Isobaric VaporâLiquid Equilibrium for Two Binary Systems of 3,3

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Isobaric Vapor−Liquid Equilibrium for Two Binary Systems of 3,3Dimethyloxetane + Methyl Cyclohexane and 3‑Chloro-2,2-dimethyl1-propanol + Methyl Cyclohexane at 101.3 kPa Daixiang Wei, Lingqi Kong,* Xinshun Tan, and Shiqing Zheng

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Research Center of Computers and Chemical engineering, Qingdao University of Science and Technology, Qingdao 266042, China ABSTRACT: The binary vapor−liquid equilibrium (VLE) data at the pressure of 101.3 kPa, which are 3,3-dimethyloxetane + methyl cyclohexane and 3-chloro-2,2-dimethyl-1-propanol + methyl cyclohexane, have been measured using a modified Rose vapor-recirculating equilibrium still. The reliability of VLE data was verified by thermodynamic consistency of area test of Herington and point test of Van Ness. The experimental data were regressed with activity coefficient models of Wilson, nonrandom two-liquid, and UNIQUAC, respectively, and the corresponding binary interaction parameters were obtained using the maximum likelihood method. The rootmean square deviations between calculated and experimental data for the vapor phase molar fraction and equilibrium temperature were less than 0.0119 and 0.58 K, which indicated that the fitted results for the three models were within acceptable limits.

1. INTRODUCTIOǸ Ibuprofen1,2 is one of the most known nonsteroidal antiinflammatory drugs and has important value in clinical medical research and practice. Ibuprofen sodium is an intermediate of ibuprofen and generally obtained from isobutyl benzene involving five steps of Friedel-Crafts reaction with propanoyl chloride, condensation with neopentyl glycol, 1,2-aryl-translocation catalytic rearrangement, hydrolysis reaction with sodium hydroxide, and cooling crystallization processes. In these production processes, the condensation reaction is a reversible reaction, and water is continuously generated in the reaction. It is necessary to remove water from the reaction system by adding a solvent in order to increase the positive reaction rate and shorten the condensation reaction time in the mild environment. Petroleum ether is an important solvent and is widely used in the chemical industry to make the reaction mild, side reactions decrease, and product yield improve.3 However, petroleum ether is difficult to recycle because of its wide-boiling temperature property of its many components, which results in pollution of material and the environment. In our current research work, methyl cyclohexane as a kind of high performance solvent can overcome this disadvantage. Meanwhile, the byproduct of 3-chloro-2,2-dimethyl-1-propanol and a small amount of 3,3-dimethyloxetane which were generated during the processes of condensation, rearrangement, and hydrolysis stages, and the solvent of methyl cyclohexane were presented in the mother liquor of sodium ibuprofen. The effective separation and recycling of these components can decrease the consumption of material and lower the cost of production. It is obvious that all the VLE data is an important basis for the research and design of separation technologies. Unfortunately, the binary experimental data of © XXXX American Chemical Society

3,3-dimethyloxetane + methyl cyclohexane, and 3-chloro-2,2dimethyl-1-propanol + methyl cyclohexane have not been reported yet in any related literature. The system of these components is a polar nonideal one, and the binary interaction parameters of the polar nonideal system are strongly dependent on experimental data; therefore, it is very necessary to study the vapor−liquid equilibrium data of the above systems. In this paper, the binary vapor−liquid equilibrium data at a pressure of 101.3 kPa for 3,3-dimethyloxetane + methyl cyclohexane and 3-chloro-2,2-dimethyl-1-propanol + methyl cyclohexane were obtained by a modified Rose vaporrecirculating equilibrium still, and the VLE data were checked for thermodynamic consistency by the area test of Herington4 and point test of Van Ness.5 In addition, the binary interaction parameters6,7 were fitted with the activity coefficient models of Wilson,8 universal quasichemical (UNIQUAC)9,10 and the nonrandom two-liquid (NRTL),11 respectively, and the average absolute deviations (AADs) as well as the root-mean square deviations (RMSDs) were obtained. The results showed that the deviation for correlation results of three models was within a reasonable range. The correlate results offered reliable data for the simulation and calculation of these systems.

2. EXPERIMENT SECTION 2.1. Materials. In this work, all of the chemicals used were methyl cyclohexane, 3-chloro-2,2-dimethyl-1-propanol, and Received: October 25, 2018 Accepted: December 27, 2018

A

DOI: 10.1021/acs.jced.8b00966 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Materials Description at 101.3 kPaa substance

CAS

methyl cyclohexane 3,3-dimethyloxetane

108-87-2 6921-35-3

3-chloro-2,2-dimethyl-1propanol

13401-56-4

source

purification method

Tianjin Zhiyuan Chemical Reagent Co., Ltd. none Shanghai Aladdin Biochemical Technology Co., dehydration Ltd. distillation Shanghai Aladdin Biochemical Technology Co., distillation Ltd.

final mass fraction purity

analysis method

99.85 99.64

GCb GCb

99.58

GCb

a

Standard uncertainties u(P) = 0.1 kPa. bGas chromatography.

3,3-dimethyloxetane; these chemicals were all analytical grade. CAS number, reagents source, reagents purification method, and reagents final mass fraction were shown in Table 1. A gas chromatograph (GC, GC-7890A, American Agilent Technologies Co. Ltd.) was used to analyze the purities of methyl cyclohexane, 3-chloro-2,2-dimethyl-1-propanol, and 3,3-dimethyloxetane. The water content of all reagents was determined using a Karl Fischer (DL31, Mettler Toledo). The chemicals of 3-chloro-2,2-dimethyl-1-propanol and 3,3-dimethyloxetane were used in the experiment with some further purification. Distillation and dehydration are two important methods used to purify reagents.12 Distillation utilizes the difference in relative volatility between components to remove trace impurities from reagents that GC cannot measure. The distillation experiment used a triangular spiral packing and the height of the packing column is 1.5 m. The water in 3,3dimethyloxetane was removed using 4 Å molecular sieves. Using both methods to improve the purity of the reagents ensures the reliability of the experimental results. The boiling temperature of methyl cyclohexane, 3-chloro-2,2-dimethyl-1propanol, and 3,3-dimethyloxetane was 373.35 K, 439.15 K, and 352.80 K at 101.3 kPa. The experiments showed that no azeotropic points were detected between the two binary systems. Therefore, the temperature ranges of 3,3-dimethyloxetane + methyl cyclohexane system and 3-chloro-2,2-dimethyl1-propanol + methyl cyclohexane were 352.80−373.35 K and 373.35−439.15 K, respectively. 2.2. Apparatus and Procedures. A modified Rose vaporrecirculating still13,14 was used to carry out VLE data at an atmospheric pressure (101.3 kPa), and the structure diagram was presented in Figure 1. In our previous work15,16 it has been confirmed that the equilibrium still is reliable. A certain proportion of the sample solution was added to the equilibrium still, heating was started, and the heating rate was maintained, and circulating condensed water was added to the coil condenser. After a period of time, the sample solution started to boil, and the condensed vapor phase was continuously circulated, which made the vapor−liquid two phases fully contact and established a balance as quickly as possible. A pressure gauge produced by Changchun Meteorological Instrument Co was used to measure the total pressure, whose accuracy was ±0.1 kPa. Equilibrium temperature was measured through a precision mercury thermometer produced by Changzhou Xinhua Instrument Factory with an accuracy of ±0.1 K. The equilibrium data of the temperature and pressure was recorded when the temperature of system remained stable for at least 60 min,16 and then the microsampler was used to take the vapor−liquid two-phase samples for chromatographic analysis. In this experiment, the volume of each vapor−liquid sample was controlled within 3 μL to minimize the effect of sampling on the equilibrium state. 2.3. Analysis. These collected samples were measured to confirm the mass composition of the liquid and condensed

Figure 1. Equilibrium still: (1) temperature thermometer; (2) equilibrium chamber; (3) temperature measurement point; (4) liquid-phase sampling port; (5) heating rod; (6) vapor-phase sampling port; (7) condenser.

vapor phase with gas chromatography. The gas chromatograph was equipped with a DB-1701 capillary column (30 m × 250 μm × 0.25 μm), the carrier gas was hydrogen with purity of 99.99% by weight, and the gas flow rate was 40 mL·min−1. The chromatographic conditions were as follows: the initial temperature of the oven of the 3,3-dimethyloxetane + methyl cyclohexane system was 333.15 K, and then the temperature ramped 25 K·min−1 to 523.15 K. The oven temperature of 3chloro-2,2-dimethyl-1-propanol + methyl cyclohexane system was 373.15 K. And also, the vaporization chamber temperature, FID detector temperature, feed amount, flow rate, and the split ratio were 523.15 K, 623.15 K, 1 μL, 1 mL·min−1, and 100, respectively. The gas chromatograph was corrected with standard solutions which were prepared using gravimetric method with an electronic balance whose accuracy was ±0.0001 g. The mass composition was obtained with corrected area normalization method in the GC analysis. Each vapor− liquid sample was analyzed at least three times, and the average of them was taken to ensure the quality of the VLE data.

3. RESULTS AND DISCUSSION 3.1. Experimental Results. The basic relationship between the vapor−liquid phases at equilibrium state, considering the effects of nonideality can be described by eq 1:17,18 ÄÅ L É ÅÅ V (p − ps ) ÑÑÑ ÅÅ i i Ñ v s s ÑÑ yi pφi = γixipi φi expÅÅÅ ÑÑÑ ÅÅ RT ÑÑÖ (1) ÅÇ B



Article

Table 2. Parameters of the Extended Antoine Equationa component

C1i

C2i

C3i

C4i

C5i

C6i(×106)

C7i

C8i/K

C9i/K

methyl cyclohexane 3-chloro-2,2-dimethyl-1-propanol 3,3-dimethyloxetane

85.7762 85.9237 45.3934

−7080.80 −9942.42 −5348.49

0 0 0

0 0 0

−10.6950 −9.6557 −4.3658

8.14 × 10−6 7.93 × 10−18 9.78 × 10−18

2.00 6.00 6.00

146.58 440.18 352.00

572.10 619.06 549.87

a

Take from Aspen Plus properties databanks.

Table 3. Experimental VLE Data and Correlated Results for 3,3-Dimethyloxetane + Methyl Cyclohexane and 3-Chloro-2,2dimethyl-1-propanol + Methyl Cyclohexane Systems at 101.3 kPaa Wilson no.

T/K

x1

y1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

373.35 372.65 372.25 371.75 371.35 370.55 369.25 367.35 366.00 364.05 363.60 361.55 360.55 359.55 358.70 356.05 354.45 353.55 352.80

0 0.0050 0.0110 0.0244 0.0249 0.0416 0.0782 0.1167 0.1570 0.2205 0.2380 0.3222 0.3673 0.4165 0.4790 0.6556 0.8010 0.8899 1

0 0.0203 0.0386 0.0644 0.0771 0.1120 0.1704 0.2637 0.3234 0.4039 0.4290 0.5089 0.5468 0.5913 0.6293 0.7610 0.8519 0.9212 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

373.35 375.45 376.45 377.85 380.75 384.05 388.10 396.95 401.75 404.80 411.95 415.85 418.25 425.65 439.15

0 0.0734 0.1654 0.2804 0.4618 0.5857 0.6776 0.7906 0.8314 0.8583 0.8968 0.9093 0.9162 0.9563 1

0 0.0180 0.0324 0.0421 0.0600 0.0820 0.1139 0.1824 0.2353 0.2708 0.3700 0.4173 0.4730 0.6219 1

γ1

γ2

ΔT/K

UNIQUAC Δy1

NRTL

ΔT/K

Δy1

ΔT/K

Δy1

0.05 0.28 0.25 0.16 0.16 0.06 0.60 0.35 0.39 0.27 0.25 0.07 0.06 0.19 0.06 0.32 0.26 0.25 0.01

0 0.0024 0.0033 0.0090 0.0023 0.0045 0.0220 0.0064 0.0090 0.0132 0.0196 0.0170 0.0150 0.0182 0.0064 0.0063 0.0063 0.0002 0

0.05 0.28 0.25 0.16 0.16 0.06 0.60 0.33 0.37 0.25 0.24 0.06 0.06 0.19 0.06 0.30 0.24 0.23 0.01

0 0.0024 0.0033 0.0090 0.0023 0.0044 0.0217 0.0068 0.0095 0.0138 0.0202 0.0176 0.0156 0.0189 0.0071 0.0071 0.0056 0.0003 0

0.05 0.57 0.35 0.37 0.15 0.10 0.13 0.24 0.25 0.51 0.44 0.59 1.26 1.10 0.02

0 0.0002 0.0017 0.0002 0.0040 0.0056 0.0024 0.0036 0.0013 0.0078 0.0053 0.0019 0.0260 0.0303 0

0.05 0.57 0.16 0.01 0.21 0.39 0.49 0.25 0.20 0.83 0.42 0.78 1.56 0.41 0.02

0 0.0024 0.0035 0.0073 0.0110 0.0115 0.0081 0.0101 0.0052 0.0133 0.0062 0.0001 0.0300 0.0143 0

3,3-Dimethyloxetane + Methyl Cyclohexane 1 0.05 0 2.0985 1.0065 0.24 0.0011 1.9863 1.0045 0.19 0.0016 1.5148 1.0055 0.22 0.0099 1.7976 1.0035 0.11 0.0015 1.5972 1.0055 0.05 0.0029 1.3405 1.0137 0.43 0.0155 1.4666 0.9924 0.06 0.0151 1.3897 0.9942 0.05 0.0173 1.3065 1.0040 0.06 0.0178 1.3031 0.9970 0.06 0.0227 1.2119 1.0260 0.11 0.0131 1.1766 1.0457 0.15 0.0078 1.1559 1.0544 0.19 0.0081 1.0971 1.0998 0.05 0.0061 1.0507 1.1664 0.01 0.0048 1.0106 1.3149 0.07 0.0093 1.0110 1.3024 0.01 0.0019 1 0.01 0 3-Chloro-2,2-dimethyl-1-propanol + Methyl Cyclohexane 1 0.05 0 2.5597 1.0009 0.52 0.0008 1.9643 1.0645 0.20 0.0001 1.4129 1.1759 0.23 0.0014 1.0763 1.4259 0.15 0.0035 1.0070 1.6571 0.11 0.0043 1.0203 1.8492 0.26 0.0014 0.9816 2.1037 0.06 0.0044 1.0014 2.1771 0.05 0.0001 0.9959 2.2989 0.75 0.0092 1.0046 2.3150 0.47 0.0047 0.9741 2.2318 0.69 0.0004 1.0093 2.0743 1.43 0.0294 0.9929 2.4403 0.73 0.0211 1 0.02 0

a

Standard uncertainties are u(T) = 0.1 K, u(p) = 0.1 kPa, and u(x1) = u(y1) = 0.001.

components makes them more difficult to be liquefied than ÅÄÅ ViL(p − ps ) ÑÉÑ water. So, the Poynting factor expÅÅÅÅ RT i ÑÑÑÑ can approximate ÅÅÇ ÑÑÖ to 1, and Raoult’s law can be modified and written to eq 2:

In this equation, xi yi, represent the mole fractions of the liquid phase and the vapor phase, respectively, p and T are the pressure and the temperature of the system at equilibrium state, respectively, γi is the activity coefficient of component i, pis is the vapor pressure of the component i at equilibrium temperature, ϕiv is the vapor phase fugacity coefficient of component i, ϕis is the fugacity coefficient of component i in the saturated state, ViL is the liquid phase molar volume of component i, and R is the gas constant. The vapor phase was taken into account for an ideal gas at 101.3 kPa and the temperature of the experimental cases, because the low critical temperature of the above three

yp = pis xiγi i

(2)

where pis was calculated by the extended Antoine equation, as presented in eq 3: ln(pis /kPa) = C1i + C

C 2i + C4iT + C5i lnT + C6iT C7i T + C 3i DOI: 10.1021/acs.jced.8b00966 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


Article

for C 8i ≤ T ≤ C 9i

(3)

The Antoine parameter values for all components of the experiment were from the Aspen Plus V7.2 databank, and detailed data was present in Table 2. The experimental data of 3,3-dimethyloxetane + methyl cyclohexane, and 3-chloro-2,2dimethyl-1-propanol + methyl cyclohexane, and the corresponding calculated activity coefficients were presented in Table 3. 3.2. Thermodynamic Consistency Tests. The quality of binary vapor−liquid equilibrium data was examined using two thermodynamic consistency test methods of Herington area test4 based on the Gibbs−Duhem18 theorem and Van Ness point test.5 In the Herington area test, the criterion passes the thermodynamic consistency test for the isobaric experimental data if the result of |D − J| is no more than 10,19 which is expressed in eqs 4 to 8: D = 100

(area+) − (area−) |A | = 100 (area+) + (area−) B

C J= 150 Tmin

A=

x1= 1

∫x =0

ln(γ1/γ2) dx1

1

B=

x1= 1

∫x =0

|ln(γ1/γ2)| d x1

1

C = Tmax − Tmin

Figure 3. Diagram of ln(γ1/γ2) to x1 for the 3-chloro-2,2-dimethyl-1propanol (1) + methyl cyclohexane (2) system.

(4)

For the Van Ness point test, the standard for passing the thermal consistency test is that Δy be no more than 1, which is expressed as follows by eq 6:

(5)

Δy =

(6)

1 N

N

∑ 100|yical

− yiexp |

(9)

i=1

In this equation, N represents the number of the vapor−liquid equilibrium points, yiexp and yical are the measured experimental data points, calculated data, respectively. The values of Δy obtained by activity coefficient models of Wilson, UNIQUAC, and NRTL are 0.9748, 0.9479, and 0.7210 for the 3,3dimethyloxetane + methyl cyclohexane system; and 0.9454, 0.6943, and 0.6532 for the 3-chloro-2,2-dimethyl-1-propanol + methyl cyclohexane system. The Van Ness test results indicated that the experimental data were reliable. The deviations dispersion in each model was studied, respectively. The model residuals were plotted against the liquid-phase composition xi to determine if the deviations scatter randomly around zero. The residual plots of δT δyi for the 3,3dimethyloxetane + methyl cyclohexane and 3-chloro-2,2dimethyl-1-propanol + methyl cyclohexane were presented by Figures 4−7, showing the models for the experimental data were basically reasonable. 3.3. Data Correlation. To describe the relationship of vapor−liquid two phases of the 3,3-dimethyloxetane + methyl cyclohexane, and 3-chloro-2,2-dimethyl-1-propanol + methyl cyclohexane systems, The binary experimental data were regressed with three different models, which are presented as follows by eqs 10 to 15:

(7) (8)

where area− and area+ represent the areas below and above of the abscissa axis in the ln(γ1/γ2)−x1 plot, separately. TMAX, TMIN represent the highest and lowest boiling temperatures of systems, separately. The relationship diagrams of ln(γ1/γ2)−x1 were shown in Figure 2 and Figure 3. The results of |D − J| for 3,3-dimethyloxetane + methyl cyclohexane, and 3-chloro-2,2dimethyl-1-propanol + methyl cyclohexane were 1.0608 and 1.5870, respectively. The results showed that the binary experimental data passed the test of the Herington method.

NRTL: ln γi =

∑j xjτjiGji ∑κ xkGki

+

∑ j

ij y jjτ − ∑m xmτmjGmj zzz jj ij z ∑k xkGkj zz ∑k xkGkj j k { xjGij

(10)

Figure 2. Diagram of ln(γ1/γ2) to x1 for the 3,3-dimethyloxetane (1) + methyl cyclohexane (2) system.

Gij = exp( −aijτij)τij = aij + D

bij T

(11) DOI: 10.1021/acs.jced.8b00966 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


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Figure 7. 3-Chloro-2,2-dimethyl-1-propanol + methyl cyclohexane δy1 residual diagram; ●, NRTL model; ▲, UNIQUAC model; ■, Wilson model.

Figure 4. 3,3-Dimethyloxetane + methyl cyclohexane δT residual diagram; ●, NRTL model; ▲, UNIQUAC model; ■, Wilson model.

UNIQUAC: ln γi = ln −

Φi θ z + qi ln i xi Φi 2 qit

ln

tit

−

ij bij yz τij = expjjjaij + zzz j T z{ k

qit

∑j θjtτij t jt

+ li + qit −

Φi xi

(12)

(13)

Wilson:

ij yz j z ln γi = 1 − lnjjj∑ Aji xjzzz − jj zz k j {

Figure 5. 3,3-Dimethyloxetane + methyl cyclohexane δy1 residual diagram; ●, NRTL model; ▲, UNIQUAC model; ■, Wilson model.

ln Aij = aij +

∑ j

Aji xj ∑k Ajk xk

(14)

bij (15)

T 20

The maximum likelihood function is a generalization of the least-squares method. In the data regression, the error effects of the system pressure Pi, the equilibrium temperature Ti, and the composition xi and yi were considered, and the binary interaction parameters were calculated by the maximum likelihood objective function, shown in eq 16: ÄÅ N Å ÅÅi T exp − T cal y2 i P exp − P cal y2 Åj j i z i z zzz + jjj i zzz OF = ∑ ÅÅÅÅjjjj i z j z Å ∂ ∂ T P i=1 Å { k { ÅÅÇk ÉÑ 2 2 i y exp − y cal zy ÑÑÑÑ ij x exp − xical yz i z zz + jjjj i zz ÑÑÑ + jjjj i zz jj zz ÑÑ ∂ ∂ x y k { k { ÑÑÑÖ (16) where ∂T ∂P ∂x as well as ∂y are the standard deviation of temperature, pressure, liquid, and vapor phase molar fraction, respectively. The (AADs) and (RMSDs) of the equilibrium temperature and vapor phase molar fraction were calculated, respectively, which are expressed in eqs 17 and 18:

Figure 6. 3-Chloro-2,2-dimethyl-1-propanol + methyl cyclohexane δT residual diagram; ●, NRTL model; ▲, UNIQUAC model; ■, Wilson model.

E



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Table 4. Correlation Parameters, Root Mean Square Deviations (RMSDs), and Average Absolute Deviations (AADS) for the Binary Systems correlation parametersα aij

model

aij

NRTL UNIQUAC Wilson

7.2693 3.7515 −7.7111

−1.9363 −7.0600 3.3425

NRTL UNIQUAC Wilson

28.8273 2.2176 −27.4082

2.4519 −14.8047 1.3859

AAD =

1 N

RMSD =

bij/K

RMSDs bij/K

α

T/K

3,3-Dimethyloxetane + Methyl Cyclohexane −2378.6149 622.8193 0.3 0.28 −1201.7298 2299.8517 0.26 2485.8911 −1114.3780 0.25 3-Chloro-2,2-dimethyl-1-propanol + Methyl Cyclohexane −10000.0000 −1151.0062 0.3 0.53 −621.0387 5147.5505 0.54 9741.8988 −542.6952 0.58

AADs y1

T/K

y1

0.0091 0.0095 0.0097

0.22 0.21 0.20

0.0072 0.0095 0.0097

0.0104 0.0116 0.0119

0.37 0.41 0.42

0.0065 0.0069 0.00945

N

∑ (Iical − Iiexp) i=1

1 N

(17)

N

∑ (Iical − Iiexp)2 i=1

(18)

where I represents vapor phase molar fraction yi or temperature T. The fitted binary interaction parameters and the AADs, RMSDs of the equilibrium temperature T, as well as vapor phase molar fraction yi were shown in Table 4. The RMSDs and AADs of the vapor phase molar fraction yi were observed to be no more than 0.0119, 0.0097, respectively. The RMSDs as well as AADs of the equilibrium temperature T were not more than 0.58 and 0.42 K, separately. So the deviation between the experimental data and calculation results was acceptable. The calculation results of the two systems using the NRTL activity coefficient model were presented in Figures 8−11.

Figure 9. T−x−y diagram for the 3-chloro-2,2-dimethyl-1-propanol (1) + methyl cyclohexane (2) system at 101.3 kPa: ■, T−y1 (experimental data); ▲, T−x1 (experimental data); , calculated x1 with NRTL model; ---, calculated y1 with NRTL model.

4. CONCLUSION In this article, the binary vapor−liquid equilibrium data at the pressure of 101.3 kPa for 3,3-dimethyloxetane + methyl cyclohexane, and 3-chloro-2,2-dimethyl-1-propanol + methyl cyclohexane were determined using a modified Rose vaporrecirculating equilibrium still. The reliability of the isobaric

Figure 10. x−y diagram for the 3,3-dimethyloxetane (1) + methyl cyclohexane (2) at 101.3 kPa: ■, experimental data; , calculated x1,y1 with NRTL model.

vapor−liquid equilibrium data was tested with the Herington and the Van Ness tests, respectively. The experimental data were correlated using Wilson, UNIQUAC, NRTL models, and the corresponding binary interaction parameters were obtained. The RMSDs for equilibrium temperature as well as vapor phase molar fraction were less than 0.58 K and 0.0119,

Figure 8. T−x−y diagram for the 3,3-dimethyloxetane (1) + methyl cyclohexane (2) system at 101.3 kPa: ■, T−y1 (experimental data); ▲, T−x1 (experimental data); , calculated x1 with NRTL model; ---, calculated y1 with NRTL model. F



Article

(9) 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, 116−128. (10) Maurer, G.; Prausnitz, J. M. On the Derivation and Extension of the UNIQUAC Equation. Fluid Phase Equilib. 1978, 2, 91−99. (11) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135−144. (12) Sun, Y.; Fu, D.; Ma, S.; Ma, Z.; Sun, L. Isobaric Vapor−Liquid Equilibrium Data for Two Binary Systemsn-Hexane + 1,2-Dimethoxyethane and Methylcyclopentane + 1,2-Dimethoxyethane at 101.3 kPa. J. Chem. Eng. Data 2018, 63, 395−401. (13) Huang, X. J.; Xia, S. Q.; Ma, P. S.; Song, S.; Ma, B. J. Vapor− Liquid Equilibrium of N-Formylmorpholine with Toluene and Xylene at 101.33 kPa. J. Chem. Eng. Data 2008, 53, 252−255. (14) Yang, S. K.; Wang, Y. J.; Wang, X. J.; Zhu, Y.; Chen, N. Isobaric vapor−liquid equilibrium of binary systems of decane with p-, o-, mxylene at 20 kPa. Fluid Phase Equilib. 2013, 337, 109−114. (15) Zhu, Z. Y.; Ma, Y. X.; Gao, J. Isobaric Vapor−Liquid Equilibria for Binary Systems of Acetic Acid + Benzene, Chloroacetic Acid + Benzene, and Dichloroacetic Acid + Benzene at 101.33 kPa. J. Chem. Eng. Data 2010, 55, 3387−3390. (16) Gao, J.; Zhao, L. W.; Zhang, L. Z.; Xu, D. M.; Zhang, Z. S. Isobaric Vapor−Liquid Equilibrium for Binary Systems of 2,2,3,3Tetrafluoro-1-propanol + 2,2,3,3,4,4,5,5-Octafluoro-1-pentanol at 53.3, 66.7, 80.0 kPa. J. Chem. Eng. Data 2016, 61, 3371−3376. (17) Prausnitz, J. M.; Lichtenthaler, R. N.; Azevedo, E. G. d. Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd ed.; Prentice Hall PTR: Upper Saddle River, NJ, 1999. (18) Smith, J. M.; Van Ness, H. C.; Abbott, M. M. Introduction to Chemical Engineering Thermodynamics, 6th ed.; McGraw-Hill: New York, 2001. (19) Wisniak, J.; Pérez-Correa, J. R.; Mejía, A.; Segura, H. Comments on“Experimental Measurements of Vapor−Liquid Equilibrium Data for the Binary Systems of Methanol + 2-Butyl Acetate, 2Butyl Alcohol + 2-Butyl Acetate, and Methyl Acetate + 2-Butyl Acetate at 101.33 kPa. J. Chem. Eng. Data 2013, 58, 3563−3566. (20) Anderson, T. F.; Abrams, D. S.; Grens, E. A. Evaluation of parameters for nonlinear thermodynamic models. AIChE J. 1978, 24, 20−29.

Figure 11. x−y diagram for the 3-chloro-2,2-dimethyl-1-propanol (1) + methyl cyclohexane (2) at 101.3 kPa: ■, experimental data; , calculated x1,y1 with NRTL model.

respectively. The fitted results showed three models within acceptable limits. The VLE data extended the physical database, and provided data support for further research of the 3,3-dimethyloxetane + methyl cyclohexane and 3-chloro2,2-dimethyl-1-propanol + methyl cyclohexane systems. The binary interaction parameters will facilitate the design and optimization for the purification process of these components.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Lim, G. P.; Yang, F.; Chu, T.; Chen, P.; Beech, W.; Teter, B.; Tran, T.; Ubeda, O.; Ashe, K. H.; Frautschy, S. A.; et al. Ibuprofen suppresses plaque pathology and inflammation in a mouse model for Alzheimer’s disease. J. Neurosci. 2000, 20, 5709−5714. (2) Palayoor, S. T.; Youmell, M. Y.; Calderwood, S. K.; Coleman, C. N.; Price, B. D. Constitutive activation of IkappaB kinase alpha and NF-kappaB in prostate cancer cells is inhibited by ibuprofen. Oncogene 1999, 18, 7389−7394. (3) Liu, X. T.; S, J.; Yang, X. M. Green synthesis process of 1chloroethyl-4-isobutylphenone: China, Patent. 200510200040.1, 2007. (4) Herington, E. Tests for the consistency of experimental isobaric vapor−liquid equilibrium data. J. Inst. Pet. 1951, 37, 457−470. (5) van Ness, H. C.; Byer, S. M.; Gibbs, R. E. Vapor-Liquid equilibrium: Part I. An appraisal of data reduction methods. AIChE J. 1973, 19, 238−244. (6) Zhang, L. Z.; Gao, Y. C.; Xu, D. M.; Zhang, Z. S.; Gao, J.; Pratik, D. Isobaric Vapor−Liquid Equilibrium for Binary Systems of Allyl Alcohol with Water, Methanol, and Ethanol at 101.3 kPa. J. Chem. Eng. Data 2016, 61, 2071−2077. (7) Liu, X.; Zhang, Y.; Li, M.; Li, X.; Li, G.; Wang, Y.; Gao, J. Isobaric Vapor−liquid Equilibrium for Three Binary Systems of Ethyl Acetate + Propyl Acetate, Ethyl Acetate + Propylene Carbonate, and Propyl Acetate + Propylene Carbonate at 101.3 kPa. J. Chem. Eng. Data 2018, 63, 1588−1595. (8) Wilson, G. M. Vapor-Liquid Equilibrium. XI. A New Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc. 1964, 86, 127−130. G


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