11/8/20074th Challenge IFPSC1 Establishing Benchmarks for the Fourth Industrial Fluid Properties Simulation Challenge James D. Olson The Dow Chemical Company November 8, 2007

11/8/20074th Challenge IFPSC2 Overview zThe Fourth Challenge  Three Categories of Benchmarks zBenchmark Data Sources  Literature and estimations from DIPPR and PPDS zThe 17 Benchmarks and Uncertainties  Second virial coefficient Benchmark value was revised

11/8/20074th Challenge IFPSC3 Acknowledgements – Data Reviewed by: zDan Friend – NIST zRob Chirico – NIST (TRC) zMarcia Huber - NIST

11/8/20074th Challenge IFPSC4 Industrial Fluid Properties Simulation Challenge zIndustrial use of molecular simulation:  Qualitative use vs quantitative chemical use: xQualitative - explore structure and mechanisms at the molecular level, pico-sec time scale; e.g., to study formation and structure of surfactant micelles. xQuantitative - produce process design data for state conditions not (easily) accessible to lab measurements.

11/8/20074th Challenge IFPSC5 The Fourth Challenge zThe primary objective of the Fourth Industrial Fluid Properties Simulation Challenge is to test the transferability of methods and force fields to a wide variety of properties for a given small molecule.

11/8/20074th Challenge IFPSC6 Three Categories of Benchmarks zCategory 1 (100 points total)  Saturated liquid phase density at 375 K (11 points max)  Saturated vapor phase density at 375 K (11 points max)  Second virial coefficient at 375 K (11 points max)  Vapor pressure at 375 K (11 points max)  Heat of vaporization at 375 K (11 points max)  Normal boiling temperature at kPa (15 points max)  Critical density (15 points max)  Critical temperature (15 points max)

11/8/20074th Challenge IFPSC7 Three Categories of Benchmarks zCategory 2 (100 points total)  Saturated liquid phase heat capacity at 375 K (15 points max)  Saturated vapor phase heat capacity at 375 K (15 points max)  Saturated liquid phase isothermal compressibility at 375 K (20 points max)  Saturated vapor phase isothermal compressibility at 375 K (20 points max)  Surface tension at 375 K (30 points max)

11/8/20074th Challenge IFPSC8 Three Categories of Benchmarks zCategory 3 (100 points total)  Saturated liquid phase viscosity at 375 K (25 points max)  Saturated vapor phase viscosity at 375 K (25 points max)  Saturated liquid phase thermal conductivity at 375 K (25 points max)  Saturated vapor phase thermal conductivity at 375 K (25 points max)

11/8/20074th Challenge IFPSC9 Benchmark Data Sources zThe previous three Challenges used data measured specifically for the challenge, e.g., liquid viscosity of 2-propanol + nonane mixtures. zNo new experimental data were measured for the Fourth Challenge. Also, for several EO properties no data have ever been measured above 280 K. zAppropriately larger uncertainties were assigned.

11/8/20074th Challenge IFPSC10 Benchmark Data Source Strategy zThree data sources were used (similar strategy to that used in an industrial process design) :  Data published in peer-reviewed scientific literature.  Data from AICHE DIPPR Database – correlations fitted to experimental data where available or estimation methods.  Data from Physical Properties Data Service (PPDS) – associated with UK NPL

11/8/20074th Challenge IFPSC14 Second Virial Coefficient at 375 K zBenchmark = cm 3 /g  Uncertainty = 4.9 %  Maximum allowed Deviation = 25 % zBenchmark taken as mean between the value derived from the Walters and Smith PVT data and the value derived from the Hurly sound speed data. zBenchmark value was revised after discovery of Hurly sound speed data for ethylene oxide

11/8/20074th Challenge IFPSC16 Saturated Liquid-Phase Density at 375 K zBenchmark = g/cm 3  Uncertainty = 0.5 %  Maximum allowed Deviation = 5 % zBenchmark taken from DIPPR density equation fitted to available experimental data.

11/8/20074th Challenge IFPSC18 Saturated Vapor-Phase Density at 375 K zBenchmark = g/cm 3  Uncertainty = 4.1 %  Maximum allowed Deviation = 20 % zBenchmark calculated from second virial equation – agrees within uncertainty with the PPDS value.

11/8/20074th Challenge IFPSC19 Vapor Pressure at 375 K zBenchmark = 1437 kPa  Uncertainty = 1.5 %  Maximum allowed Deviation = 8 % zBenchmark taken from DIPPR vapor pressure equation fitted to available experimental data.

11/8/20074th Challenge IFPSC20 Heat of Vaporization at 375 K zBenchmark = 453 J/g  Uncertainty = 1.8 %  Maximum allowed Deviation = 10 % zBenchmark taken from DIPPR heat of vaporization equation fitted to data derived from the vapor pressure via the Clapeyron equation.

11/8/20074th Challenge IFPSC21 Normal Boiling Point at kPa zBenchmark = K  Uncertainty = 0.2 %  Maximum allowed Deviation = 5 % zBenchmark taken from data of Giauque and co-workers, J. Amer. Chem. Soc. (1949) 71, 2176

11/8/20074th Challenge IFPSC22 Critical Density zBenchmark = g/cm 3  Uncertainty = 5.1 %  Maximum allowed Deviation = 25 % zBenchmark taken from Ambrose & Townsend, "Vapor-Liquid Critical Properties“, National Physical Laboratory, Middlesex, United Kingdom (1977)

11/8/20074th Challenge IFPSC23 Critical Temperature zBenchmark = K  Uncertainty = 0.2 %  Maximum allowed Deviation = 5 % zBenchmark taken from Ambrose & Townsend, “Vapor-Liquid Critical Properties“, National Physical Laboratory, Middlesex, United Kingdom (1977)

11/8/20074th Challenge IFPSC24 Saturated Liquid Heat Capacity at 375 K zBenchmark = 2.30 J/[g-K]  Uncertainty = 8.3 %  Maximum allowed Deviation = 40 % zBenchmark taken from an extrapolation of the measured data of Giauque and coworkers compared to PPDS and DIPPR

11/8/20074th Challenge IFPSC26 Saturated Vapor Heat Capacity at 375 K zBenchmark = 1.67 J/[g-K]  Uncertainty = 15 %  Maximum allowed Deviation = 50 % zBenchmark taken from PPDS real gas correction to ideal gas heat capacity.

11/8/20074th Challenge IFPSC27 Saturated Liquid Isothermal Compressibility at 375 K zBenchmark = 2.60 [10 6 kPa] -1  Uncertainty = 23.1 %  Maximum allowed Deviation = 50 % zBenchmark calculated from Brelvi- O'Connell correlation.

11/8/20074th Challenge IFPSC28 Saturated Vapor Isothermal Compressibility at 375 K zBenchmark = 819 [10 6 kPa] -1  Uncertainty = 9.2 %  Maximum allowed Deviation = 45 % zBenchmark calculated from second virial equation.

11/8/20074th Challenge IFPSC29 Surface Tension at 375 K zBenchmark = N/m  Uncertainty = 12.5 %  Maximum allowed Deviation = 50 % zBenchmark taken from DIPPR surface tension equation fitted to data given by Jasper.

11/8/20074th Challenge IFPSC30 Saturated Liquid Viscosity at 375 K zBenchmark = Pa-s  Uncertainty = 13.2 %  Maximum allowed Deviation = 50 % zBenchmark taken from DIPPR viscosity equation fitted to experimental data of Maass and Boomer.

11/8/20074th Challenge IFPSC32 Saturated Vapor Viscosity at 375 K zBenchmark = Pa-s  Uncertainty = 6.5 %  Maximum allowed Deviation = 30 % zBenchmark taken from PPDS estimation.

11/8/20074th Challenge IFPSC33 Saturated Liquid Thermal Conductivity at 375 K zBenchmark = 0.12 W/[m-K]  Uncertainty = 25 %  Maximum allowed Deviation = 50 % zBenchmark taken from DIPPR thermal conductivity equation fitted to data estimated by Missenard method (there are no experimental data at any temperature).

11/8/20074th Challenge IFPSC34 Saturated Vapor Thermal Conductivity at 375 K zBenchmark = W/[m-K]  Uncertainty = 14.7 %  Maximum allowed Deviation = 50 % zBenchmark taken from DIPPR thermal conductivity equation fitted to data measured by Senftleben.