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Densities, Refractive Indices, Viscosities, and Spectroscopic Study of 1‑Amino-2-propanol + 1‑Butanol and + 2‑Butanol Solutions at (288.15 to 333.15) K Vuk D. Spasojević,‡ Bojan D. Djordjević,† Slobodan P. Šerbanović,† Ivona R. Radović,† and Mirjana Lj. Kijevčanin*,† †

Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia Institute for Nuclear Sciences Vinča, University of Belgrade, Mike Petrovića Alasa 12-14, 11000 Belgrade, Serbia

‡

S Supporting Information *

ABSTRACT: Densities, refractive indices, and viscosities of 1-amino-2-propanol (monoisopropanolamine (MIPA)) + 1-butanol and 1-amino-2-propanol + 2butanol solutions are reported over the entire range of mole fractions and the temperature range from (288.15 to 333.15) K. The Redlich−Kister relation was used for correlation of measured results of excess molar volumes, viscosities, and refractive indices as a function of temperature and composition. Partial molar volumes at infinite dilution were determined from apparent molar volumes. Negative values for excess molar volumes, refractive indices, and viscosity deviations are observed over the entire composition range. The viscosities of 1amino-2-propanol with 1-butanol and 1-amino-2-propanol with 2-butanol are well represented by an Arrhenius equation. Activation energies for viscous flows are determined by linearization of the Arrhenius equation, providing a clear explanation of the influence on hydrogen bonding. In order to confirm molecular interactions between compounds obtained by analysis of infinite dilution of solute, a FT-IR spectroscopy study was performed at T = 298.15 K. Interactional and structural effects were investigated through calculations of excess Gibbs free energy of activation of viscous flow. carbon dioxide absorption.3 Besides its main use in the process of carbon dioxide removal, MIPA has found wide use in many other chemical processes such as an emulsifying agent, crosslinking catalyst, pigment dispersant, and corrosion inhibitor. Also, some authors showed the potential of utilization of MIPA as a carbon dioxide capture absorbent, even at elevated partial pressures.4 Investigations of solubility, diffusivity, and kinetics of absorption reactions showed that MIPA has a similar absorption rate as MEA.5,6 The similarity of reaction with other primary alkanol amines was confirmed by Henni et al.7 and Hikita et al.8 Density and viscosity are fundamental thermophysical properties present in all models used for process or equipment design. Therefore, knowledge and investigation which will provide precise and reliable data regarding these properties are crucial.9 The main aim of this work is presentation of experimental measurements of densities, refractive indices and viscosities of industrially very important alcohol solution of alkanol amines. Although volumetric data of aqueous solutions of MIPA is well investigated,10,11 few data is available for volumetric properties such as density, viscosity, or refractive

1. INTRODUCTION Intense climate change in the past decade is a result of increased emissions of so-called greenhouse gases. One of the reasons for the huge increase of concentration of these gases is fossil fuels combustion. The dominant sectors with more than 50 % of all greenhouse gases emission are industrial and energy sectors.1 One of the leading technologies in global efforts in reduction of emission and mitigation of negative greenhouse gases effects is hemisorption with utilization of amino alcohols as absorbents. Various amino alcohols were used in treatments of acid gases in different industries such as gas, oil, or other chemical production industries.2 The use of alcohols as solvents for alkanol amines could provide many improvements. The presence of additional hydroxyl groups from alcohols can increase solubility of the alkanol amine + alcohol binary mixture in water. Another effect is the increase of carbon dioxide loading capacity due to the increase of alkanol amine + alcohol solution alkalinity. The most important positive effect is that the low boiling temperature of alcohols could contribute to a significant reduction of energy requirements for solvent regeneration and thus a reduction of the overall cost of the carbon dioxide removal process. With its amino and hydroxyl functional groups alkanol amines reacts with CO2 as weak base with acid gases, showing similar behavior as most widely commercially used monoethanolamine (MEA) in process of © 2014 American Chemical Society

Received: December 21, 2013 Accepted: April 7, 2014 Published: April 18, 2014 1817

dx.doi.org/10.1021/je401036f | J. Chem. Eng. Data 2014, 59, 1817−1829

Journal of Chemical & Engineering Data

Article

uncertainty of ± 2·10−5, and the uncertainty is ± 2·10−4 for refractive index deviations. Viscosities η of alcohol solutions of alkanol amine were measured with a digital Stabinger viscometer (model SVM 3000/G2). The dynamic viscosity is directly measured by the SVM 3000/G2, as

index of binary mixtures of alcohols with MIPA. 1-Amino-2propanol (monoisopropanolamine or MIPA) is a primary amine soluble in water, with a low alkalinity.

2. EXPERIMENTAL SECTION For the investigation of thermophysical properties of alkanol amine solution, the following chemicals have been used: 1amino-2-propanol (ω ≥ 0.98), 1-butanol (ω ≥ 0.99), and 2butanol (ω ≥ 0.99), all supplied by Merck and used without further purification (sample description is given in Table 1).

η=

MIPA 1-butanol 2-butanol

source Merck (Germany) Merck (Germany) Merck (Germany)

CAS number

mass fraction purity

purification method

78-96-6

≥ 0.98

none

71-36-3

≥ 0.99

none

78-92-2

≥ 0.99

none

(1)

where u1 is the speed of the tube, u2 is the rotor speed, and k is the mean adjustment coefficient of the instrument, determined by the manufacturer using a calibration technique and directly integrated into the instrument software. The instrument measuring ranges were adjusted by the manufacturer. The uncertainty of the dynamic viscosity measurements is below 1.5 % and ± 3·10−3 mPa·s for viscosity deviations, for the temperature and viscosity range used in this work. Comparison of experimentally received data with representative literature data for pure components is given in Table 2.12−25 Detailed description of the above-mentioned instruments have been given in our previous papers.26−29 With the goal to explain molecular structure and interactions, as well as the presence of potential new hydrogen bonds, FT-IR spectroscopy analysis was performed. A COLET 6700 FT-IR spectrometer was utilized to record the FT-IR spectra of pure components and binary mixtures. For each spectrum 32 scans were made with a selected resolution of 2 cm−1. Spectroscopic measurements were performed at T = 298.15 K.

Table 1. Sample Description chemical name

ku 2 (u1 − u 2)

Degassing of all chemicals was conducted before sample preparations, which were kept in dark bottles in an inert atmosphere. In order to prevent or remove eventually dissolved air, degassing of pure components by ultrasonic bath at an elevated temperature of 323.15 K for 30 min was used. Density measurements were performed using an Anton Paar DMA 5000 digital vibrating U-tube densimeter (with automatic viscosity correction) and with the stated instrument accuracy of ± 5·10−3 kg·m−3. The temperature in the cell was regulated to ± 0.001 K with a built in solid-state thermostat. Calibration of instruments with Milli-Q water and dry air as standards was performed before measurements. Uncertainty in the density is within ± 1·10−2 kg·m−3 with a 0.95 level of confidence (k ≈ 2) and excess molar volume uncertainty is estimated as ± 2·10−9 m3·mol−1. Mixtures were prepared gravimetrically using a Mettler AG 204 balance with a precision of 1·10−7 kg. The uncertainty of the mole fraction calculation was less than ± 1· 10−4. Refractive index measurements were carried out on Anton Paar RXA 156 refractometer. The refractive index data have the

3. RESULTS AND DISCUSSION Using approach given in our previous papers26−29 excess molar volumes, refractive index deviations and viscosity deviations were determined. Excess molar volumes VE were calculated from eq 2: N

VE =

∑ xiMi[(1/ρ) − (1/ρi )]

(2)

i=1

Refractive index deviations ΔnD were obtained using eq 3:

Table 2. Densities ρ, Refractive Indices nD, and Viscosities η of the Pure Components at Temperature T and Atmospheric Pressurea T component

10−3·ρ/kg·m−3

K

this work

lit

293.15

0.960625

1.4479

298.15

0.956644

1-butanol

298.15

0.805752

0.961223b 0.96038c 0.95946d 0.957114b 0.95640c 0.95651g 0.80564h 0.80560i

1.397 17

2-butanol

298.15

0.802528

0.80262h 0.80244i

1.3952

MIPA

η/mPa·s

nD this work

lit

this work

1.4461e 1.44609f

31.24

lit

23.26

24.234e

1.3972h 1.3972i

2.539

1.3950h 1.3950i

3.093

2.593j 2.524k 2.5710l 3.132m 3.068n 2.9975o

1.4459

a

Standard uncertainties u for each variables are u(T) = 0.01 K ; u(p) = 5 % ; u(x1) = 0.0001, and the combined expanded uncertainties uc are uc(ρ) = ± 1·10−2 kg·m−3; uc(nD) = ± 1·10−4; and relative standard uncertainty ur(η) = 0.015, with 0.95 level of confidence (k ≈ 2). bAlvarez et al.12 c Mokraoui et al.13 dHerba et al.14 eGomez-Diaz et al.15 fMaham et al.16 gRayer et al.;17 hLoras et al.;18 iTRCThermodynamic TablesHydrocarbons.19 jShan et al.20 kRauf et al.21 lTRC Tables 1995.22 mAlmasi et al.23 nMartinez et al.24 oLomte et al.25 1818



Article

Table 3. Densities ρ, Refractive Indices nD, Viscosities η, Excess Molar Volumes VE, Deviations in Refractive Indices ΔnD and Viscosity Deviations Δη, Excess Gibbs Free Energy for Activation of Viscous Flow ΔG*E of the MIPA (1) + 1-Butanol (2) and + 2-Butanol (2) Systems at T = (288.15 to 333.15) K and Atmospheric Pressurea x1

10−3·ρ/ kg·m−3

106·VE/m3·mol−1

η/ mPa·s

Δη/ mPa·s

ΔG*E/ kJ·mol−1

−0.029 −0.059 −0.081 −0.095 −0.102 −0.097 −0.093 −0.079 −0.053

3.367 4.019 4.952 6.238 8.046 10.48 13.85 18.20 24.34 32.26 43.70

−3.382 −6.503 −9.230 −11.45 −13.05 −13.71 −13.40 −11.29 −7.401

−189.55 −306.34 −360.17 −367.26 −346.97 −295.91 −255.03 −173.45 −111.69

−0.028 −0.060 −0.082 −0.098 −0.104 −0.100 −0.093 −0.080 −0.054

2.914 3.444 4.218 5.202 6.617 8.455 10.88 14.08 18.34 23.93 31.68

−2.347 −4.463 −6.341 −7.799 −8.840 −9.282 −8.962 −7.582 −4.861

−163.62 −263.85 −312.70 −324.32 −309.01 −277.23 −229.59 −168.87 −100.24

−0.028 −0.061 −0.083 −0.100 −0.107 −0.103 −0.094 −0.081 −0.053

2.539 2.989 3.620 4.398 5.507 6.858 8.782 11.03 14.18 18.16 23.54

−1.650 −3.130 −4.442 −5.431 −6.182 −6.352 −6.208 −5.159 −3.276

−137.43 −226.45 −273.41 −285.91 −294.37 −234.84 −221.49 −152.42 −89.742

−0.026 −0.062 −0.084 −0.104 −0.110 −0.105 −0.096 −0.081 −0.054

2.228 2.615 3.129 3.756 4.639 5.721 7.156 8.892 11.17 14.06 17.90

−1.179 −2.240 −3.171 −3.853 −4.339 −4.466 −4.302 −3.585 −2.257

−117.68 −195.18 −236.57 −248.26 −245.26 −207.81 −185.74 −136.19 −79.945

−0.855 −1.625 −2.306 −2.782 −3.130 −3.202 −3.070

−94.564 −161.28 −200.13 −213.17 −217.41 −182.97 −164.80

102·ΔnD

nD

MIPA (1) + 1-butanol (2) T = 288.15 K 0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.813 353 0.827 167 0.841 339 0.855 625 0.870 246 0.885 140 0.900 478 0.916 099 0.932 069 0.948 249 0.964 544

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.809 564 0.823 338 0.837 455 0.851 736 0.866 053 0.881 200 0.896 524 0.912 152 0.928 119 0.944 296 0.960 598

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.805 752 0.819 488 0.833 571 0.847 825 0.862 123 0.877 169 0.892 563 0.908 181 0.924 144 0.940 310 0.956 618

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.801 912 0.815 611 0.829 669 0.843 892 0.858 167 0.873 195 0.888 575 0.904 186 0.920 144 0.936 303 0.952 612

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000

0.798 039 0.811 706 0.825 735 0.839 932 0.854 420 0.869 288 0.884 561 0.900 162

−0.076 −0.137 −0.177 −0.200 −0.203 −0.200 −0.182 −0.149 −0.094

−0.075 −0.132 −0.174 −0.193 −0.200 −0.196 −0.181 −0.148 −0.094

−0.074 −0.130 −0.172 −0.191 −0.198 −0.195 −0.180 −0.148 −0.093

−0.073 −0.129 −0.170 −0.189 −0.197 −0.194 −0.179 −0.148 −0.093

−0.072 −0.128 −0.169 −0.188 −0.195 −0.193 −0.178

1.4013 1.4058 1.4104 1.4151 1.4198 1.4246 1.4295 1.4345 1.4395 1.4446 1.4500 T= 1.3992 1.4038 1.4084 1.4130 1.4178 1.4226 1.4275 1.4324 1.4375 1.4426 1.4480 T= 1.3972 1.4018 1.4064 1.4110 1.4157 1.4205 1.4254 1.4304 1.4354 1.4406 1.4460 T= 1.3951 1.3998 1.4043 1.4089 1.4136 1.4184 1.4234 1.4283 1.4334 1.4385 1.4440 T= 1.3930 1.3977 1.4022 1.4068 1.4115 1.4163 1.4213 1.4262

293.15 K

298.15 K

303.15 K

308.15 K −0.026 −0.063 −0.086 −0.109 −0.114 −0.110 −0.100 1819

1.962 2.298 2.726 3.230 3.944 4.788 5.904 7.231



Article

Table 3. continued x1

10−3·ρ/ kg·m−3

106·VE/m3·mol−1

102·ΔnD

nD

η/ mPa·s

Δη/ mPa·s

ΔG*E/ kJ·mol−1

8.949 11.10 13.88

−2.541 −1.585

−120.62 −70.118

MIPA (1) + 1-butanol (2) T = 288.15 K 0.8000 0.8997 1.0000

0.916 116 0.932 266 0.948 577

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.794 130 0.807 768 0.821 766 0.835 940 0.850 406 0.865 257 0.880 518 0.896 106 0.912 054 0.928 196 0.944 515

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.790 180 0.803 791 0.817 764 0.831 911 0.846 355 0.861 194 0.876 438 0.892 017 0.907 960 0.924 096 0.940 423

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.786 179 0.799 764 0.813 705 0.827 834 0.842 264 0.857 087 0.872 324 0.887 889 0.903 828 0.919 961 0.936 293

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.782 125 0.795 685 0.809 606 0.823 708 0.838 127 0.852 936 0.868 161 0.883 720 0.899 655 0.915 789 0.932 130

0.0000 0.1000 0.2005 0.3000 0.3999

0.778 012 0.791 549 0.805 451 0.819 532 0.833 936

−0.148 −0.092

−0.072 −0.127 −0.168 −0.186 −0.194 −0.192 −0.178 −0.148 −0.092

−0.072 −0.127 −0.168 −0.185 −0.194 −0.191 −0.177 −0.147 −0.092

−0.072 −0.126 −0.167 −0.185 −0.194 −0.192 −0.177 −0.147 −0.092

−0.072 −0.126 −0.166 −0.185 −0.193 −0.191 −0.177 −0.147 −0.091

−0.072 −0.126 −0.166 −0.184

T= 1.4313 1.4365 1.4419 T= 1.3910 1.3956 1.4001 1.4047 1.4094 1.4142 1.4191 1.4242 1.4292 1.4344 1.4399 T= 1.3888 1.3934 1.3980 1.4026 1.4073 1.4121 1.4170 1.4221 1.4272 1.4324 1.4378 T= 1.3867 1.3913 1.3958 1.4005 1.4051 1.4099 1.4149 1.4200 1.4250 1.4303 1.4358 T= 1.3846 1.3892 1.3937 1.3983 1.4030 1.4078 1.4128 1.4178 1.4229 1.4282 1.4337 T= 1.3824 1.3870 1.3915 1.3961 1.4008

308.15 K −0.082 −0.053 313.15 K −0.029 −0.065 −0.090 −0.112 −0.118 −0.115 −0.102 −0.084 −0.051

1.739 2.030 2.389 2.801 3.377 4.049 4.929 5.957 7.272 8.900 10.96

−0.631 −1.199 −1.704 −2.049 −2.300 −2.340 −2.236 −1.841 −1.134

−75.570 −133.21 −169.92 −186.59 −193.30 −161.82 −147.59 −108.40 −60.882

−0.029 −0.067 −0.093 −0.115 −0.123 −0.118 −0.105 −0.086 −0.053

1.547 1.801 2.104 2.445 2.915 3.454 4.159 4.969 5.989 7.238 8.798

−0.471 −0.897 −1.278 −1.532 −1.718 −1.737 −1.654 −1.357 −0.833

−55.931 −107.63 −144.05 −160.38 −171.22 −141.14 −130.24 −96.907 −55.015

−0.031 −0.069 −0.096 −0.118 −0.128 −0.121 −0.108 −0.088 −0.055

1.382 1.606 1.865 2.144 2.535 2.973 3.541 4.192 4.994 5.960 7.166

−0.355 −0.676 −0.973 −1.160 −1.301 −1.309 −1.239 −1.014 −0.626

−30.939 −79.135 −110.60 −135.71 −149.63 −122.75 −112.30 −84.718 −51.251

−0.029 −0.071 −0.098 −0.122 −0.132 −0.124 −0.111 −0.090 −0.057

1.239 1.436 1.662 1.887 2.218 2.579 3.047 3.568 4.211 4.976 5.915

−0.270 −0.515 −0.755 −0.890 −0.998 −0.996 −0.944 −0.768 −0.470

−13.271 −51.471 −88.049 −111.76 −126.88 −100.08 −96.406 −72.182 −43.081

−0.221 −0.411 −0.593 −0.704

−14.614 −54.281 −88.634 −106.24

318.15 K

323.15 K

328.15 K

333.15 K −0.029 −0.074 −0.100 −0.128 1820

1.138 1.302 1.499 1.699 1.973



Article


10−3·ρ/ kg·m−3

106·VE/m3·mol−1

102·ΔnD

nD

η/ mPa·s

Δη/ mPa·s

ΔG*E/ kJ·mol−1

2.286 2.663 3.099 3.618 4.225 4.986

−0.776 −0.782 −0.733 −0.598 −0.375

−106.71 −94.864 −85.201 −66.660 −46.534

4.590 5.068 5.970 7.261 9.219 11.68 14.95 19.39 25.16 32.94 43.70

−3.445 −6.439 −9.064 −11.02 −12.47 −13.11 −12.58 −10.72 −6.850

−301.08 −448.39 −516.23 −484.12 −458.50 −406.74 −323.83 −240.72 −135.58

3.738 4.160 4.888 5.949 7.373 9.189 11.60 14.80 18.77 24.30 31.68

−2.381 −4.436 −6.171 −7.543 −8.518 −8.902 −8.493 −7.310 −4.583

−254.51 −379.95 −418.14 −415.85 −401.08 −354.86 −283.80 −226.58 −121.52

3.074 3.450 4.048 4.884 5.960 7.338 9.121 11.45 14.41 18.35 23.54

−1.677 −3.118 −4.330 −5.302 −5.970 −6.236 −5.952 −5.032 −3.138

−210.08 −314.63 −349.19 −360.00 −350.31 −317.46 −260.88 −197.57 −106.64

2.552 2.889 3.378 4.059 4.898 5.963 7.316 9.136 11.31 14.16 17.89

−1.201 −2.240 −3.095 −3.791 −4.259 −4.442 −4.153 −3.509 −2.201

−167.69 −259.49 −283.66 −299.83 −295.79 −272.90 −207.37 −162.55 −92.810

MIPA (1) + 1-butanol (2) T = 288.15 K −0.193 −0.191 −0.177 −0.147 −0.091

0.5000 0.6001 0.7000 0.8000 0.8997 1.0000

0.848 734 0.863 951 0.879 505 0.895 441 0.911 577 0.927 930

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.810 524 0.823 697 0.837 759 0.852 257 0.867 392 0.882 695 0.898 243 0.914 159 0.930 494 0.947 198 0.964 544

0.020 −0.023 −0.057 −0.107 −0.130 −0.125 −0.104 −0.080 −0.035

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.806 487 0.819 706 0.833 763 0.848 265 0.863 403 0.878 701 0.894 252 0.910 183 0.926 524 0.943 272 0.960 598

0.015 −0.028 −0.062 −0.113 −0.134 −0.129 −0.108 −0.082 −0.040

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.802 373 0.815 665 0.829 720 0.844 235 0.859 380 0.874 691 0.890 255 0.906 210 0.922 526 0.939 290 0.956 618

0.007 −0.036 −0.071 −0.122 −0.143 −0.137 −0.117 −0.087 −0.044

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.798 174 0.811 527 0.825 623 0.840 158 0.855 316 0.870 629 0.886 197 0.902 141 0.918 502 0.935 275 0.952 612

0.000 −0.046 −0.082 −0.133 −0.153 −0.146 −0.121 −0.092 −0.045

T = 333.15 K 1.4056 −0.139 1.4106 −0.127 1.4156 −0.115 1.4208 −0.093 1.4260 −0.059 1.4315 MIPA (1) + 2-butanol (2) T = 288.15 K 1.3995 1.4039 −0.071 1.4082 −0.140 1.4128 −0.188 1.4177 −0.207 1.4228 −0.204 1.4280 −0.187 1.4332 −0.167 1.4386 −0.136 1.4442 −0.092 1.4500 T = 293.15 K 1.3974 1.4018 −0.066 1.4062 −0.136 1.4107 −0.185 1.4156 −0.205 1.4207 −0.202 1.4259 −0.184 1.4312 −0.164 1.4366 −0.134 1.4422 −0.091 1.4480 T = 298.15 K 1.3952 1.3996 −0.064 1.4040 −0.132 1.4086 −0.181 1.4135 −0.201 1.4186 −0.197 1.4239 −0.181 1.4292 −0.162 1.4345 −0.131 1.4402 −0.089 1.4460 T = 303.15 K 1.3930 1.3974 −0.062 1.4019 −0.128 1.4065 −0.175 1.4114 −0.196 1.4165 −0.192 1.4218 −0.176 1.4271 −0.158 1.4325 −0.127 1.4382 −0.086 1.4440

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Article


10−3·ρ/ kg·m−3

106·VE/m3·mol−1

η/ mPa·s

Δη/ mPa·s

ΔG*E/ kJ·mol−1

−0.063 −0.126 −0.170 −0.188 −0.186 −0.170 −0.155 −0.123 −0.082

2.144 2.444 2.860 3.407 4.080 4.929 5.962 7.358 9.005 11.12 13.88

−0.877 −1.630 −2.257 −2.758 −3.081 −3.222 −2.996 −2.522 −1.575

−132.28 −203.50 −228.87 −244.32 −239.24 −231.12 −174.37 −138.58 −79.890

−0.061 −0.121 −0.164 −0.181 −0.180 −0.165 −0.150 −0.118 −0.078

1.818 2.083 2.436 2.887 3.435 4.114 4.924 6.014 7.280 8.894 10.96

−0.652 −1.209 −1.674 −2.040 −2.274 −2.380 −2.202 −1.849 −1.149

−103.90 −158.53 −179.69 −193.57 −192.24 −192.53 −143.65 −116.86 −68.014

−0.059 −0.116 −0.156 −0.174 −0.171 −0.160 −0.145 −0.113 −0.076

1.558 1.795 2.094 2.466 2.917 3.470 4.113 4.982 5.972 7.219 8.798

−0.490 −0.912 −1.264 −1.539 −1.708 −1.790 −1.644 −1.377 −0.854

−75.773 −121.00 −141.19 −154.06 −152.71 −160.48 −116.02 −96.742 −57.617

−0.058 −0.109 −0.145 −0.163 −0.159 −0.153 −0.138 −0.107 −0.068

1.348 1.556 1.814 2.124 2.499 2.954 3.477 4.164 4.955 5.938 7.166

−0.375 −0.697 −0.970 −1.176 −1.303 −1.363 −1.257 −1.046 −0.645

−54.797 −88.760 −108.92 −119.18 −119.00 −129.54 −97.671 −81.363 −48.422

−0.295 −0.550 −0.755 −0.920 −1.018 −1.052 −0.972 −0.804

−46.162 −77.994 −84.330 −99.354 −101.58 −104.06 −81.389 −67.187

102·ΔnD

nD

MIPA (1) + 1-butanol (2) T = 288.15 K 0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.793 881 0.807 298 0.821 466 0.836 030 0.851 209 0.866 532 0.882 111 0.898 074 0.914 445 0.931 229 0.948 577

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.789 487 0.803 008 0.817 246 0.831 847 0.847 055 0.862 397 0.877 993 0.893 970 0.910 355 0.927 181 0.944 515

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.784 988 0.798 619 0.812 957 0.827 606 0.842 848 0.858 232 0.873 856 0.889 829 0.906 227 0.923 110 0.940 423

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.780 380 0.794 161 0.808 592 0.823 300 0.838 586 0.853 992 0.869 642 0.885 646 0.902 064 0.918 943 0.936 293

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000

0.775 656 0.789 608 0.804 150 0.818 925 0.834 264 0.849 702 0.865 379 0.881 417 0.897 859

−0.006 −0.059 −0.097 −0.148 −0.167 −0.157 −0.131 −0.099 −0.049

−0.016 −0.076 −0.115 −0.167 −0.184 −0.172 −0.143 −0.107 −0.056

−0.027 −0.096 −0.138 −0.189 −0.206 −0.192 −0.157 −0.117 −0.064

−0.042 −0.119 −0.163 −0.215 −0.230 −0.212 −0.174 −0.129 −0.068

−0.060 −0.146 −0.193 −0.245 −0.257 −0.235 −0.193 −0.142

T= 1.3907 1.3952 1.3996 1.4043 1.4093 1.4144 1.4197 1.4250 1.4304 1.4362 1.4419 T= 1.3883 1.3929 1.3974 1.4021 1.4071 1.4123 1.4176 1.4229 1.4284 1.4342 1.4399 T= 1.3859 1.3905 1.3951 1.3999 1.4049 1.4102 1.4154 1.4208 1.4263 1.4322 1.4378 T= 1.3835 1.3881 1.3928 1.3977 1.4028 1.4080 1.4133 1.4187 1.4242 1.4302 1.4358 T= 1.3810 1.3857 1.3905 1.3955 1.4006 1.4059 1.4112 1.4166 1.4221

308.15 K

313.15 K

318.15 K

323.15 K

328.15 K −0.055 −0.101 −0.134 −0.152 −0.148 −0.144 −0.128 −0.100 1822

1.179 1.358 1.576 1.845 2.154 2.529 2.969 3.521 4.163



Article

Table 3. continued 10−3·ρ/ kg·m−3

x1

106·VE/m3·mol−1

102·ΔnD

nD

η/ mPa·s

Δη/ mPa·s

ΔG*E/ kJ·mol−1

4.947 5.915

−0.493

−40.201

−0.237 −0.441 −0.596 −0.730 −0.808 −0.823 −0.764 −0.628 −0.383

−38.830 −67.229 −59.736 −79.526 −84.163 −78.593 −65.108 −53.235 −31.980

MIPA (1) + 1-butanol (2) T = 288.15 K 0.8999 1.0000

0.914 764 0.932 130

0.0000 0.1003 0.2005 0.3000 0.3999 0.5000 0.6001 0.7000 0.8000 0.8999 1.0000

0.770 820 0.784 956 0.799 616 0.814 474 0.829 873 0.845 357 0.861 071 0.877 143 0.893 609 0.910 537 0.927 930

−0.076

−0.079 −0.174 −0.225 −0.278 −0.288 −0.262 −0.214 −0.157 −0.083

T = 328.15 K 1.4281 −0.061 1.4337 T = 333.15 K 1.3784 1.3832 −0.052 1.3881 −0.092 1.3932 −0.121 1.3983 −0.135 1.4036 −0.138 1.4090 −0.132 1.4144 −0.117 1.4200 −0.092 1.4260 −0.055 1.4315

1.054 1.211 1.398 1.637 1.897 2.212 2.590 3.042 3.571 4.210 4.986

a

Standard uncertainties u for each variables are u(T) = 0.01 K ; u(p) = 5 % ; u(x1) = 0.0001, and the combined expanded uncertainties uc are uc(ρ) = ± 1·10−2 kg·m−3; uc(nD) = ± 1·10−4; and relative standard uncertainty ur(η) = 0.015, with 0.95 level of confidence (k ≈ 2). N

∑ xinDi

ΔnD = nD −

atmospheric pressure are given in Table 3. Redlich−Kister equation fitting coefficients of the derived properties also are given in the Supporting Information (Table S1). Changes of excess molar volumes with composition at various temperatures for MIPA + 1-butanol and MIPA + 2butanol are presented in Figure 1. MIPA + 1-butanol excess volume data show negative values over entire composition range, with minimum value at x1 = 0.5. Temperature dependence is weak due to good packing of chain molecules of 1-butanol and MIPA. Excess volume of MIPA + 2-butanol shows S-curve at lower temperature, with positive values from x1 = 0 to 0.1, while with higher MIPA concentrations these values are negative. When temperature rises interstitial accommodation of molecules in mixture with 2-butanol as branched component prevails leading to more compact structure and more negative VE than in the mixture with 1butanol. Accordingly, obtained results show that changes of excess molar volumes are much more temperature dependent for system with 2-butanol in comparison to system with 1butanol. Such behavior might be a consequence of a steric hindrance of 2-butanol. At concentration range from x1 = 0.0 to x1 = 0.1, steric hindrance of 2-butanol molecule surrounded with other 2-butanol molecules is preventing good packing of molecules. As concentration of MIPA is increased, more and more of MIPA molecules are in contact with alcohol molecules enabling interstitial accommodation. This accommodation is possible due to relatively small difference in molar volume of MIPA and 2-butanol molecules. Deviations in refractive indices data show negative values over the entire composition range. Minimum values were obtained around x1 = 0.5 for MIPA + 1-butanol and x1 = 0.4 for MIPA + 2-butanol, as it can be seen in Figure 2. As in the case of excess molar volumes, temperature influence is more intense for the system with 2-butanol compared to that for the system with 1-butanol. Viscosity deviations for both mixtures show the same temperature dependence and negative values over the entire composition range (Figure 3). Slightly higher excess values are obtained for mixture with 1-butanol due to better molecular accommodation without steric hindrance.

(3)

i=1

while for the viscosity deviation Δη calculations the following equation was used: N

Δη = η −

∑ xiηi

(4)

i=1

In eqs 2, 3,and 4, N denotes a number of components; xi is a mole fraction of the component i in the mixture; Mi is its molecular weight; ρ, nD,and η are the measured densities, refractive indices and viscosities of a mixture, while ρi, nDi,and ηi are the measured densities, refractive indices and viscosities of a pure component i, respectively. In order to have deeper insight in the present molecular interactions in investigated binary mixtures, excess Gibbs free energy of activation of viscous flow (ΔG*E) has been calculated from experimental results of density and viscosity, using eq 5:30 N

ΔG*E = RT[ln ηV −

∑ xi ln ηiVi ] i=1

(5)

where R is the gas constant, T is thte temperature, xi is the mole fraction of component i, η and ηi are the viscosities of mixture and pure component i, while V and Vi are the molar volumes of a mixture and a pure component i. Excess volume data, deviations of refractive index and viscosity, and excess Gibbs free energy of activation of viscous flow were correlated using the Redlich−Kister relation: n

Y (x) = x1x 2 ∑ ai(x1 − x 2)i i=0

(6)

where Y and ai denote values of excess molar properties and parameters of Redlich−Kister relation. Experimental data of densities, refractive indices, viscosities, and calculated values of excess molar volumes, deviations in refractive indices, viscosity deviations and excess Gibbs free energy for activation of viscous flow of the MIPA (1) + 1-Butanol (2) and MIPA (1) + 2Butanol (2) system at T = (288.15 to 333.15) K and 1823



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Figure 2. Δ nD values of (a) MIPA (1) + 1-butanol (2) and (b) MIPA (1) + 2-butanol (2) at temperatures ■, 288.15 K; ●, 298.15 K; ▲, 308.15 K; ◆, 318.15 K; ★, 328.15 K. The lines present the results calculated by eq 6.

Figure 1. VE values of (a) MIPA (1) + 1-butanol (2) and (b) MIPA (1) + 2-butanol (2) at temperatures ■, 288.15 K; ●, 298.15 K; ▲, 308.15 K; ◆, 318.15 K; ★, 328.15 K. The lines present the results calculated by eq 6.

In addition, changes of excess Gibbs free energy of activation of viscous flow with composition at various temperatures for MIPA + 1-butanol and MIPA + 2-butanol are presented in Figure 4. Generally, the positive ΔG*E values indicate presence of molecular interactions between unlike molecules, while negative values indicate that dominant molecular interactions are consequence of dispersion forces. Negative ΔG*E values are reported for entire composition range of 1-butanol and 2butanol mixtures with MIPA. Minimum values were received around composition of x1=0.35. Minimum value of excess Gibbs free energy of activation of viscous flow for mixture of MIPA and 2-butanol are higher than with 1-butanol, which could be consequence of steric hindrance of 2-butanol. In order to investigate effects of molecular structure of solutes on alcohol structure, a thermal expansion coefficient was used.31 According to this approach solutions can be analyzed as partly structured liquids, represented by mixtures of two species. The first is the species with relatively low density, a bulky “ice like“, while the other, denser species, is formed by bending or deformation of hydrogen bonds that are crucial for maintaining a bulky structure. Hepler31 suggested that the sign of the second derivative of the partial molar volume at infinite

dilution of the solute, with respect to the temperature change (d2V̅ ∞/dT2), can be used for classification of solutes as “structure makers” or “structure breakers”, where a positive sign is associated for structure making solute and a negative sign for structure breaking solute. Although the Hepler thermal expansion approach was initially used for aqueous solutions of alcohols and aqueous solutions of different organic components,32,33 the same analogy was used for investigation of the applicability of the proposed approach on alcohol solutions of alkanol amines. First, molar volumes of pure components were calculated based on densities of pure components. The apparent molar volumes of alcohols (Vap,2) and MIPA (Vap,1) were calculated using the following equations:

1824

Vap,2 = V 20 +

VE (1 − x1)

(7)

Vap,1 = V10 +

VE x1

(8)



Article

Figure 4. ΔG*E values of (a) MIPA (1) + 1-butanol (2) and (b) MIPA (1) + 2-butanol (2) at temperatures ■, 288.15 K; ●, 298.15 K; ▲, 308.15 K; ◆, 318.15 K; ★, 328.15 K. The lines present the results calculated by eq 6.

Figure 3. Δη values of (a) MIPA (1) + 1-butanol (2) and (b) MIPA (1) + 2-butanol (2) at temperatures: ■, 288.15 K; □, 293.15 K; ●, 298.15 K; ○, 303.15 K; ▲, 308.15 K; Δ, 313.15 K; ◆, 318.15 K; ◊, 323.15 K; ★, 328.15 K; ☆, 333.15 K. The lines present the results calculated by eq 6.

V01

Based on the presented experimental results, viscosity data could be well represented by the Arrhenius equation:

V02

where and are the molar volumes of pure MIPA and alcohols, respectively. Extrapolation of eq 7 using x1 = 1 lead to partial molar volumes of alcohol at infinite dilution (V∞ 2 ) and similarly for eq 8, if x1 = 0, partial molar volumes of MIPA at infinite dilution (V∞ 1 ) were obtained. Obtained partial molar volumes at infinite dilution and molar volumes of pure MIPA, 1-butanol and 2-butanol are listed in Table 4. The thermal expansion model proposed by Hepler31 shows that addition of MIPA to either 1-butanol or 2-butanol has no effect on the change of molecular structure of both alcohols. The first drivative of partial molar volume of MIPA shows linear temperature dependence, and accordingly, the second drivative will be equal to zero. Therefore, MIPA is “neutral” as a structure making or structure braking component. Since all values of molar volume at infinite dilution were smaller than the corresponding molar volumes of pure components at the same temperatures, such behavior could be only described by either newly formed hydrogen or dipole−dipole bonds or better molecular structure packing.

η = η0e Ea / RT

(9)

After linearization, eq 9 could be given in the following form: ln(η /mPa ·s) = ln(η0 /mPa·s) +

Ea RT

(10)

where η is the viscosity in mPa·s, η0 is the system dependent constant, Ea is the activation energy for viscous flow in kJ· mol−1, R is the gas constant in kJ·mol−1·K−1, and T is the temperature in K. Values of system dependent constant, as well as activation energy for various temperatures and composition range is given in Table 5. As it can be seen from values presented within Table 5, the activation energy for pure 1-butanol is around 19.40 kJ·mol−1, while an increase in concentration of MIPA caused an increase in activation energy for pure MIPA. According to lattice theory, liquids are composed of a matrix of molecules and vacancies which are scattered throughout. 1825



Article

Table 4. Partial Molar Volumes at Infinite Dilution of MIPA in 1-Butanol or 2-Butanol, V∞ 1 , Partial Molar Volumes at Infinite Dilution of 1-Butanol or 2-Butanol in MIPA, V∞ 2 , and Molar Volumes of Pure Compounds from (288.15 to 333.15) K at Atmospheric Pressure T/K

3 −1 106·V∞ 1 /m ·mol

288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15

77.03 77.37 77.71 78.04 78.39 78.73 79.08 79.43 79.79 80.16

288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15

77.63 78.09 78.35 78.62 78.88 79.11 79.34 79.55 79.74 79.92

3 −1 106·V∞ 2 /m ·mol

MIPA (1) + 1-butanol (2) 90.18 90.61 91.04 91.49 91.94 92.40 92.87 93.35 93.84 94.34 MIPA (1) + 2-butanol (2) 90.96 91.38 91.73 92.28 92.75 93.20 93.66 94.12 94.65 95.17

0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.5997 0.7000 0.7998 0.8997 1.0000 0.0000 0.1000 0.2005 0.3000 0.3999 0.5000 0.5997 0.7000 0.7998 0.8997 1.0000

ln(η0/mPa·s)

(Ea/R)/K

MIPA (1) + 1-butanol (2) −6.891 04 2332.87 −6.658 70 2306.61 −7.283 26 2555.88 −7.835 40 2779.40 −8.356 30 3002.02 −8.974 51 3253.84 −9.602 09 3513.09 −10.2411 3773.95 −10.9432 4057.56 −11.6051 4328.80 −12.3346 4624.21 MIPA (1) + 2-butanol (2) −9.479 18 3162.28 −9.044 10 3067.03 −9.004 88 3103.05 −9.142 94 3199.95 −9.524 22 3374.80 −9.880 55 3543.70 −10.3330 3743.57 −10.7801 3946.22 −11.2512 4154.82 −11.7789 4383.89 −12.3347 4624.21

106·V02/m3·mol−1

77.87 78.19 78.51 78.84 79.18 79.52 79.87 80.22 80.58 80.94

91.13 91.56 91.99 92.43 92.88 93.33 93.80 94.28 94.77 95.27

77.87 78.19 78.52 78.85 79.18 79.52 79.87 80.22 80.58 80.94

91.45 91.90 92.38 92.86 93.36 93.88 94.42 94.98 95.56 96.16

butanol reduces the OH−N interactions. Also, an essential factor leading to the negative VE values rises from different molecular sizes of the binary components (molar volumes at 298.15 K for pure compound are 78.51·10−6 m3·mol−1 for MIPA, 91.99·10−6 m3·mol−1 for 1-butanol, and 92.36·10−6 m3· mol−1 for 2-butanol) suggesting that molecules pack well into each other’s structures resulting in a contraction in volume and, hence, negative VE values. On the other hand, the presence of one methyl and one ethyl group at 2° carbon atom in 2-butanol and one propyl group at 1° carbon atom in 1-butanol creates steric hindrance near the OH group in the order 2-butanol >1-butanol. Namely, this sterically hindered effect of branched alcohol gives some smaller negative values of mixture with 2-butanol at lower investigated temperatures. Free activation energy is required for molecule movement into vacancies and overcoming the energy barrier. Since both 1butanol and 2-butanol have the same molecular weight, theoretically they have same energy barrier due to the same size of the vacancies. Activation energies presented in Table 5, show that activation energy for 2-butanol (26.291 kJ·mol−1) is about 35 % higher than for 1-butanol (19.395 kJ·mol−1). This increase of activation energy is a consequence of the ability of rotation of linear molecule of 1-butanol, while branching of 2butanol prevents this rotation, making it more rigid to viscous flow. The activation energy for pure MIPA is around 38.45 kJ· mol−1 showing good agreement comparing to the values of Rayer5 (38.97 kJ·mol−1). The difference in the obtained results could be explained as a consequence of different measuring techniques and purities of used components. Value of activation energy of pure MIPA is much higher than value of other primary alkanol amines, such as monoethanolamine, MEA (29.2 kJ·mol−1)34 and is close to the values of tertiary alkanol amine (38.0 kJ·mol−1), e.g. methyldiethanolamine, MDEA.7,11 This could be a consequence of formation of new stronger

Table 5. Values of System Dependent Constant and Activation Energy for Flow of MIPA (1) + 1-Butanol (2) and MIPA (1) + 2-Butanol (2) over the Entire Composition and Temperature Range Calculated from eq 10 x1

106·V01/m3·mol−1

Ea/kJ·mol−1 19.395 19.177 21.250 23.108 24.959 27.052 29.208 31.377 33.735 35.990 38.446 26.291 25.499 25.799 26.604 28.058 29.462 31.124 32.809 34.543 36.448 38.446

During viscous flow, group or single molecules take place in vacancies followed by simultaneous formation of new vacancies. Negative VE values indicate the presence of chemical interactions between unlike molecules in mixtures. The mixture with 2-butanol becomes less negative bearing in mind that 21826



Article

hydrogen bonds. Due to presence of amino functional groups, as well as OH groups within alkanol amines and alcohols, there are several possibilities of formation of hydrogen bonds between alkanol amine and 1-butanol and alkanol amine and 2-butanol, but also the formation of intra hydrogen bonding within species. Enthalpies of different hydrogen bonds are presented in Table 6.35,36 From Table 6 it could be seen that the value of the Table 6. Typical Enthalpies for Different Types of Hydrogen Bonds34,35 type of hydrogen bond

entalpy/kJ·mol−1

F−H···F O−H···N O−H···O N−H···N N−H···O

161.5 29.0 21.0 13.0 8.0

Figure 5. Infrared spectra of pure MIPA (black), pure 1-butanol (magenta), and the mixture of MIPA + 1-butanol with xMIPA = 0.3 (red), xMIPA = 0.5 (green), xMIPA = 0.7 (blue), and xMIPA = 0.9 (cyan).

activation energy for pure MIPA (38.44 kJ·mol−1) could not be only due to hydrogen bonds between the nitrogen atom of the first molecule and the hydrogen atom of the OH group of the second molecule of MIPA. It is most likely that hydrogen bonds are taking place simultaneously on two different ends of opposite oriented molecules of MIPA, forming first a hydrogen bond between nitrogen of the first molecule and hydrogen (from OH group) of second molecule of MIPA. A second hydrogen bond is formed between oxygen (from OH group) of the first molecule and hydrogen (from amino group) of the second molecule of MIPA. The sum of these two hydrogen bonds is around 37 kJ·mol−1, which is close to results received by experiment. Additional energy need (1.44 kJ·mol−1) could be a consequence of conformation reasons. Presented values of pure 1-butanol and 2-butanol suggest the presence of hydrogen bonds, since both alcohols in hydrogen bonds formation could behave as proton donors and acceptors. Recent studies37,38 showed the ability of a water molecule to participate in multiple hydrogen bonding, known as bifurcation property. According to these studies, one molecule of water is participating in 3.69 hydrogen bonds. With the goal to describe the molecular structure, interactions and presence of potential new hydrogen bonds, FT-IR spectroscopy analysis was performed. A NICOLET 6700 FT-IR spectrometer was utilized to record the FT-IR spectra of pure components and binary mixtures. For each spectrum 32 scans were made with a selected resolution of 2 cm−1. All of the spectroscopic measurements were carried out at 298.15 K. Negative values of excess volumes indicate changes in molecular structure and intermolecular bonding. If this is due to newly formed intermolecular hydrogen bonding, it must be detected within FT-IR spectrum with change of concentration. As ncan be seen from Figures 5 and 6, both spectra showed that there is no change in positions of measured peaks. The difference in the spectra is noticed only in the intensity of the peaks which is a consequence of concentration change. Presence of potentially newly formed intermolecular hydrogen bonds, between alkanol amine and alcohols would be manifested within FT-IR spectra, through concentration or elongation of OH bond and shift of the characteristic wavenumber. From Figure 6, characteristic wavenumbers were observed for the OH group for 1-butanol (3340 cm−1) and 2-butanol (3345 cm−1), which are a consequence of the stretch of the OH bond due to self-association of molecules.

Figure 6. Infrared spectra of pure MIPA (black), pure 2-butanol (magenta), and the mixture of MIPA + 2-butanol with xMIPA = 0.3 (red), xMIPA = 0.5 (green), xMIPA = 0.7 (blue), and xMIPA = 0.9 (cyan).

Since for both systems with 1-butanol and 2-butanol, no shift of wavenumber or concentration-elongation of the OH bond was detected throughout the entire composition range, an assumption can be made that there are no newly formed intermolecular hydrogen bonds between alkanol amine and alcohols. Shifting of peaks, present mainly due to broad OH and N−H functional groups, occurs if the concentration range is changed from pure alcohols toward pure MIPA. Values of transmittance are given as normalized transmittance. All lines of obtained FT-IR spectra are slightly shifted so they can be easily compared.

4. CONCLUSION Densities, refractive indices, and viscosities of the binary mixtures of MIPA and 1-butanol and MIPA and 2-butanol have been measured experimentally over the (288.15 to 333.15) K temperature range. Criteria proposed by Hepler has shown that addition of MIPA to 1-butanol or 2-butanol had no effect on change of alcohols structures. All values of molar volume at 1827



Article

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infinite dilution were smaller than the corresponding molar volumes of pure components at the same temperatures. Linearization of the Arrhenius equation was introduced in order to explain the possible formation of hydrogen bonds, as well as its energy quantification. Negative values of excess volumes might be a consequence of accommodation of MIPA molecules, occupying the void spaces in the structure of alcohol lattice similar to aqueous solutions. FT-IR analysis also confirmed an unchanged molecular structure of both alcohols when MIPA is introduced in the mixture. As a consequence, negative values of all excess properties are reported in the entire concentration range. Negative values of excess molar volume, viscosity deviation, excess Gibbs free energy of activation of flow, and results received through experimental measurements performed by FT-IR spectroscopy offer a clear conclusion that molecular interactions between MIPA and 1- and 2-butanol, if they exist, are less likely to occur or are very weak. Such behavior of investigated properties of binary mixtures could be a consequence of the predominance of structural effects rather than interactional effects.

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ASSOCIATED CONTENT

S Supporting Information *

Tables S1 lists parameters of eq 6 for the investigated properties (VE, ΔnD, Δη, and ΔG*E) and σ for MIPA (1) + 1-butanol (2) or +2-butanol (2) mixtures from (288.15 to 333.15) K. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Phone: +381 11 3370523. Fax: +381 11 3370387. E-mail: [email protected]. Funding

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). Notes

The authors declare no competing financial interest.

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REFERENCES

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