Cloud Point Phenomena in the (Aniline or N ... - ACS Publications

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Cloud Point Phenomena in the (Aniline or N,N‑Dimethylaniline + Water) Solutions, and Cosolvent Effects of Liquid Poly(ethylene glycol) Addition: Experimental Measurements and Modeling Nikola D. Grozdanić,† Danijela A. Soldatović,‡ Slobodan P. Šerbanović,† Ivona R. Radović,† and Mirjana Lj. Kijevčanin*,† †

Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade, Serbia Public Company Nuclear Facilities of Serbia, 12-14 Mike Petrovica Alasa, Vinca, 11351 Belgrade, Serbia

‡

ABSTRACT: In this work, liquid phase behavior (cloud point phenomena) was studied for two binary and four aqueous pseudobinary systems containing aniline or N,N-dimethylaniline and poly(ethylene glycol) 200 or poly(ethylene glycol) 400, (PEG200 and PEG400, respectively) in the temperature range T = (290.15 to 351.15) K and an ambient pressure of 0.1 MPa. Experimental data (cloud-points) were obtained by the visual cloud point method. The studied systems exhibit an upper critical solution temperature (UCST) type of phase behavior and the immiscibility increases with increasing the average molar mass of poly(ethylene glycols). PEG200/PEG400 showed as a good cosolvent for aniline in water. The experimental data were correlated using non-random two-liquid model (NRTL) with one form of temperature dependent parameters.

1. INTRODUCTION Amines are organic compounds that contain a nitrogen atom with a lone pair of electrons. Aniline1 is an organic compound consisting of a phenyl group attached to an amino group. The main use of aniline is in the manufacture of precursors to polyurethane, which is a polymer that has various applications. Aniline also has industry application as an intermediate in the preparation of a great number of dyes and other organic compounds of commercial interest. The very first artificially produced chemical dye was produced from aniline, and most still use it as a precursor substance. Acetaminophen is also produced from aniline, as are herbicides and nanowire for use as a semiconducting electrode bridge. Pure aniline is a highly poisonous, oily, colorless substance with a pleasant odor. N,N-Dimethylaniline is also an organic chemical compound with dimethylamino group attached to a phenyl group, and it is a substituted derivative of aniline. On the other side, PEGs of lower molecular mass are polymers that are water-soluble in all proportions at all temperatures due to the hydrophilic ethylene oxide groups they contain. They are good proton donor and proton acceptors,2 so they form strong intra- and intermolecular hydrogen bonds.3 They are environmentally friendly polymers, are highly polar,4,5 and have many applications in industrial manufacturing, as food additives, and in medicine. Also, they are widely used as cosolvents in the pharmaceutical and cosmetic industries because of their physiological acceptance. Because of their biodegradability, low toxicity,6 relatively low melting points, and practical nonvolatility,7−9 they are widely © XXXX American Chemical Society

used polymers in industrial applications, biotechnology, and various aqueous two-phase partitioning studies,10 both in fundamental and applied research. Due to all the aforementioned properties, PEGs also appeared as good and sustainable solvents for several organic compounds of common interest.11 Systems that use PEGs as a solvent or a cosolvent are very economical because the cost is relatively lower than other solvents. Several factors, such as good physical properties, the end use of the product, and the aforementioned cost of the polymer, have an effect on attempts to exploit polyethylene glycols. In this work, the liquid−liquid equilibria of aniline + water and N,N-dimethylaniline + water as well as aniline + (water + PEG200), aniline + (water + PEG400), N,N-dimethylaniline + (water + PEG200), and N,N-dimethylaniline + (water + PEG400) binary and pseudobinary mixtures are studied. Thus, the measurements of liquid−liquid phase demixing temperatures (cloud points) for two binary and four pseudobinary systems were made using visual cloud point method. Detailed description of cloud point method is given in our previous study.12 Systems of aniline and N,N-dimethylaniline with water were already investigated in the literature, through experimental measurements Klauck et al.13 and Stephenson et al.14 and the polynomial modeling of Pepelyaev et al.15 Received: May 20, 2014 Accepted: December 31, 2014

A

DOI: 10.1021/je500448j J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

evaporation of components. On top of the cell there is a Teflon cap that physically stops evaporation. A 2 L glass beaker filled with ethanol, water or silicon oil, as a thermostatic liquid, was used for temperature controlled bath. Ethanol was used for the measurements at the temperature range T = (273.15 to 293.15) K, water T = (293.15 to 333.15) K, or silicon oil T = (333.15 to 393.15) K. Temperature in the bath was controlled with a Pt100 temperature probe with an accuracy of ±0.03 K. In order to ensure temperature uniformity in a thermostatic bath, thermostatic liquid was mixed by a Teflon stirrer. Lamp was used for determination of the cloud points and was placed close to the glass cell for better visualization and recording the exact temperature of demixing or mixing. Solutions were prepared in a cell where components were added through a glass neck using a syringe with a long Hamilton needle.26 Heterogeneous solution of known composition was heated until it became homogeneous and then cooled off to obtain phase separation. The temperature at which two phases start to demix during cooling was taken as a cloud point temperature. All the measurements were performed slowly and repeated three times to ensure data accuracy. The liquid mole fraction was determined gravimetrically using a Mettler analytical semimicrobalance (model AG 204) with precision of 1·10−4 g. The uncertainty in the mole fraction calculation was less than ±1·10−4. Densities ρ of pure substances were measured using an Anton Paar DMA 5000 digital vibrating U-tube densimeter with a procedure described earlier.27,28 The temperature in the cell was regulated to ±0.001 K by a built in solid-state thermostat. The experimental uncertainty in density is about ±1·10−2 kg·m−3.

The results showed that liquid PEG is a good cosolvent for aniline in water and this has practical impact on its applications in dye industry. Activity coefficient nonrandom two liquid model (NRTL) 16,17 is chosen to correlate the binary experimental data. This work represents continuation of our ongoing research in the area of experimental determination of thermodynamic properties of mixtures18−20 and liquid−liquid equilibria.12

2. EXPERIMENTAL SECTION Materials. Poly(ethylene glycol) of two different average molecular masses (200 and 400) were purchased from SigmaAldrich. The stated mass purities of PEG 200 and PEG 400 were better than 0.99. Anilin was obtained from Sigma-Aldrich (stated mass purity 0.995). Merck was the supplier for N,Ndimethylaniline (stated mass purity better than 0.99). Water was doubly distilled and deionized (Millipore Co. equipment, Bedford, MA). All chemicals were used without further purification (sample description is given in Table 1). Purity Table 1. Sample Description chemical name aniline N,Ndimethylaniline poly(ethylene glycol) 200 poly(ethylene glycol) 400

source Sigma-Aldrich (Switzerland) Merck (Germany) Sigma-Aldrich (Belgium) Sigma-Aldrich (Belgium)

mass fraction purity

purification method

62-53-3

≥0.995

none

121-69-7

≥0.99

none

25322-68 -3 25322-68 -3

≥0.99

none

≥0.99

none

CAS number

3. RESULTS AND DISCUSSION The experimentally determined cloud points for two binary systems: aniline (1) + water (2), N,N-dimethylaniline (1) + water (2) and four pseudobinary systems: aniline (1) + (water + PEG 200) (2), aniline (1) + (water + PEG 400) (2), N,Ndimethylaniline (1) + (water + PEG 200) (2), and N,Ndimethylaniline (1) + (water + PEG 400) (2) are listed in Tables 3 to 7. All the systems show an UCST-type of phase

of pure components was confirmed by measuring densities ρ at 298.15 K and atmospheric pressure using DMA 5000. Obtained values are compared with literature data. They were in good agreement with literature values (Table 2).21−24 Table 2. Density, ρ, of Pure Compounds at 298.15 K and Atmospheric Pressurea 10−3ρ/(kg·m−3) compound aniline N,N-dimethylaniline poly(ethylene glycol) 200 poly(ethylene glycol) 400

experimental 1.01739 0.95205 1.12071 1.12317

Table 3. Liquid−Liquid Phase Demixing Temperatures (Cloud Points), at 0.1 MPa, for Systems Aniline (1) + H2O (2) and N,N-Dimethylaniline (1) + H2O (2); TCP Are Liquid-Phase Demixing (Cloud Point) Temperatures; (xH2O)T and (xAniline)T Refer to Mole Fractions of H2O and Aniline in the Mixture, Respectivelya

literature e

1.01750 0.95200d 1.12069b 1.12249c

a Standard uncertainty u for each variable is u(T)=1K; u(p)=5%, and the combined expanded uncertainty uc is uc(ρ)= ± 1·10−2kg·m−3, with 0.95 level of confidence (k ≈ 2), eHyeon-Deok et al.21 dGorisankar et al.20 bVisak et al.23 cOttani et al.24

(xH2O)T

(xAniline)T

TCP

(xH2O)T

(xDMA)T

TCP

0.1313 0.1568 0.1747 0.2015 0.9980 0.9991 0.9993 0.9995

0.8687 0.8432 0.8253 0.7985 0.0020 0.0009 0.0007 0.0005

321.15 331.15 340.15 349.15 351.15 340.15 328.15 312.15

K 0.2304 0.2376 0.2577 0.2693 0.2868 0.2919 0.9780 0.9860 0.9900 0.9980

Apparatus and Procedure. Temperature−composition phase diagrams of liquid−liquid equilibrium (LLE) were obtained in temperature range T = (290.15 to 351.15) K at ambient pressure of 0.1 MPa. Method that was used for the determination of the present cloud point data is visual method−turbidity that indicates the beginning of phase demixing was observed by eye while heating or cooling solution. Apparatus that was used for the determination of the cloud point data consists of special Pyrex glass cell12,25 that is equipped with Teflon stirrer, a long neck that allows immersion of the cell in a temperature controlled bath and reduces

0.7696 0.7624 0.7423 0.7307 0.7132 0.7081 0.0220 0.0140 0.0100 0.0020

313.15 321.15 329.15 334.15 339.15 343.15 341.15 333.15 326.15 312.15

K

a

Standard uncertainty u for each variable is u(T) = 1 K, u(x) = 0.0001, u(p) = 5% B



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Table 4. Liquid−Liquid Phase Demixing Temperatures (Cloud Points), at 0.1 MPa, for System Aniline (1) + (PEG200 + H2O) (2); TCP Are Liquid-Phase Demixing (Cloud Point) Temperatures; (xH2O)T, (xAniline)T, and (xPEG)T Refer to Mole Fractions of H2O, Aniline, and PEG200 in the Mixture, Respectivelya (xH2O)T

(xAniline)T

(xPEG)T

Table 6. Liquid−Liquid Phase Demixing Temperatures (Cloud Points), at 0.1 MPa, for System N,N-Dimethylaniline (1) + (PEG200 + H2O) (2); TCP Are Liquid-Phase Demixing (Cloud Point) Temperatures; (xH2O)T, (xDMA)T, and (xPEG)T Refer to Mole Fractions of H2O, N,N-Dimethylaniline and PEG200 in the Mixture, Respectivelya

TCP

(xH2O)T

(xDMA)T

(xPEG)T

TCP /K 0.7064 0.6814 0.6354 0.6013 0.5525 0.5217 0.4696 0.4445 0.4378 0.3774 0.3350

0.2299 0.2572 0.3073 0.3445 0.3977 0.4313 0.4881 0.5154 0.5227 0.5886 0.6348

0.0637 0.0614 0.0573 0.0542 0.0498 0.0470 0.0423 0.0401 0.0395 0.0340 0.0302

K

304.15 324.15 335.15 339.15 344.15 345.15 341.15 335.15 329.15 312.15 290.15

0.1940 0.1762 0.1679 0.1415 0.1037 0.0701 0.0344 0.0260 0.0162 0.0093

(xH2O)T

0.4217 0.3200 0.4808 0.3736 0.2866 0.4522 0.2683 0.3465 0.5033 0.4636 0.5259 0.2475 0.2407

0.5615 0.6602 0.5041 0.6082 0.6926 0.5319 0.7104 0.6345 0.4822 0.5208 0.4603 0.7306 0.7372

(xDMA)T

(xPEG)T

TCP

TCP K

K 0.0168 0.0198 0.0151 0.0182 0.0208 0.0159 0.0213 0.0190 0.0145 0.0156 0.0138 0.0219 0.0221

305.15 312.15 315.15 322.15 331.15 336.15 332.15 324.15 314.15 301.15

Table 7. Liquid−Liquid Phase Demixing Temperatures (Cloud Points), at 0.1 MPa, for System N,N-Dimethylaniline (1) + (PEG400 + H2O) (2); Tcp Are Liquid-Phase Demixing (Cloud Point) Temperatures; (xH2O)T, (xDMA)T, and (xPEG)T Refer to Mole Fractions of H2O, N,N-Dimethylaniline and PEG400 in the Mixture, Respectivelya

Table 5. Liquid−Liquid Phase Demixing Temperatures (Cloud Points), at 0.1 MPa, for System Aniline (1) + (PEG400 + H2O) (2); TCP Are Liquid-Phase Demixing (Cloud Point) Temperatures; (xH2O)T, (xAniline)T, and (xPEG)T Refer to Mole Fractions of H2O, Aniline, and PEG400 in the Mixture, Respectivelya (xPEG)T

0.3331 0.3027 0.2884 0.2429 0.1781 0.1204 0.0590 0.0447 0.0278 0.0159

Standard uncertainty u for each variable is u(T) = 1 K, u(x) = 0.0001, u(p) = 5%


(xAniline)T

0.4729 0.5211 0.5437 0.6156 0.7182 0.8095 0.9066 0.9293 0.9560 0.9748

a

a

(xH2O)T

TCP

0.3302 0.2614 0.1843 0.1295 0.1041 0.0703 0.0377

338.15 337.15 324.15 339.15 332.15 333.15 326.15 339.15 317.15 330.15 313.15 318.15 314.14

0.4863 0.5933 0.7133 0.7985 0.8380 0.8906 0.9414

0.1835 0.1453 0.1024 0.0720 0.0579 0.0391 0.0209

307.15 328.15 349.15 351.15 345.15 324.15 310.15

a


cloud point maximum is higher for the system with PEG 200 than for that with PEG400. Two phases region exists in mole fraction range from 0.25 to 0.6 and 0.25 to 0.5 at ambient temperature for PEG 200 and PEG 400, respectively. For both systems, heterogeneous region is narrowing down with increasing temperature. Figure 3 represent systems of N,Ndimethylaniline in combination with PEG 200 and PEG 400. It is shown that both systems have two phases region between 0.005 and 0.55 mole fraction at 300 K, but the immiscibility region is wider and cloud point maximum quite higher for the system with PEG 400. Aniline and N,N-dimethylaniline are fully soluble in poly(ethylene glycol) 200 or poly(ethylene glycol) 400. Liquid− liquid equilibria of these pseudobinary systems follow an upper critical solution temperature (UCST) type of behavior in which liquid phase separation is provoked as temperature decreases. Because poly(ethylene glycols) are good proton donors and acceptors, they form strong hydrogen bonds. At lower temperatures, hydrogen bonds between water and poly(ethylene glycols) are stronger so pseudobinary mixture exists in two phases (heterogeneous solution). At higher temper-

a


behavior and tendency for forming homogeneous or heterogeneous regions at different temperatures. Cloud point diagrams for two binary mixtures containing aniline or N,N-dimethylaniline in combination with water are wall-type diagrams and they are shown in Figure 1. Diagram shows that N,N-dimethylaniline is less soluble in water than aniline because of the hydrophobic dimethylamino group attached to the phenyl group. Experimental data for the system aniline (1) + water (2) is in very good agreement with experimental data from literature,13 with absolute deviation of 0.025 at 323.15 K as well as for the system of N,N-dimethylaniline (1) + water (2),14 with absolute deviation of 0.006 at 343.15 K. Figure 2, which represents two systems, aniline + (water + PEG200) and aniline + (water + PEG400) shows that immiscibility region is wider and the C



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Figure 1. Temperature−composition liquid−liquid phase diagrams at 0.1 MPa for two binary systems: (○) aniline (1) + H2O (2); (·) N,Ndimethylaniline (1) + H2O (2); (+) literature data for system aniline (1) + H2O (2);13 (◇) literature data for system N,N-dimethylaniline (1) + H2O (2);14 lines represent modeling using NRTL model: (-·-·) aniline + water and (···) N,N-dimethylaniline + water.

Figure 3. Temperature−composition liquid−liquid phase diagrams at 0.1 MPa: (▲) binary system N,N-dimethylaniline (1) + water (2), (·) pseudobinary system N,N-dimethylaniline (1) + (water + PEG200) (2) and (○) pseudobinary system N,N-dimethylaniline (1) + (water + PEG400) (2).

where I and II represent equilibrium phases, xi and γi denote mole fraction and activity coefficient of component i, respectively Mass balance equation is given as

∑ xiI = ∑ xiII = 1 i

(2)

i

NRTL model is defined as ⎛ τ G τ21G21 ⎞ GE = x1x 2⎜ 12 12 + ⎟ RT x1 + G21x 2 ⎠ ⎝ x 2 + G12x1

(3)

E

where G , the molar excess Gibbs energy, is a function of composition, R is universal gas constant, x1 and x2 are mole fractions of components 1 and 2, respectively. The activity coefficients γ of compounds in a binary system are expressed with the following equations:

Figure 2. Temperature−composition liquid−liquid phase diagrams at 0.1 MPa: (▲) binary system aniline (1) + water (2), (·) pseudobinary system aniline (1) + (water + PEG200) (2) and (○) pseudobinary system aniline (1) + (water + PEG400) (2).

(4)

⎞2 ⎤ ⎛ G12 ln γ2 = x1 + τ12⎜ ⎟⎥ ⎢⎣ (x1 + G21x 2)2 ⎝ x 2 + G12x1 ⎠ ⎥⎦

(5)

⎡

2⎢

τ21G21

Binary interaction parameters are defined as follows:

atures, hydrogen bonds get weaker in relation to the other bonds that are dominant so mixture exists in one phase (homogeneous solution).

4. MODELING Binary experimental liquid−liquid equilibria data (cloud points) were correlated using NRTL model,29,30 as was shown in our previous work.31 Liquid−liquid equilibrium (LLE) calculations were achieved by solving the thermodynamic criteria and mass balance equation. Thermodynamic criterium for liquid−liquid equilibria32 is given as γi IxiI = γi IIxiII

⎡ ⎞2 ⎤ ⎛ τ12G12 G21 ln γ1 = x 22⎢ + τ ⎟⎥ ⎜ 21 ⎢⎣ (x 2 + G12x1)2 ⎝ x1 + G21x 2 ⎠ ⎥⎦

G12 = exp( −α12τ12)

τ12 =

G12 = exp( −α21τ21)

τ21 =

G12 ≠ G21

Δg12 RT

(6)

Δg21 RT

(7)

α12 = α12

where α is NRTL excess free energy nonrandomness parameter, T is a temperature, and R is an universal gas constant. Parameters Δg12 and Δg21 are NRTL excess free energy model binary interaction temperature dependent parameters.

(1) D



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5. CONCLUSION In this work, we have performed experimental determination of liquid−liquid equilibrium data for water, liquid poly(ethylene glycol) 200 and poly(ethylene glycol) 400 with organic aromatic solvents of common interest, aniline and N,Ndimethylaniline, using visual cloud method technique at temperature range T = (290.15 to 351.15) K and ambient pressure of 0.1 MPa. All the curves show an immiscibility region at wide range of molar fractions and temperatures. In addition, experimental data for two analyzed binary systems were correlated by NRTL model with temperature dependent parameters Δg12 and Δg21. Chosen form of temperature dependent parameters could reproduce most accurately the experimental mutual solubility for all mixtures, with good results and overall deviations less than 1.86%.

Temperature has strong influence on excess properties or equilibrium calculation, thus one form of temperature dependence for parameters Δg12 and Δg21 was introduced: Form I Δg12 = A12 + B12 T Δg21 = A 21 + B21T

(8)

The corresponding sets of binary interaction parameters (Aij and Bij, in eqs 8) were determined by minimizing the objective function (eq 9) using Monte Carlo method with linear congruental generator of pseudorandom numbers33 n

Fobj =

m

∑ ∑ (γjI,ixjI,i − γjII,ixjII,i)2 → min

■

(9)

i=1 j=1

where n is a number of experimental data, and m is number of components. With obtained optimized parameters, using eq 1, mole fractions xI1,cal and xII1,cal were calculated by sequential application of the bisection34 method at xI1,cal direction from 0 to 1 and at xII1,cal direction from 1 to 0, over entire range of investigated temperatures T. According to the results of our preliminary investigations, the nonrandomness parameter α12 was set as constant value 0.3 for all selected pseudobinary systems. A deviation of calculated liquid composition from the experimental values is expressed as absolute average deviations Δ(x), and absolute average percent deviations PD(x), for each binary system Δ(x) =

Corresponding Author

*E-mail: [email protected]. Phone: +381 11 337 0523. Fax: +381 11 337 0387. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS The authors gratefully acknowledge the financial support received from the Research Fund of Ministry of Science and Environmental Protection, Serbia and the Faculty of Technology and Metallurgy, University of Belgrade (Project No. 172063).

■

n

1 2n

I I II II − x1,cal |i + |x1,exp − x1,cal |i ] ∑ [|x1,exp i=1

100 2n

PD(x), % =

+

n

⎡

i=1

⎣

∑ ⎢⎢ II (x1,exp

(10)

−

II x1,cal )

II x1,exp

i

⎤ ⎥ ⎥ i⎦

(11)

Results for applied model and parameters are presented in Table 8. For all systems, form I with temperature dependent parameters gave satisfactory results. Overall absolute average percent deviations PD(x) for all systems was less than 1.86%. For system aniline + water form I achieved better results, 1.80% compared to 1.86% for system N,N-dimethylaniline + water. Table 8. Determined Parameters (Aij and Bij), Absolute Average Deviations Δ(x), and Absolute Average Percent Deviations PD(x) between Calculated and Experimental Data for Two Binary Systems Using Temperature Dependence Form of NRTL Model A12

B12 K

51746 14801

A21

B21

PD(x)

0.0113

1.80

0.0095

1.86

K

Aniline + Water 3976.7 −5.8997 N,N-Dimethylaniline + Water −18.161 8171.6 −14.532

−126.40

Δ(x)

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I I − x1,cal (x1,exp ) I x1,exp

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