Viscosity and Density of Binary Mixtures of Ethanol + Igepal (CO-520

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

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Viscosity and Density of Binary Mixtures of Ethanol + Igepal (CO-520, CO-630, CO-720, and CA-720) Camila Leite Paiva, Regiane Silva Pinheiro, Filipe Xavier Feitosa, and Hosiberto Batista de Sant’Ana*

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Grupo de Pesquisa em Termofluidodinâmica Aplicada, Departamento de Engenharia Química, Centro de Tecnologia, Universidade Federal do Ceará, Campus do Pici, Bloco 709, 60455-760, Fortaleza − CE, Brasil ABSTRACT: Surfactants are widely used for academic and industrial purposes. For this reason, thermodynamic and physical properties of surfactant and cosurfactant mixtures can provide important information about the nature of the molecular interactions present. In this work, volumetric and transport data of surfactant binary mixtures of the ethanol + Igepal series (Igepal CO-520, Igepal CO-630, Igepal CO-720, and Igepal CA720) were determined experimentally within a range of temperature of T = 293.15− 323.15 K, at atmospheric pressure. From these data, the following derivative properties have been calculated: the excess molar volume, viscosity deviation, and coefficient of thermal expansion. All of these mixtures showed that attractive intermolecular forces are dominant.

1. INTRODUCTION Surface-active compounds are a group of organic molecules that have attracted great interest from researchers because of their wide range of industrial applications such as detergents,1 lubricants,2 petroleum emulsion demulsifiers,3 corrosion inhibitors,4 and emulsifiers.5 The use of surfactants in emulsions6 leads industry to seek new products that could present some important properties (e.g., low cost, ecofriendly compounds and highly efficient surfactants systems). Although the formulation of emulsions demands a high energy expenditure, their high earned value products are appealing.7 Nonionic surfactants are a surfactant class compatible with all others because they do not neutralize their charges and are used to improve the detergency performance of systems with cationic8 or anionic9 surfactants. The relevance of these surfactants has increased over the last several decades, especially because of industrial expansion, their high consumption,10 and the low toxicity of their degradation byproducts.11 Among the nonionic surfactants, ethoxylated alkyl phenol classes of surfactants12 are widely used. Additionally, their physicochemical properties are strongly temperature-dependent,13 and in many cases, there is a need to add a cosurfactant to stabilize the systems thermodynamically.14 In this context, the aim of this work is to report volumetric and transport properties, such as the density (ρ), dynamic viscosity (η), excess volume (VE), viscosity deviation (Δη), and thermal expansion coefficients (α) of binary mixtures of the ethanol + Igepal series (Igepal CO-520, Igepal CO-630, Igepal CO-720, and Igepal CA-720), that could be useful in better understanding the intermolecular interaction behavior of these systems because of the range of the ethoxylated chain, along with the hydrophobic chain.

be emphasized that all chemicals were used as received (i.e., without any further purification). The water content of Igepal CO-520, Igepal CO-630, Igepal CO-720, and Igepal CA-720 was determined using Karl Fischer titration, and the values were respectively 0.82, 1.11, 1.25, and 0.86%. The binary mixtures were prepared, at atmospheric pressure, at T = (293.15, 303.15, 313.15, 323.15) K by using of a gravimetric method, in a test tube sealed right after being weighed. After that, these mixtures were shaken for at least 1 min in a vortex mixer and set in an ultrasonic bath (Elmasonic S 60 H) to ensure the removability of any bubble formed during mixture preparation. Afterward, by using a 5 mL syringe, sample properties were measured by using a viscodensimeter (Anton Paar SVM 3000, digital oscillation U-tube) that simultaneously measured ρ and η of the mixtures. This apparatus has been calibrated by using Cannon mineral oil (CAS no. 68037.01.4) in the temperature range from 273.15 to 393.15 K. From these data, important derivative properties have been calculated, such as the excess volume (VE), viscosity deviation (Δη), and thermal expansion coefficients (α). All deviation properties have been calculated by comparing to ideal solution behavior by following the thermodynamic definition of excess properties (or deviation properties). The chemical structures of Igepal are reported in Figure 1. The density and viscosity of ethanol were determined and compared with the literature values presented in Table 2. To our knowledge, there is no data for the density and viscosity of the Igepal series reported in the literature. 2.2. Thermodynamic Correlation. Density data were correlated by using a second-degree polynomial expression

2. EXPERIMENTAL SECTION 2.1. Materials and Measurements. The chemicals used to prepare the binary mixtures are described in Table 1. It should

Received: September 3, 2018 Accepted: January 17, 2019

© XXXX American Chemical Society

A

DOI: 10.1021/acs.jced.8b00793 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Name, Furnisher, Mole Fraction Purity, CAS, and a Comparison between the Average Degree of Polymerization (n) and the Number-Average Molecular Weight (Mn) of Chemicals Used in This Work chemical name

source

mole fraction puritya

CAS

formula

ethanol Igepal CO-520 Igepal CO-630 Igepal CO-720 Igepal CA-720

Dinâmica Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich

0.995 0.999 0.999 0.999 0.999

64-17-5 68412-54-4 68412-54-4 68412-54-4 9036-19-5

C2H5OH (C4H4O)nC15H24O

(C2H4O)nC14H22O

na

Mna (g/mol)

∼5 9−10 10.5−12 10.5−12

46.05 441 617 749 735

a

Values reported by Sigma-Aldrich.

Figure 1. Chemical structures of Igepal-CO and Igepal-CA.

related to the molar fraction and a first-degree polynomial expression related to the temperature, according to eq 1

Table 2. Comparison of the Measured Values for Pure Component Density, ρ, and Viscosity, η, with Literature Data for T = (293.15 to 323.15) K −3

ρ (g cm ) exp

lit

293.15

0.7907 0.7822

exp

lit

0.7859a

1.23

1.203d

0.7895

b

1.02

1.002d

c

0.85

0.8298e

0.71

0.715d

313.15

0.7734

0.7721

323.15

0.7601

0.7632c

a e

η (mPa·s)

T/K 303.15

Reference 15. Reference 19.

b

Reference 16.

ρ = A + Bx1 + Cx12 + DT

c

Reference 17.

d

(1)

where ρ is the density, x1 is the molar fraction, T is the temperature, and A, B, C, and D are adjusted parameters. Equation 2 was used to correlate the experimental values of viscosity, ln η = E +

F + Gw1 T

(2)

where η is the dynamic viscosity, T is the temperature, w1 is the mass fraction, and E, F, and G are adjusted parameters.

Reference 18.

Table 3. Densities, ρ, Dynamic Viscosities, η, and Experimental Data for Pure Components (Ethanol (1), Igepal CO-520, Igepal CO-630, Igepal CO-720, and Igepal CA-720) and Their Binary Mixtures as a Function of Temperature at P = 101.3 kPaa ρ/g·cm−3

η/mPa·s

T/K 293.15 x1 0.000 0.107 0.207 0.301 0.399 0.501 0.600 0.701 0.799 0.901 1.000 x1 0.000 0.106

303.15

T/K 313.15

Ethanol + Igepal CO-520 1.0279 1.0205 1.0248 1.0173 1.0192 1.0117 1.0158 1.0084 1.0102 1.0026 1.0021 0.9945 0.9909 0.983 0.9742 0.9664 0.9481 0.9402 0.899 0.8907 0.7822 0.7734 Ethanol + Igepal CO-630 Reference 1.0586 1.0509 1.0433 1.0561 1.0484 1.0408 1.0355 1.0324 1.0268 1.0233 1.0178 1.0096 0.9985 0.9821 0.9561 0.9071 0.7907

323.15 1.0131 1.0098 1.0041 0.9996 0.9953 0.9869 0.9752 0.9585 0.9308 0.8791 0.7601 1.0357 1.0331 B

293.2 x1 0.000 0.107 0.207 0.301 0.399 0.501 0.600 0.701 0.799 0.901 1.000 x1 0.000 0.106

355.74 258.67 207.54 189.18 133.37 95.67 60.89 36.21 17.45 6.30 1.23 366.22 312.89

303.15

313.15

Ethanol + Igepal CO-520 169.46 90.68 132.79 73.69 105.24 59.40 97.39 55.36 70.61 41.23 53.20 32.30 35.32 22.24 22.42 14.79 11.72 8.26 4.67 3.57 1.02 0.85 Ethanol + Igepal CO-630 184.95 103.02 160.67 91.383

323.15 53.11 44.21 36.38 34.21 26.04 21.04 14.91 10.30 6.07 2.80 0.71 62.25 56.49



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Table 3. continued ρ/g·cm−3

η/mPa·s

T/K 293.15 x1 0.200 0.330 0.415 0.502 0.604 0.700 0.805 0.900 1.000 x1 0.000 0.106 0.310 0.412 0.600 0.647 0.803 0.875 0.916 1.000 x1 0.000 0.108 0.218 0.322 0.503 0.601 0.708 0.902 1.000

303.15

1.0531 1.0478 1.0434 1.0371 1.0263 1.0129 0.9862 0.9382 0.7907 1.0659 1.0651 1.0589 1.0539 1.0354 1.0354 1.0038 0.9755 0.9432 0.7907 1.0745 1.0709 1.0668 1.0640 1.0537 1.0447 1.0296 0.9569 0.7907

T/K 313.15

323.15

Ethanol + Igepal CO-630 1.0453 1.0376 1.0404 1.0329 1.0358 1.0281 1.0293 1.0217 1.0187 1.0109 1.005 0.9974 0.9783 0.9703 0.9301 0.9219 0.7822 0.7734 Ethanol + Igepal CO-720 1.0581 1.0505 1.0573 1.0495 1.0511 1.0434 1.0461 1.0384 1.0276 1.0196 1.0276 1.0196 0.9961 0.988 0.9674 0.9592 0.9348 0.9265 0.7822 0.7734 Ethanol + Igepal CA - 720 1.0667 1.0589 1.0631 1.0554 1.0589 1.0513 1.0561 1.0483 1.0458 1.0379 1.0369 1.0290 1.0219 1.0138 0.9487 0.9392 0.7822 0.7734

293.2 x1 0.200 0.330 0.415 0.502 0.604 0.700 0.805 0.900 1.000 x1 0.000 0.106 0.310 0.412 0.600 0.647 0.803 0.875 0.916 1.000 x1 0.000 0.108 0.218 0.322 0.503 0.601 0.708 0.902 1.000

1.0300 1.0252 1.0202 1.0138 1.0031 0.9894 0.9622 0.9138 0.7601 1.0428 1.0418 1.0356 1.0307 1.0118 1.0118 0.9798 0.9512 0.9182 0.7601 1.0513 1.0478 1.0438 1.0406 1.0300 1.0212 1.0053 0.9252 0.7601

303.15

281.37 236.62 190.43 145.44 101.63 58.52 30.11 10.98 1.23 383.07 335.21 261.15 216.88 131.11 118.87 47.75 24.82 12.14 1.23 392.20 388.84 315.83 221.00 145.27 128.58 83.50 14.98 1.23

313.15

Ethanol + Igepal CO-630 145.48 83.329 124.89 72.62 102.73 60.86 80.84 49.1624 59.39 37.53 36.11 23.80 19.93 13.90 7.98 6.01 1.02 0.85 Ethanol + Igepal CO-720 197.77 113.08 173.39 99.13 138.27 80.68 117.61 70.04 75.56 47.30 69.14 43.73 30.11 20.30 16.74 11.95 8.93 6.70 1.02 0.85 Ethanol + Igepal CA - 720 202.92 116.63 201.22 115.11 166.45 96.65 121.34 73.02 83.91 52.55 75.01 47.23 50.88 33.26 10.76 8.03 1.02 0.85

323.15 51.84 45.65 38.86 32.04 25.27 16.54 10.13 4.65 0.71 70.16 61.52 50.94 44.93 31.64 29.34 14.43 8.84 5.18 0.71 72.62 71.48 60.86 47.28 35.10 31.76 23.06 6.10 0.71

Standard uncertainties, u: u(x1) = 0.0003, u(T) = 0.01 K, u(η) = 0.02η mPa·s, u(P) = 0.1 kPa, and u(ρ) = 0.0015 g·cm−3.

a

Table 4. Adjusted ρ Parameters for Each Ethanol + Igepal System, from Equation 1 Igepal CO-520

Igepal CO-630

Igepal CO-720

Igepal CA-720

1.2532 0.1939 −0.3812 −0.0008

1.2698 0.2438 −0.4362 −0.0008

1.2831 0.2702 −0.4537 −0.00087

1.28887 0.24217 −0.42167 −0.00087

A B C D

Table 5. Adjusted η Parameters for Each Ethanol + Igepal System, from Equation 2 E F G

V =

∑ xiMi(ρ

−1

−1

− ρi )

∑ xiηi

Igepal CO-720

Igepal CA-720

−13.004 5530.611 −11.772

−12.542 5404.739 −11.193

−12.375 5378.833 −14.060

K

(5)

j=0

The thermal expansion coefficient (α) describes how volume changes with a change in temperature at constant pressure. From this data, we could infer the intermolecular forces present in the fluid. The thermal expansion coefficient was calculated using eq 6

(3)

where xi, Mi, ρi, and ρ are the molar fraction, molecular mass, density of pure component i, and density of the mixture, respectively. Viscosity deviation (Δη) calculations were carried out by using eq 4 Δη = η −

Igepal CO-630

−14.227 5864.805 −12.936

y = x1(1 − x1) ∑ Aj (1 − 2x1) j

Furthermore, the excess volume (VE) was calculated from density measurements according to the following equation E

Igepal CO-520

1 i ∂ρ y α = − jjj zzz ρ k ∂T { P

(4)

where η is the dynamic viscosity of the mixture and ηi and xi denote the viscosities and mole fractions of pure components, respectively. The values of the excess volume and viscosity deviation (VE and Δη) were fit by using a polynomial equation proposed by Redlich−Kister20 as follows

(6)

where ρ is the density, T is the temperature, and the term

( ∂∂Tρ )p

is obtained by differentiating eq 1. The excess molar volume (VE) is the difference between the volume in a real mixture and that of the volume in an ideal C



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Table 6. Excess Volume for the Binary Mixtures (Ethanol (1) + Igepal CO-520, or + Igepal CO-630, or + Igepal CO-720, or + Igepal CA-720) at T = (293.15 to 323.15) K VE/cm3·mol−1 T/K 293.15 x1 0.000 0.107 0.207 0.301 0.399 0.501 0.600 0.701 0.799 0.901 1.000 x1 0.000 0.106 0.200 0.330 0.415 0.502 0.604 0.700 0.805 0.900 1.000 x1 0.000 0.106 0.310 0.412 0.600 0.647 0.803 0.875 0.916 1.000 x1 0.000 0.108 0.218 0.322 0.503 0.601 0.708 0.902 1.000

0.000 −0.315 0.092 −0.431 −0.728 −0.868 −0.952 −1.024 −0.932 −0.738 0.000 0.000 −0.314 −0.468 −0.680 −0.871 −0.924 −0.799 −1.059 −0.936 −0.729 0.000 0.000 −1.117 −1.362 −1.281 −1.307 −1.589 −1.353 −1.504 −0.917 0.000 0.000 0.399 0.574 −0.237 −0.590 −0.704 −0.859 −0.918 0.000

303.15

313.15

Ethanol + Igepal CO-520 0.000 0.000 −0.331 −0.312 0.073 0.081 −0.499 −0.548 −0.778 −0.788 −0.954 −0.987 −1.024 −1.015 −1.054 −1.093 −0.964 −1.012 −0.773 −0.802 0.000 0.000 Ethanol + Igepal CO-630 0.000 0.000 −0.329 −0.348 −0.448 −0.434 −0.840 −0.935 −0.959 −0.991 −0.955 −1.033 −0.894 −0.930 −1.097 −1.201 −0.990 −1.036 −0.767 −0.811 0.000 0.000 Ethanol + Igepal CO-720 0.000 0.000 −1.143 −1.051 −1.411 −1.424 −1.338 −1.368 −1.411 −1.415 −1.670 −1.665 −1.461 −1.489 −1.555 −1.598 −0.930 −0.966 0.000 0.000 Ethanol + Igepal CA-720 0.000 0.000 0.395 0.328 0.614 0.492 −0.224 −0.266 −0.609 −0.641 −0.769 −0.820 −0.958 −0.981 −0.953 −0.845 0.000 0.000

323.15 0.000 −0.331 0.050 −0.255 −1.027 −1.201 −1.242 −1.367 −1.132 −0.790 0.000

Figure 2. Influence of temperature on the excess molar volume of a binary mixture of ethanol (1) + Igepal CO-520. Temperatures: (■) 293.15 K, (●) 303.15 K, (▲) 313.15 K, and (▼) 323.15 K. All lines were obtained from a Redlich−Kister polynomial fit.

0.000 −0.353 −0.538 −1.070 −1.099 −1.197 −1.184 −1.470 −1.355 −1.189 0.000 0.000 −1.118 −1.545 −1.588 −1.694 −1.972 −1.799 −1.993 −1.336 0.000


0.000 0.280 0.338 −0.381 −0.788 −1.065 −1.122 −0.450 0.000

From eqs 6 and 7, it could be stated that ÄÅ ÉÑ ÅÅ ÑÑ 2 E ÑÑ 1 ÅÅÅjij ∂Vm zyz Ñ α = ÅÅÅjj zzz + ∑ (αixiVi )ÑÑÑ j ÑÑ V ÅÅk ∂T { i=1 ÅÅÇ ÑÑÖ P , xi

where α and αi are the thermal expansion coefficients of mixtures and pure compounds, respectively.

3. RESULTS AND DISCUSSION Table 3 shows experimental density and dynamic viscosity data for pure components and their binary mixtures. As expected, for liquids, it could be observed that density and viscosity values decrease with increasing temperature, and by the increasing ethanol molar fraction, as a less-dense fluid. Table 4 shows fitted parameters adjusted to density, from eq 1. Moreover, Table 5 presents viscosity-adjusted parameters for each ethanol + Igepal system, from eq 2. Table 6 and Figures 2 to 5 show excess volumes for the binary mixtures (ethanol (1) + Igepal CO-520, or + Igepal CO-630,

mixture under the same pressure, temperature, and composition conditions. This difference could be positive or negative, which is related to the expansive or contractive behavior of the mixtures. The relationship between VEm and molar volume is given in the following equation 2

V=

∑ xiVi + VmE i=1

(8)

(7)

where xi and Vi are, respectively, the molar fraction and molar volume of compound i. D



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Table 7. continued Δη/mPa·s T/K 293.15 x1 0.000 0.106 0.200 0.330 0.415 0.502 0.604 0.700 0.805 0.900 1.000 x1 0.000 0.106 0.310 0.412 0.600 0.647 0.803 0.875 0.916 1.000 x1 0.000 0.108 0.218 0.322 0.503 0.601 0.708 0.902 1.000


0.00 −14.68 −11.78 −9.26 −24.46 −37.51 −44.18 −52.07 −42.32 −26.86 0.00 0.00 −7.39 −3.55 −8.87 −22.86 −17.15 −28.70 −24.14 −21.24 0.00 0.00 39.05 8.95 −45.27 −50.32 −28.78 −31.79 −24.39 0.00

303.15

313.15

Ethanol + Igepal CO-630 0.00 0.00 −4.80 −0.82 −2.65 0.76 0.58 3.28 −5.96 0.20 −11.77 −2.56 −14.49 −3.80 −20.02 −7.66 −16.98 −6.88 −11.48 −5.09 0.00 0.00 Ethanol + Igepal CO-720 0.00 0.00 −3.52 −2.05 1.49 2.39 0.90 3.20 −4.16 1.56 −1.33 3.26 −9.67 −2.66 −8.88 −2.94 −8.66 −3.60 0.00 0.00 Ethanol + Igepal CA-720 0.00 0.00 20.20 11.03 7.59 5.29 −16.55 −6.32 −17.48 −5.85 −6.64 0.14 −9.04 −1.37 −9.96 −4.12 0.00 0.00

323.15 0.00 0.76 1.91 3.70 2.12 0.69 0.18 −2.61 −2.59 −2.24 0.00 0.00 −1.28 2.31 3.38 3.15 4.11 0.04 −0.55 −1.39 0.00 0.00 6.66 3.94 −2.17 −1.36 2.33 1.37 −1.63 0.00

Figure 5. Influence of temperature on the excess molar volume of a binary mixture of ethanol (1) + Igepal CA-720. Temperatures: (■) 293.15 K, (●) 303.15 K, (▲) 313.15 K, and (▼) 323.15 K. All lines were obtained from a Redlich−Kister polynomial fit.

Table 7. Viscosity Deviations for the Binary Mixtures (Ethanol (1) + Igepal CO-520, or + Igepal CO-630, or + Igepal CO-720, or + Igepal CA-720) at T = (293.15 to 323.15) K Δη/mPa·s T/K 293.15 x1 0.000 0.107 0.207 0.301 0.399 0.501 0.600 0.701 0.799 0.901 1.000

0.00 −59.14 −74.81 −59.85 −80.92 −82.46 −82.14 −71.02 −55.04 −30.14 0.00

313.15

323.15

Ethanol + Igepal CO-520 0.00 0.00 −18.65 −7.38 −29.35 −12.69 −21.36 −8.28 −31.65 −13.61 −31.87 −13.38 −33.08 −14.54 −28.96 −12.92 −23.16 −10.65 −13.08 −6.20 0.00 0.00

303.15

0.00 −3.30 −5.88 −3.14 −6.16 −5.82 −6.77 −6.08 −5.18 −3.12 0.00

Figure 6. Influence of temperature on the viscosity deviation for a binary mixture of ethanol (1) + Igepal CO-520. Temperatures: (■) 293.15 K, (●) 303.15 K, (▲) 313.15 K, and (▼) 323.15 K. All lines were obtained from a Redlich−Kister polynomial fit.

or + Igepal CO-720, or + Igepal CA-720) at T = (293.15 to 323.15) K. It could be observed that there is a prevalence of E



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Table 8. Thermal Expansion Coefficients for the Binary Mixtures (Ethanol (1) + Igepal CO-520, or + Igepal CO-630, or + Igepal CO-720, or + Igepal CA-720) at T = (293.15 to 323.15) K α × 104/K−1 T/K 293.15 x1 0.000 0.107 0.207 0.301 0.399 0.501 0.600 0.701 0.799 0.901 1.000 x1 0.000 0.1059 0.2002 0.3297 0.4146 0.5021 0.6039 0.7004 0.8049 0.8997 1.000 x1 0.000 0.106 0.310 0.412 0.600 0.647 0.803 0.875 0.9158 1.000 x1 0.000 0.108 0.218 0.322 0.503 0.601 0.708 0.902 1.000

Figure 7. Influence of temperature on the viscosity deviation for a binary mixture of ethanol (1) + Igepal CO-630. Temperatures: (■) 293.15 K, (●) 303.15 K, (▲) 313.15 K, (▼) 323.15 K. All lines were obtained from a Redlich−Kister polynomial fit.

Figure 8. Influence of temperature on the viscosity deviation for binary mixture of ethanol (1) + Igepal CO-720. Temperatures: (■) 293.15 K, (●) 303.15 K, (▲) 313.15 K, (▼) 323.15 K. All lines were obtained from a Redlich−Kister polynomial fit.

7.795 7.818 7.861 7.888 7.930 7.995 8.083 8.218 8.442 8.898 10.208 7.535 7.553 7.575 7.613 7.645 7.691 7.772 7.875 8.088 8.502 10.088 7.619 7.625 7.670 7.706 7.844 7.844 8.091 8.326 8.611 10.271 7.582 7.607 7.637 7.657 7.732 7.798 7.913 8.514 10.303

303.15

313.15

Ethanol + Igepal CO-520 7.853 7.900 7.876 7.934 7.919 7.978 7.946 8.004 7.990 8.050 8.054 8.116 8.145 8.211 8.285 8.352 8.513 8.585 8.978 9.062 10.319 10.436 Ethanol + Igepal CO-630 7.590 7.646 7.609 7.664 7.631 7.688 7.667 7.723 7.701 7.759 7.750 7.807 7.830 7.891 7.937 7.998 8.154 8.221 8.576 8.653 10.198 10.31 Ethanol + Igepal CO-720 7.676 7.731 7.681 7.738 7.727 7.784 7.764 7.821 7.903 7.965 7.903 7.965 8.153 8.220 8.395 8.467 8.688 8.766 10.383 10.501 Ethanol + Igepal CA-720 7.637 7.694 7.663 7.719 7.694 7.749 7.714 7.771 7.790 7.849 7.857 7.917 7.972 8.036 8.587 8.674 10.415 10.534

323.15 7.967 7.993 8.038 8.075 8.109 8.179 8.277 8.421 8.671 9.181 10.619 7.702 7.721 7.744 7.781 7.819 7.868 7.952 8.062 8.290 8.729 10.495 7.788 7.796 7.842 7.880 8.027 8.027 8.289 8.538 8.845 10.685 7.749 7.775 7.805 7.829 7.910 7.978 8.104 8.806 10.718

negative values for VE for all of the studied systems that could be assigned to strong intermolecular forces between different species.21 For ethanol + Igepal CO-630 and ethanol + Igepal CO-720 systems, the excess molar volume assumes negative values for all compositions in the studied temperature range. Likewise, the ethanol + Igepal CO-520 system presents negative behavior, with a slightly positive tendency for molar fraction compositions of around 0.2. Nevertheless, the ethanol + Igepal CA-720 system shows negative excess molar volume for all

Figure 9. Influence of temperature on the viscosity deviation for a binary mixture of ethanol (1) + Igepal CA-720. Temperatures: (■) 293.15 K, (●) 303.15 K, (▲) 313.15 K, and (▼) 323.15 K. All lines were obtained from a Redlich−Kister polynomial fit. F



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Additionally, the viscosity deviation decreases as the temperature increases once the viscosity is reduced by increasing temperature, as expected for pure liquids and liquid mixtures, especially for Tr below 0.7, as stated by Pollig, Prausnitz, and O’Connell.25 It is interesting that viscosity originates from cohesive forces between molecules that are relatively close to each other. For this reason, increasing temperature leads to an increase in the average kinetic energy due to the effects of intermolecular forces.25 Therefore, IMFs become weaker and thereby viscosity decreases. Table 8 and Figures 10 to 13 show the thermal expansion for binary mixtures calculated by using eq 8. It can be observed that

Figure 10. Influence of temperature and composition on the thermal expansion coefficient for the ethanol + Igepal CO-520 system.

temperatures studied and ethanol molar fraction compositions higher than 0.3. It is interesting to emphasize that Igepal CA-720 behavior could be related to a branched hydrophobic alkylic chain, especially when compared to Igepal CO-720. The changing alkyl side chain from a branched to a linear one (e.g., Igepal CA-720 to Igepal CO-720) could lead to a better mixing process with ethanol by reducing steric hindrance. As a consequence, excess molar volume is expected to decrease when we have a branched chain by comparison to a linear chain22 (Figures 4 and 5). In addition, IMFs could be attributed to negative values for the viscosity deviation as a result of the formation of hydrogen bonds. The same results have been observed by Liu et al.,23 reporting hydrogen bonding formation between hydroxyls of polymer. These negative excess molar volumes could be related to a volume contraction.24 Table 7 and Figures 6 to 9 depict the viscosity deviation for the ethanol + Igepal series (Igepal CO-520, Igepal CO-630, Igepal CO-720, or Igepal CA-720) in the temperature range of T = 293.15−323.15 K at atmospheric pressure. From these data, a negative trend could be seen for most of the systems, especially at low temperatures. This behavior can be understood as a sign that attractive intermolecular forces are stronger than the repulsive ones.21 Nevertheless, some positive data were observed with the increase in temperature, together with the increase in the hydrophilic chain length. For the ethanol + Igepal CO-520 system, negative values were observed for all studied temperatures and compositions. Furthermore, for the ethanol + Igepal CO-630 and ethanol + Igepal CO-720 systems a negative viscosity deviation is prevailing, but there is a positive tendency for high temperatures and an ethanol molar fraction composition of between 0.2 and 0.6. On the other hand, for the ethanol + Igepal CA-720 system, a negative viscosity deviation behavior was observed for ethanol molar fraction compositions greater than 0.3. It is interesting that when the temperature increases there is a reduction in the intensity of this positive deviations data. Once again, for the ethanol + Igepal CA-720 system, there is a distinct behavior that could be attributed to the difference in the molecular structure of the branched hydrophobic side chain, as was previously observed for density data.

Figure 11. Influence of temperature and composition on the thermal expansion coefficient for ethanol + Igepal CO-630 system.

Figure 12. Influence of temperature and composition on the thermal expansion coefficient for ethanol + Igepal CO-720 system.

there is an increase in the thermal expansion coefficient with the increase in temperature, at fixed composition. Also, an increase in the thermal expansion coefficient with increasing ethanol molar fraction composition, at fixed temperature, could be seen. G



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REFERENCES

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Figure 13. Influence of temperature and composition on the thermal expansion coefficient for the ethanol + Igepal CA-720 system.

These results were expected for regular liquids, once the increase in the fluid temperature causes an increase in its molecules’ internal energy. As the energy increases, a molar volume increase is verified. These relationships between energy and density could lead to decreasing in the thermal expansion coefficient (α) that could be related to the increase in bond intensity. It is interesting that other properties could also be important in the characterization of surfactant mixtures, such as the critical micellar concentration (cmc), speed of sound, refractive index, and surface tension, especially in industrial applications.

4. CONCLUSIONS The density and viscosity of the ethanol + Igepal series (Igepal CO-520, Igepal CO-630, Igepal CO-720, or Igepal CA-720) were determined for pure and binary mixtures at T = (293.15 to 323.15) K and atmospheric pressure. As expected for liquid mixtures, there is a decrease in these properties by increasing temperature. The excess molar volume (VE) and viscosity deviation (Δη) show a negative trend that could be related to a contraction forces between dissimilar molecules and a predominance of dispersion forces, respectively. It has been seen that the hydrophobic alkyl chain modification is responsible for the different behaviors of VE and Δη, together with the increase in the hydrophilic ethoxylated chain length.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Hosiberto Batista de Sant’Ana: 0000-0001-7558-3018 Notes

The authors declare no competing financial interest. Funding

The authors are grateful to CNPq (Conselho Nacional de ́ DesenvolvimentoCientifico e Tecnológico, Brasil), CAPES ́ (Coordenaçãode Aperfeiçoamento de Pessoal de Nivel Superior, Brasil),and Petrobras - Petróleo Brasileiro S.A. for financial support. H



Article

(22) Gahlyan, S.; Rani, M.; Lee, I.; Moon, I.; Maken, S. K. Measurement and Correlation of Excess Molar Volumes for Mixtures of 1-Propanol and Aromatic Hydrocarbons. 2015. Korean J. Chem. Eng. 2015, 32, 168−177. (23) Liu, Q.; Zhang, X.; Ma, B.; Lin, Y. Densities and Viscosities for Binary Mixtures of Polyoxymethylene Dimethyl Ethers with Different CH 2 O Chain Length n = 2, 3, 4 at Different Temperatures. J. Chem. Thermodyn. 2017, 113, 151−161. (24) Saleh, M. A.; Akhtar, S. Physics and Chemistry of Liquids : An International Excess Molar Volumes of Aqueous Solutions of 1Propanol, 2-Propanol, Allyl Alcohol and Propargyl Alcohol. Phys. Chem. Liq. 1998, 36, 53−65. (25) Poling, B. E.; Prausnitz, J. M. The Properties of Gases and Liquids, 5th ed.; New York, 2001.

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Viscosity and Density of Binary Mixtures of Ethanol + Igepal (CO-520

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