In Memoriam: Anthony (Tony) Goodwin Tracing Tonys Scientific - PowerPoint PPT Presentation

In Memoriam: Anthony (Tony) Goodwin Tracing Tony’s Scientific Footprints Kenneth N. Marsh, J. P. Martin Trusler, William A. Wakeham

Tracing Tony’s Scientific Footprints Scientific Career (Education and Employment) 1981-87 University College London 1987-88 NIST (Gaithersburg) 1988-91 BP (Sunbury) 1991-93 NIST (Gaithersburg) 1993-98 University of Idaho 1998-2014 Schlumberger (Cambridge, Ridgefield, Sugar Land) 2 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Tracing Tony’s Scientific Footprints Scientific Career (Scientific Community) • International Association of Transport Properties • International Association of Chemical Thermodynamics (Chair 2008-2014) • International Union of Pure & Applied Chemistry (Fellow) • Royal Society of Chemistry (Fellow) • Journal of Chemical Thermodynamics (Editor 2002- 2005) • Journal of Chemical & Engineering Data (Associate Editor 2005 – 2012) 3 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

University College London BSc in Chemistry, 1 st Class (1984) • • PhD (1988) • PhD advisor Michael Ewing • Thesis title: “Thermophysical Properties from the Speed of Sound” • Two sub-themes: • organic vapors at low reduced temperatures and low pressures (< 0.1 MPa) • gases at high pressures (up to 7 MPa) 4 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Heat Capacities & Acoustic Virial Coefficients of Organic Vapors • Interest in properties of organic vapors at low reduced temperatures • Conditions under which pV m T measurements were unreliable because of sorption errors Speed of sound ⇒ perfect-gas heat capacity • and acoustic virial coefficients Acoustic virial coefficients ⇒ ordinary virial • coefficients • Requires sound-speed measurements at low pressures: spherical resonators are the ideal tool   c a π f ≈   ≈ f ν Q 0 n 0 n −  2 π a  γ 1 D h 5 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Second Acoustic Virial Coefficients of C 4 and C 5 Alkanes -500 Speed of sound: -1000 2 = + + 2 +  c A A p A p β a /(cm 3 ·mol -1 ) 0 1 2 -1500 = pg A RT γ / M 0 = -2000 RTA / A β 2-Methylpropane 1 0 a Butane -2500 Dimethylpropane 2-Methylbutane Second acoustic virial coefficient: Pentane -3000 ′ 250 270 290 T /K 310 330 β = + γ − pg 2 B 2( 1) TB 5 a Δ β a /(cm 3 ·mol -1 ) ′′ + γ − γ pg pg 2 {( 1) / } T B 0 -5 Second virial coefficient: [ ] ( ) { -10 } = − 3 − − B b 1 λ 1 exp( ε / k T ) 1 250 270 290 T /K 310 330 0 B 6 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Speed of Sound and Second Virial Coefficients of Methanol 335 325 c /(m·s -1 ) 315 280 K 290 K -500 305 300 K 310 K 320 K 330 K 340 K 360 K -1000 295 1 10 p /kPa 100 -1500 B /(cm 3 ·mol -1 ) -2000 Dymond et al -2500 Goodwin et al. -3000 275 300 325 T /K 350 7 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

High-Pressure Spherical Resonator • First application of spherical resonator at “industrial” high pressure • Designed and built at UCL in Tony’s PhD project • Applied to argon, compressed air, methane and a natural gas at pressures up to 7 MPa 8 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

High-Pressure Speeds of Sound Methane Argon 460 255 K 273 K 300 K 255 K 273 K 300 K 330 440 c /(m·s -1 ) c /(m·s -1 ) 420 310 400 380 290 0 1 2 3 p /MPa 4 5 6 7 0 1 2 3 p /MPa 4 5 6 7 0.02% 0.01% Deviations from Setzmann- Δ c / c Wagner EoS (1992) 0.01% Δ c / c 0.00% 0.00% Deviations from Tegeler- Span-Wagner EoS (1999) -0.01% -0.01% 0 1 2 3 p /MPa 4 5 6 7 0 1 2 3 p /MPa 4 5 6 7 9 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Footprints: UCL 1. M.B. Ewing, A.R.H. Goodwin, M.L. McGlashan, J.P.M. Trusler, J. Chem. Thermodyn. 19 (1987) 721-739 2. M.B. Ewing, A.R.H. Goodwin, M.L. McGlashan, J.P.M. Trusler, J. Chem. Thermodyn. 20 (1988) 243-256. 3. M.B. Ewing, A.R.H. Goodwin, J.P.M. Trusler, J. Chem. Thermodyn. 21 (1989) 867-877. 4. M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 23 (1991) 1107-1120. 5. M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 23 (1991) 1163-1168. 6. M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 24 (1992) 1257-1274. 7. M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 24 (1992) 531-547. 8. M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 24 (1992) 301-315. 9. S.J. Boyes, M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 24 (1992) 1151-1166. 10. M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 25 (1993) 1503-1511. 11. M.B. Ewing, A.R.H. Goodwin, J. Chem. Thermodyn. 25 (1993) 423-427. 10 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

NIST • 1987-88 Guest Scientist • developed and applied spherical-resonator apparatus to determine thermophysical properties of refrigerant working fluids • microwave measurements of thermal expansion of a spherical resonator for primary acoustic thermometry • 1991-93 Research Chemist • developed and applied RF cavity resonator for measurements of fluid relative permittivity, phase boundaries and densities • measured static relative permittivity of water • measured dipole moments and vapour pressures of refrigerant working fluids Working with: Mike Moldover, Anneke Levelt-Sengers, Jim Mehl, Keith Gillis, Graham Morrison, Lloyd Weber, Jan Sengers (University of Maryland) Diego Fernández and others. 11 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Thermodynamic Properties of Refrigerant Working Fluids • Spherical acoustic resonator used to measure sound speeds in gas phase • Perfect-gas heat capacity and second and third acoustic virial coefficients obtained • Square-well potential models used to extract ordinary second and third virial coefficients • Three papers: R134a, R123, R141b “He was a remarkably productive scientist and an energetic and enthusiastic collaborator.” - Mike Moldover 12 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Primary Acoustic Thermometry = + + + 2 2 c A A p A p  0 1 2 = pg A RT γ / M 0 • Acoustic and microwave resonances 2   + T f ( T , p ) Δ f ( T , p ) = lim a a   + T f ( T , p ) Δ f ( T , p ) →   p 0 0 a 0 a 0 2   + f ( T , p ) Δ f ( T , p ) × m 0 m 0   + f ( T , p ) Δ f ( T , p )     m m • T 0 = temperature of the triple point of water Triple point temperatures of Hg and Ga • measured T – T 90 measured between (217 and 303) K • 13 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Application of RF Cavity Resonators ≈ 2 π f 1 / ε LC C 2 H 6 + CO 2 Near-Critical Behaviour 0 r − + ≈ ( ε 1 ) /( ε 2 ) A ρ r r ε = + A x A x A ε 1 ε , 1 2 ε , 2  , RF cavity;  , LF capacitor 14 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Static Relative Permittivity of Water at Ambient Pressure • Precision concentric-cylinder capacitor 85 • LCR meter and transformer bridge for 80 capacitance measurements 75 ε r 70 65 60 55 T /K 270 290 310 330 350 370 0.2 LCR 0.1 TB Δε r 0.0 -0.1 -0.2 270 290 310 330 T /K 350 370 15 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Vapour Pressure Measurements Vapour Pressure of R134a 1000 p /kPa 100 Dynamic Static Fit 10 210 230 250 270 T /K 290 310 5.0 10 4 Δ p / p 0.0 -5.0 210 230 250 270 T /K 290 310 16 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015

Adapting Acoustic Resonators for Difficult Fluids 17 19th Symposium on Thermophysical Properties, Boulder CO, 21-26 June 2015