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Isobaric VaporLiquid Equilibrium for the Binary Systems of sec Butyl Acetate Methyl Ethyl Ketone 2Methoxyethanol or 12 Dimethoxyethane at 1013 kPa Zhankun Jiang Shoutao Ma Lei Wang Guoxin Sun and Yu Cui School of Chemistry and Chemical Engineering University of Jinan Jinan 250022 China Key Laboratory of Chemical Sensing Analysis in Universities of Shandong School of Chemistry and Chemical Engineering University of Jinan Jinan 250022 China School of Chemical Engineering and Technology Tianjin University No 92 Weijin Road Nankai District Tianjin 300072 China ABSTRACT The isobaric vaporliquid equilibrium VLE data of methyl ethyl ketone MEK secbutyl acetate SBAC 2methoxyethanol SBAC and 1 2dimethoxy ethane DME SBAC were determined at 1013 kPa by using an Ellis vaporliquid equilibrium still The experimental data passed the thermodynamic consistency test by Herington method and Wisniak test The VLE values were correlated by the nonrandom twoliquid NRTL universal quasichemical activity coefficience UNIQUAC and Wilson activitycoefficient models The results indicated that the three models had good agreement with the experimental data The 2methoxyethanol SBAC system forms a minimum temperature binary azeotrope at 1013 kPa The azeotropic temperature is 38386 K and the composition of SBAC is 851 mol 1 INTRODUCTION Secbutyl acetate SBAC has high octane number nontoxic noncorrosion and low oxygen content1 It has got wide application in industry Methyl ethyl ketone MEK 2 methoxyethanol and 12dimethoxyethane DME are ex cellent solvents2 The mixtures of these solvents which were generated abundantly in fields such as cellulose material and the printing ink productions need to be purified for reuse To our knowledge3 no vapor liquid equilibrium VLE data are available for MEK SBAC 2methoxyethanol SBAC and DME SBAC mixtures The experimental isobaric VLE data of the MEK SBAC 2 methoxyethanol SBAC and DME SBAC mixtures were measured to meet the need of process design and performance evaluation The consistency test of the experimental data were carried out with Herington test4 and Wisniak test5 The VLE data were regressed using Wilson6 nonrandom twoliquid NRTL7 and universal quasichemical UNIQUAC8 equa tions The three models with their bestfitted binary parameters were applied to correlate the VLE of the binary systems which were then compared with experimental data 2 EXPERIMENTAL SECTION 21 Chemicals The chemicals used were SBAC MEK 2 methoxyethanol and DME All of the chemicals were analytical reagents The source molecular formula CAS RN and mass fraction of the reagents are listed in Table 1 respectively The mass fraction was measured by a gas chromatograph GC equipped with a thermal conductivity detector TCD All of the chemicals were stored over activated 4Å molecular sieves to keep them dry No further purification has been made for the chemicals before use As additional purity checks some physical properties of the pure components were measured and compared with reported values The results are presented in Table 2 The densities were measured at 29815 K by the pycnometer method The refractive indexes were measured at 29815 K with an Abbe refractometer and the normal boiling points at 1013 kPa were measured using the Ellis vaporliquid equilibrium still 22 Analysis The compositions of the vapor condensate and the liquid phase at equilibrium were analyzed by a gas chromatography GC GC9790 Zhejiang Fu Li Analytical Instrument Co Ltd and calibrated with solutions prepared by gravimetrical standard TCD was used together with a SE30 packed column 3 mm 2 m Jinan Yuan Bo Chemical Instrument Company China Highpurity hydrogen 99999 was taken as carrier gas at a flow rate of 20 mL min1 The temperature of injector oven and detector were kept at 4132 K 3732 K and 4182 K respectively The area normalization method was used to gain quantitative results in the GC analysis The analysis was performed at least two times for each sample In the process the standard uncertainty of the measured mole fractions was 0005 23 Apparatus and Procedure An Ellis equilibrium still12 was used in the experiments The structure of the still is shown in Figure 1 The apparatus was validated by measuring the VLE data of ethanol isobutanol at 1013 kPa The data were Received July 12 2015 Accepted December 16 2015 Article pubsacsorgjced XXXX American Chemical Society A DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX compared with those in the literature13 The results are listed in Table 3 and plotted in Figure 2 It can be seen from Figure 2 that our data agree well with those from the literature First a series of solution samples with different concen trations were prepared in advance and separately added to the still slowly Then the heating rate was regulated to keep the vapor condensation speed at 60100 drops per minute The heater for overheating vapor stream was modulated to make sure that the vapor temperature was equal to or a little higher less than 05 K than the equilibrium temperature The system was kept at constant vapor and equilibrium temperatures for at least 60 min so as to guarantee that the equilibrium state was reached Then the equilibrium temperature was recorded and the liquid and vapor samples were collected The temperatures were measured with a calibrated thermometer graduated in 001 K while the uncertainty of the thermometer is 005 K The pressure of the system was measured by testo511 digital vacuum gauge with an uncertainty of 03 kPa 3 RESULTS AND DISCUSSION 31 Pure Component Vapor Pressures The vapor pressures of the pure components were calculated using an extended Antoine vapor pressure eq 1 where PS is the saturated vapor pressure Pa of pure component and T is the temperature K The parameters C1 to C5 which were obtained from ASPEN are listed in Table 4 Table 1 Materials Description at 1013 kPaa chemical name secbutyl acetate methyl ethyl ketone 2methoxyethanol 12dimethoxyethane isobutanol ethanol source Zhongchuang China Damao China Damao China Damao China Damao China Sinopharm China molecular formula C6H12O2 C4H8O C3H8O2 C4H10O2 C4H10O C2H6O CASRN 105464 78933 109864 110714 78831 64175 initial weight fraction purity 998 995 995 995 995 997 purification method dehydration dehydration dehydration dehydration dehydration dehydration final weight fraction purity 9989 9968 9974 9997 9978 9992 analysis method GCb GC GC GC GC GC auP 03 kPa bGas chromatography Table 2 Boiling Points Tb at 1013 kPa Densities ρ and Refractive Index nD at 29815 K of Pure Components Compared with Literature Dataa Tb K ρ kgm3 nD component this work literature this work literature this work literature secbutyl acetate 38512 38515b 8638 8652d 13872 13875b sethyl ethyl ketone 35276 35279b 7997 7996d 13761 13764b 2methoxyethanol 39748 39750c 9601 9600c 14002 14002b 12dimethoxyethane 35771 35775b 8604 8613e 13780 13781b auP 03 kPa uTb 005 K uρ 01 kgm3 unD 00001 bLiterature9 cLiterature10 dLiterature3 eLiterature11 Figure 1 Ellis still 1 heater 2 tube delivering mixture 3 liquid phase sampling valve 4 equilibrium temperature thermometer 5 heater for overheating vapor stream 6 vapor temperature thermometer 7 separator for liquid and vapor phases 8 vapor condenser 9 cooler 10 to pressurestabilizing system 11 flow meter drop counter 12 vapor condensate container 13 vapor condensate sampling valve 14 valve for drainage of still Table 3 Isobaric VLE Data for Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System Ethanol 1 Isobutanol 2 at 1013 kPaa no x1 y1 1 0000 0000 2 0041 0125 3 0085 0231 4 0136 0341 5 0198 0451 6 0252 0526 7 0302 0584 8 0358 0642 9 0432 0722 10 0525 0787 11 0581 0818 12 0649 0854 13 0711 0885 14 0751 0905 15 0812 0934 16 0889 0966 17 0948 0984 18 1000 1000 auP 03 kPa and ux1 uy1 0005 Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX B P C C T C T C T ln ln C S 1 2 3 4 5 1 32 Experimental Results The isobaric VLE experimental data and the corresponding calculated activity coefficients for MEK 1 SBAC 2 SBAC 1 2methoxyethanol 2 and DME 1 SBAC 2 at 1013 kPa are listed in Tables 57 respectively The general equilibrium relationship between the vapor phase and the liquid phase14 can be expressed as follows φ γφ Py P x e i i i i i i V P P RT V S S i i L S 2 where subscript i is the thermodynamic properties of component i y is the mole fraction of gas phase φV is the fugacity coefficient in the mixture vapor phase x is the mole fraction of liquid phase γi is the activity coefficient of component i φs is the fugacity coefficient in the saturate state VL is the liquid mole volume of pure liquid P is the total pressure of the equilibrium system and R is the gas constant The exponential term in eq 2 is close to unity at 1013 kPa After neglected the vapor nonideality and the pressure dependence of the liquid phase fugacity eq 2 can be simplified to eq 3 γ yP xP i i i i S 3 33 Thermodynamic Consistency Tests In order to confirm the thermodynamic consistency of these experimental data we verified all experimental data according to the Herington test4 and Wisniak test5 The Herington test is used to examine the thermodynamic consistency of the VLE data by area test while the Wisniak test conducts the pointto point test and area test simultaneously In the Herington test the criteria of consistency is that the value of DJ cannot be larger than 10 As to the Wisniak test the criteria is that the coefficient E is smaller than 35 where γ γ γ γ D x x 100 ln d ln d 0 1 1 2 1 0 1 1 2 1 4 J T T T 150 max min min 5 E L x W x L x W x 100 d d d d k k k k 0 1 1 0 1 1 0 1 1 0 1 1 6 Δ Δ L T x s x s T k i i i i i o o o 7 γ Δ W RT x s x x y x ln ln k i i i i i i i o 8 Figure 2 x1y1 diagram of ethanol 1isobutanol 2 at 1013 kPa experimental data literature data13 Table 4 Extended Antoine Equation Coefficients C1C5 for the Chemicals component C1 C2 C3 C4 C5 T range K secbutyl acetate 52601 60979 42398 215 1018 6 17415 to 56100 methyl ethyl ketone 72698 61436 75779 565 1006 2 18648 to 53550 2methoxyethanol 20263 12472 27385 264 1005 2 18805 to 56400 12dimethoxyethane 61814 61029 56547 118 1017 6 21515 to 53615 Table 5 Experimental VLE Data for Temperature T Activity Coeffiecient γ Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System Methyl Ethyl Ketone 1 secButyl Acetate 2 at 1013 kPaa T K x1 y1 γ1 γ2 38512 0000 0000 09937 37869 0090 0226 11563 10309 37512 0166 0392 12049 09893 37184 0266 0513 10796 10006 36965 0321 0590 10934 09804 36797 0377 0643 10648 09849 36647 0428 0684 10420 09990 36522 0470 0719 10358 09993 36422 0505 0746 10307 09987 36315 0546 0779 10268 09850 36184 0591 0798 10111 10440 36071 0640 0828 10017 10543 35980 0668 0847 10100 10475 35892 0705 0866 10046 10649 35819 0728 0875 10043 11125 35734 0766 0894 10028 11215 35654 0800 0908 09995 11705 35569 0837 0925 09986 12157 35500 0863 0938 10039 12234 35453 0888 0947 09996 12978 35423 0897 0952 10036 13114 35379 0914 0959 10068 13484 35341 0934 0967 10055 14369 35340 0946 0971 09972 15498 35276 1000 1000 09915 aStandard uncertainties u are uT 005 K uP 03 kPa and ux1 uy1 0005 Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX C Tmax and Tmin K are the maximum and the minimum boiling points of the system respectively Ti o represents the boiling point of component i Δsi o is the molar entropy of vaporization of component i k donates each experimental point The check results of thermodynamic consistency tests which are listed in Table 8 passed those tests The results indicate these binary VLE data are thermodynamically consistent 34 Data Regression The experimental data of three binary systems were regressed according to the NRTL UNIQUAC and Wilson models with Aspen software The Maximum likelihood objective function was used for the regression Maximum likelihood is a generalization of the least squares method In the maximum likelihood objective function errors in T P x and y are considered The objective function is minimized by manipulating the physical property parameters identified in the regression case and manipulating the estimated value corresponding to each measurement The function is presented in eq 9 σ σ σ σ Q T T P P x x y y i n i i T i i P i x i i y 1 exp est 2 exp est 2 exp i est 2 exp est 2 9 where n is the number of experimental points T is the equilibrium temperature superscript exp and est are abbreviation of experiment and estimate respectively σ is the standard deviation of the indicated data and Q is the objective function to be minimized by data regression The correlated binary interaction parameters from exper imental data are stated in Table 9 combined with the root meansquare deviations RMSD in vapor phase mole fraction and temperature It is observed that the RMSD of temperature for the activity models are less than 063 and those of vapor phase composition are no more than 0018 The calculated values of the vapor phase composition and temperature by these three models show reasonably good agreement with the experimental values The azeotropic temperature and composition of SBAC 2 methoxyethanol at 1013 kPa here are 38386 K 851 mol SBAC The experimental Txy diagrams of binary systems MEK SBAC SBAC 2methoxyethanol and DME SBAC together with correlated curves with UNIQUAC UNIQUAC or NRTL model are shown in Figure 3 Figure 4 and Figure 5 respectively 4 CONCLUSIONS Isobaric VLE values were determined experimentally for MEK SBAC SBAC 2methoxyethanol and DME SBAC systems with Ellis equilibrium still at 1013 kPa The results show that SBAC 2methoxyethanol system forms a minimum temperature azeotrope and the other two systems do not form Table 6 Experimental VLE Data for Temperature T Activity Coeffiecient γ Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System Secbutyl Acetate 1 2 methoxyethanol 2 at 1013 kPaa T K x1 y1 γ1 γ2 39748 0000 0000 10060 39655 0024 0058 17199 09994 39310 0119 0249 16431 09840 39118 0191 0354 15387 09802 38964 0258 0440 14796 09740 38858 0324 0502 13882 09836 38761 0379 0546 13302 10069 38692 0429 0583 12786 10304 38630 0479 0629 12582 10257 38597 0509 0651 12376 10353 38555 0551 0671 11951 10808 38515 0595 0698 11638 11159 38484 0636 0715 11263 11841 38458 0673 0737 11060 12258 38433 0718 0763 10817 12917 38408 0735 0773 10786 13275 38403 0762 0790 10648 13701 38396 0819 0824 10355 15142 38386 0851 0849 10301 15823 38391 0877 0865 10162 17172 38394 0903 0884 10083 18620 38412 0939 0914 09977 21657 38429 0962 0941 09969 23895 38512 1000 1000 09937 aStandard uncertainties u are uT 005 K uP 03 kPa and ux1 uy1 0005 Table 7 Experimental VLE Data for Temperature T Activity Coefficient γ Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System 12Dimethoxyethane 1 secButyl Acetate 2 at 1013 kPaa T K x1 y1 γ1 γ2 38512 0000 0000 09937 38176 0066 0154 11333 09973 37945 0146 0293 10427 09787 37702 0223 0408 10143 09731 37528 0284 0487 10005 09676 37355 0347 0560 09893 09613 37242 0394 0606 09752 09621 37113 0439 0650 09734 09654 36984 0490 0692 09658 09738 36897 0509 0707 09758 09889 36873 0538 0727 09553 09887 36746 0571 0755 09711 09973 36574 0646 0808 09689 10021 36415 0715 0852 09681 10168 36274 0783 0891 09670 10273 36141 0850 0925 09632 10804 36048 0911 0955 09560 11230 35950 0972 0986 09544 11497 35771 1000 1000 09965 auT 005 K uP 03 kPa and ux1 uy1 0005 Table 8 Thermodynamic Consistency Check system D J DJ L W E methyl ethyl ketone secbutyl acetate 822 1376 554 339 359 287 2methoxyethanol secbutyl acetate 1401 481 920 397 414 217 12dimethoxyethane secbutyl acetate 2020 1149 871 187 195 209 Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX D an azeotrope Thermodynamic consistency of the experimental data was verified according to Herington test and Wisniak method The VLE values were correlated by the NRTL UNIQUAC and Wilson activitycoefficient models The corresponding binary interaction parameters of the models were obtained by maximum likelihood method The RMSD of temperature for the three activity models are less than 063 and those of vapor phase composition are no more than 0018 For the SBAC 2methoxyethanol system the azeotropic temper ature is 38386 K and the composition of SBAC is 851 mol at 1013 kPa AUTHOR INFORMATION Corresponding Authors Tel 86 15053121073 Email address chmjiangzkujn educn Z Jiang Tel 86 053182767937 Email address chmcuiyujnedu cn Y Cui Funding We thank the outstanding young scientist award fund in Shandong Province BS2014NJ020 and Science and technol ogy developing program of universities in Shandong Province J14LC06 for the financial support Notes The authors declare no competing financial interest Table 9 Correlation Parameters and Root Mean Square Deviations for the Binary Systems correlation parametersa RMSD system models aijb ajic bij bji σy1d σTe methyl ethyl ketone 1 secbutyl acetate 2 NRTLf 56649 45668 18774487 13435545 0010 051 UNIQUAC 22980 23811 6974681 6558358 0010 051 Wilson 01883 28340 948668 11359585 0008 058 secbutyl acetate 1 2methoxyethanol 2 NRTL 46877 85541 25408531 35813473 0009 022 UNIQUAC 30193 28736 16326304 13419977 0008 022 Wilson 51638 16461 21387127 514284 0010 023 12dimethoxyethane 1 secbutyl acetate 2 NRTL 76852 123747 23986011 38419444 0017 056 UNIQUAC 32430 50218 9504824 14659673 0018 059 Wilson 55647 39500 13626158 11278345 0016 063 aab parameters of the NRTL UNIQUAC or Wilson model bSubscripts ij represents the pair interaction cSubscripts ji represents the pair interaction dσy1 i1 n y1i est y1i exp2n12 eσT i1 n Ti est Ti exp2n12 fThe value of αij was fixed at 03 for the three binary systems as these systems belong to type I according to the definition in the literature7 Figure 3 Experimental data and calculated data for the system of methyl ethyl ketone 1 secbutyl acetate 2 at 1013 kPa experimental x1 experimental y1 calculated x1 with UNIQUAC model calculated y1 with UNIQUAC model Figure 4 Experimental data and calculated data for the system of sec butyl acetate 1 2methoxyethanol 2 at 1013 kPa experimental x1 experimental y1 calculated x1 with UNIQUAC model calculated y1 with UNIQUAC model Figure 5 Experimental data and calculated data for the system of 12 dimethoxyethane 1 secbutyl acetate 2 at 1013 kPa experimental x1 experimental y1 calculated x1 with NRTL model calculated y1 with NRTL model Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX E REFERENCES 1 Wang H Wu C Bu X Tang W Li L Qiu T A benign preparation of secbutanol via transesterification from secbutyl acetate using the acidic Imidazolium ionic liquids as catalysts Chem Eng J 2014 246 366372 2 Ware G Methyl Ethyl Ketone Reviews of Environmental Contamination and Toxicology Springer New York 1988 3 TRC Thermodynamic Tables NonHydrocarbons Thermodynam ics Research Center NISTTRC Table Database Win Table Gaithersburg 2004 4 Herington E Tests for the consistency of experimental isobaric vaporliquid equilibrium data J Inst Pet 1951 37 457470 5 Wisniak J A new test for the thermodynamic consistency of vaporliquid equilibrium Ind Eng Chem Res 1993 32 15311533 6 Wilson G M VaporLiquid Equilibrium XI A New Expression for the Excess Free Energy of Mixing J Am Chem Soc 1964 86 127130 7 Renon H Prausnitz J M Local compositions in thermody namic excess functions for liquid mixtures AIChE J 1968 14 135 144 8 Abrams D S Prausnitz J M Statistical thermodynamics of liquid mixtures A new expression for the excess Gibbs energy of partly or completely miscible systems AIChE J 1975 21 116128 9 Carl L Y Chemical Properties Handbook McGrawHill Book Co New York 1999 10 Joung S N Yoo C W Shin H Y Kim S Y Yoo KP Lee C S Huh W S Measurements and correlation of highpressure VLE of binary CO2alcohol systems methanol ethanol 2 methoxyethanol and 2ethoxyethanol Fluid Phase Equilib 2001 185 219230 11 Valtz A Coquelet C BoukaisBelaribi G Dahmani A Belaribi F B Volumetric Properties of Binary Mixtures of 12 Dichloroethane with Polyethers from 28315 to 33315 K and at Atmospheric Pressure J Chem Eng Data 2011 56 16291657 12 Ellis S A new equilibrium still and binary equilibrium data Trans Inst Chem EngLondon 1952 30 5864 13 Resa J M Gonzalez C Goenaga J M Iglesias M Density Refractive Index and Speed of Sound at 29815 K and VaporLiquid Equilibria at 1013 kPa for Binary Mixtures of Ethyl Acetate 1 Pentanol and Ethanol 2Methyl1propanol J Chem Eng Data 2004 49 804808 14 Smith J M Van N H C Abbott M M Introduction to Chemical Engineering Thermodynamics McGrawHill New York 2001 Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX F
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Isobaric VaporLiquid Equilibrium for the Binary Systems of sec Butyl Acetate Methyl Ethyl Ketone 2Methoxyethanol or 12 Dimethoxyethane at 1013 kPa Zhankun Jiang Shoutao Ma Lei Wang Guoxin Sun and Yu Cui School of Chemistry and Chemical Engineering University of Jinan Jinan 250022 China Key Laboratory of Chemical Sensing Analysis in Universities of Shandong School of Chemistry and Chemical Engineering University of Jinan Jinan 250022 China School of Chemical Engineering and Technology Tianjin University No 92 Weijin Road Nankai District Tianjin 300072 China ABSTRACT The isobaric vaporliquid equilibrium VLE data of methyl ethyl ketone MEK secbutyl acetate SBAC 2methoxyethanol SBAC and 1 2dimethoxy ethane DME SBAC were determined at 1013 kPa by using an Ellis vaporliquid equilibrium still The experimental data passed the thermodynamic consistency test by Herington method and Wisniak test The VLE values were correlated by the nonrandom twoliquid NRTL universal quasichemical activity coefficience UNIQUAC and Wilson activitycoefficient models The results indicated that the three models had good agreement with the experimental data The 2methoxyethanol SBAC system forms a minimum temperature binary azeotrope at 1013 kPa The azeotropic temperature is 38386 K and the composition of SBAC is 851 mol 1 INTRODUCTION Secbutyl acetate SBAC has high octane number nontoxic noncorrosion and low oxygen content1 It has got wide application in industry Methyl ethyl ketone MEK 2 methoxyethanol and 12dimethoxyethane DME are ex cellent solvents2 The mixtures of these solvents which were generated abundantly in fields such as cellulose material and the printing ink productions need to be purified for reuse To our knowledge3 no vapor liquid equilibrium VLE data are available for MEK SBAC 2methoxyethanol SBAC and DME SBAC mixtures The experimental isobaric VLE data of the MEK SBAC 2 methoxyethanol SBAC and DME SBAC mixtures were measured to meet the need of process design and performance evaluation The consistency test of the experimental data were carried out with Herington test4 and Wisniak test5 The VLE data were regressed using Wilson6 nonrandom twoliquid NRTL7 and universal quasichemical UNIQUAC8 equa tions The three models with their bestfitted binary parameters were applied to correlate the VLE of the binary systems which were then compared with experimental data 2 EXPERIMENTAL SECTION 21 Chemicals The chemicals used were SBAC MEK 2 methoxyethanol and DME All of the chemicals were analytical reagents The source molecular formula CAS RN and mass fraction of the reagents are listed in Table 1 respectively The mass fraction was measured by a gas chromatograph GC equipped with a thermal conductivity detector TCD All of the chemicals were stored over activated 4Å molecular sieves to keep them dry No further purification has been made for the chemicals before use As additional purity checks some physical properties of the pure components were measured and compared with reported values The results are presented in Table 2 The densities were measured at 29815 K by the pycnometer method The refractive indexes were measured at 29815 K with an Abbe refractometer and the normal boiling points at 1013 kPa were measured using the Ellis vaporliquid equilibrium still 22 Analysis The compositions of the vapor condensate and the liquid phase at equilibrium were analyzed by a gas chromatography GC GC9790 Zhejiang Fu Li Analytical Instrument Co Ltd and calibrated with solutions prepared by gravimetrical standard TCD was used together with a SE30 packed column 3 mm 2 m Jinan Yuan Bo Chemical Instrument Company China Highpurity hydrogen 99999 was taken as carrier gas at a flow rate of 20 mL min1 The temperature of injector oven and detector were kept at 4132 K 3732 K and 4182 K respectively The area normalization method was used to gain quantitative results in the GC analysis The analysis was performed at least two times for each sample In the process the standard uncertainty of the measured mole fractions was 0005 23 Apparatus and Procedure An Ellis equilibrium still12 was used in the experiments The structure of the still is shown in Figure 1 The apparatus was validated by measuring the VLE data of ethanol isobutanol at 1013 kPa The data were Received July 12 2015 Accepted December 16 2015 Article pubsacsorgjced XXXX American Chemical Society A DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX compared with those in the literature13 The results are listed in Table 3 and plotted in Figure 2 It can be seen from Figure 2 that our data agree well with those from the literature First a series of solution samples with different concen trations were prepared in advance and separately added to the still slowly Then the heating rate was regulated to keep the vapor condensation speed at 60100 drops per minute The heater for overheating vapor stream was modulated to make sure that the vapor temperature was equal to or a little higher less than 05 K than the equilibrium temperature The system was kept at constant vapor and equilibrium temperatures for at least 60 min so as to guarantee that the equilibrium state was reached Then the equilibrium temperature was recorded and the liquid and vapor samples were collected The temperatures were measured with a calibrated thermometer graduated in 001 K while the uncertainty of the thermometer is 005 K The pressure of the system was measured by testo511 digital vacuum gauge with an uncertainty of 03 kPa 3 RESULTS AND DISCUSSION 31 Pure Component Vapor Pressures The vapor pressures of the pure components were calculated using an extended Antoine vapor pressure eq 1 where PS is the saturated vapor pressure Pa of pure component and T is the temperature K The parameters C1 to C5 which were obtained from ASPEN are listed in Table 4 Table 1 Materials Description at 1013 kPaa chemical name secbutyl acetate methyl ethyl ketone 2methoxyethanol 12dimethoxyethane isobutanol ethanol source Zhongchuang China Damao China Damao China Damao China Damao China Sinopharm China molecular formula C6H12O2 C4H8O C3H8O2 C4H10O2 C4H10O C2H6O CASRN 105464 78933 109864 110714 78831 64175 initial weight fraction purity 998 995 995 995 995 997 purification method dehydration dehydration dehydration dehydration dehydration dehydration final weight fraction purity 9989 9968 9974 9997 9978 9992 analysis method GCb GC GC GC GC GC auP 03 kPa bGas chromatography Table 2 Boiling Points Tb at 1013 kPa Densities ρ and Refractive Index nD at 29815 K of Pure Components Compared with Literature Dataa Tb K ρ kgm3 nD component this work literature this work literature this work literature secbutyl acetate 38512 38515b 8638 8652d 13872 13875b sethyl ethyl ketone 35276 35279b 7997 7996d 13761 13764b 2methoxyethanol 39748 39750c 9601 9600c 14002 14002b 12dimethoxyethane 35771 35775b 8604 8613e 13780 13781b auP 03 kPa uTb 005 K uρ 01 kgm3 unD 00001 bLiterature9 cLiterature10 dLiterature3 eLiterature11 Figure 1 Ellis still 1 heater 2 tube delivering mixture 3 liquid phase sampling valve 4 equilibrium temperature thermometer 5 heater for overheating vapor stream 6 vapor temperature thermometer 7 separator for liquid and vapor phases 8 vapor condenser 9 cooler 10 to pressurestabilizing system 11 flow meter drop counter 12 vapor condensate container 13 vapor condensate sampling valve 14 valve for drainage of still Table 3 Isobaric VLE Data for Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System Ethanol 1 Isobutanol 2 at 1013 kPaa no x1 y1 1 0000 0000 2 0041 0125 3 0085 0231 4 0136 0341 5 0198 0451 6 0252 0526 7 0302 0584 8 0358 0642 9 0432 0722 10 0525 0787 11 0581 0818 12 0649 0854 13 0711 0885 14 0751 0905 15 0812 0934 16 0889 0966 17 0948 0984 18 1000 1000 auP 03 kPa and ux1 uy1 0005 Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX B P C C T C T C T ln ln C S 1 2 3 4 5 1 32 Experimental Results The isobaric VLE experimental data and the corresponding calculated activity coefficients for MEK 1 SBAC 2 SBAC 1 2methoxyethanol 2 and DME 1 SBAC 2 at 1013 kPa are listed in Tables 57 respectively The general equilibrium relationship between the vapor phase and the liquid phase14 can be expressed as follows φ γφ Py P x e i i i i i i V P P RT V S S i i L S 2 where subscript i is the thermodynamic properties of component i y is the mole fraction of gas phase φV is the fugacity coefficient in the mixture vapor phase x is the mole fraction of liquid phase γi is the activity coefficient of component i φs is the fugacity coefficient in the saturate state VL is the liquid mole volume of pure liquid P is the total pressure of the equilibrium system and R is the gas constant The exponential term in eq 2 is close to unity at 1013 kPa After neglected the vapor nonideality and the pressure dependence of the liquid phase fugacity eq 2 can be simplified to eq 3 γ yP xP i i i i S 3 33 Thermodynamic Consistency Tests In order to confirm the thermodynamic consistency of these experimental data we verified all experimental data according to the Herington test4 and Wisniak test5 The Herington test is used to examine the thermodynamic consistency of the VLE data by area test while the Wisniak test conducts the pointto point test and area test simultaneously In the Herington test the criteria of consistency is that the value of DJ cannot be larger than 10 As to the Wisniak test the criteria is that the coefficient E is smaller than 35 where γ γ γ γ D x x 100 ln d ln d 0 1 1 2 1 0 1 1 2 1 4 J T T T 150 max min min 5 E L x W x L x W x 100 d d d d k k k k 0 1 1 0 1 1 0 1 1 0 1 1 6 Δ Δ L T x s x s T k i i i i i o o o 7 γ Δ W RT x s x x y x ln ln k i i i i i i i o 8 Figure 2 x1y1 diagram of ethanol 1isobutanol 2 at 1013 kPa experimental data literature data13 Table 4 Extended Antoine Equation Coefficients C1C5 for the Chemicals component C1 C2 C3 C4 C5 T range K secbutyl acetate 52601 60979 42398 215 1018 6 17415 to 56100 methyl ethyl ketone 72698 61436 75779 565 1006 2 18648 to 53550 2methoxyethanol 20263 12472 27385 264 1005 2 18805 to 56400 12dimethoxyethane 61814 61029 56547 118 1017 6 21515 to 53615 Table 5 Experimental VLE Data for Temperature T Activity Coeffiecient γ Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System Methyl Ethyl Ketone 1 secButyl Acetate 2 at 1013 kPaa T K x1 y1 γ1 γ2 38512 0000 0000 09937 37869 0090 0226 11563 10309 37512 0166 0392 12049 09893 37184 0266 0513 10796 10006 36965 0321 0590 10934 09804 36797 0377 0643 10648 09849 36647 0428 0684 10420 09990 36522 0470 0719 10358 09993 36422 0505 0746 10307 09987 36315 0546 0779 10268 09850 36184 0591 0798 10111 10440 36071 0640 0828 10017 10543 35980 0668 0847 10100 10475 35892 0705 0866 10046 10649 35819 0728 0875 10043 11125 35734 0766 0894 10028 11215 35654 0800 0908 09995 11705 35569 0837 0925 09986 12157 35500 0863 0938 10039 12234 35453 0888 0947 09996 12978 35423 0897 0952 10036 13114 35379 0914 0959 10068 13484 35341 0934 0967 10055 14369 35340 0946 0971 09972 15498 35276 1000 1000 09915 aStandard uncertainties u are uT 005 K uP 03 kPa and ux1 uy1 0005 Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX C Tmax and Tmin K are the maximum and the minimum boiling points of the system respectively Ti o represents the boiling point of component i Δsi o is the molar entropy of vaporization of component i k donates each experimental point The check results of thermodynamic consistency tests which are listed in Table 8 passed those tests The results indicate these binary VLE data are thermodynamically consistent 34 Data Regression The experimental data of three binary systems were regressed according to the NRTL UNIQUAC and Wilson models with Aspen software The Maximum likelihood objective function was used for the regression Maximum likelihood is a generalization of the least squares method In the maximum likelihood objective function errors in T P x and y are considered The objective function is minimized by manipulating the physical property parameters identified in the regression case and manipulating the estimated value corresponding to each measurement The function is presented in eq 9 σ σ σ σ Q T T P P x x y y i n i i T i i P i x i i y 1 exp est 2 exp est 2 exp i est 2 exp est 2 9 where n is the number of experimental points T is the equilibrium temperature superscript exp and est are abbreviation of experiment and estimate respectively σ is the standard deviation of the indicated data and Q is the objective function to be minimized by data regression The correlated binary interaction parameters from exper imental data are stated in Table 9 combined with the root meansquare deviations RMSD in vapor phase mole fraction and temperature It is observed that the RMSD of temperature for the activity models are less than 063 and those of vapor phase composition are no more than 0018 The calculated values of the vapor phase composition and temperature by these three models show reasonably good agreement with the experimental values The azeotropic temperature and composition of SBAC 2 methoxyethanol at 1013 kPa here are 38386 K 851 mol SBAC The experimental Txy diagrams of binary systems MEK SBAC SBAC 2methoxyethanol and DME SBAC together with correlated curves with UNIQUAC UNIQUAC or NRTL model are shown in Figure 3 Figure 4 and Figure 5 respectively 4 CONCLUSIONS Isobaric VLE values were determined experimentally for MEK SBAC SBAC 2methoxyethanol and DME SBAC systems with Ellis equilibrium still at 1013 kPa The results show that SBAC 2methoxyethanol system forms a minimum temperature azeotrope and the other two systems do not form Table 6 Experimental VLE Data for Temperature T Activity Coeffiecient γ Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System Secbutyl Acetate 1 2 methoxyethanol 2 at 1013 kPaa T K x1 y1 γ1 γ2 39748 0000 0000 10060 39655 0024 0058 17199 09994 39310 0119 0249 16431 09840 39118 0191 0354 15387 09802 38964 0258 0440 14796 09740 38858 0324 0502 13882 09836 38761 0379 0546 13302 10069 38692 0429 0583 12786 10304 38630 0479 0629 12582 10257 38597 0509 0651 12376 10353 38555 0551 0671 11951 10808 38515 0595 0698 11638 11159 38484 0636 0715 11263 11841 38458 0673 0737 11060 12258 38433 0718 0763 10817 12917 38408 0735 0773 10786 13275 38403 0762 0790 10648 13701 38396 0819 0824 10355 15142 38386 0851 0849 10301 15823 38391 0877 0865 10162 17172 38394 0903 0884 10083 18620 38412 0939 0914 09977 21657 38429 0962 0941 09969 23895 38512 1000 1000 09937 aStandard uncertainties u are uT 005 K uP 03 kPa and ux1 uy1 0005 Table 7 Experimental VLE Data for Temperature T Activity Coefficient γ Liquid Phase Mole Fraction x and Gas Phase Mole Fraction y for the System 12Dimethoxyethane 1 secButyl Acetate 2 at 1013 kPaa T K x1 y1 γ1 γ2 38512 0000 0000 09937 38176 0066 0154 11333 09973 37945 0146 0293 10427 09787 37702 0223 0408 10143 09731 37528 0284 0487 10005 09676 37355 0347 0560 09893 09613 37242 0394 0606 09752 09621 37113 0439 0650 09734 09654 36984 0490 0692 09658 09738 36897 0509 0707 09758 09889 36873 0538 0727 09553 09887 36746 0571 0755 09711 09973 36574 0646 0808 09689 10021 36415 0715 0852 09681 10168 36274 0783 0891 09670 10273 36141 0850 0925 09632 10804 36048 0911 0955 09560 11230 35950 0972 0986 09544 11497 35771 1000 1000 09965 auT 005 K uP 03 kPa and ux1 uy1 0005 Table 8 Thermodynamic Consistency Check system D J DJ L W E methyl ethyl ketone secbutyl acetate 822 1376 554 339 359 287 2methoxyethanol secbutyl acetate 1401 481 920 397 414 217 12dimethoxyethane secbutyl acetate 2020 1149 871 187 195 209 Journal of Chemical Engineering Data Article DOI 101021acsjced5b00582 J Chem Eng Data XXXX XXX XXXXXX D an azeotrope Thermodynamic consistency of the experimental data was verified according to Herington test and Wisniak method The VLE values were correlated by the NRTL UNIQUAC and Wilson activitycoefficient models The corresponding binary interaction parameters of the models were obtained by maximum likelihood method The RMSD of temperature for the three activity models are less than 063 and those of vapor phase composition are no more than 0018 For the SBAC 2methoxyethanol system the azeotropic temper ature is 38386 K and the composition of SBAC is 851 mol at 1013 kPa AUTHOR INFORMATION Corresponding Authors Tel 86 15053121073 Email address chmjiangzkujn educn Z Jiang Tel 86 053182767937 Email address chmcuiyujnedu cn Y Cui Funding We thank the outstanding young scientist award fund in Shandong Province BS2014NJ020 and Science and technol ogy developing program of universities in Shandong Province J14LC06 for the financial support Notes The authors declare no competing financial interest Table 9 Correlation Parameters and Root Mean Square Deviations for the Binary Systems correlation parametersa RMSD system models aijb ajic bij bji σy1d σTe methyl ethyl ketone 1 secbutyl acetate 2 NRTLf 56649 45668 18774487 13435545 0010 051 UNIQUAC 22980 23811 6974681 6558358 0010 051 Wilson 01883 28340 948668 11359585 0008 058 secbutyl acetate 1 2methoxyethanol 2 NRTL 46877 85541 25408531 35813473 0009 022 UNIQUAC 30193 28736 16326304 13419977 0008 022 Wilson 51638 16461 21387127 514284 0010 023 12dimethoxyethane 1 secbutyl acetate 2 NRTL 76852 123747 23986011 38419444 0017 056 UNIQUAC 32430 50218 9504824 14659673 0018 059 Wilson 55647 39500 13626158 11278345 0016 063 aab parameters of the NRTL UNIQUAC or Wilson model bSubscripts ij represents the pair interaction cSubscripts ji represents the pair interaction dσy1 i1 n y1i est y1i exp2n12 eσT i1 n Ti est Ti exp2n12 fThe value of αij was fixed at 03 for the three binary systems as these systems belong to type I according to the definition in the literature7 Figure 3 Experimental data and calculated data for the system of methyl ethyl ketone 1 secbutyl acetate 2 at 1013 kPa experimental x1 experimental y1 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