11/8/20074th challenge ifpsc1 establishing benchmarks for the fourth industrial fluid properties...
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11/8/2007 4th Challenge IFPSC 1
Establishing Benchmarks
for the Fourth Industrial Fluid
Properties Simulation Challenge
James D. Olson
The Dow Chemical Company
November 8, 2007
11/8/2007 4th Challenge IFPSC 2
Overview
The Fourth Challenge Three Categories of Benchmarks
Benchmark Data Sources Literature and estimations from DIPPR and PPDS
The 17 Benchmarks and Uncertainties Second virial coefficient Benchmark value was
revised
11/8/2007 4th Challenge IFPSC 3
Acknowledgements – Data Reviewed by:
Dan Friend – NIST
Rob Chirico – NIST (TRC)
Marcia Huber - NIST
11/8/2007 4th Challenge IFPSC 4
Industrial Fluid Properties Simulation Challenge
Industrial use of molecular simulation: Qualitative use vs quantitative chemical use:
Qualitative - explore structure and mechanisms at the molecular level, pico-sec time scale; e.g., to study formation and structure of surfactant micelles.
Quantitative - produce process design data for state conditions not (easily) accessible to lab measurements.
11/8/2007 4th Challenge IFPSC 5
The Fourth Challenge
The 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.
11/8/2007 4th Challenge IFPSC 6
Three Categories of Benchmarks
Category 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 101.325 kPa (15 points max) Critical density (15 points max) Critical temperature (15 points max)
11/8/2007 4th Challenge IFPSC 7
Three Categories of Benchmarks
Category 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)
11/8/2007 4th Challenge IFPSC 8
Three Categories of Benchmarks
Category 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)
11/8/2007 4th Challenge IFPSC 9
Benchmark Data Sources
The previous three Challenges used data measured specifically for the challenge, e.g., liquid viscosity of 2-propanol + nonane mixtures.
No new experimental data were measured for the Fourth Challenge. Also, for several EO properties no data have ever been measured above 280 K.
Appropriately larger uncertainties were assigned.
11/8/2007 4th Challenge IFPSC 10
Benchmark Data Source Strategy
Three 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
Max
Benchmark Data - Fourth Challenge IFPSC Benchmark AllowedUncertainty Deviation
Benchmark (%) (%)Category 1
saturated liquid phase density (g/cm 3̂) 0.744 0.5 5.0saturated vapor phase density (g/cm 3̂) 0.024 4.1 20.0second virial coefficient (cm 3̂/g) -7.59 4.9 25.0vapor pressure (kPa) 1437.1 1.5 8.0heat of vaporization (J/g) 453 1.8 10.0normal boiling temperature at 101.325 kPa (K) 283.7 0.2 5.0critical density (g/cm^3) 0.314 5.1 25.0critical temperature (K) 469.15 0.2 5.0
Category 2saturated liquid phase heat capacity (Cp) (J/g K) 2.30 8.3 40.0saturated vapor phase heat capacity (Cp) (J/g K) 1.67 15.0 50.0saturated liquid phase isothermal compressibility 1/(10 6̂ kPa) 2.60 23.1 50.0saturated vapor phase isothermal compressibility 1/(10 6̂ kPa) 819.00 9.2 45.0surface tension (N/m) 0.012 12.5 50.0
Category 3saturated liquid phase viscosity (Pa s) 1.51E-04 13.2 50.0saturated vapor phase viscosity (Pa s) 1.24E-05 6.5 30.0saturated liquid phase thermal conductivity (W/m K) 0.12 25.0 50.0saturated vapor phase thermal conductivity (W/m K) 0.0204 14.7 50.0
Max
Benchmark Data - Fourth Challenge IFPSC Benchmark AllowedUncertainty Deviation
Benchmark (%) (%)Category 1
saturated liquid phase density (g/cm^3) 0.744 0.5 5.0saturated vapor phase density (g/cm^3) 0.024 4.1 20.0second virial coefficient (cm^3/g) -7.59 4.9 25.0vapor pressure (kPa) 1437.1 1.5 8.0heat of vaporization (J/g) 453 1.8 10.0normal boiling temperature at 101.325 kPa (K) 283.7 0.2 5.0critical density (g/cm^3) 0.314 5.1 25.0critical temperature (K) 469.15 0.2 5.0
Category 2saturated liquid phase heat capacity (Cp) (J/g K) 2.30 8.3 40.0saturated vapor phase heat capacity (Cp) (J/g K) 1.67 15.0 50.0saturated liquid phase isothermal compressibility 1/(10^6 kPa) 2.60 23.1 50.0saturated vapor phase isothermal compressibility 1/(10^6 kPa) 819.00 9.2 45.0surface tension (N/m) 0.012 12.5 50.0
Category 3saturated liquid phase viscosity (Pa s) 1.51E-04 13.2 50.0saturated vapor phase viscosity (Pa s) 1.24E-05 6.5 30.0saturated liquid phase thermal conductivity (W/m K) 0.12 25.0 50.0saturated vapor phase thermal conductivity (W/m K) 0.0204 14.7 50.0
Experimental studies that include 375 KExperimental data only up to 280 KNo experimental data
0.0
10
20
30
40
50
60
0.0 5.0 10 15 20 25 30
Maximum Allowed Deviationvs
Benchmark Uncertainty
Max
imu
m A
llow
ed D
evi
atio
n (
%)
Benchmark Uncertainty (%)
11/8/2007 4th Challenge IFPSC 14
Second Virial Coefficient at 375 K
Benchmark = -7.59 cm3/g Uncertainty = 4.9 % Maximum allowed Deviation = 25 %
Benchmark taken as mean between the value derived from the Walters and Smith PVT data and the value derived from the Hurly sound speed data.
Benchmark value was revised after discovery of Hurly sound speed data for ethylene oxide
-700
-600
-500
-400
-300
-200
300 320 340 360 380 400 420 440
2nd Virial Coefficient of Ethylene Oxide
B derived from Walters and Smith PVT data
NIST - Hurly; B derived from sound speed data
Stryjek data
Revised Benchmark value and uncertainty
B(c
m3
/mo
le)
T(K)
11/8/2007 4th Challenge IFPSC 16
Saturated Liquid-Phase Density at 375 K
Benchmark = 0.744 g/cm3
Uncertainty = 0.5 % Maximum allowed Deviation = 5 %
Benchmark taken from DIPPR density equation fitted to available experimental data.
0.40
0.50
0.60
0.70
0.80
0.90
1.00
200 250 300 350 400 450 500
DIPPR Density Equation fitted to EO Density Data
Density - Experimental Data
Density - DIPPR Equation 105
Den
sit
y (g
/cc
)
T(K)
Benchmark
11/8/2007 4th Challenge IFPSC 18
Saturated Vapor-Phase Density at 375 K
Benchmark = 0.024 g/cm3
Uncertainty = 4.1 % Maximum allowed Deviation = 20 %
Benchmark calculated from second virial equation – agrees within uncertainty with the PPDS value.
11/8/2007 4th Challenge IFPSC 19
Vapor Pressure at 375 K
Benchmark = 1437 kPa Uncertainty = 1.5 % Maximum allowed Deviation = 8 %
Benchmark taken from DIPPR vapor pressure equation fitted to available experimental data.
11/8/2007 4th Challenge IFPSC 20
Heat of Vaporization at 375 K
Benchmark = 453 J/g Uncertainty = 1.8 % Maximum allowed Deviation = 10 %
Benchmark taken from DIPPR heat of vaporization equation fitted to data derived from the vapor pressure via the Clapeyron equation.
11/8/2007 4th Challenge IFPSC 21
Normal Boiling Point at 101.325 kPa
Benchmark = 283.7 K Uncertainty = 0.2 % Maximum allowed Deviation = 5 %
Benchmark taken from data of Giauque and co-workers, J. Amer. Chem. Soc. (1949) 71, 2176
11/8/2007 4th Challenge IFPSC 22
Critical Density
Benchmark = 0.314 g/cm3
Uncertainty = 5.1 % Maximum allowed Deviation = 25 %
Benchmark taken from Ambrose & Townsend, "Vapor-Liquid Critical Properties“, National Physical Laboratory, Middlesex, United Kingdom (1977)
11/8/2007 4th Challenge IFPSC 23
Critical Temperature
Benchmark = 469.15 K Uncertainty = 0.2 % Maximum allowed Deviation = 5 %
Benchmark taken from Ambrose & Townsend, “Vapor-Liquid Critical Properties“, National Physical Laboratory, Middlesex, United Kingdom (1977)
11/8/2007 4th Challenge IFPSC 24
Saturated Liquid Heat Capacity at 375 K
Benchmark = 2.30 J/[g-K] Uncertainty = 8.3 % Maximum allowed Deviation = 40 %
Benchmark taken from an extrapolation of the measured data of Giauque and coworkers compared to PPDS and DIPPR
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
250 300 350 400
Saturated Liquid Heat Capacity, J/[g-K]Ethylene Oxide
DIPPR
PPDS
Experimental Data
Benchmark Extrapolation
Sat
ura
ted
Liq
uid
Hea
t C
apac
ity,
J/[
g-K
]
T(K)
11/8/2007 4th Challenge IFPSC 26
Saturated Vapor Heat Capacity at 375 K
Benchmark = 1.67 J/[g-K] Uncertainty = 15 % Maximum allowed Deviation = 50 %
Benchmark taken from PPDS real gas correction to ideal gas heat capacity.
11/8/2007 4th Challenge IFPSC 27
Saturated Liquid Isothermal Compressibility at 375 K
Benchmark = 2.60 [106 kPa]-1
Uncertainty = 23.1 % Maximum allowed Deviation = 50 %
Benchmark calculated from Brelvi-O'Connell correlation.
11/8/2007 4th Challenge IFPSC 28
Saturated Vapor Isothermal Compressibility at 375 K
Benchmark = 819 [106 kPa]-1
Uncertainty = 9.2 % Maximum allowed Deviation = 45 %
Benchmark calculated from second virial equation.
11/8/2007 4th Challenge IFPSC 29
Surface Tension at 375 K
Benchmark = 0.012 N/m Uncertainty = 12.5 % Maximum allowed Deviation = 50 %
Benchmark taken from DIPPR surface tension equation fitted to data given by Jasper.
11/8/2007 4th Challenge IFPSC 30
Saturated Liquid Viscosity at 375 K
Benchmark = 0.000151 Pa-s Uncertainty = 13.2 % Maximum allowed Deviation = 50 %
Benchmark taken from DIPPR viscosity equation fitted to experimental data of Maass and Boomer.
0.00010
0.00020
0.00030
0.00040
0.00050
0.00060
250 300 350 400
Saturated Liquid Viscosity, Pa-sEthylene Oxide
DIPPR
PPDS
Experimental Data
Benchmark Extrapolation
Sat
ura
ted
Liq
uid
Vis
cos
ity,
Pa-
s
T(K)
11/8/2007 4th Challenge IFPSC 32
Saturated Vapor Viscosity at 375 K
Benchmark = 0.0000124 Pa-s Uncertainty = 6.5 % Maximum allowed Deviation = 30 %
Benchmark taken from PPDS estimation.
11/8/2007 4th Challenge IFPSC 33
Saturated Liquid Thermal Conductivity at 375 K
Benchmark = 0.12 W/[m-K] Uncertainty = 25 % Maximum allowed Deviation = 50 %
Benchmark taken from DIPPR thermal conductivity equation fitted to data estimated by Missenard method (there are no experimental data at any temperature).
11/8/2007 4th Challenge IFPSC 34
Saturated Vapor Thermal Conductivity at 375 K
Benchmark = 0.0204 W/[m-K] Uncertainty = 14.7 % Maximum allowed Deviation = 50 %
Benchmark taken from DIPPR thermal conductivity equation fitted to data measured by Senftleben.