Thermodynamic and Spectral Studies of Molecular Interactions in

Jul 21, 2015 - This article presents densities, ρ, and speeds of sound, u, of 1-butoxy-2-propanol CH3(CH2)3OCH2CH(OH)CH3 with alcohols, viz., 1-hexan...
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Thermodynamic and Spectral Studies of Molecular Interactions in Binary Liquid Mixtures of 1‑Butoxy-2-propanol with 1‑Alcohols Gyan Prakash Dubey* and Prabjot Kaur* Department of Chemistry, Kurukshetra University, Kurukshetra-136119, India S Supporting Information *

ABSTRACT: This article presents densities, ρ, and speeds of sound, u, of 1-butoxy-2propanol CH3(CH2)3OCH2CH(OH)CH3 with alcohols, viz., 1-hexanol CH3(CH2)5OH, 1octanol CH3(CH2)7OH, and 1-decanol CH3(CH2)9OH at 293.15, 298.15, 303.15, 308.15, and 313.15 K over the entire composition range. These experimental data of density and speed of sound were used to calculate the values of excess molar volumes, VEm, excess molar isentropic compression, κES,m, and deviation in speeds of sound, μD. The calculated excess properties are discussed in terms of molecular interaction between present investigated binary mixtures and with Fourier transform infrared spectroscopy. These excess functions and their deviations in sound velocity have also been correlated using Redlich−Kister type polynomial equation by the method of least-squares for the estimation of the binary coefficients and the standard errors. The calculated properties were interpreted in terms of molecular interactions and structural effects.

1. INTRODUCTION For characterization of interactions between the mixture component molecules, thermophysical properties are a constitutive information source. In the presence of hydrogen-bond network significantly change is seen in properties of these systems. Solvents with a spatial network of hydrogen bonds are characterized by relatively large free volume and small values of compressibility. Alkoxy alkanols are the combinations of ethers, alcohols, and hydrocarbon chains in one molecule, providing versatile solvency characteristics with polar and nonpolar properties.1,2 These substances possess both hydrophilic and hydrophobic functional groups which accounts for their frequent uses as cosolvents in organic/water product formulations and cleaning solutions. Alcohols also play an important role in many chemical reactions due to the ability to undergo self-association with manifold internal structures and are in wide use in industry and science as reagents, solvents, and fuels and attract great attention as useful solvents in the green technology.3 Alkoxy alkanols + alcohol mixtures are industrially relevant and used as gasoline additives due to their octane number enhancing and pollution reducing properties. From a theoretical point of view, the study of alkoxy alkanols + alcohols mixtures is particularly important due to their complexity, related to the partial destruction of H-bonds between alcohols molecules by the active alkoxy alkanol molecules and to the new −OH−O bonds created upon mixing.4,5 The binary mixtures of (alkoxy alkanol + alcohols) have been studied extensively and systematically in recent years.6−9 The present work is part of a general experimental and theoretical investigation on alkoxy alkanol +1-alcohols mixtures. As far we know there is no experimental data of densities and speeds of sound on a binary mixture of 1-butoxy-2-propanol with higher alcohols (1-hexanol, 1-octanol, and 1-decanol) that have been reported in the literature. Recently, several authors10−13 have studied the thermodynamic studies of the binary mixture of © XXXX American Chemical Society

1-butoxy-2-propanol with lower alcohols (ethanol, 1-butanol and 2-butanol). Therefore, it offers us a good opportunity to study the mixing behavior of 1-butoxy-2-propanol with higher alcohols. In continuation of our earlier work on the studies of molecular interaction in nonaqueous binary mixtures containing alcohols,14−16 we report the result of our study on the binary mixtures of 1-butoxy-2-propanol with higher alcohols (1hexanol, 1-octanol,and 1-decanol). In this paper we report the densities, ρ, and speeds of sound, u, for the binary liquid mixtures containing 1-butoxy-2-propanol with higher alcohols (1-hexanol, 1-octanol, and 1-decanol) at temperatures of (293.15, 298.15, 303.15, 308.15, and 313.15) K over the entire composition range. From the data, thus obtained, various derived properties such as excess molar volumes,VEm, excess molar isentropic compression, κES,m, and deviation in speeds of sound, uD, has been calculated. These excess properties reflect of the origin of the nonideality in the mixture, especially in the mixtures that show strong interactions between the unlike molecules.17 The work has been mainly concerned with the study of the changes arising from increasing the alkyl chain length of the alcohol molecule (n = 6, 8, and 10): CnH2n+1OH. Furthermore, FT-IR spectra of the pure components and that of various binary mixtures over the different compositions range at room temperature were recorded. The FT-IR spectroscopy is a successful method to probe the molecular structure of association effects among molecules. These techniques offer the advantages to measure the association properties and hydrogen bonding capability, to assess interactions by analyzing band shifts and shape.15 Received: January 9, 2015 Accepted: July 8, 2015

A

DOI: 10.1021/acs.jced.5b00031 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Specification of Chemical Samples

a

chemical name

CAS no.

provenance

initial mass fraction purity

1-butoxy-2-propanol 1-hexanol 1-octanol 1-decanol

5131-66-8 111-27-3 111-87-5 112-30-1

Sigma-Aldrich, India SD. Fine Chemicals, India SD. Fine Chemicals, India SD. Fine Chemicals, India

0.995 0.989 0.987 0.987

purification method

final mass fraction purity

analysis method

distillation distillation distillation

0.995 0.995 0.998 0.995

GCa GCa GCa

Gas chromatography.

2. EXPERIMENTAL SECTION 2.1. Materials. 1-Butoxy-2-propanol was furnished by SigmaAldrich. All alcohols, i.e., 1-hexanol (analytical reagent grade), 1-

comparing the experimental data of pure liquids with the corresponding literature values (Table 2). 2.4. FT-IR Measurements. FT-IR measurements of binary liquid mixtures of 1-butoxy-2-propanol with 1-alcohols at different concentrations were recorded using ABB Horizon (MB 3000) spectrometer, which have resolution better than 4 cm−1 and maximum signal-to-noise ratio (root-mean-square, 60 s, 4 cm−1, at peak response); 50 000:1. All data analysis was performed in Microsoft Excel and Origin 6.1 software.

Table 2. Comparison of Experimental Values of Density (ρ) and Speed of Sound (u) of Pure Liquids with the Corresponding Literature Values at Temperatures of 298.15 K and Atmospheric Pressurek ρ·10−3/kg·m−3 compound

exp.

1-butoxy-2-propanol 1-hexanol

0.874632 0.815652

1-octanol

0.821877

1-decanol

0.826489

u/m·s−1

lit. a

0.874630 0.81565c 0.81565d 0.82187e 0.82181d 0.82647f 0.82637g

exp. b

3. RESULTS AND DISCUSSION Experimental data of density and speed of sound are given in Table 3. The experimental values of density are used to calculate the excess molar volumes, VEm, of the mixtures as

lit. a

1260.9 1303.54 1347.32 1379.43

b

1263.00 1303.3h 1303.3i 1348.0j 1347.43i 1380.0h 1380.01i

2

VmE =

∑ xiMi(ρ−1 − ρi−1)

(1)

i=1

where Mi and ρi are the molar mass and density of pure components, respectively, and ρ is the density of the mixture. The molar isentropic compression, κS,m have been calculated from the relation:

a

Dubey et al.16 bPal et al.10 cPena et al.21 dJimaz et al.22 eIloukhani et al.23 fDubey et al.24 gDzida25 hMarks et al.24 iKandary27 jLobe et al.28 k Standard uncertainties s are s(ρ) = 5.10−2/(kg m‑3), s(u) = 0.1/(m s‑1).

κS,m = −(∂V /∂p)s = VκS =

∑ xiMi /(ρu)2

(2)

where V is the molar volume and κS = 1/(ρu ) is the isentropic compression. The excess molar isentropic compression has been calculated as 2

octanol (analytical reagent grade), and 1-decanol (laboratory reagent grade) were procured from SD Fine Chemicals, India. All chemicals were fractionally distilled and dried over 0.4 nm molecular sieves. The mass fraction purities tested by gas chromatography. Karl Fischer analysis of the chemicals shows water content 0.02%. The details of chemicals used in the present work was also given in Table 1 and the purities of solvents were further ascertained by comparing their densities and speeds of sound at 298.15 K with values reported in the literature10,18−26 as shown in Table 2. 2.2. Methods. Each binary mixture were prepared by weighing appropriate amounts of 1-butoxy-2-propanol and each alcohol mentioned above on an A&D Company limited electronic balance (Japan, model GR-202) electronic balance, with a precision of ± 0.01 mg, by syringing each component into airtight narrow mouthed stoppered bottles to minimize evaporation losses. The pure components were separately degassed shortly before sample preparation. The probable error in mole fraction was estimated to be less than ± 1·10−4. 2.3. Density and Speed of Sound Measurements. Densities ρ and speeds of sound u were measured by using a digital vibrating tube density and speed of sound analyzer (Anton Paar DSA 5000). The details of calibration of the instrument and the experimental procedure have been described elsewhere.14−16 The precision in density and speed of sound measurements are ± 1·10−3 kg·m−3 and ± 1·10−2 m·s−1, respectively. The repeatability and the uncertainty in experimental measurements have found to be lower than (± 2·10−3 and 5·10−2) kg·m−3 for the density and (± 1·10−2 and 1·10−1) m s−1 for the speed of sound. The experimental measurements of ρ and u were ascertained by

id E κS,m = κS,m − κS,m

(3)

where κidS,m is defined by Kiyohara and Benson: id κS,m =

29−34

∑ xi[κS,*i − TAP,*i{(∑ xiAP,*i /∑ xiAP,*i /∑ xiCP,*i) − (AP,*i /C P,*i)}]

(4)

where AP,i * (=Vm,i * αP,i * ) is the product of molar volume and the isobaric expansion, CP,i * the molar isobaric heat capacity, κS,i * the product of the molar volume, Vm,i * , and the isentropic compression, κS,i, of the pure liquid component i and T is the temperature. The calculated values of VEm and κES,m are presented in Table 4. The uncertainty of reported excess molar volumes and isentropic compression were estimated using the error propagation formula to be close to (± 3·10−3 and ± 2·10−3) kg· m−3. The deviations in speeds of sound from their values in an ideal mixture are calculated from equation:

u D = u − u id

(5)

id

where u was calculated using the equation: id u id = (Vmid)1/2 (KS,m )−1/2 ∑ ϕρ i i

(6)

i

where φi is the volume fraction of the ith component. B

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Table 3. Densities (ρ), Speeds of Sound (u) for (1-Butoxy-2-propanola + 1-Alcohols) at Different Temperatures and Atmospheric Pressureb ρ·10−3/kg·m−3 x1

a

293.15 K

298.15 K

303.15 K

0 0.0518 0.1036 0.1519 0.2018 0.2517 0.3050 0.4039 0.5050 0.6125 0.7004 0.8053 0.8563 0.8999 0.9525 1

0.819239 0.823008 0.826694 0.830079 0.833500 0.836866 0.840350 0.846625 0.852782 0.859007 0.863833 0.869405 0.871983 0.874142 0.876729 0.879031

0.815652 0.819382 0.823015 0.826359 0.829737 0.833058 0.836501 0.842692 0.848766 0.854908 0.859669 0.865156 0.867697 0.869839 0.872379 0.874632

0.812043 0.815740 0.819322 0.822624 0.825955 0.829228 0.832626 0.838734 0.844723 0.850781 0.855462 0.860881 0.863380 0.865487 0.867998 0.870204

0 0.0529 0.1119 0.1505 0.2023 0.2537 0.3044 0.3997 0.4991 0.6003 0.7046 0.8011 0.8455 0.9049 0.9507 1

0.825337 0.828126 0.831221 0.833282 0.835989 0.838700 0.841355 0.846378 0.851646 0.857051 0.862686 0.867950 0.870382 0.873676 0.876245 0.879031

0.821877 0.824628 0.827672 0.829699 0.832362 0.835025 0.837633 0.842569 0.847747 0.853058 0.858589 0.863764 0.866154 0.869381 0.871903 0.874632

0.818400 0.821112 0.824102 0.826099 0.82871 0.831327 0.833892 0.838739 0.843823 0.849037 0.854468 0.859542 0.861888 0.865059 0.867531 0.870204

0 0.0501 0.1066 0.1507 0.253 0.3119 0.3516 0.4159 0.5018 0.6016 0.7014 0.8012 0.8541 0.9003 0.9507 1

0.829898 0.831883 0.834139 0.835913 0.840195 0.842719 0.844462 0.847357 0.851375 0.856262 0.861444 0.866957 0.869997 0.872764 0.875842 0.879031

0.826489 0.828442 0.830661 0.832399 0.836598 0.839079 0.840791 0.843619 0.847552 0.852349 0.857425 0.862821 0.865805 0.868514 0.871538 0.874632

0.823069 0.824990 0.827171 0.828871 0.832987 0.835422 0.837092 0.839865 0.843715 0.848411 0.853382 0.858662 0.861591 0.864233 0.867195 0.870204

um·s−1 308.15 K

313.15 K

293.15 K

1-butoxy-2-propanol (1) + 1-hexanol (2) 0.808402 0.804743 1320.38 0.812058 0.808363 1317.97 0.815594 0.811850 1315.65 0.818853 0.815060 1313.51 0.822136 0.818301 1311.34 0.825367 0.821486 1309.19 0.828711 0.824784 1306.98 0.834746 0.830729 1302.79 0.840644 0.836543 1298.62 0.846611 0.842419 1294.21 0.851232 0.846971 1290.65 0.856563 0.852220 1286.58 0.859027 0.854652 1284.55 0.861108 0.856680 1282.81 0.863577 0.859128 1280.78 0.865737 0.861241 1278.98 1-butoxy-2-propanol (1) + 1-octanol (2) 0.814903 0.811385 1364.08 0.817574 0.814012 1359.61 0.820510 0.816895 1354.59 0.822463 0.818817 1351.25 0.825035 0.821337 1346.83 0.827610 0.823864 1342.45 0.830125 0.826335 1338.16 0.834878 0.831000 1330.08 0.839868 0.835893 1321.69 0.844985 0.840911 1313.12 0.850315 0.846134 1304.28 0.855293 0.851009 1296.04 0.857584 0.853261 1292.24 0.860700 0.856315 1287.14 0.863123 0.858689 1283.21 0.865737 0.861241 1278.98 1-butoxy-2-propanol (1) + 1-decanol (2) 0.819635 0.816188 1396.65 0.821526 0.818053 1391.49 0.823665 0.820143 1385.62 0.825325 0.821774 1380.88 0.829359 0.825713 1370.03 0.831733 0.828039 1363.47 0.833370 0.829639 1358.78 0.836084 0.832294 1351.35 0.839850 0.835972 1341.42 0.844447 0.840464 1329.78 0.849310 0.845217 1317.66 0.854473 0.850260 1304.99 0.857336 0.853057 1298.27 0.859925 0.855586 1292.30 0.862813 0.858408 1285.67 0.865737 0.861241 1278.98

298.15 K

303.15 K

308.15 K

313.15 K

1303.54 1301.11 1298.74 1296.57 1294.34 1292.14 1289.82 1285.51 1281.22 1276.66 1272.98 1268.79 1266.71 1264.89 1262.79 1260.90

1286.68 1284.24 1281.82 1279.59 1277.32 1275.04 1272.66 1268.24 1263.83 1259.17 1255.38 1251.06 1248.93 1247.08 1244.9 1242.94

1270.00 1267.53 1265.03 1262.76 1260.41 1258.04 1255.59 1251.04 1246.48 1241.66 1237.77 1233.31 1231.12 1229.23 1226.96 1224.91

1253.54 1251.02 1248.46 1246.13 1243.69 1241.25 1238.70 1233.99 1229.28 1224.33 1220.31 1215.70 1213.44 1211.50 1209.17 1207.02

1347.32 1342.77 1337.68 1334.37 1329.92 1325.5 1321.15 1312.91 1304.33 1295.56 1286.54 1278.19 1274.31 1269.16 1265.18 1260.90

1330.99 1326.37 1321.17 1317.79 1313.24 1308.73 1304.28 1295.88 1287.14 1278.21 1269.02 1260.53 1256.59 1251.36 1247.31 1242.94

1314.28 1308.65 1303.42 1300.02 1295.45 1290.91 1286.44 1278.01 1269.23 1260.27 1251.07 1242.55 1238.60 1233.37 1229.31 1224.91

1297.72 1293.05 1287.75 1284.23 1279.55 1274.88 1270.28 1261.67 1252.68 1243.54 1234.12 1225.38 1221.34 1215.9 1211.66 1207.02

1379.43 1374.26 1368.38 1363.74 1352.70 1346.23 1341.82 1334.54 1324.54 1312.58 1300.23 1287.51 1280.58 1274.42 1267.65 1260.90

1362.40 1357.19 1351.25 1346.56 1335.39 1328.87 1324.41 1317.06 1306.98 1294.93 1282.49 1269.69 1262.73 1256.54 1249.73 1242.94

1345.62 1340.35 1334.32 1329.56 1318.25 1311.64 1307.13 1299.70 1289.50 1277.33 1264.78 1251.87 1244.85 1238.61 1231.76 1224.91

1329.07 1324.30 1318.30 1313.40 1302.10 1295.29 1290.47 1282.75 1272.51 1260.33 1247.68 1234.63 1227.69 1221.41 1214.41 1207.02

Dubey et al.16 bStandard uncertainties s are s(ρ) = 5·10−2/(kg m‑3), s(u) = 0.1/(m·s−1).

The composition dependence of VEm, κES,m, and uD for each mixture are correlated by Redlich−Kister polynomial equation:35

where p is number of estimated parameters and Ai’s are polynomial coefficients obtained by fitting eq 7 to the experimental results using a least-squares regression method with all points weighted equally. The standard deviation (σ) was calculated using the relation:

p

Y (x) = x1x 2 ∑ Ai (x 2 − x1)i − 1 i=1

(7) C

DOI: 10.1021/acs.jced.5b00031 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 4. Excess Molar Volumes (VEm) and Excess Molar Isentropic Compression (κES,m) for (1-Butoxy-2-propanol + 1-Alcohols) at Different Temperatures and Atmospheric Pressure VEm·106/m3·mol−1 x1

293.15 K

298.15 K

0.0518 0.1036 0.1519 0.2018 0.2517 0.3050 0.4039 0.5050 0.6125 0.7004 0.8053 0.8563 0.8999 0.9525

−0.0108 −0.0222 −0.0342 −0.0457 −0.0586 −0.0668 −0.0795 −0.0909 −0.0899 −0.0763 −0.06 −0.0431 −0.0269 −0.0121

−0.0124 −0.0228 −0.0356 −0.0471 −0.0601 −0.0691 −0.0819 −0.0933 −0.0927 −0.0795 −0.0622 −0.0452 −0.0313 −0.0149

0.0529 0.1119 0.1505 0.2023 0.2537 0.3044 0.3997 0.4991 0.6003 0.7046 0.8011 0.8455 0.9049 0.9507

−0.0140 −0.0242 −0.0351 −0.0376 −0.0411 −0.0395 −0.0354 −0.0283 −0.0184 −0.0101 −0.0027 0.0018 0.0041 0.0027

−0.0155 −0.0258 −0.0368 −0.0397 −0.0427 −0.0409 −0.0367 −0.0299 −0.0203 −0.0112 −0.0048 −0.0007 0.0029 0.0016

0.0501 0.1066 0.1507 0.2530 0.3119 0.3516 0.4159 0.5018 0.6016 0.7014 0.8012 0.8541 0.9003 0.9507

−0.0050 −0.0030 0.0031 0.0129 0.0248 0.0320 0.0423 0.0549 0.0663 0.0681 0.0577 0.0508 0.0384 0.0268

−0.0070 −0.0060 0.0005 0.0101 0.0205 0.0270 0.0391 0.0527 0.0623 0.0643 0.0549 0.0468 0.0348 0.0216

303.15 K

κES,m/mm3·mol·MPa−1 308.15 K

n

σ = [∑ {Y (x)exptl − Y (x)cal }2 /(n − p)]1/2 i=1

313.15 K

1-butoxy-2-propanol (1) + 1-hexanol (2) −0.0149 −0.0163 −0.0186 −0.0249 −0.0268 −0.0291 −0.038 −0.0402 −0.0421 −0.0495 −0.0513 −0.0538 −0.0619 −0.0642 −0.0668 −0.0712 −0.0724 −0.0753 −0.0843 −0.0877 −0.0901 −0.0957 −0.0980 −0.1008 −0.0955 −0.0972 −0.0995 −0.0802 −0.0833 −0.0857 −0.0647 −0.0664 −0.0685 −0.0469 −0.0489 −0.0521 −0.0324 −0.0354 −0.0348 −0.0173 −0.0195 −0.0219 1-butoxy-2-propanol (1) + 1-octanol (2) −0.0170 −0.0182 −0.0191 −0.0270 −0.0281 −0.0293 −0.0389 −0.0384 −0.0403 −0.0408 −0.0419 −0.0430 −0.0439 −0.0461 −0.0473 −0.0427 −0.0442 −0.0460 −0.0381 −0.0391 −0.0413 −0.0312 −0.0323 −0.0343 −0.0215 −0.0228 −0.0247 −0.0127 −0.0143 −0.0159 −0.0053 −0.0073 −0.0080 −0.0012 −0.0014 −0.0034 0.0015 0.0002 −0.0017 0.0009 −0.0005 −0.0021 1-butoxy-2-propanol (1) + 1-decanol (2) −0.0080 −0.0110 −0.0139 −0.0090 −0.0120 −0.0154 −0.0020 −0.0040 −0.0089 0.0070 0.0034 0.0000 0.0163 0.0146 0.0099 0.0242 0.0218 0.0174 0.0356 0.0329 0.0280 0.0493 0.0466 0.0421 0.0591 0.0555 0.0511 0.0607 0.0568 0.0524 0.0517 0.0479 0.0437 0.0421 0.0385 0.0344 0.0319 0.0272 0.0231 0.0182 0.0150 0.0108

298.15 K

303.15 K

308.15 K

−0.0663 −0.1277 −0.1874 −0.2396 −0.2891 −0.3306 −0.3786 −0.4093 −0.3883 −0.3334 −0.2684 −0.2053 −0.1409 −0.0701

−0.0812 −0.1482 −0.2113 −0.2684 −0.3187 −0.3627 −0.4131 −0.4451 −0.4258 −0.3636 −0.2944 −0.2268 −0.1594 −0.0822

−0.0966 −0.1667 −0.2393 −0.2987 −0.3496 −0.3955 −0.4546 −0.4836 −0.4611 −0.3977 −0.3225 −0.2515 −0.1845 −0.0969

−0.0375 −0.0664 −0.0932 −0.1098 −0.1264 −0.1346 −0.1374 −0.1331 −0.1148 −0.0922 −0.0683 −0.0470 −0.0278 −0.0138

−0.0466 −0.0764 −0.1053 −0.1208 −0.1385 −0.1472 −0.1506 −0.1462 −0.1272 −0.1043 −0.0774 −0.0553 −0.0361 −0.0209

0.0277 −0.0081 −0.0397 −0.0624 −0.0865 −0.0997 −0.1104 −0.1145 −0.1040 −0.0914 −0.0717 −0.0494 −0.0383 −0.0250

−0.0125 −0.0221 −0.0239 −0.0249 −0.0239 −0.0256 −0.0182 −0.0039 0.0135 0.0286 0.0290 0.0319 0.0292 0.0200

−0.0187 −0.0324 −0.0327 −0.0345 −0.0358 −0.0348 −0.0285 −0.0133 0.0049 0.0200 0.0212 0.0228 0.0223 0.0130

−0.0258 −0.0415 −0.0401 −0.0441 −0.0430 −0.0435 −0.0375 −0.0218 −0.0047 0.0103 0.0122 0.0144 0.0129 0.0057

negative to positive as the size of the 1-alcohol molecule increases from 1-hexanol to 1-decanol. A close perusal of Table 4 reveals that there is a slight decrease in the magnitude of excess molar volumes with increase in temperature for all binary mixtures, indicating the increase of interaction with temperatures. The variations of VEm are the consequence of different contributions deriving from a structural modification of the mixed species, changes in the free volumes and interstitial accommodation of unlike molecules. Moreover, the specific intermolecular interactions that take place during the mixing process can be classified as follows: (i) favorable interactions (H-bonding) between polar groups (−O− and −OH), responsible for

(8)

where Y(x)exptl and Y(x)cal are the values of the experimental and calculated property (VEm, κES,m, and uD), respectively, and n is the number of experimental data points. As reflected in the Figure 1, VEm at 298.15 K is negative for the two (1-butoxy-2-propanol + 1-hexanol/1-octanol) binary systems over the whole composition range. The VEm curve for (1-butoxy-2-propanol + 1-decanol) binary mixture displays a positive deviation with a slight tendency to negative values at lower mole fraction. It indicates that VEm values change from D

DOI: 10.1021/acs.jced.5b00031 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Figure 2. Excess molar isentropic compression against mole fractions x1 1-butoxy-2-propanol + x2 1-hexanol (■); x2 1-octanol (●); x2 1-decanol (▲); at 298.15 K. The smoothing of the curves has been drawn from eq 7.

Figure 1. (a) Excess molar volume against mole fractions x1 1-butoxy-2propanol + x2 1-hexanol (■); x2 1-octanol (●); x2 1-decanol (▲); 298.15 K. The smoothing of the curves have been drawn from eq 7. (b) Excess molar volume against mole fractions x1 1-butoxy-2-propanol + x2 1-methanol (■) Pal et al.;13 x2 1-ethanol (●) Ku et al.;12 x2 1-propanol (▲) Pal et al.;13 x2 1-butanol (▼) Pal et al.;11 x2 1-hexanol (⧫) Dubey et al.16; x2 1-octanol (◀) Dubey et al.;16 x2 1-decanol (▶) Dubey et al.;16 at 298.15 K. The smoothing of the curves has been drawn from eq 7.

Figure 3. Deviation of speed of sound against mole fractions x1 1butoxy-2-propanol + x2 1-hexanol (■); x2 1-octanol (●); x2 1-decanol (▲); at 298.15 K. The smoothing of the curves has been drawn from eq 7.

negative contribution to VEm, and (ii) unfavorable interactions involving polar substituent and apolar groups (alkyl chains).36 The observed behavior of VEm can be analyzed qualitatively in terms of the following resulting effects: (1) Depolymerization of self-associated 1-butoxy-2-propanol by the 1-alcohols and self-associated alcohols by the 1butoxy-2-propanol. (2) Intermolecular H-bond formation between 1-butoxy-2propanol and 1-alcohols. The former effect results in expansion of volume and later contributes contraction in volume.9 The magnitudes of VmE (Figure 1a) suggest that the later effect is dominant in case of 1-hexanol and 1-octanol systems, while the former effect is dominant in 1-decanol system. This fact can be described by considering the steric hindrance effects of the alkyl chain of the 1decanol, because the hydrophobic character of the 1-alcohols is

amplified by an increase in chain length and consequently, the molecular interactions between alkoxy alkanol and 1-alcohol molecules weaken. So the values of VEm follows the order: 1 − hexanol > 1 − octanol > 1 − decanol

Recently, several authors10−13 have studied the thermodynamic studies of binary mixture of 1-butoxy-2-propanol with lower alcohols (methanol, ethanol, 1-propanol, and 1-butanol). Figure 1b shows the comparison of higher alcohols with lower alcohols at 298.15 K. It is clearly seen in the Figure 1b with increase in number of carbon atom the molecular interactions between alkoxy alkanol and alcohol molecules weaken. This may be due to the steric hindrance effect of the alkyl chain in higher alcohols. Further, the comparison of our data with ethanol at temperature ((298.15 and 308.15) K) is given in Supporting Information as Figure S1. It is evident from the figure that with increase in E

DOI: 10.1021/acs.jced.5b00031 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 5. Coefficients of Ai, of eq 7 and Standard Deviations σ for (1-Butoxy-2-propanol + 1-Alcohols) at Different Temperatures and Atmospheric Pressure T/K

293.15 298.15 303.15 308.15 313.15 298.15 303.15 308.15 298.15 303.15 308.15

293.15 298.15 303.15 308.15 313.15 298.15 303.15 308.15 298.15 303.15 308.15

293.15 298.15 303.15 308.15 313.15 298.15 303.15 308.15 298.15 303.15 308.15

A1

A2

A3

A4

A5

1-butoxy-2-propanol (x1) + 1-hexanol (x2) VEm·106/m3·mol−1 −0.3560 −0.0922 0.0308 0.0696 0.1395 −0.3706 −0.0902 0.0946 0.0448 −0.3781 −0.0897 0.0753 0.0497 −0.3865 −0.0889 0.0558 0.0407 −0.3999 −0.0878 0.0965 0.0471 −0.0974 κES,m/mm3·mol−1·MPa−1 −1.6181 −0.1275 0.1509 −1.7578 −0.1221 0.0515 −1.9059 −0.1248 −0.0719 uD/m·s−1 6.9970 −1.0012 −0.0843 1.0286 7.3323 −1.0023 0.3991 0.7223 0.7223 7.6883 −1.1814 0.2800 0.8330 0.8330 1-butoxy-2-propanol (x1) + 1-octanol (x2) VEm·106/m3·mol−1 −0.1101 0.1757 −0.0887 0.0268 0.1282 −0.1161 0.1732 −0.0970 0.0317 0.1088 −0.1221 0.1746 −0.0871 0.0365 0.0735 −0.1298 0.1877 −0.0529 −0.1368 0.1865 −0.0635 κES,m/mm3·mol−1·MPa−1 −0.5251 0.2358 −0.1504 −0.0015 0.2413 −0.5821 0.2471 −0.0820 −0.4437 0.1830 −0.2523 −0.6897 0.9498 uD/m·s−1 2.2092 −0.1143 0.1455 0.2913 −0.5512 2.3317 −0.0250 0.1606 2.4703 −0.1175 −0.0402 0.2426 0.9150 1-butoxy-2-propanol (x1) + 1-decanol (x2) VEm·106/m3·mol−1 0.2193 0.2540 −0.0288 0.0708 0.2071 0.2648 −0.0625 0.0328 0.1954 0.2730 −0.0944 0.1853 0.2656 −0.1336 0.1624 0.2642 −0.0619 0.0010 −0.1838 κES,m/mm3·mol−1·MPa−1 −0.0165 0.3183 0.1000 −0.0509 0.3275 0.0179 −0.0945 0.3102 0.1151 0.0385 −0.3099 uD/m·s−1 1.6986 0.4191 −0.9140 1.7608 0.3775 −0.6750 1.8478 0.4315 −1.0587 −0.1666 0.9412

study. On increasing, the temperature dissociation induces in the mixture releasing an increased number of free 1-butoxy-2propanol and 1-alcohols dipoles and also leads to an expansion in volume, which allows more favorable packing. This leads to contraction in volume, which causes a decrease in compressibility of the mixture, but this effect is reversed in case of 1-decanol due to small differences in molecular size. The Redlich−Kister polynomial equation was applied successfully for the correlation of these excess properties (VEm, κES,m, and uD). The calculated values of the coefficients (Ai) along with the standard deviations are given in Table 5.

σ

0.0021 0.0018 0.0022 0.0019 0.0024

4. FT-IR STUDIES To explore the molecular structure of association effects among molecules, FT-IR spectroscopy is a successful method. FT-IR

0.0067 0.0068 0.0067 0.0300 0.0250 0.0269

0.0014 0.0015 0.0016 0.0016 0.0015 0.0029 0.0032 0.0084 0.0106 0.0110 0.0150

Figure 4. Normalized FT-IR spectra of mole fractions x1 1-butoxy-2propanol + x2 1-hexanol; x1 = 0.1 (); x1 = 0.5 (red line); x1 = 0.9 (green line).

0.0023 0.0015 0.0015 0.0019 0.0017 0.0029 0.0031 0.0031 0.0151 0.0151 0.0158

temperature interactions become strong between alkoxy alkanols and alcohols as compared to lower temperature. Figures 2 and 3 depicted the behavior of κES,m and uD of binary mixture of 1-butoxy-2-propanol with alcohols are consistent with VEm. Due to the formation of hydrogen bonds, differences in sizes and shapes of the component molecules of the mixture and fitting of the component molecules into each other’s structure, thereby reducing the compressibility of the mixture, resulting in negative κES,m and positive uD. The magnitude of κES,m decreases with increase in temperature and becomes more and more negative whereas uD values increases with increase in temperature and becomes more and more positive for all binary mixtures under

Figure 5. Normalized FT-IR spectra of mole fractions x1 1-butoxy-2propanol + x2 1-octanol; x1 = 0.1 (); x1 = 0.5 (red line); x1 = 0.9 (green line).

spectra of the pure components and that of various binary mixtures over the different compositions range at room F

DOI: 10.1021/acs.jced.5b00031 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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forces are dominating on the former in the case of 1-decanol. Thermodynamic and FT-IR studies provide a comprehensive exploration of intermolecular association arising from the Hbonding between 1-butoxy-2-propanol and alcohols molecules.

■

ASSOCIATED CONTENT

S Supporting Information *

Figure S1: Excess molar volume against mole fractions x1 1butoxy-2-propanol + x2 1-ethanol (□) Ku et al.;12 x2 1-hexanol (○); x2 1-octanol (Δ);x2 1-decanol (∇); at 298.15 K and (■) Ku et al.;12 x2 1-hexanol (●); x2 1-octanol (▲);x2 1-decanol (▼) ; at 308.15 K, the smoothing of the curves have been drawn from eq 7. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00031.

■

Corresponding Authors

Figure 6. Normalized FT-IR spectra of mole fractions x1 1-butoxy-2propanol + x2 1-decanol; x1 = 0.1 (); x1 = 0.5 (red line); x1 = 0.9 (green line).

*Tel.: +91-94162-21007. Fax: +91-1744-238277. E-mail: gyan. dubey@rediffmail.com. *E-mail: [email protected].

Table 6. Neat FT-IR Stretching Frequencies of −OH (cm-1) in 1-Butoxy-2-propanol (1) + 1-Alcohols (2) x1

1-butoxy-2-propanol +1-hexanol

1-butoxy-2-propanol +1-octanol

1-butoxy-2-propanol +1-decanol

0.1 0.5 0.9

3348 3387 3418

3325 3371 3425

3333 3356 3418

AUTHOR INFORMATION

Funding

Authors gratefully acknowledge financial support for the work by Government of India through University Grants Commission, New Delhi (Letter No. F. 39-745/2010 (SR) dated 11/01/ 2011). Notes

The authors declare no competing financial interest.

■

temperature were recorded. This technique offers the advantages to measure the association properties, to assess interactions by analyzing band shifts, shape and hydrogen bonding capability.10 Two types of hydrogen bonds (inter and intra molecular) are readily distinguish by the FT-IR technique. Generally, intermolecular hydrogen bonds give rise to broad bands whereas bands arising from intramolecular hydrogen bonds are sharp bands.37 Figures 4 to 6 shows the FT-IR spectra in the range (3000 to 3600) cm−1 recorded for O−H stretching band of 1butoxy-2-propanol and 1-alcohols mixtures at different mole fractions and shows that the absorbance intensity of O−H band decreases and wavenumber increases with increasing concentration of 1-butoxy-2-propanol in the mixture. Table 6, shows the wavenumber increases with an increase in concentration for 1butoxy-2-propanol. Significant blue shifts in the band position of the O−H band are observed with the addition of 1-butoxy-2propanol, which indicates the intermolecular H-bonding takes place between 1-butoxy-2-propanol and 1-alcohols,38 which give evidence to our thermodynamic result.

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