ACS Spring National meeting Chicago, Illinois, March 27, 2007

1. New Global Communication Process in Thermodynamics and its Impact on Quality of Published Experimental Data ACS Spring National meeting Chicago, Illinois, March 27, 2007 Michael Frenkel Thermodynamics Research Center (TRC) National Institute of Standards and Technology (NIST) Boulder, Colorado

2. Outline • Global Information Systems: • Purpose, Requirements, Components • Application to the Field of Thermodynamics: Impact Areas, Components, and their Architecture • From Data to Wisdom in one Gigantic Step • Impact on Chemical Process Design: • “Bundling” with Simulation Engines • New Capabilities for the “on-Demand” Design • Impact on Efficiency of Information Delivery: • Establishing Global Data Communication Process • Delivering Information from “Data Producers” to “Data Users” • Impact on Publication Quality: • Information Integration and Publication Quality • Some Surprising Findings

3. Global Information Systems: Information Systems Designed to… • Collect, Process, Integrate, Evaluate, and Communicate the Entire “Body of Knowledge” Pertaining to a Field and • Support Any Application Requiring This Knowledge in an “on-Demand” Mode with Definitive Information Quality Assessments

4. ThermoML Global Information Systems Application to the Field of Thermodynamics • Software tools for mass-scale data capture • Guided Data Capture (GDC) software • Comprehensive Data Storage Facility • SOURCE Data Archival System • Data Entry Facility • NIST/TRC Data Entry Facility • Data Communications Standard • ThermoML • Data Reader Software • ThermoML Opener into Microsoft Excel • Software Expert Systems • ThermoData Engine (TDE) software • Web Communication Portal • NIST Web-Oracle infrastructure

5. Efficiency of Information Delivery Journal Publication Quality Instrument Calibration & Validation Chemical Process Design Scientific Discovery Process Molecular Modeling & Property Prediction Strategic Experiment Planning Global Information System In Thermodynamics

6. Guided Data Capture (GDC) software Metadata: Phases, Constraints, Variables, Units, Uncertainties Numerical Data Graphical Representation

7. SOURCE Data Archival System SINGLEVALUE CMPID FIXEDCONDITION ALTCMPNM ONEVARDATA Pure Compounds ONEVAR SAMPLES TWOVARDATA • Structure is based on the Gibbs Phase Rule • Accommodates a wide variety of reported data representations (absolute, ratio, difference, a variety of composition measures, etc.) TWOVAR Binary Mixtures SYSREF BINREF BINSINGLEVALUE BINONEVAR BINONEVARDATA Ternary Mixtures BOINTWOVAR Reactions BINTWOVARDATA BINTHREEVAR REFINFO BINTHREEVARIDATA TERNSINGLEVALUE TERNREF TERNONEVAR TERNONEVARDATA AUTHREF TERNTWOVAR TERNTWOVARDATA TERNTHREEVAR TERNTHREEVARDATA AUTHOR REACTCHANGED REACT REF REACTEQUIDATA REACTEQUIL4DATA

8. Data Processing at NIST Thermodynamics Research Center Incoming Data Flow 500,000 data points/year In-House Data Processing Major journal cooperation • NIST/TRC Data Entry Facility Communications Data Capture Software Support Data Capture from international data repository resources (Russia/China) Managerial support Access to NIST SOURCE/Oracle Database Unix Network Workstation Communications Windows Network Tools Hardcopy digitizing Guided Data Capture: GDC software Student-based operation: University of Colorado, Boulder Colorado School of Mines, Golden

9. ThermoML ThermoML

11. ThermoML Opener into Microsoft Excel <?xml version="1.0" encoding="UTF-8"?> <?xml-stylesheet href="http://www-i.boulder.nist.gov/div838/trc/journals/jced/ThermoMLtoHTML.xsl" type="text/xsl"?> <!--Created by Guided Data Capture (GDC) Software (http://www.trc.nist.gov)--> <DataReport xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xsi:noNamespaceSchemaLocation="http://www.trc.nist.gov/ThermoML.xsd"> <Version> <nVersionMajor>2</nVersionMajor> <nVersionMinor>0</nVersionMinor> </Version> <Citation> <TRCRefID> <yrYrPub>2005</yrYrPub> <sAuthor1>ash</sAuthor1> <sAuthor2></sAuthor2> <nAuthorn>0</nAuthorn> </TRCRefID> <eType>journal</eType> <eSourceType>Original</eSourceType> <sAuthor>Ashour, I.[Ibrahim]</sAuthor> <sPubName>J. Chem. Eng. Data</sPubName> <yrPubYr>2005</yrPubYr> <dateCit>2005-02-10</dateCit> <sTitle>Liquid-Liquid Equilibrium of MTBE + Ethanol + Water and MTBE + 1-Hexanol + Water over the Temperature Range of 288.15 to 308.15 K</sTitle> <sAbstract>Liquid-liquid equilibrium data for methyl tert-butyl ether (MTBE) + ethanol + water and MTBE + 1-hexanol + water have been experimentally measured over the temperature range of 288.15 to 308.15 K. The equilibrium data of this work, in addition to the available MTBE-containing LLE data in the technical literature, are analyzed using UNIQUAC, NRTL, UNIFAC-LL, and UNIFAC-DMD models as programmed by the Aspen Plus simulator. On the basis of analyses of the experimental data of this work, UNIFAC-LLE and UNIFAC-DMD showed the best predictive performance for the mole fraction of the target species (MTBE) in both the organic and aqueous phases.</sAbstract> <sKeyword>Liquid-Liquid Equilibrium</sKeyword> <sKeyword>MTBE</sKeyword> <sKeyword>Ethanol</sKeyword> <sKeyword>Water</sKeyword> <sKeyword>1-Hexanol</sKeyword> <sVol>50</sVol> <sPage>113-118</sPage> </Citation>

12. ThermoData Engine (TDE) software Used for > 200 years in all critical data evaluation worldwide Developed at NIST:Implemented for the first time in 2004

13. General Algorithm for Dynamic Data EvaluationThermoData Engine (TDE) Load from database Trivial normalization Non-trivial normalization within block First property block Add predicted values Enforce inter-block consistency Select models &fit properties Process “Other” properties Enforce consistency within block Calculate uncertainties Next block? Y N Output

14. First software implementation of the dynamic data evaluation concept – NIST/Boulder 2004

15. Three-tier Web Database Process Flow HTTP Listener HTTP Listener Web User Interface Web User Interface Business Logic Data Definition Business Logic Data Definition WEB DEVELOPMENT SERVER WEB SERVER JDBC JDBC • NIST Web-Oracle infrastructure

18. A ThermoML file available for free download Primary purpose: machine-to-machine communication Searchable database on the Web for humans is in development

19. Combining on-demand critical data evaluation with global data delivery

20. Version 2006 New landmark cooperation: NIST & AspenTech “…this achievement represents unprecedented opportunities for our customers in the design and improvement of their manufacturing processes. …” Mark Fusco, AspenTech, President and CEO Press release: January 31, 2007 Cambridge, MA Critically evaluated data for 14,000 chemicals 45,000 corporate users

21. Data On-Demand • Implemented with • Aspen Technology • Data generated by TDE • are available through • AspenPlus 2006 (Jan 2007) • 45,000 Corporate clients • are receiving access New/Improved Processes NIST/TRC SOURCE Data System Simulation Engine WEB ThermoML O/P ThermoData Engine (TDE) Local SOURCE

23. AspenTech (USA) Virtual Materials Group (Canada) Nat’l Engineering Lab (UK) Fiz Chemie (Germany) Global Data Communications: Role of NIST Committee on Printed & Electronic Publication (CPEP) International Association of Chemical Thermodynamics (IACT) IUPAC Industrial Engineers Experimentalists NIST Guided Data Capture (GDC) Applications Measurements J. Chem. Eng. Data (ACS) J. Chem. Thermodyn. (Elsevier) Fluid Phase Equilib. (Elsevier) Int. J. Thermophys. (Springer) Thermochimica Acta (Elsevier) Users Products “Reader” Software ThermoML NIST ThermoML Archive WEB Industry: DIPPR

24. Data Producers (Article Authors) Article submission Major Journals NIST/TRC In-House Data Capture Inconsistencies to be resolved After peer review Article Authors Data Capture Problems communicated GDC GDC communication line Files are converted to ThermoML format TDE communication line NIST/TRC SOURCEData System ThermoML On-demand critical data evaluation ThermoData Engine Data files in ThermoML format are posted on the Web Process design, optimization, and basic research Archive of published experimental data in ThermoML format Data Users Cooperation with journals for global data dissemination in ThermoML format • J. Chem Eng. Data • J. Chem. Thermodyn. • Fluid Phase Equilib. • Int. J. Thermophys. • Thermochim. Acta • ~600 articles/year • ~100,000 data pts/yr • ~80% of data in field

25. Data Analysis: GDC Communication Line A B Specific density / (gcm-3) T / K T / K Mass (specific) density as a function of temperature for mixtures of chlorobenzene and dimethyl carbonate. The lines represent results for various mixture compositions. The figures show the reported experimental data before (A) and after (B) correction. The circle indicates the erroneous values in the upper figure. The graphs were created with the GDC software.

26. Data Analysis: GDC Communication Line A B T / K Mole fraction of tetrahydrofuran Mole fraction of tetrahydrofuran Boiling temperatures Tb at constant pressure for (tetrahydrofuran + tetrachloroethene). The figures show the reported experimental data before (A) and after (B) correction. The arrows indicate boiling temperatures for the pure components critically evaluated with the ThermoData Engine (TDE) software. □ , Tb= (337.38 ± 0.03) K at p = 95.8 kPa for tetrahydrofuran critically evaluated with TDE. , Tb= (392.16 ± 0.06) K at p = 95.8 kPa for tetrachloroethene critically evaluated with TDE. The graphs were created with the GDC software.

27. Liquid phase region Liquid phase region Saturated liquid density curve Saturated liquid density curve 2-Phase (Liquid + Gas) region 2-Phase (Liquid + Gas) region Data Analysis: TDE Communication Line A B Densities for tetrahydrofuran. Experimental data (red) are reported for density as a function of temperature and pressure in the liquid phase before (A) and after (B) correction. The saturation line (i.e., the line of separation between the one- and two-phase regions) critically evaluated with TDE is shown in the plot. The blue lines correspond to the isobars evaluated by TDE for the single phase region. The graphs were created with the TDE software.