Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX-XXX
pubs.acs.org/jced
Density, Viscosity, and Vapor−Liquid Equilibrium Data for the Binary Mixture at Atmosphere Pressure: Cyclopropyl Methyl Ketone + 2‑Acetylbutyrolactone, Cyclopropyl Methyl Ketone + 5‑Chloro-2pentanone Xiaoda Wang,† Yuan Gao,† Jinbei Yang,†,‡ Zhixian Huang,† and Ting Qiu*,† †
School of Chemical Engineering, Fuzhou University, Fuzhou, 350108 Fujian, China Department of Biological and Chemical Engineering, Fuqing Branch of Fujian Normal University, Fuqing, 350300 Fujian, China
‡
ABSTRACT: The density and viscosity of the cyclopropyl methyl ketone (CPMK) + 2acetylbutyrolactone (ABL) and CPMK + 5-chloro-2-pentanone (CPE) binary mixtures were measured at the temperature range of 303.15 to 333.15 K at atmospheric pressure (about 101.325 ± 0.3 kPa). The excess molar volume and viscosity deviation were calculated based on the experimental data of density and viscosity, and they could be accurately described by the Redlich− Kister equation. In addition, the vapor−liquid equilibrium (VLE) data for the CPMK-ABL binary system were measured at atmospheric pressure. It was shown that there is no azeotrope in this binary mixture. The VLE data were correlated with NRTL, Wilson, and UNIQUAC models and the interaction parameters obtained were reported. The prediction accuracies of these models were about the same.
1. INTRODUCTION
2. EXPERIMENTAL SECTION CPMK, ABL, and CPE were supplied by Shanghai Aladdin BioChem Technology Co., Ltd. Both the initial mass fraction purity of CPMK and ABL were 0.98, and that of CPE was 0.96. They were further purified to 0.995 with a glass distillation column in our laboratory. Table 1 lists the details of the chemicals used in present work. The densities ρ of the samples were measured in a standard 10 mL pycnometer with accuracy of ±10−4 g·cm−3 at the temperature range of 303.15 to 333.15 K at atmosphere pressure. The equipment was open to atmosphere to maintain atmosphere pressure. The pycnometer was cleaned, dried, and weighed carefully before filled with sample. Then, it was kept in a thermostat water bath with temperature control precision of ±0.01 K. After the thermal equilibrium reached, the pycnometer was taken out of the thermostat water bath and weighed after being wiped. The liquid kinematic viscosity was measured by an Ubbelohde viscometer with capillary diameter of 0.36 mm at the temperature range of 303.15 to 333.15 K at atmosphere pressure. The measurement accuracy of the viscometer is ±0.0001 mPa·s. The flow time t in the capillary was recorded by a second chronograph. The Ubbelohde capillary was submerged in a thermostat water bath to maintain the measure temperature. The kinematic viscosity ν was calculated by ν = kt,
Cyclopropyl methyl ketone (CPMK) is an important organic intermediate. It has application in synthesizing anti-aids drugs and agrochemicals, such as efavirenz, pitavastatin, and cyproconazole.1 The mature CPMK production technology takes 2-acetylbutyrolactone (ABL) as raw material.2 Since only 50−85% ABL could be converted to CPMK in the reaction, the separation of CPMK and ABL is inevitable after the reaction. Due to the large boiling-point difference between CPMK and ABL, distillation is a good choice for their separation. In addition, CPMK could also be produced from 5-chloro-2pentanone (CPE). The separation of CPMK from CPE could also be conducted by distillation. In order to minimize the energy consumption of the CPMK-ABL or CPMK-CPE separation, process simulation should be conducted to optimize the operation condition of the distillation column. The thermodynamic properties of the components are of great importance for the simulation.3 However, there is little information about the thermodynamic properties for the CPMK-ABL and CPMK-CPE binary systems in the literatures. Therefore, this work focused on measuring the density, viscosity, and vapor−liquid equilibrium of the CPMK-ABL and CPMK-CPE binary systems. The experimental data of density and viscosity were used to calculate the excess molar volume and viscosity deviation, which were finally correlated by the Redlich−Kister equation. The data of vapor−liquid equilibrium (VLE) were used to obtain the binary interaction parameter of the NRTL, Wilson, and QUNIQUAC models. © XXXX American Chemical Society
Received: April 11, 2017 Accepted: October 13, 2017
A
DOI: 10.1021/acs.jced.7b00344 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 1. Nomenclature of the Chemicals chemicals (abbreviation) cyclopropyl methyl ketone (CPMK) 2-acetylbutyrolactone (ABL) 5-chloro-2-pentanone (CPE) a
CAS number
formula
mole mass (g/mol)
initial purity (mass fraction)
purification method
final purity (mass fraction)
765-43-5
C5H8O
84.12
98.0%a
distillation
99.5%a
517-23-7
C6H8O3
128.13
98.0%a
distillation
99.5%a
5891-21-4
C5H9ClO
120.58
96.0%a
distillation
99.5%a
manufacturer Shanghai Aladdin Bio-Chem Technology Co., LTD Shanghai Aladdin Bio-Chem Technology Co., LTD Shanghai Aladdin Bio-Chem Technology Co., LTD
Analyzed by GC.
where k = 0.001295 mm2·s−2 is the calibration viscometer constant supplied by the manufacturer. The dynamic viscosity η was calculated by η = νρ, where ρ is the liquid density. The VLE experiments were conducted in a modified Rose equilibrium still, as it was done in our previous work.4 The apparatus schematic is illustrated in the literature.4 A mercury thermometer with an accuracy of ±0.1 K was used to measure the phase equilibrium temperature. About 40 mL liquid mixture was put into the equilibrium still in each run of experiment. The liquid in the still was heated by an electrical heating bar inserted into the bottom of the equilibrium still. The equilibrium still was well designed to ensure the circulation flow of liquid and vapor phases to establish the vapor−liquid two-phase equilibrium. It took approximately 3 h for the CPMK-ABL binary system to reach vapor−liquid equilibrium. Both the compositions of liquid phase and condensed vapor phase were analyzed by a gas chromatograph. The internal standard method was applied with cyclohexanone as internal standard substance. The gas chromatograph (GC2014, Shimadzu Corporation) was equipped with a flame ionization detector (FID) and a RTX-5 capillary column (30 m × 0.25 mm × 0.25 mm). Nitrogen gas with a purity of 99.99 mass% was used as carrier gas at the velocity of 1 mL/min. An optimized temperature control program was implemented (363 K for 1 min, a ramp of 15 K/min to 433 K, 433 K for 1 min, a ramp of 50 K/min to 523 K, 523 K for 1 min,). The temperature of the injection port and detector were controlled at 523 and 553 K, respectively. One μL sample was injected each time. The measurement accuracy of the gas chromatography is ±0.0005. The measurement of saturated vapor pressure was also conducted in the modified Rose equilibrium still. A vacuum pump was connected to the Rose equilibrium still to maintain the pressure, when the saturated vapor pressure was measured. When the density, viscosity and VLE were measured, the measuring apparatus were open to atmosphere to maintain atmosphere pressure of the measuring system. The barometer showed that the atmosphere pressure was about 101.325 ± 0.3 kPa.
Table 2. Experimental Densities for the CPMK-ABL and CPMK-CPE Binary Systems at Different Temperatures at 101.325 ± 0.3 kPaa ρ (g/cm3) system
xCPMK
303.15 K
313.15 K
323.15 K
333.15 K
CPMK-ABL
1.0000 0.8999 0.7999 0.6999 0.5999 0.4999 0.4002 0.3004 0.2009 0.0998 0.0000 0.8999 0.7999 0.6999 0.5999 0.4999 0.4002 0.3004 0.2009 0.0998 0.0000
0.8898 0.9245 0.9583 0.9911 1.0225 1.0528 1.0819 1.1097 1.1362 1.1619 1.1857 0.9105 0.9302 0.9489 0.9665 0.9828 0.998 1.0125 1.0261 1.0391 1.0513
0.8803 0.9155 0.9492 0.9821 1.0138 1.0443 1.0737 1.1018 1.1285 1.1543 1.1783 0.9011 0.921 0.9397 0.9571 0.9733 0.9885 1.0029 1.0163 1.0291 1.0411
0.8706 0.9059 0.9396 0.9724 1.0042 1.0348 1.0642 1.0923 1.1191 1.1449 1.1689 0.8916 0.9117 0.9304 0.9477 0.9639 0.9791 0.9934 1.0067 1.0194 1.0312
0.8612 0.8965 0.9302 0.9631 0.9948 1.0254 1.0548 1.0829 1.1097 1.1356 1.1594 0.8824 0.9026 0.9211 0.9383 0.9544 0.9695 0.9836 0.9968 1.0093 1.0208
CPMK-CPE
a
Standard uncertainties u are u(P) = 0.3 kPa, u(T) = 0.1 K, u(x) = 0.001, u(ρ) = 0.0005 g/cm3.
3. RESULTS AND DISCUSSION 3.1. Density and Viscosity. Table 2 shows the densities for the CPMK-ABL and CPMK-CPE binary systems at the temperature range of 303.15 to 333.15 K at atmospheric pressure over the entire range of concentration. The density of CPMK decreases from 0.8898 g/cm3 to 0.8612 g/cm3 with temperature increasing from 303.15 to 333.15 K. The dependence of the measured CPMK density on temperature is shown in Figure 1 to compare them with those reported in literatures.5−7 It can be seen that the densities measured in this work are close to those reported in literatures.5−7 In the same temperature range, the densities of the pure ABL and CPE
Figure 1. Comparison of CPMK densities between this work and literatures.5−7
decrease from 1.1857 g/cm3 to 1.1594 g/cm3 and from 1.0513 g/cm3 to 1.0208 g/cm3, respectively, with the decrease of B
DOI: 10.1021/acs.jced.7b00344 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
The excess molar volume VEm for the CPMK-ABL and CPMK-CPE binary mixtures was calculated by the following relation:9
temperature. Arguably, the density of CPE is lower than 1.0513 g/cm3. Nevertheless, the literature reported that the density of CPE is 1.0492 g/cm3 at 298.15 K, which is slightly lower than our predicted value.8 The low CPE purity (97%) led to the inaccuracy of density measurement in the literature.8 The densities of the CPMK-ABL and CPMK-CPE binary systems increase with the decrease of CPMK concentration, since the density of CPMK is lower than those of ABL and CPE. The experimental viscosities for the CPMK-ABL and CPMKCPE binary systems investigated at the temperature range of 303.15 to 333.15 K at atmospheric pressure are given in Table 3
VmE = Vm − (xCPMKVm,CPMK + xABL (or CPE)Vm,ABL (or CPE)) (2)
Vm is the molar volume of the mixture. Vm, CPMK, Vm, ABL, and Vm, CPE are the molar volume of pure CPMK, ABL, and CPE, respectively. Vm was calculated by Vm = (xCPMKMCPMK + xABL (or CPE)MABL (or CPE))/ρ
MCPMK, MABL, and MCPE are the molar mass of CPMK, ABL, and CPE, respectively. VEm are illustrated in Figure 2 for all the measured temperatures. The results indicate that VEm are negative both for the CPMK-ABL and CPMK-CPE binary systems over the entire mole fraction range. The negative behavior of the excess mole volume of the CPMK-ABL mixture should be the contribution of the structural effects of the components in the mixture.10,11 Mixing CPMK and ABL would dissociate the mutual dipolar interaction between the components with similar structure in the pure liquid, forming new dipolar interaction between the unlike components of CPMK and ABL. The polar carbonyl group of CPMK tends to interact strongly with the polar ABL molecule, leading to the contraction in mixture volume, finally resulting in the negative value of VEm. Similar phenomenon was observed for the tetrahydrofuran + methyl acrylate system.12 The results also show that VEm becomes more negative with rising temperature. This should be attributed to the formations of more dipolar associations between unlike components and more free volume which is more favorable for the mutual packing of CPMK and ABL molecule at higher temperature. The explanations for the negative VEm of CPMK-CPE system are similar to that of CPMK-ABL system. The viscosity deviation Δη for the CPMK-ABL and CPMKCPE binary systems was calculated using the following equation:
Table 3. Experimental Viscosities for the CPMK-ABL and CPMK-CPE Binary Systems at Different Temperatures at 101.325 ± 0.3 kPaa η (mPa·s) system
xCPMK
303.15 K
313.15 K
323.15 K
333.15 K
CPMK-ABL
1.0000 0.8999 0.7999 0.6999 0.5999 0.4999 0.4002 0.3004 0.2009 0.0998 0.0000 0.8999 0.7999 0.6999 0.5999 0.4999 0.4002 0.3004 0.2009 0.0998 0.0000
0.5572 0.6546 0.7830 0.9813 1.1983 1.4519 1.7857 2.1640 2.6328 3.1953 3.7942 0.7027 0.7363 0.8390 0.8757 0.9550 1.0699 1.1348 1.2229 1.4272 1.5819
0.5015 0.5854 0.6912 0.8642 1.0545 1.3055 1.5987 1.9452 2.3685 2.8894 3.4240 0.6216 0.6493 0.7366 0.7715 0.8296 0.9252 0.9766 1.0431 1.2103 1.3181
0.4524 0.5436 0.6390 0.7780 0.9344 1.1539 1.4153 1.7479 2.1177 2.6087 3.0670 0.5513 0.5783 0.6490 0.6787 0.7322 0.8063 0.8507 0.9043 1.0297 1.0781
0.3942 0.4933 0.5704 0.6958 0.8398 1.0255 1.2776 1.5707 1.8923 2.3296 2.7192 0.4968 0.5207 0.5818 0.6086 0.6517 0.7131 0.7484 0.7927 0.8933 0.9667
CPMK-CPE
Δη = η − xCPMKηCPMK − xABL (or CPE)ηABL (or CPE)
a
Standard uncertainties u are u(P) = 0.3 kPa, u(T) = 0.1 K, u(x) = 0.001, u(η)= 0.005η.
(4)
ηCPMK, ηABL, and ηCPE represent the viscosities of pure CPMK, ABL, and CPE, respectively. Figure 3 illustrates that the viscosity deviations are negative over the entire composition range, and they increase with temperature increasing from 303.15 to 333.15 K. The values of VEm and Δη were correlated with the Redlich− Kister equation:13,14
for the entire composition range. The viscosity of CPMK increases from 0.4577 mPa·s to 0.6262 mPa·s with temperature decreased from 333.15 to 303.15 K, while the viscosities of ABL and CPE increase from 2.3454 mPa·s to 3.2000 mPa·s and from 0.9667 mPa·s to 1.5819 mPa·s, respectively. Both the viscosity of ABL and CPE are higher than that of CPMK, which leads to the monotonous viscosity increases of CPMK-ABL and CPMKCPE binary mixtures with the decrease of CPMK concentration. The composition dependences of density ρ and viscosity η for the CPMK-ABL and CPMK-CPE binary mixtures could be described by the following polynomial: 3 2 f = a0xCPMK + a1xCPMK + a 2xCPMK + a3
(3)
r=3
Y = xCPMK(xCPMK − 1)∑ A r (1 − 2xCPMK )r − 1 r=1
(5)
Y represents or Δη. The coefficients Ar were determined by the method of least-squares. Table 6 summaries the fitted coefficients along with the standard deviations: VEm
n
(1)
σ=
f represents ρ or η. The coefficients of eq 1 were determined with the experimental densities and viscosities by the leastsquares, respectively, and they are listed in Table 4. The correlation coefficient R was used to describe the fitting precision. Temperature dependences of the coefficients in eq 1 are listed in Table 5 for the CPMK-ABL and CPMK-CPE binary systems.
∑ i=1
(Yexp − Ycal)i2 n−k
(6)
n and k are the number of experimental points and the number of coefficients, respectively. The subscripts “exp” and “cal” respect the experiment and calculation results, respectively. The small values of standard deviation suggest that the correlated results are believable. For graphic comparison, the values of VEm C
DOI: 10.1021/acs.jced.7b00344 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 4. Coefficients of Eq 1 and the Correlation Factors R Obtained for the Experimental Densities and Viscosities of the CPMK-ABL and CPMK-CPE Binary Systems for Different Temperatures ρ(g/cm3) T
CPMK-ABL
a0
a1
a2
a3
R
303.15K 313.15K 323.15K 333.15K
0.0060 0.0077 0.0082 0.0084
−0.0693 −0.0715 −0.0722 −0.0727
−0.2327 −0.2341 −0.2344 −0.2359
1.1857 1.1783 1.1689 1.1595
1.0000 1.0000 1.0000 1.0000
T 303.15K 313.15K 323.15K 333.15K
a0 −1.0864 −0.8410 −0.8452 −0.6396
a1 4.5069 3.9260 3.7255 3.0864
a2 −6.6683 −6.0165 −5.5049 −4.7778
a3 3.8012 3.4320 3.0866 2.7402
R 0.9999 0.9999 0.9997 0.9995
T 303.15K 313.15K 323.15K 333.15K
a0 −0.0119 −0.0131 −0.0144 −0.0158
a1 −0.0309 −0.0308 −0.0306 −0.0300
a2 −0.1188 −0.1170 −0.1157 −0.1139
a3 1.0513 1.0411 1.0312 1.0209
R 1.0000 1.0000 1.0000 1.0000
T 303.15K 313.15K 323.15K 333.15K
a0 −0.3026 −0.2991 −0.2075 −0.1837
a1 1.0438 0.9406 0.7025 0.5663
a2 −1.7691 −1.4621 −1.1252 −0.8996
a3 1.5814 1.3219 1.0855 0.9142
R 0.9999 0.9998 0.9992 0.9990
η(mPa·s)
ρ(g/cm3)
η(mPa·s)
CPMK-CPE
Table 5. Temperature Dependence of the Coefficients in Eq 1 for the CPMK-ABL and CPMK-CPE Binary Systems ρ
system
CMPK-ABL
CMPK-CPE
η
a0 = 0.00008T − 0.0169 R = 0.8310
a0 = 0.0134T − 5.1042 R = 0.8908
a1 = 0.00011T − 0.0367 R = 0.8804
a1 = − 0.0446T + 18.0071 R = 0.9666
a 2 = 0.00010T − 0.2028 R = 0.9483
a 2 = 0.0618T − 25.413 R = 0.9961
a3 = 0.00088T + 1.4531 R = 0.9969
a3 = − 0.0353T + 14.4911 R = 0.9997
a0 = 0.00013T + 0.0276 R = 0.9988
a0 = 0.0045T − 1.6745 R = 0.8840
a1 = 0.00003T − 0.0398 R = 0.8626
a1 = − 0.0167T + 6.1283 R = 0.9784
a 2 = 0.00016T − 0.1672 R = 0.9961
a 2 = 0.0295T − 10.6850 R = 0.9939
a3 = 0.00101T + 1.3578 R = 0.9999
a3 = − 0.0224T + 8.3459 R = 0.9919
and Δη calculated by Redlich−Kister equation are plotted in Figures 2 and 3, respectively. Temperature dependences of the coefficients in eq 5 were listed in Table 7 for the CPMK-ABL and CPMK-CPE binary systems. The excess Gibbs free energy was computed from the molar volume and viscosity of the system:
The phase equilibrium temperature increases monotonously from 384.8 K (the boiling temperature of CPMK) to 530.9 K (the boiling temperature of ABL) with the mole fraction of ABL increasing from 0 to 1, suggesting that there is no azeotrope between CPMK and ABL at the measured pressure. The VLE data for the CPMK-CPE binary system were not successfully determined, since the stable VLE state was not realized in the equilibrium still even in 2 days. The thermodynamic consistency test was employed to estimate the reliability of the measured VLE data with the method proposed by Herington.15,16 Two parameters should be calculated for the application of this method:
⎡ ⎛ ⎞ ηVm ⎟ ΔGmE = RT ⎢ln⎜⎜ ⎢ ⎝ ηABL (or CPE)Vm,ABL (or CPE) ⎟⎠ ⎣ ⎛ ⎞⎤ ηCPMK Vm,CPMK ⎟⎥ − xCPMK ln⎜⎜ ⎟⎥ V η m,ABL (or CPE) ⎝ ABL (or CPE) ⎠⎦
(7)
The calculated results are plotted in Figure 4. For the CPMK-ABL system, ΔGEm changes from positive value to negative value with the increase of xCPMK. For the CPMK-CPE system, the values of ΔGEm are found to be negative at the whole range of xCPMK. 3.2. Vapor−Liquid Equilibrium. The VLE data for the CPMK-ABL binary system are given in Table 8 and Figure 5.
D = 100 ×
∫x
xCPMK = 1 CPMK = 0
∫x J = 150 × D
ln(γCPMK /γABL)dxCPMK
xCPMK = 1 CPMK = 0
ln|γCPMK /γABL|dxCPMK
Tmax − Tmin Tmin
(8)
(9) DOI: 10.1021/acs.jced.7b00344 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Figure 2. Variation of excess molar volume VEm with CPMK mole fraction xCPMK for the (A) CPMK-ABL and (B) CPMK-CPE binary systems at different temperatures. The points represent the experimental value. The lines represent the values calculated by Redlich−Kister eq (eq 5).
Figure 3. Variation of viscosity deviation Δη with CPMK mole fraction xCPMK for the (A) CPMK-ABL and (B) CPMK-CPE binary systems at different temperatures. The points represent the experimental value. The lines represent the values calculated by Redlich−Kister eq (eq 5).
The measured VLE data are considered to be credible, if (D− J) < 10. Tmax and Tmin are the maximum and minimum boiling temperature of the CPMK-ABL system, respectively. There is no maximum or minimum azeotrope in the CPMK-ABL binary system. The liquid activity coefficient is calculated by the following equation:
ln pis (Pa) = A −
Pyi ϕiv pis ϕi sxi
(11)
In order to correlate the coefficients A, B, and C for CPMK and ABL, the saturated vapor pressures of CPMK and ABL were measured experimentally at different temperatures. For ABL, the saturated vapor pressure measurement was conducted in the temperature range of 384.8 to 530.9 K. We could not conduct the vapor pressure measurement in the same temperature range in the glass Rose equilibrium still for CPMK, because it could not bear the high pressure (>101.325 kPa) which CPMK produced in the temperature range of 384.8 to 530.9 K. When the Antoine’s constants for the temperature range
