Experimental determination and modeling of the volumetric properties, refractive indices and viscosities of the volumetric properties, refractive indices and viscosities of the multicomponent organic solvent mixtures

U ovoj doktorskoj disertaciji izvršeno je eksperimentalno merenje gustine ρ, indeksa refrakcije nD i viskoznosti η osam binarnih i četiri ternerna sistema na atmosferskom pritisku i u temperaturnom intervalu od 288.15 K do 323.15 K sa korakom od 5 K. Izabrani su binarni sistemi: dimetiladipat + 1-butanol, dimetiladipat + 2-butanol, dimetiladipat + 2-butanon, dimetiladipat + tetrahidrofuran, 2-butanon + 1-butanol, 2- butanon + 2-butanol, tetrahidrofuran + 1-butanol, tetrahidrofuran + 2-butanol, i ternerni sistemi: dimetiladipat + 2-butanon + 1-butanol, dimetiladipat + 2-butanon + 2-butanol, dimetiladipat + tetrahidrofuran + 1-butanol i dimetiladipat + tetrahidrofuran + 2- butanol. Eksperimentalna merenja izvršena su na digitalnom gustinomeru Anton Paar DMA 5000, refraktometru Anton Paar RXA 156 i viskozimetru Anton Paar SVM 3000. Na osnovu eksperimentalno izmerenih vrednosti ρ, nD i η, izračunate su vrednosti dopunske molarne zapremine VE, promene indeksa refrakcije ΔnD i promene viskoznosti Δη pri mešanju. Eksperimentalni podaci obrađeni su pomoću empirijskih jednačina Redlich-Kister i Nagata-Tamura. Uspešnost predviđanja vrednosti VE, ΔnD i Δη ternernih sistema ispitana je primenom empirijskih modela polinomskog tipa: Radojković, Kohler, Jacob-Fitzner, Colinet, Tsao-Smith, Toop, Scatchard i Rastogi. Modelovanje volumetrijskih svojstava obuhvatilo je: korelisanje vrednosti VE binarnih sistema, kao i korelisanje i predviđanje vrednosti VE ternernih smeša pomoću Peng- Robinson-Stryjek-Vera kubne jednačine stanja (PRSV CEOS) kombinovane sa modelima za dopunsku Gibbs-ovu energiju (CEOS/GE) u koje su ugrađena dva pravila mešanja, van der Waals jedan fluid (vdW1) i model razvijen od strane Twu i saradnika (TCBT). Na osnovu vrednosti nD čistih komponenata, izvršeno je predviđanje vrednosti VE, kao i predviđanje vrednosti nD binarnih sistema, korišćenjem Lorentz-Lorentz, Dale-Gladstone, Eykman, Arago-Biot, Newton i Oster pravila mešanja. Izvršen je pregled i testiranje 43 korelativne metode za izračunavanje vrednosti viskoznosti. Za modelovanje η binarnih sistema korišćene su dve grupe modela: korelativni (Teja-Rice, McAllister 3 i McAllister 4) i prediktivni (UNIFAC-VISCO). Prilikom predviđanja vrednosti η UNIFAC-VISCO modelom, na osnovu eksperimentalnih merenja, optimizacionim metodama određene su nove vrednosti interakcionih parametara...In this dissertation, densities ρ, refractive indices nD and viscosities η of eight binary and four ternary systems were experimentally measured at atmospheric pressure and at temperatures between 288.15 K and 323.15 K with a 5 K temperature increment. The following binary and ternary systems were selected: dimethyladipate + 1-butanol, dimethyladipate + 2-butanol, dimethyladipate + 2-butanone, dimethyladipate + tetrahydrofuran, 2-butanone + 1-butanol, 2-butanone + 2-butanol, tetrahydrofuran + 1- butanol, tetrahydrofuran + 2-butanol, and dimethyladipate + 2-butanone + 1-butanol, dimethyladipate + 2-butanone + 2-butanol, dimethyladipate + tetrahydrofuran + 1- butanol and dimethyladipate + tetrahydrofuran + 2-butanol. Experimental measurements were conducted on digital densimeter Anton Paar DMA 5000, refractometer Anton Paar RXA 156 and viscometer Anton Paar SVM 3000. Experimentally measured ρ, nD and η were used in calculation of the excess molar volumes VE, deviations of refractive indices nD and viscosity deviations . Experimental data were correlated by the Redlich-Kister and Nagata-Tamura equations. Prediction quality for the VE, nD and of the ternary systems was evaluated using the empirical polynomial models developed by: Radojković, Kohler, Jacob-Fitzner, Colinet, Tsao-Smith, Toop, Scatchard and Rastogi. Modeling of the volumetric properties included correlation of the binary, as well as the correlation and prediction of the ternary VE values, using the Peng-Robinson-Stryjek-Vera cubic equation of state (PRSV CEOS) combined with models for the excess Gibbs energy (CEOS/GE) and two mixing rules: van der Waals one fluid (vdW1) and the mixing rule developed by Twu et al. (TCBT). Refractive indices of the pure components were used for the prediction of VE and nD of the binary mixtures using the Lorentz-Lorentz, Dale-Gladstone, Eykman, Arago-Biot, Newton and Oster mixing rules. 43 viscosity correlation methods were analyzed and tested. Modeling of the η of the binary systems encompassed the application of the correlative (Teja-Rice, McAllister 3 and McAllister 4) and predictive (UNIFAC-VISCO) models. Prediction of η by the UNIFAC-VISCO model included optimization of the experimental data to develop the new interaction parameters of the UNIFAC-VISCO model..

Correlation of the liquid mixture viscosities

In this paper forty two selected correlation models for liquid mixture viscosities of organic compounds were tested on 219 binary and 41 ternary sets of experimental data taken from literature. The binary sets contained 3675 experimental data points for 70 different compounds. The ternary sets contained 2879 experimental data points for 29 different compounds. The Heric I, Heric-Brewer II, and Krishnan-Laddha models demonstrated the best correlative characteristics for binary mixtures (overall absolute average deviation < 2%). The Heric I, Heric-Brewer II, Krishnan-Laddha and Heric II models demonstrated the best correlative characteristics for ternary mixtures (overall absolute average deviation < 3%)

Supplementary Material to Prediction of high pressure liquid heat capacities of organic compounds by a group contribution method

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