: - metadata ( identification of chemical components, phases, units,
constraints, chemical composition, state variables, measurement purpose and method …)
- numerical data ( values of state variables, property, and the estimated uncertainty)
Physicochemical Property Data
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J. Chem. Eng. Data 2005, 50, 546-550Uncertainty Reporting for Experimental Thermodynamic PropertiesQian Dong, Robert D. Chirico, Xinjian Yan, and Michael Frenkel
“Estimates of uncertainty are the measure of data qualityfor all experimentally determined quantities and form thebasis for the understanding, evaluation, and applicationof all scientific data. …Although few scientists would disagree that thereporting of reliable uncertainty information is important,it is broadly recognized that the nature and extent of thatreporting in the literature is highly variable”.
Data Uncertainty (1)(1)
Chemical Science and Technology Laboratory
1. Source and purity of sample
2. Measurement technique limits
3. Calibration of instruments
4. Care used to perform the measurement
5. Completeness and adequacy of description of procedure
6. Agreement among duplicate measurements, or between
measurements on standard samples and other accepted values
7. Special effect such as contamination or decomposition of sample
8. Estimates of uncertainty, precision, or reproducibility given by the
investigator
9. Experience and credibility of the investigator
Data Uncertainty (2)
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ILThermo DatabaseILThermo DatabaseMain Menu Main Menu
Web Presentation of Physicochemical Web Presentation of Physicochemical Property Data for Ionic LiquidsProperty Data for Ionic Liquids
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Chemical Science and Technology Laboratory
Search CriteriaSearch CriteriaIons
CASRNFormulaChargeNames
PropertyCategoryDescription
Ionic LiquidsCASRNFormulaMolecular weightNames
BibliographyAuthor’s nameJournal titleArticle titleYear of publication
To be addedMeasurement methodSample purityOther statistics
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How to Search A Piece of DataHow to Search A Piece of Data by Ions ?by Ions ?Reference:Title: Thermochemistry of ionic liquid heat-transfer fluidsAuthors: M. E. Van Valkenburg, R. L. Vaughn, M.
Williams and J. S. WilkesSource: Thermochim. Acta 425 (2005) 181-188
Measurements of :−Heat capacity at constant pressure−Specific density−Triple point temperature−Thermal conductivity−Viscosity−Normal melting temperature−Enthalpy of TransitionTotal 16 property data sets
BF4
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Chemical Science and Technology Laboratory
Chemical Science and Technology Laboratory
Provide users worldwide with free internet access to literature information on experimental investigations on ionic liquids
Assist researchers in their literature search, data evaluation, systematic studies on the direction of future investigations
Allow chemical engineers access to complete and up-to-date physicochemical property data of ionic liquids
Anticipated Functionality from ILThermoAnticipated Functionality from ILThermo
