3.3 Calculate the pure component (Physical properties)
3.3.4 Calculated P 2 subl
TheP2subl can be calculated by Lee-Kesler method as
ln(Prsubl) = f(0)(Tr) +ωf(1)(Tr), (3.64)
f(0)(Tr) =5.92714−6.09648
Tr −1.28862 ln(Tr) +0.169347Tr6, (3.65)
f(1)(Tr) =15.2518−15.6875
Tr −13.472 ln(Tr) +0.43577Tr6, (3.66)
Pisubl =PrsublPc, (3.67)
Bibliography
[1] J. M. Prausnitz, R. N. Lichtenthaler, and E. G. de Azevedo,Molecular ther-modynamics of fluid-phase equilibria. Pearson Education, 1998.
[2] D.-Y. Peng and D. B. Robinson, “A new two-constant equation of state,”
Industrial & Engineering Chemistry Fundamentals, vol. 15, pp. 59–64, Feb 1976.
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an equation of state. fugacities of gaseous solutions.,” Chemical Reviews, vol. 44, pp. 233–244, Feb 1949.
[4] R. Stryjek and J. H. Vera, “Vapor—liquid equilibrium of hydrochloric acid solutions with the prsv equation of state,” Fluid Phase Equilibria, vol. 25, no. 3, pp. 279–290, 1986.
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[6] R. F. Fedors, “method for estimating both the solubility parameters and mo-lar volumes of liquids,” Polymer Engineering & Science, vol. 14, no. 2, pp. 147–154, 1974.
[7] R. C. Reid, J. M. Prausnitz, and T. K. Sherwood, “properties of gases and liquids, 1977,”MaGraw˜ Hill, p. 12.
[8] K. C. Murdock, R. G. Child, P. F. Fabio, R. D. Angier, R. E. Wallace, F. E. Durr, and R. V. Citarella, “Antitumor agents. 1. 1, 4-bis [(aminoalkyl) amino]-9, 10-anthracenediones,” Journal of medicinal chemistry, vol. 22, no. 9, pp. 1024–1030, 1979.
[9] K. U. Ramrao, C. A. Ramkumar, N. A. Anant, and A. N. Ramanuja, “Phase transfer catalysed n-monoalkylation of amino anthraquinones,” Synthetic communications, vol. 21, no. 10-11, pp. 1129–1135, 1991.
[10] A. Jain, G. Yang, and S. H. Yalkowsky, “Estimation of melting points of organic compounds,”Industrial & Engineering Chemistry Research, vol. 43, pp. 7618–7621, Oct 2004.
[11] A. P. Krapcho, K. L. Avery Jr, K. J. Shaw, and J. D. Andrews, “Reactions of 2, 3-dihydro-9, 10-dihydroxy-1, 4-anthracenedione (leucoquinizarin) with hydrazine and substituted hydrazines,” The Journal of Organic Chemistry, vol. 55, no. 16, pp. 4960–4961, 1990.
[12] A. Eckert and K. Steiner, “Zur kenntnis der anthrimide,” Monatshefte f¨ur Chemie/Chemical Monthly, vol. 35, no. 9, pp. 1129–1151, 1914.
[13] M. Goi, K.; Konishi, “Preparation of some acid anthraquinone dyes from tetrachlorophthalic anhydride,” Osaka-furitsu Kogyo Shoreikan Hokoku, vol. 24, p. 5156, 1960.
[14] J. Marrero and R. Gani, “Group-contribution based estimation of pure com-ponent properties,” Fluid Phase Equilibria, vol. 183, pp. 183 – 208, 2001.
Proceedings of the fourteenth symposium on thermophysical properties.
[15] J. M. O. J. P. Poling, B. E.; Prausnitz, The Properties of Gases and Liquids.
McGraw-Hill: New York, 5th ed.;, 2001. ed., 2001.
[16] E. H. Ruediger, M. L. Kaldas, S. S. Gandhi, C. Fedryna, and M. S. Gibson,
“Reactions of 1,5-dichloroanthraquinone with nucleophiles,”The Journal of Organic Chemistry, vol. 45, no. 10, pp. 1974–1978, 1980.
[17] W. H. Beisler and L. W. Jones, “A study of 1-hydroxylamino-anthraquinone and some of its derivatives1,” Journal of the American Chemical Society, vol. 44, no. 10, pp. 2296–2306, 1922.
[18] G. Soave, “Equilibrium constants from a modified redlich-kwong equation of state,”Chemical Engineering Science, vol. 27, pp. 1197–1203, Jun 1972.
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Engineering Chemistry Research, vol. 35, pp. 1483–1486, Jan 1996.
Chapter 4
REGULAR SOLUTION MODELS
4.1 Solution model
The solution containing mixtures of polymer and solvent, Flory Huggins teory is most commonly used. In this study, we used the regular solution model coupled with the Flory - Huggins equation is reproduced by Iwaiet al.[1] as
lny2= ∆hm2 RT
T Tm−1
− v2
RT(δ1−δ2)2−ln(v2/v1)−1+v2/v1, (4.1) where∆hm2 andTmare the melting enthalpy and melting temperature of solid component, respectively. v1 and v2 are the molar volume of sc-CO2 and solid component. The solubility parameter of sc-CO2was calculated by the method of Giddings [2].
δ1/(MPa)0.5=2.0455×1.25Pc0.5 ρR
2.66
, (4.2)
ρR( =ρ/ρc) is the reduced density of CO2,ρ, the density of sc-CO2wasρc, and Pc are the critical density and pressure of CO2. The solute solubility parameter was assumed to change as a function of the CO2density in the present work,
δ2=a+bρCO2, (4.3)
and
δ2=a+bρCOc
2, (4.4)
Table 4.1 summarized parameters of equation 4.3 and 4.4 and average ab-solute relative deviation (AARD) between the experimental and calculated val-ues. Figure 4.1 to figure 4.6 illustrated plot of mol fraction 107y2 against density ρ/(mol·m−3) to correlate results for anthraquinone derivatives used from regular solution model with Flory-Huggins equation (equation 4.3) and 4.4), and that ac-curate results of the solubility was obtained by regular solution model with Flory-Huggins theory.
Table 4.1: Parameters of equation 4.3 and 4.4 and average absolute relative devi-ation (AARD) between the experimental and calculated values
System a/ (Pa) b c AARD / %
(Pa·m3·mol−1)
1,4-diaminoanthraquinone 21072 0.44969 8.4
22359 0.0080908 1.4007 6.80
1,4-bis(ethylamino)anthraquinone 16650 0.39085 9.6
17454 0.0070670 1.4207 8.3
1-amino-4-hydroxyanthraquinone 20051 0.46311 18.1
21679 0.0032350 1.4858 6.5
1-hydroxy-4-nitroanthraquinone 19072 0.50536 10.9
20097 0.058520 1.2083 6.7
1,4-diamino-2,3-dichloroanthraquinone 15993 0.55732 26.2
17947 0.004193 1.478 11.2
1,8-dihydroxy-4,5-dinitroanthraquinone 19272 0.5200 14.5
18565 1.4701 0.90117 14.8
1-aminoanthraquinone 18888 0.48273 24.1
20536 0.0050054 1.4467 11.8
1-nitroanthraquinone 16301 0.56996 16.5
17602 0.040204 1.2578 10.8
Figure 4.1: Plot of mol fraction 107y2against densityρ/(mol·m−3) to correlate re-sults for 1,4-diaminoanthraquinone (C.I. Disperse Violet 1) from regular solution model with Flory-Huggins equation (equation 4.3 and 4.4).
Figure 4.2: Plot of mol fraction 107y2 against density ρ/(mol·m−3) to correlate results for 1,4-bis(ethylamino)anthraquinone (C.I. Solvent Blue 59) from regular solution model with Flory-Huggins equation (equation 4.3 and 4.4).
Figure 4.3: Plot of mol fraction 107y2 against density ρ/(mol·m−3) to correlate results for 1-amino-4-hydroxyanthraquinone (C.I. Disperse Red 15) from regular solution model with Flory-Huggins equation (equation 4.3 and 4.4).
Figure 4.4: Plot of mol fraction 107y2against densityρ/(mol·m−3) to correlate re-sults for 1-hydroxy-4-nitroanthraquinone from regular solution model with Flory-Huggins equation (equation 4.3 and 4.4).
Figure 4.5: Plot of mol fraction 107y2against densityρ/(mol·m−3) to correlate re-sults for 1-aminoanthraquinone from regular solution model with Flory-Huggins equation (equation 4.3 and 4.4).
Figure 4.6: Plot of mol fraction 107y2against densityρ/(mol·m−3) to correlate re-sults for 1,8-dihydroxy-4,5-dinitroanthrquinone from regular solution model with Flory-Huggins equation (equation 4.3 and 4.4).
Bibliography
[1] Y. Iwai, Y. Koga, T. Fukuda, and Y. Arai, “Correlation of solubilities of high-boiling components in supercritical carbon dioxide using a solution model,”
Journal of chemical engineering of Japan, vol. 25, no. 6, pp. 757–760, 1992.
[2] J. C. Giddings, M. N. Myers, L. McLaren, and R. A. Keller, “High pres-sure gas chromatography of nonvolatile species,”Science, vol. 162, no. 3849, pp. 67–73, 1968.
Chapter 5
SUMMARY
This thesis reported the measurement and correlation of solubility anthraquinone derivatives in supercritical carbon dioxide, contain eight binary system as follows:
1. 1,4-diaminoanthraquinone (C.I. Disperse Violet 1) + Carbon dioxide 2. 1,4-bis(ethylamino)anthraquinone (C.I. Solvent Blue 59) + Carbon dioxide 3. 1-amino-4-hydroxyanthraquinone (C.I. Disperse Red 15) + Carbon dioxide 4. 1-hydroxy-4-nitroanthraquinone + Carbon dioxide
5. 1,4-diamino-2,3-dichloroanthraquinone + Carbon dioxide 6. 1,8-dihydroxy-4,5-dinitroanthrquinone + Carbon dioxide 7. 1-aminoanthraquinone (Smoke Orange G) + Carbon dioxide 8. 1-nitroanthraquinone + Carbon dioxide
In this chapter summarized solubilities of anthraquinone dyestuffs in supercritical carbon dioxide by using the data experimentally measured by us, and have
pub-lished in scientific international journals [1, 2, 3, 4]. The solubilities of these com-pounds were correlated with several semiempirical equations [5, 6, 7, 8, 9, 10], and equation of state (EOS), focused on the solubility change of anthraquinone deriva-tives containing the substituent groups —NO2, —OH, —NH2because among the dyestuffs used in dyeing processes, there exist anthraquinone derivatives formed by several functional groups. The solubility changes of anthraquinone derivatives in sc-CO2 by the substituent groups on the anthraquinone. Table 5.1 summa-rized the solubility changes of anthraquinone derivatives in sc-CO2 at 383,15 K and pressure of 25 MPa. These solubility changes in accordance with the trend results from the molecular interactions among the CO2 molecule with function-alized benzenes consisting of —NO2, —OH, —NH2 substituents examined by using the density functional theory [11].
Figure 5.1 and figure 5.2 illustrated solubility of anthraquinone in (sc-CO2) as a function of molecular weight at T = 383.15 and P = 25 MPa. It was found that solubility is not affected by molecular weight. Figure 5.3 is solubility of anthraquinone in (sc-CO2) as a function of melting point (K) at T = 383.15 and P = 25 MPa. This figure show that melting slightly affects the solubility in an-thraquinone. Figure 5.4 illustrated solubility of anthraquinone in (sc-CO2) as a function of sublimation pressure (Pa) at T = 383.15 and P = 25 MPa. It was found that sublimation pressure most significantly affect to the solubility, solubility in-crease with increasing sublimation pressure. The solubilities of anthraquinone derivatives above were measured over the pressure ranges (12.5 to 25.0) MPa and at the temperatures of (323.15, 353.15, and 383.15) K by a flow-type apparatus, and correlated successfully in terms of the density of carbon dioxide with the empirical equations of Mendez - Santiago - Teja, Chrastil, Sung - Shim,
Kumar-Table 5.1: Solubility of antraquinone derivatives at 383,15 K and pressure of 25 MPa
Chemical name Chemical structure Solubility (y2) Ref.
(·107)
1-aminoanthraquinone 351.3 [4]
1-nitroanthraquinone 252.3 [4]
1-amino-4-hydroxyanthraquinone 244.5 [2]
1,4-bis(ethylamino)anthraquinone 148.5 [1]
1-hydroxy-4-nitroanthraquinone 86.40 [2]
1,4-diamino-2,3-dichloroanthraquinone 52.35 [3]
1,4-diaminoanthraquinone 26.10 [1]
1,8-dihydroxy-4,5-dinitroanthraquinone 11.15 [3]
Figure 5.1: Solubility of anthraquinone in (sc-CO2) as a function of molecular weight at T = 383.15 and P = 25 MPa .
Johnston, and also correlated satisfactorily with Flory - Huggins theory ,and the Peng - Robinson equation of state modified by Stryjek and Vera (PRSV EOS) with the conventional mixing rules. The solubility of 1-aminoanthraquinone (Smoke Orange G) in the entire region of measurements is highest. Good agreement be-tween the experimental and calculated solubility of the dyestuffs was obtained.
Figure 5.2: Increase rate solubility of anthraquinone in (sc-CO2) as a function of molecular weight at T = 383.15 and P = 25 MPa .
Figure 5.3: Solubility of anthraquinone in (sc-CO2) as a function of melting point (K) at T = 383.15 and P = 25 MPa .
Figure 5.4: Solubility of anthraquinone in (sc-CO2) as a function of sublimation pressure (Pa) at T = 383.15 and P = 25 MPa .
Bibliography
[1] R. S. Alwi, T. Tanaka, and K. Tamura, “Measurement and correlation of solubility of anthraquinone dyestuffs in supercritical carbon dioxide,” The Journal of Chemical Thermodynamics, 2014.
[2] K. Tamura and R. S. Alwi, “Solubility of anthraquinone derivatives in su-percritical carbon dioxide,” Dyes and Pigments, vol. 113, pp. 351 – 356, 2015.
[3] R. S. Alwi and K. Tamura, “Measurement and correlation of derivatized an-thraquinone solubility in supercritical carbon dioxide,”Journal of Chemical
& Engineering Data, vol. 60, no. 10, pp. 3046–3052, 2015.
[4] K. Tamura, R. S. Alwi, T. Tanaka, and K. Shimizu, “Solubility of 1-aminoanthraquinone and 1-nitroanthraquinone in supercritical carbon diox-ide,” The Journal of Chemical Thermodynamics, vol. 104, pp. 162 – 168, 2017.
[5] J. Mendez-santiago and A. S. Teja, “solubility of solids in supercritical flu-ids,”Fluid Phase Equilib, vol. 158–160, pp. 501–510, 1999.
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[7] K. D. Bartle, A. a. Clifford, and G. F. Shilstone, “Estimation of solubilities in supercritical carbon dioxide: A correlation for the peng-robinson interaction parameters,”The Journal of Supercritical Fluids, vol. 5, no. 3, pp. 220–225, 1992.
[8] S. K. Kumar and K. P. Johnston, “Modelling the solubility of solids in su-percritical fluids with density as the independent variable,” The Journal of Supercritical Fluids, vol. 1, no. 1, pp. 15–22, 1988.
[9] H.-D. Sung and J.-J. Shim, “Solubility of ci disperse red 60 and ci disperse blue 60 in supercritical carbon dioxide,”Journal of Chemical & Engineering Data, vol. 44, no. 5, pp. 985–989, 1999.
[10] C. Garlapati and G. Madras, “Solubilities of solids in supercritical fluids using dimensionally consistent modified solvate complex models,” Fluid Phase Equilibria, vol. 283, no. 1, pp. 97 – 101, 2009.
[11] A. Torrisi, C. Mellot-Draznieks, and R. G. Bell, “Impact of ligands on co2 adsorption in metal-organic frameworks: First principles study of the in-teraction of co2 with functionalized benzenes. ii. effect of polar and acidic substituents.,”J. Chem. Phys., vol. 132, no. 4, p. 044705, 2010.
A CKNOWLEDGMENT
I would like to thank Prof Dr. Kazuhiro Tamura, my supervisor, for his many suggestions and constant support during this study. I am also thankful to Dr.
Hidenori Higashi, for his guidance through the early years.
I would like also to thank Prof. Dr. Toshiro Yamada, Prof. Dr. Tsuyoshi Asakawa, Assoc. Prof. Akio Ohta, and Assoc. Prof. Kobayashi Fumihisa, who are my thesis commite for their suggestions on my thesis.
I should also mention that my research in Kanazawa university were supported in part by the Japan Society for the promotion science.
Of course, I am grateful to my parents, my husband, and my children for their patience andlove. Without them this work would never have come into existence.
Finally, I wish to thank the following: Hirakhi, Tatsuro Tanaka, Eji Tatskawa, and Shimizu Keisuke (for their assistances); Assistant Prof. Tada Kaoru, Dr.
Osawa (for his assistance as official in chemical engineering laboratory); Ikeda, Uchida, Mia, Abrai, Nakanotti, Kawamura (for their friendship, and for the good and bad times we had together); all official of Kanazawa University (for their support).
Chapter 6
PUBLISHED PAPERS
1. Ratna Surya Alwi, Tatsuro Tanaka, Kazuhiro Tamura, Measurement and correlation of solubility of anthraquinone dyestuffs in supercritical carbon dioxide, The Journal of Chemical Thermodynamics 74 (2014) 119 - 125.
2. Kazuhiro Tamura, Ratna Surya Alwi, Solubility of anthraquinone derivatives in supercritical carbon dioxide, Dyes and Pigments 113 (2015) 351 -356.
3. Ratna Surya Alwi and Kazuhiro Tamura, Measurement and correlation of derivatized anthraquinone solubility in supercritical carbon dioxide, Journal of Chemical Engineering Data, 60 (2015) 3046?3052.
4. Kazuhiro Tamura, Ratna Surya Alwi, Tatsuro Tanaka, Keisuke Shimizu, Solubility of 1- aminoanthraquinone and 1-nitroanthraquinone in supercrit-ical carbon dioxide, The Journal of Chemsupercrit-ical Thermodynamics 104 (2017) 162 - 168.
5. Ratna Surya Alwi, Kazuhiro Tamura,Tatsuro Tanaka, Keisuke Shimizu,