11/8/20074th Challenge IFPSC1 Establishing Benchmarks for the Fourth Industrial Fluid Properties...

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


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


Acknowledgements – Data Reviewed by:

Dan Friend – NIST

Rob Chirico – NIST (TRC)

Marcia Huber - NIST


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.


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.


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)



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)



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)


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.


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 (%)


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)


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


Saturated Vapor-Phase Density at 375 K



Benchmark calculated from second virial equation – agrees within uncertainty with the PPDS value.


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.


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.


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


Critical Density



Benchmark taken from Ambrose & Townsend, "Vapor-Liquid Critical Properties“, National Physical Laboratory, Middlesex, United Kingdom (1977)


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)


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)


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.


Saturated Liquid Isothermal Compressibility at 375 K

Benchmark = 2.60 [106 kPa]-1


Benchmark calculated from Brelvi-O'Connell correlation.


Saturated Vapor Isothermal Compressibility at 375 K

Benchmark = 819 [106 kPa]-1


Benchmark calculated from second virial equation.


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.


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)


Saturated Vapor Viscosity at 375 K

Benchmark = 0.0000124 Pa-s Uncertainty = 6.5 % Maximum allowed Deviation = 30 %

Benchmark taken from PPDS estimation.


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).


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.

Date post:	16-Dec-2015
Category:	Documents
Upload:	lonnie-linscott
View:	226 times
Download:	2 times

11/8/20074th Challenge IFPSC1 Establishing Benchmarks for the Fourth Industrial Fluid Properties...

Documents