Selecting Critical Properties of Terpenes and Terpenoids through Group-Contribution Methods and Equations of State

Μέγεθος: px

Εμφάνιση ξεκινά από τη σελίδα:

Download "Selecting Critical Properties of Terpenes and Terpenoids through Group-Contribution Methods and Equations of State"

ÍΒενιαμίν Βενιζέλος
5 χρόνια πριν
Προβολές:

1 Supporting Information Selecting Critical Properties of Terpenes and Terpenoids through Group-Contribution Methods and Equations of State Mónia A. R. Martins, 1,2 Pedro J. Carvalho, 1 André M. Palma, 1 Urszula Domańska, 2 João A. P. Coutinho 1 and Simão P. Pinho 3* 1 CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro, Portugal. 2 Physical Chemistry Department, Warsaw University of Technology, Warsaw, Poland. 3 Associate Laboratory LSRE/LCM, Departamento de Tecnologia Química e Biológica, Instituto Politécnico de Bragança, Bragança, Portugal. *Corresponding author: Phone: ; Fax: ; spinho@ipb.pt. 1

2 Table S1. Joback group-contributions used in this work. Group k tck / K pck / bar =C =C(ds) =CH =CH(ds) =CH ACOH (phenol) C C (ss) C=O (ss) CH CH (ss) CH CH 2 (ss) CH O O (ss) OH

3 Table S2. Constantinou and Gani group-contributions used in this work. Group k First Order tc1k / K pc1k / bar AC ACCH ACCH ACCH ACH ACOH C C=C C=CH C=CH CH CH=CH CH=CH CH CH 2 CO CH CH 3 O CH-O OH Second Order tc2j / K pc2j / bar 6 membered ring membered ring AC-O-CH m C-CH m =CH n C cyclic =O CH 2 -CH m =CH n CH 3 -CH m =CH n CH m, cyclic -OH CH n =CH m -CH p =CH k COH

4 Table S3. Wilson-Jasperson atomic contributions used in this work. Atom Δtck Δpck C H O Group Δtcj Δpcj OH (C 5 or more) >CO O

5 Table S4. Density, ρ, of pure components at different temperatures and at p = 0.1 MPa. a T / K ( )-menthone T / K (1R)-( )- fenchone T / K (S)-(+)- carvone T / K Carvacrol T / K Eucalyptol T / K DL-citronellol T / K Eugenol T / K Geraniol a Standard uncertainties, u, are u(t) = 0.01 K and u(ρ) = g cm -3. For (R)-(+)-limonene and p-cymene are u(t) = 0.02 K, u(ρ) = g cm -3. 5

6 Table S4. Density, ρ, of pure components at different temperatures and at p = 0.1 MPa. a (cont.) T / K (-)-isopulegol T / K Linalool T / K L(-)-menthol T / K Thymol T / K α-pinene oxide T / K (R)-(+)-Limonene T / K α-pinene T / K β- pinene T / K p-cymene a Standard uncertainties, u, are u(t) = 0.01 K and u(ρ) = g cm -3. For (R)-(+)-limonene and p-cymene are u(t) = 0.02 K, u(ρ) = g cm -3. 6

7 Table S5. Average relative deviation between the experimental and the predicted densities and vapor pressures, calculated using the PR and SRK EoS, with critical properties estimated by Joback, Constantinou and Gani, and Wilson and Jasperson methods. SRK PengRobinson %ARD Joback CG WJ Joback CG WJ Density Pvap Density Pvap Density Pvap Density Pvap Density Pvap Density Pvap Non-cyclic Geraniol DL-citronellol Linalool Monocyclic ( )-menthone ( )-isopulegol L( )-menthol (S)-(+)-carvone (R)-(+)-limonene Aromatic monocyclic Thymol Eugenol Carvacrol p-cymene Tricyclic α-pinene β-pinene (1R)-( )-fenchone Eucalyptol Average

8 Table S6. Average relative deviation of experimental and calculated vapor pressures using the EoS SRK and PR at different temperatures for substances presenting higher deviations. DL-citronellol Geraniol ( )-isopulegol p-cymene T / K SRK PR T / K SRK PR T / K SRK PR T / K SRK PR Average

9 ( )-menthone (S)-(+)-carvone Eucalyptol ( )-isopulegol p-cymene (1R)-( )-fenchone Carvacrol Eugenol β-pinene lnp/ Pa / T/ K DL-citronellol Linalool (R)-(+)-Limonene α-pinene Geraniol L( )-menthol Thymol lnp/ Pa / T/ K -1 Figure S1. Vapor pressures, p, of pure terpenes and terpenoids as a function of temperature collected from literature: ( )-menthone, 61 (1R)-( )-fenchone, 62 (S)-(+)- carvone, 63 carvacrol, 64 eucalyptol, 65 eugenol, 66 ( )-isopulegol: not published yet, β- pinene, 67 p-cymene, 68 DL-citronellol, 69 geraniol, 69 linalool, 70 L( )-menthol, 71 (R)-(+)- limonene, 65 thymol, 72 and α-pinene. 67 9

10 1.05 Linalool L( )-menthol Thymol Eucalyptol 1.00 ρ/ g cm T/ K Figure S2. Experimental density (symbols) and calculated (lines) by PR EoS using critical properties estimated by Joback method at different temperatures and at p = 0.1 MPa ln p / Pa Linalool L( )-menthol Thymol Eucalyptol /T/ K -1 Figure S3. Experimental vapor pressures (symbols) and calculated (lines) by PR EoS using critical properties estimated by Joback method at different temperatures. 10

11 ρ/ g cm ( )-menthone (1R)-( )-fenchone (S)-(+)-carvone Carvacrol Eucalyptol DL-citronellol Eugenol Geraniol T/ K ρ/ g cm ( )-isopulegol Linalool L( )-menthol (R)-(+)-Limonene Thymol α-pinene β-pinene p-cymene T/ K Figure S4. Experimental density (symbols) and calculated (lines) by EoS using critical properties estimated using the same EoS and experimental density and vapor pressure data. Dotted and full lines correspond to SRK and PR EoS, respectively. 11

12 ln p/ Pa ( )-menthone (1R)-( )-fenchone (S)-(+)-carvone Carvacrol Eucalyptol DL-citronellol Eugenol Geraniol /T/ K -1 ln p/ Pa ( )-isopulegol Linalool L( )-menthol (R)-(+)-Limonene Thymol α-pinene β-pinene p-cymene /T/ K -1 Figure S5. Experimental vapor pressures (symbols) and calculated (lines) by PR EoS using critical properties estimated using the same EoS and experimental density and vapor pressure data. Dotted and full lines correspond to SRK and PR EoS, respectively. 12

Σχετικά έγγραφα

Supporting Information

Supporting Information Aqueous Biphasic Systems Composed of a Water Stable Ionic Liquid + Carbohydrates and their Applications Mara G. Freire a,b*, Cláudia L. S. Louros a, Luís Paulo N. Rebelo b and João