Volumetric and Ultrasonic Studies of Molecular Interactions in n

Article pubs.acs.org/jced

Volumetric and Ultrasonic Studies of Molecular Interactions in n‑Alkoxypropanols + Alkyl Acetates Mixtures at Different Temperatures Amalendu Pal,*,† Harsh Kumar,‡ Ritu Maan,§ and Harish Kumar Sharma§ †

Department of Chemistry, Kurukshetra University, Kurukshetra 136119, Haryana, India Department of Chemistry, Dr. B.R. Ambedkar National Institute of Technology, Jalandhar 144011, Punjab, India § Department of Chemistry, M. M. University, Mullana, Ambala, Haryana, India ‡

S Supporting Information *

ABSTRACT: Densities and ultrasonic velocities have been measured over the whole composition range for the binary liquid mixtures of dipropylene glycol monomethyl ether (mixture of isomers) {CH3(OC3H6)2OH}, dipropylene glycol monopropyl ether (mixture of isomers) {CH3(CH2)2(OC3H6)2OH}, and dipropylene glycol monobutyl ether (mixture of isomers){CH3(CH2)3(OC3H6)2OH} with alkyl acetates using an Anton Paar DSA 5000 density and speed sound analyzer in the temperature interval (288.15 to 308.15) K and atmospheric pressure. From these experimental data, excess molar volume, VEm and deviations in isentropic compressibility, ΔκS, have been calculated. The computed results of these quantities have been correlated using the Redlich−Kister polynomial equation to obtain the binary coefficients and standard deviations.

1. INTRODUCTION Understanding the mixing behavior of liquid mixtures is an important aspect of large scale preparations in the chemical, agricultural, and pharmaceutical industries. Esters find diverse applications in tanning leathers, dying textiles, paint additives, and as industrial solvents for making cellulose and fats, cosmetics, and for imparting thermoplastic behavior1,2 to goods. They have nature-identical flavor which makes them an essential part of artificial flavoring. On the other hand, alkoxypropanols are widely used in plastic factories and in pharmaceutical companies. Molecular interactions existing between glycols3,4 and n-alkanols5−8 with alkyl acetates have already been reported in literature. Earnest and conscientious activity has been perfomred to obtain data for acetonitriles,9 acrylonitrile10 and various alkanes11,12 with esters in terms of density and ultrasonic velocity. Binary mixtures of chloroalkanols,13,14 fatty acids,15 and diethers16−18 with esters have been studied in detail. In literature there also exists thermodynamic properties of esters with (mono and poly) ethers.16−20 We have also published data in our previous research writings on the mixing behavior of alkoxypropanols + alkanols21,22 and alkoxyethanols + alkyl acetates.23 Considering the richness of significance of the esters and alkoxypropanols, a rigorously attentive study has been made and the perceptible change in behavior on mixing is considered and explained. Ultrasonic speed may be considered as a thermodynamic property, provided that a negligible amount of ultrasonic absorption of the acoustic waves of low frequency and of low amplitude is observed; in which case, the ultrasonic absorption of the acoustic waves is negligible.24 The present study reports the © 2013 American Chemical Society

density and speed of sound measurements for the mixture of dipropylene glycol monomethyl ether (mixture of isomers) (DPGMME), dipropylene glycol monopropyl ether (mixture of isomers) (DPGMPE), and dipropylene glycol monobutyl ether (mixture of isomers) (DPGMBE) with methyl acetate (MA), ethyl acetate (EA), and n-butyl acetate (BA) using an automatic density and ultrasonic velocity analyzer Anton Paar DSA 5000 at temperature T = (288.15, 293.15, 298.15, 303.15, and 308.15) K. The aim of the present work is to provide data for the characterization of the molecular interaction of these binary mixtures to explain the effects of increasing the oxypropylene group with a common alkyl group in alkoxypropanol. An attempt is also made to compare the results by collecting the data on alkoxyethanols + esters mixtures. Further, the sensitivity behavior of a mixture toward temperature and composition is studied in terms of excess molar volumes and deviations in isentropic compressibility. In addition, the binary coefficients and standard deviations have been calculated using the Redlich−Kister polynomial.

2. EXPERIMENTAL SECTION 2.1. Materials. Dipropylene glycol monomethyl ether (Sigma Aldrich, Germany, mass fraction purity, 0.98, mixture of isomers), dipropylene glycol monopropyl ether (Sigma Aldrich, Germany, mass fraction purity, 0.985, mixture of isomers), dipropylene glycol monobutyl ether (Sigma Aldrich, Received: July 9, 2013 Accepted: October 8, 2013 Published: October 24, 2013 3190

dx.doi.org/10.1021/je400637y | J. Chem. Eng. Data 2013, 58, 3190−3200

Journal of Chemical & Engineering Data

Article

Table 1. Specification of Chemical Samples chemical

CAS No.

source

mass fraction purity

dipropylene glycol monomethyl ether (mixture of isomers) dipropylene glycol monopropyl ether (mixture of isomers) dipropylene glycol monobutyl ether (mixture of isomers) methyl acetate ethyl acetate n-butyl acetate

34590-94-8 94247-68-4 35884-42-5 79-20-9 141-78-6 123-86-4

Sigma Aldrich, Germany Sigma Aldrich, Germany Sigma Aldrich, Germany Merck, Germany SD Fine Chemicals Ltd., Mumbai, India SISCO Research Laboratories, India

0.98 0.985 0.99 0.99 0.995 0.99

purification method used used used used used used

as as as as as as

such such such such such such

Table 2. Experimental Densities (ρ), and Speeds of Sound (c) of the Pure Component Liquids Together With Literature Values ρ·10−3/(kg·m−3) components

T/K

exptl

dipropylene glycol monomethyl ether

288.15 293.15 298.15 303.15 308.15 288.15 293.15 298.15 303.15 308.15 288.15 293.15 298.15 303.15 308.15 288.15 293.15 298.15 303.15

0.96460 0.96014 0.95567 0.95117 0.94665 0.92456 0.92017 0.91577 0.91134 0.90690 0.91712 0.91287 0.90860 0.90431 0.90001 0.94088 0.93439 0.92782 0.92119

308.15 288.15 293.15 298.15

0.91450 0.90694 0.90089 0.89480

303.15

0.88866

308.15

0.88247

288.15 293.15 298.15

0.88596 0.88087 0.87574

303.15

0.87058

308.15

0.86541

dipropylene glycol monopropyl ether

dipropylene glycol monobutyl ether

methyl acetate

ethyl acetate

n-butyl acetate

Germany, mass fraction purity, > 0.99, mixture of isomers), methyl acetate (Merck-Schuchardt, Germany, zur syntheses mass fraction purity, > 0.99), ethyl acetate (S. D. Fine Chemicals, India, mass fraction purity, 0.995) and n-butyl acetate (SISCO Research laboratories Pvt. Ltd. India, mass fraction purity, 0.99) were used directly without further purification. The specifications of the chemicals are also given

c/(m·s−1) lit.

0.951025 0.941925

0.916425 0.907525

0.908925 0.900325

0.927926 0.928514 0.921814 0.92043 0.915214

0.894613 0.894814 0.88963 0.888714 0.88253 0.882714

0.876428 0.876229 0.875714 0.870430 0.8712331 0.87132 0.87133 0.870614 0.865514

exptl

lit.

1348.3 1330.5 1312.7 1294.9 1277.2 1306.8 1289.3 1271.4 1253.6 1235.7 1314.3 1297.5 1279.6 1261.9 1244.2 1200.4 1179.0 1155.9 1133.0

1110.0 1187.9 1165.8 1143.2 1120.8 1098.4 1233.3 1213.1 1192.4

1171.8

1172.033

1151.4

in Table 1. Dark glass bottles have been used to store all the liquids so that there is no loss of moisture content. Storage of liquids over molecular sieves before experimental measurements reduced water content. All liquids were degassed under vacuum. The purities of liquids were checked by a comparison of the densities, and ultrasonic velocities at the desired 3191



Article

The calculated values of VEm and ΔκS of the mixtures are fitted to a Redlich- Kister35 type polynomial equation at each temperature,

temperatures, with their corresponding literature values3,13,14,25−33 as reported in Table 2. 2.2. Apparatus and Procedure. The densities, ρ, and speeds of sound, c, of pure liquids and of the mixtures were measured using an automatic density and speed of sound analyzer Anton Paar DSA 5000 densimeter. Keeping in mind that both the thermophysical parameters, that is, densities and speeds of sound are extremely sensitive to temperature, the temperature inside the densimeter was controlled to ± 0.001 K by a built-in Peltier device. Before each series of measurements, the apparatus was calibrated with double-distilled degassed water in the experimental temperature range. The reproducibility of the density and speed of sound measurements was ± 1· 10−3 kg·m−3 and ± 1·10−2 m·s−1, respectively, and the corresponding uncertainties have been assumed to be less than 5·10−2 kg·m−3 and 5·10−1 m·s−1. The weighings were done with an electronic balance having a precision of ± 0.01 mg. For each mole fraction obtained, there was an uncertainty of 1·10−4 from measured masses of the components. All molar quantities reported in this study were based on the IUPAC relative atomic mass table.34

Y (x) = x1x 2 ∑ Ai (x1 − x 2)i

where Y(x) stands for VEm or ΔκS. The coefficients Ai for the correlation of Y(x) composition data which have been evaluated using the least-squares method are given in Table 4 along with the standard deviations σ. The standard deviations have been calculated by n

σ = [∑ (Y (x) − Y (x)calcd )2 /(p − k)]1/2 i

(1)

where x1, x2; M1, M2; ρ1, ρ2 represent the mole fractions, molar masses, and densities of the components 1 and 2, respectively. ρ is the densities of the resulting binary mixtures. The uncertainty in the values of VEm is found to be ± 0.003 cm3 mol−1. The values of VEm at various temperatures are provided in Supporting Information, Table S1. The values of VEm for DPGMBE with alkyl acetates at T = 298.15 K are graphically represented in Figure 1. Isentropic compressibility, κS, has been calculated from the experimental density and speed of sound through the given equation κS = (ρ u 2)−1

(2)

The resulting values of κS, at different temperatures are included in Supporting Information, Table S1. The values of κS for DPGMME with methyl acetate at different temperatures were plotted in Figure 2. The deviations of isentropic compressibility, ΔκS were calculated from their values in an ideal mixture using the equation ΔκS = κS − κSid

(3)

where κSid =

∑ (κS*,i)·ϕi

(6)

where p is the number of experimental points and k is the number of experimental parameters. Figure 1 shows the variation of VEm against composition for the binary mixtures at 298.15 K. The experimental data at various other temperatures have been found to be somewhat the same and so have not been mentioned. For each binary mixture that has been studied in the present investigation, VEm and ΔκS are positive over the whole mole fraction range at all temperatures. 3.2. Excess Molar Volume. Thermodynamic excess properties are sensitive to intermolecular interactions present between unlike molecular entities in mixtures. So the variation of excess molar volume against composition and temperature is an important quantitative treatment. Figure 1 shows that VEm values are positive for all the three binary mixtures over the whole mole fraction range. Excess molar volume has been found to be positive which represents an intercalation packing effect. There is an expansion of the mixture caused by rupture of hydrogen bonds in self-associated alkoxypropanols due to the presence of molecules of alkyl acetates. Excess molar volume is the result of different kinds of interactions capable of existing between the binary mixtures. The positive values of excess molar volumes for the mixtures of the alkoxypropanols and alkyl acetates are due to the difference in molecular sizes of the components, which leads to lesser dipole−dipole interactions present in alkyl acetates. It has been suggested that the hydrocarbon chain in alkoxypropanols plays a prominent role because upon increasing the carbon chain length, the van der Waal’s interactions dominate which is not compensated by the presence of hydrogen bonding. This behavior is similar for propylene glycol monoalkyl ether with esters36 but with a marked decrease in VEm here. The values are graphically represented in Figure 3 in which the results have been compared for PGMBE and DPGMBE with alkyl acetates at T = 298.15 K. A close perusal of Figure 3 shows that for each ester, the VEm values become less positive with the addition of a −OC3H6 group in the molecule of propylene glycol monoalkyl ether. The magnitude of excess molar volume decreases, that is, less positive values of VEm are observed for DPGMBE as compared to PGMBE. This is because DPGMBE has an extra polar headgroup which leads to greater self-association due to more hydrogen bonding and undergoes less rupture as compared to PGMBE. This behavior is inconsistent with that of the VEm for mixture of alkyl acetates with (mono and poly) ethers.16−19 Once the alkyl chain end of the polyether is fixed, the values for VEm become negative with the increase of the polar headgroup of ethers. Alkoxypropanols possess an interesting quality of self-association while alkyl esters do not self-associate due to lack of hydrogen-bond donating ability. Moreover, they differ in terms of structures and sizes of their

3. RESULTS AND DISCUSSION 3.1. Data Processing. Experimental results of density, ρ, and speeds of sound, u, for the binary liquid mixtures dipropylene glycol monomethyl ether (1), dipropylene glycol monopropyl ether (1), and dipropylene glycol monobutyl ether (1) with methyl acetate (2), ethyl acetate (2), or n-butyl acetate (2) at temperature T = (288.15, 293.15, 298.15, 303.15 and 308.15) K have been reported as a function of composition in Table 3. The density values have been used to calculate excess molar volumes, VEm using the following relation VmE = (x1M1 + x 2M 2)/ρ − (x1M1/ρ1) − (x 2M 2 /ρ2 )

(5)

(4)

where ϕi is the volume fraction and κ*S,i is the isentropic compressibility of the pure component i. The uncertainty in the Δκs values is found to be ± 0.04 T·Pa−1. 3192


x1

T/K = 288.15

T/K = 293.15 0.91450 0.91546 0.91702 0.91981 0.92427 0.92820 0.93157 0.93499 0.93770 0.94040 0.94225 0.94480 0.94665 0.88247 0.88544 0.88829 0.89281 0.90046 0.90808 0.91465 0.92122 0.92595 0.93290 0.93797 0.94285 0.94665 0.86541 0.86807 0.87112 0.87445 0.88356 0.89330 0.90116 0.90906 0.91578 0.92432 0.93287 0.93967

0.92119 0.92201 0.92340 0.92602 0.93018 0.93386 0.93701 0.94019 0.94276 0.94530 0.94704 0.94942 0.95117 0.88866 0.89154 0.89430 0.89871 0.90618 0.91361 0.92003 0.92643 0.93104 0.93780 0.94273 0.94748 0.95117 0.87058 0.87323 0.87626 0.87957 0.88862 0.89825 0.90607 0.91393 0.92060 0.92906 0.93751 0.94426

T/K = 308.15

3193

1233.3 1235.8 1239.0 1242.7 1253.2 1265.4 1276.0 1287.3 1297.2 1310.5 1324.3 1335.7

1187.9 1193.0 1198.0 1206.5 1222.4 1239.7 1256.0 1273.1 1285.9 1305.5 1320.5 1335.8 1348.3

1200.4 1203.3 1208.3 1218.3 1235.7 1252.9 1268.0 1284.6 1298.5 1313.0 1322.8 1337.3 1348.3

T/K = 288.15

1213.1 1215.7 1219.0 1222.9 1233.5 1245.9 1256.7 1268.2 1278.4 1291.9 1306.0 1317.8

1165.8 1171.0 1176.2 1185.0 1201.2 1218.9 1235.6 1253.1 1266.1 1286.2 1301.9 1317.7 1330.5

1179.0 1181.7 1186.9 1198.0 1215.4 1233.0 1248.4 1265.0 1280.0 1294.3 1304.7 1319.0 1330.5

T/K = 293.15

1192.4 1195.1 1198.4 1202.3 1213.3 1226.0 1237.1 1248.9 1259.2 1273.1 1287.5 1299.6

1143.2 1148.7 1154.0 1163.0 1179.6 1197.7 1214.8 1232.7 1246.1 1266.9 1283.0 1299.2 1312.7

1155.9 1159.3 1164.3 1176.2 1193.8 1212.0 1228.0 1245.2 1260.7 1275.5 1286.2 1301.0 1312.7

T/K = 298.15

T/K = 303.15

T/K = 298.15

dipropylene glycol monomethyl ether (1) + methyl acetate (2) 0.0000 0.94088 0.93439 0.92782 0.0266 0.94141 0.93499 0.92853 0.0563 0.94245 0.93620 0.92980 0.1161 0.94444 0.93834 0.93220 0.2120 0.94771 0.94189 0.93606 0.3099 0.95060 0.94506 0.93945 0.4021 0.95311 0.94778 0.94241 0.5070 0.95569 0.95055 0.94539 0.5976 0.95785 0.95280 0.94780 0.7003 0.95990 0.95505 0.95020 0.7789 0.96126 0.95656 0.95183 0.9017 0.96318 0.95865 0.95403 1.0000 0.96460 0.96014 0.95567 dipropylene glycol monomethyl ether (1) + ethyl acetate (2) 0.0000 0.90694 0.90089 0.89480 0.0314 0.90956 0.90361 0.89758 0.0618 0.91215 0.90625 0.90032 0.1129 0.91620 0.91045 0.90463 0.2055 0.92307 0.91747 0.91184 0.3058 0.92995 0.92455 0.91911 0.3994 0.93590 0.93065 0.92537 0.5000 0.94180 0.93670 0.93157 0.5797 0.94605 0.94108 0.93608 0.7045 0.95230 0.94750 0.94265 0.8055 0.95682 0.95215 0.94745 0.9113 0.96120 0.95665 0.95209 1.0000 0.96460 0.96014 0.95567 dipropylene glycol monomethyl ether (1) + n- butyl acetate (2) 0.0000 0.88596 0.88087 0.87574 0.0289 0.88857 0.88349 0.87837 0.0645 0.89157 0.88649 0.88138 0.1035 0.89481 0.88976 0.88468 0.2082 0.90369 0.89868 0.89366 0.3218 0.91311 0.90819 0.90323 0.4161 0.92074 0.91588 0.91099 0.5132 0.92840 0.92361 0.91878 0.5966 0.93489 0.93015 0.92539 0.7055 0.94314 0.93846 0.93377 0.8156 0.95134 0.94675 0.94214 0.9054 0.95792 0.95337 0.948839

c/(m·s−1)

ρ·10−3/(kg·m−3)

1171.8 1174.7 1177.9 1182.1 1193.2 1206.2 1217.6 1229.6 1240.1 1254.3 1269.0 1281.5

1120.8 1126.7 1131.7 1141.0 1158.0 1176.6 1194.0 1212.3 1226.0 1247.4 1264.0 1281.0 1294.9

1133.0 1137.0 1142.4 1154.1 1172.5 1191.0 1207.4 1225.6 1240.9 1256.2 1267.0 1283.0 1294.9

T/K = 303.15

1151.4 1154.4 1157.8 1161.9 1173.3 1186.6 1198.0 1210.3 1221.1 1235.6 1250.6 1263.4

1098.4 1104.1 1109.6 1119.0 1136.3 1155.2 1173.0 1191.8 1206.1 1228.0 1245.3 1262.9 1277.2

1110.0 1114.5 1119.5 1132.0 1151.1 1170.0 1187.0 1205.5 1221.1 1237.1 1248.4 1265.0 1277.2

T/K = 308.15

Table 3. Densities (ρ) and Speeds of Sound (c) for Alkoxypropanols (1) + Methyl Acetate (2),+ Ethyl Acetate (2), and + n-Butyl Acetate (2) Mixtures at T = (288.15, 293.15, 298.15, 303.15, and 308.15) K

Journal of Chemical & Engineering Data Article


T/K = 288.15

T/K = 293.15 0.94403 0.94665

T/K = 288.15

0.91450 0.91300 0.91238 0.91110 0.90945 0.90852 0.90781 0.90742 0.90712 0.90695 0.90698 0.90700 0.90690 0.88247 0.88291 0.88410 0.88600 0.88926 0.89170 0.89530 0.89786 0.89987 0.90172 0.90375 0.90551 0.90608 0.90644 0.90690 0.86541 0.86670 0.86730 0.87026 0.87550 0.87961 0.88440 0.88875 0.89319

0.92119 0.91956 0.91881 0.91726 0.91521 0.91402 0.91305 0.91250 0.91201 0.91169 0.91162 0.91158 0.91134 0.88866 0.88903 0.89017 0.89186 0.89490 0.89714 0.90051 0.90288 0.90476 0.90651 0.90842 0.91005 0.91056 0.91091 0.91134 0.87058 0.87180 0.87252 0.87534 0.88051 0.88452 0.88921 0.89351 0.89787

3194

1233.3 1235.3 1236.4 1241.1 1248.0 1254.3 1262.4 1270.3 1279.0

1187.9 1188.5 1192.6 1200.5 1215.0 1226.0 1243.9 1256.7 1267.0 1276.8 1288.4 1298.4 1301.9 1304.0 1306.8

1200.4 1200.9 1203.8 1211.6 1225.1 1237.9 1251.5 1262.3 1272.2 1282.8 1289.8 1299.7 1306.8

1343.3 1348.3

T/K = 293.15

1213.1 1215.0 1216.3 1221.2 1228.7 1235.2 1243.6 1251.9 1260.5

1165.8 1166.3 1171.0 1179.0 1194.0 1205.6 1224.0 1237.5 1248.1 1258.3 1270.5 1280.9 1284.3 1286.0 1289.3

1179.0 1178.2 1181.6 1189.9 1204.2 1217.5 1231.8 1243.0 1253.2 1264.3 1271.5 1281.6 1289.3

1325.5 1330.5

1192.4 1194.7 1195.7 1200.9 1208.6 1215.5 1224.1 1232.6 1241.5

1143.2 1143.9 1149.0 1157.2 1172.8 1184.9 1203.9 1217.9 1228.9 1239.6 1251.8 1262.6 1265.8 1267.8 1271.4

1155.9 1155.6 1159.1 1167.9 1182.8 1196.8 1211.6 1223.5 1233.9 1245.3 1252.8 1263.3 1271.4

1307.5 1312.7

T/K = 298.15

T/K = 308.15

0.94856 0.95117

T/K = 298.15

T/K = 303.15

c/(m·s−1)

ρ·10−3/(kg·m−3)

0.9635 0.96206 0.95758 0.95308 1.0000 0.96460 0.96014 0.95567 dipropylene glycol monopropyl ether (1) + methyl acetate (2) 0.0000 0.94088 0.93439 0.92782 0.0228 0.93890 0.93250 0.92605 0.0452 0.93779 0.93151 0.92518 0.1018 0.93546 0.92943 0.92337 0.2023 0.93229 0.92662 0.92093 0.2971 0.93030 0.92489 0.91947 0.4051 0.92861 0.92346 0.91829 0.4938 0.92755 0.92256 0.91750 0.5862 0.92660 0.92180 0.91690 0.7035 0.92577 0.92111 0.91641 0.7854 0.92546 0.92086 0.91625 0.8947 0.92512 0.92062 0.91610 1.0000 0.92456 0.92017 0.91577 dipropylene glycol monopropyl ether (1) + ethyl acetate (2) 0.0000 0.90694 0.90089 0.89480 0.0155 0.90714 0.90114 0.89511 0.0461 0.90795 0.90206 0.89613 0.0961 0.90921 0.90351 0.89770 0.1937 0.91149 0.90600 0.90048 0.2722 0.91330 0.90795 0.90255 0.4037 0.91589 0.91080 0.90567 0.5082 0.91780 0.91285 0.90788 0.5979 0.91925 0.91443 0.90960 0.6900 0.92065 0.91596 0.91123 0.8000 0.92217 0.91762 0.91304 0.9042 0.92350 0.91905 0.91455 0.9407 0.92393 0.91949 0.91503 0.9657 0.92420 0.91979 0.91536 1.0000 0.92456 0.92017 0.91577 dipropylene glycol monopropyl ether (1) + n-butyl acetate (2) 0.0000 0.88596 0.88087 0.87574 0.0231 0.88719 0.88210 0.87690 0.0348 0.88770 0.88260 0.87764 0.0931 0.89041 0.88544 0.88040 0.2006 0.89535 0.89042 0.88550 0.2885 0.89912 0.89428 0.88941 0.3945 0.90355 0.89881 0.89403 0.4946 0.90761 0.90296 0.89824 0.6038 0.91178 0.90717 0.90253

x1

Table 3. continued

1171.8 1174.1 1175.3 1180.7 1188.8 1195.9 1205.0 1213.6 1222.7

1120.8 1121.5 1127.0 1135.5 1151.8 1164.2 1183.9 1198.2 1209.8 1220.8 1233.3 1244.4 1247.7 1249.7 1253.6

1133.0 1132.9 1136.5 1145.8 1161.6 1176.2 1191.6 1203.7 1214.6 1226.5 1234.2 1245.0 1253.6

1289.7 1294.9

T/K = 303.15

1151.4 1153.7 1154.9 1160.4 1169.1 1176.4 1185.7 1194.6 1204.1

1098.4 1099.4 1105.0 1114.0 1130.9 1143.6 1164.0 1178.6 1190.5 1201.7 1214.9 1226.3 1229.7 1232.3 1235.7

1110.0 1110.2 1114.0 1123.9 1140.5 1155.6 1171.7 1184.3 1195.6 1207.8 1215.7 1226.9 1235.7

1271.7 1277.2

T/K = 308.15



T/K = 288.15

T/K = 293.15 0.89686 0.90007 0.90338 0.90520 0.90599 0.90690

T/K = 288.15

0.91450 0.91294 0.91105 0.90936 0.90681 0.90536 0.90332 0.90222 0.90161 0.90123 0.90071 0.90049 0.90021 0.90001 0.88247 0.88340 0.88446 0.88619 0.88745 0.88990 0.89170 0.89405 0.89550 0.89696 0.89800 0.89905 0.89943 0.90001 0.86541 0.86781 0.86941 0.87092 0.87495

0.92119 0.91950 0.91740 0.91544 0.91250 0.91082 0.90844 0.90712 0.90631 0.90581 0.90521 0.90490 0.90455 0.90431 0.88866 0.88946 0.89038 0.89187 0.89297 0.89518 0.89680 0.89890 0.90021 0.90152 0.90251 0.90345 0.90379 0.90431

3195

0.87058 0.87291 0.87450 0.87594 0.87987

1233.3 1237.8 1240.9 1243.6 1252.0

1187.9 1190.6 1196.5 1208.1 1216.0 1233.6 1247.0 1265.1 1276.4 1288.2 1296.5 1306.1 1309.4 1314.3

1200.4 1200.0 1205.3 1211.1 1225.0 1235.1 1253.2 1267.0 1281.2 1289.0 1300.2 1306.2 1311.7 1314.3

1286.5 1292.9 1299.7 1303.2 1304.8 1306.8

T/K = 293.15

1213.1 1217.6 1220.8 1223.9 1232.5

1165.8 1168.8 1175.0 1187.1 1195.6 1213.7 1228.1 1247.0 1258.4 1269.9 1278.8 1288.3 1292.3 1297.5

1179.0 1178.2 1184.1 1190.8 1205.1 1216.0 1234.8 1249.3 1263.5 1271.2 1282.9 1287.9 1294.2 1297.5

1268.1 1274.8 1281.9 1285.7 1287.4 1289.3

1192.4 1197.0 1200.6 1203.6 1212.6

1143.2 1146.5 1153.0 1165.7 1174.5 1193.1 1208.1 1227.1 1239.2 1251.1 1260.4 1270.2 1274.1 1279.6

1155.9 1155.4 1161.8 1168.8 1184.1 1195.3 1214.8 1229.8 1244.5 1252.5 1264.6 1269.7 1276.2 1279.6

1249.4 1256.2 1263.7 1267.7 1269.3 1271.4

T/K = 298.15

T/K = 308.15

0.90148 0.90466 0.90788 0.90965 0.91045 0.91134

T/K = 298.15

T/K = 303.15

c/(m·s−1)

ρ·10−3/(kg·m−3)

0.6996 0.91520 0.91066 0.90608 0.7886 0.91820 0.91370 0.90916 0.8865 0.92127 0.91681 0.91237 0.9439 0.92295 0.91854 0.91410 0.9694 0.92368 0.91930 0.91486 1.0000 0.92456 0.92017 0.91577 dipropylene glycol monobutyl ether (1) + methyl acetate (2) 0.0000 0.94088 0.93439 0.92782 0.0209 0.93884 0.93245 0.92599 0.0654 0.93610 0.92990 0.92360 0.1173 0.93341 0.92749 0.92149 0.2201 0.92930 0.92380 0.91820 0.2953 0.92688 0.92160 0.91627 0.4314 0.92360 0.91861 0.91353 0.5500 0.92160 0.91685 0.91199 0.6488 0.92028 0.91570 0.91103 0.7189 0.91950 0.91500 0.91041 0.8228 0.91850 0.91411 0.90965 0.8810 0.91805 0.91366 0.90929 0.9491 0.91750 0.91321 0.90891 1.0000 0.91712 0.91287 0.90860 dipropylene glycol monobutyl ether (1) + ethyl acetate (2) 0.0000 0.90694 0.90089 0.89480 0.0270 0.90739 0.90146 0.89548 0.0613 0.90792 0.90210 0.89626 0.1312 0.90869 0.90313 0.89751 0.1835 0.90936 0.90393 0.89846 0.2932 0.910781 0.90558 0.90039 0.3861 0.91184 0.90684 0.90183 0.5211 0.91330 0.90851 0.90371 0.6151 0.91420 0.90955 0.90489 0.7200 0.91513 0.91060 0.90607 0.8017 0.91586 0.91143 0.90698 0.8973 0.91655 0.91220 0.90784 0.9364 0.91678 0.91247 0.90813 1.0000 0.91712 0.91287 0.90860 dipropylene glycol monobutyl ether (1) + n-butyl acetate (2) 0.0000 0.88596 0.88087 0.87574 0.0475 0.88810 0.88310 0.87802 0.0816 0.88950 0.88455 0.87950 0.1149 0.89090 0.88592 0.88094 0.2065 0.89451 0.88966 0.88477

x1

Table 3. continued

1171.8 1176.8 1180.0 1183.4 1192.8

1120.8 1124.4 1131.2 1144.4 1153.5 1172.8 1187.9 1207.8 1220.0 1232.7 1242.2 1252.2 1256.0 1261.9

1133.0 1132.7 1139.4 1146.9 1163.1 1174.6 1195.0 1210.5 1225.7 1233.9 1246.5 1251.8 1258.4 1261.9

1230.8 1237.8 1245.7 1249.6 1251.5 1253.6

T/K = 303.15

1151.4 1156.5 1160.0 1163.5 1173.0

1098.4 1102.3 1109.3 1123.0 1132.3 1152.2 1167.7 1188.2 1201.0 1214.0 1224.0 1234.4 1238.0 1244.2

1110.0 1110.2 1117.1 1125.4 1143.1 1154.7 1175.7 1191.4 1207.0 1215.6 1228.4 1234.1 1240.7 1244.2

1212.3 1219.6 1227.4 1231.6 1233.4 1235.7

T/K = 308.15



0.89825 0.90144 0.90441 0.90780 0.91023 0.91285 0.91550 0.91627 0.91712

Article

x1 is the mole fraction of alkoxypropanol. Standard uncertainties u are u(T) = 0.001 K, u(x1) = 0.0001, u(ρ) = 5·10−5 g·cm−3, u(c) = 5 ·10−1 m·s−1. The combined expanded uncertainty (k = 2) for density Uc (ρ) = ± 1 ·10−4 kg m−3 and speeds of sound Uc(c) = ± 1 m s−1.

1203.0 1212.1 1221.2 1231.4 1239.0 1247.8 1256.4 1259.0 1261.9 1222.4 1231.3 1240.0 1250.1 1257.6 1266.0 1274.3 1276.8 1279.6

1183.6 1193.0 1202.3 1212.9 1220.6 1229.7 1238.5 1241.2 1244.2

T/K = 303.15 T/K = 298.15

1242.0 1250.7 1259.2 1269.0 1276.0 1284.4 1292.4 1294.8 1297.5 1260.9 1269.2 1277.6 1286.9 1293.9 1301.9 1309.5 1311.7 1314.3 0.87910 0.88265 0.88596 0.88970 0.89236 0.89530 0.89820 0.89906 0.90001

T/K = 293.15 T/K = 288.15 T/K = 308.15 T/K = 303.15

0.88394 0.88737 0.89060 0.89426 0.89684 0.89970 0.90255 0.90340 0.90431 0.88870 0.89208 0.89523 0.89880 0.90132 0.90412 0.90688 0.90771 0.90860

T/K = 298.15 T/K = 288.15 x1

0.3101 0.4058 0.5019 0.6169 0.7042 0.8079 0.9213 0.9581 1.0000

T/K = 293.15

ρ·10−3/(kg·m−3)

Table 3. continued

0.89350 0.89677 0.89983 0.90329 0.90578 0.90851 0.91120 0.91200 0.91287

c/(m·s−1)

T/K = 308.15


Figure 1. Excess molar volume VEm at 298.15 K for DPGMBE (1) + ⧫, MA (2); ■, EA (2) and ▲, BA (2). Solid lines have been drawn from polynomial curve fitting.

Figure 2. Isentropic compressibility κs at 298.15 K for DPGMME (1) + MA (2) at different temperatures. [⧫, 288.15 K; ■, 293.15 K; ▲, 298.15 K; ×, 303.15 K; ●, 308.15 K]. Solid lines have been drawn from polynomial curve fitting.

molecules. From Figure 1, it is clear that excess molar volume decreases with increasing chain length of n-alkyl esters. The positive values of excess molar volume follow the following order majorly (with the exception of DPGMME + alkyl acetates at 288.15 K): BA < EA < MA

It is interesting that VEm is more negative for alkoxyethanols + methyl acetate.23 In presently investigated binary mixtures, positive values for all mixtures indicate toward the expansion of the mixture and nonspecific physical factors can be held responsible. It must be due to the breaking of hydrogen bonds in alkoxypropanols resulting from the introduction of alkyl ester molecules. The extent of hydrogen-bond breakage in lower esters is more as compared to that in higher esters, that is, nbutyl acetate, so VEm values are less positive for n-butyl acetate. Also, as we elongate the hydrocarbon chain in alkoxypropanols, the positive excess molar volume increases and then decreases with an increase in chain length of the alkoxypropanol as shown in Figure 4. The variation of excess molar volume with temperature at equimolar composition has been shown in Figure 5 diagrammatically. The magnitude of excess molar volume increases with an increase in temperature because the 3196



Article

Table 4. Standard Deviations (σ) and Parameters Ai of eq 5 T/K

A0

dipropylene glycol monomethyl ether (1) + methyl acetate (2) VEm·106/m3·mol−1 288.15 0.4942 293.15 0.5035 298.15 0.4995 303.15 0.4870 308.15 0.4642 ΔκS/T·Pa−1 288.15 42.841 293.15 43.675 298.15 44.174 303.15 43.677 308.15 43.057 dipropylene glycol monomethyl ether (1) + ethyl acetate (2) VEm·106/m3·mol−1 288.15 0.2512 293.15 0.2511 298.15 0.2520 303.15 0.2458 308.15 0.2524 ΔκS/T·Pa−1 288.15 17.102 293.15 16.817 298.15 16.614 303.15 16.335 308.15 17.207 dipropylene glycol monomethyl ether (1) + n-butyl acetate (2) VEm·106/m3·mol−1 288.15 0.6113 293.15 0.6393 298.15 0.6674 303.15 0.6967 308.15 0.7193 ΔκS/T·Pa−1 288.15 12.089 293.15 12.087 298.15 11.965 303.15 12.124 308.15 12.126 308.15 12.089 dipropylene glycol monopropyl ether (1) + methyl acetate (2) VEm·106/m3·mol−1 288.15 1.0819 293.15 1.0716 298.15 1.1054 303.15 1.0665 308.15 1.0798 ΔκS/T·Pa−1 288.15 65.039 293.15 70.032 298.15 72.558 303.15 77.949 308.15 79.897 dipropylene glycol monopropyl ether (1) + ethyl acetate (2) VEm·106/m3·mol−1 288.15 0.5977 293.15 0.6060 298.15 0.6199 303.15 0.6074 308.15 0.6122 ΔκS/T·Pa−1 288.15 37.679 293.15 38.814 298.15 39.016 303.15 38.935 308.15 38.123 dipropylene glycol monopropyl ether (1) + n-butyl acetate (2) VEm·106/m3·mol−1 288.15 0.7292 293.15 0.7227 298.15 0.7335 303.15 0.7478

A1

A2

A3

−0.4650 −0.4141 −0.4399 −0.3978 −0.4020 −18.474 −15.155 −17.979 −20.220 −18.546

−0.2945 −0.2626 −0.3218 −0.2688 −0.1836 −5.781 −19.808 −25.232 −17.972 −10.686

−0.1829 −0.3519 −0.2816 −0.3462 −0.3172 −19.640 −31.131 −28.478 −18.343 −25.743

−0.3201 −0.3264 −0.3089 −0.3215 −0.3212 −17.988 −17.331 −18.274 −17.943 −18.441

0.0749 0.0529 0.0282 0.0554 0.2159 2.640 2.350 2.088 3.971 1.843

0.1627 0.1977 0.1672 0.1728

−0.0810 −0.0847 −0.0937 −0.1099 −0.0655 −6.114 −6.725 −6.246 −6.506 −5.974 −6.114

0.3010 0.3734 0.3798 0.3689 0.3315 4.163 5.179 4.158 3.770 3.725 4.163

−0.1393 −0.1483 −0.1515 −0.1458 −0.2605

−0.5179 −0.5521 −0.5549 −0.5463 −0.5002

2.177

−4.500

−0.2324 −0.2572 −0.2563 −0.2074 −0.2842 −11.726 −13.997 −17.080 −14.659 −16.973

0.3966 0.4549 −0.1056 0.4085 −0.2079 16.748 30.295 33.260 −10.316 −16.217

−1.3391 −1.2992 −1.2239 −1.3759 −1.0861 −26.490 −41.758 −38.780 −45.484 −47.190

−0.2023 −0.2191 −0.2278 −0.2542 −0.2270 −3.669 −4.834 −6.105 −6.400 −4.375

0.1702 0.1074 −0.0815 0.0608 0.0694 1.567 −1.489 −7.045 −11.164 −7.740

−0.4030 −0.3652 −0.3483 −0.2981 −0.3345 −33.171 −34.986 −31.904 −32.753 −37.084

−0.5952 −0.6000 −0.5986 −0.6326

−0.1576 −0.1132 −0.1574 −0.1968

0.3615 0.3305 0.3686 0.3917

3197

A4 1.1802 1.0546 1.2422 1.1652 0.9750 27.914 55.147 56.753 41.759 31.671

σ 0.0093 0.0089 0.0083 0.0083 0.0089 0.377 0.496 0.530 0.265 0.303 0.0033 0.0033 0.0045 0.0026 0.0027 0.113 0.131 0.118 0.181 0.148

9.958 9.341 11.409 10.189 8.857

0.9459 1.1600

77.540 91.687

0.2716

29.076 31.026 41.231 51.081 45.361

0.0082 0.0079 0.0081 0.0083 0.0093 0.061 0.052 0.092 0.131 0.144 0.061 0.0189 0.0200 0.0201 0.0207 0.0205 0.930 1.300 1.332 1.230 1.311 0.0069 0.0078 0.0071 0.0067 0.0072 0.540 0.701 0.691 0.774 0.789 0.0060 0.0046 0.0068 0.0063



Article

Table 4. continued T/K

A0

308.15 0.7366 ΔκS/T·Pa−1 288.15 21.004 293.15 20.604 298.15 20.981 303.15 20.729 308.15 21.045 dipropylene glycol monobutyl ether (1) + methyl acetate (2) VEm·106/m3·mol−1 288.15 0.8089 293.15 0.8126 298.15 0.8433 303.15 0.8821 308.15 0.9024 ΔκS/T·Pa−1 288.15 102.775 293.15 105.627 298.15 111.242 303.15 116.871 308.15K 118.130 dipropylene glycol monobutyl ether (1) + ethyl acetate (2) VEm·106/m3·mol−1 288.15 0.5225 293.15 0.5256 298.15 0.5245 303.15 0.4962 308.15 0.4658 ΔκS/T·Pa−1 288.15 42.461 293.15 41.210 298.15 41.196 303.15 40.981 308.15 41.978 dipropylene glycol monobutyl ether (1) + n-butyl acetate (2) VEm·106/m3·mol−1 288.15 0.5022 293.15 0.5167 298.15 0.5127 303.15 0.5138 308.15 0.5144 ΔκS/T·Pa−1 288.15 16.735 293.15 16.507 298.15 16.850 303.15 16.352 308.15 16.483

A4

σ 0.0029 0.292 0.161 0.150 0.229 0.136

A2 0.0494 −19.359 −19.078 −15.797 −12.361 −19.039

12.231 13.815 13.647 15.753

−0.2393 −0.2749 −0.2205 −0.2728 −0.3068 18.716 16.592 15.171 15.381 18.706

−0.4864 −0.6505 −0.7475 −0.7603 −0.7971 −1.031 11.450 8.490 8.694 14.973

−0.5547 −0.5106 −0.6986 −0.6266 −0.6275 −80.764 −88.758 −87.441 −94.323 −07.506

1.1421 1.5083 1.6589 1.6182 1.6792

0.0142 0.0149 0.0155 0.0127 0.0137 0.990 1.176 0.989 1.044 1.008

−0.3191 −0.3267 −0.3164 −0.2874 −0.3232 −10.623 −15.453 −14.473 −13.249 −12.980

0.1838 0.1341 −0.1853 −0.1795 0.0333 5.360 11.006 11.040 10.117 7.295

−0.0789 −0.0191

−0.5581 −0.5080

0.1460 −21.926 −11.860 −13.954 −17.424 −19.583

−0.4101

0.0073 0.0069 0.0078 0.0079 0.0069 0.487 0.553 0.554 0.534 0.565

−0.1881 −0.1834 −0.2118 −0.1790 −0.2013 −4.904 −4.386 −3.152 −4.118 −4.639

−0.2631 −0.2958 −0.2744 −0.2883 −0.2966 −8.704 −3.161 −7.656 −0.284 −0.697

−0.1343 −0.1381 −0.1008 −0.1233 −0.0954 −3.429 −5.602 −7.850 −6.598 −4.177

Figure 3. Excess molar volume VEm at 298.15 K for PGMBE (ref 36) and DPGMBE (1) + ○, ●, MA (2); △, ▲, EA (2) and □, ■, BA (2). Solid lines have been drawn from polynomial curve fitting.

A3

−0.3360

A1 −0.6034 −5.059 −8.701 −8.402 −7.786 −8.794

0.2974

−7.926 −13.095

−7.134 −10.537 −10.180

0.0047 0.0053 0.0043 0.0043 0.0038 0.159 0.114 0.143 0.143 0.095

Figure 4. Excess molar volume VEm (x1 = 0.5) for mixtures of alkoxypropanols + alkyl esters against m, the number of alkyl chain length in alkoxypropanols at 298.15 K: ⧫, MA (2); ■, EA (2); ▲, BA (2).

self-association in alkoxypropanol molecules breaks down with an increase in temperature. 3198



Article

Figure 5. Excess molar volume VEm and deviations in isentropic compressibility Δκs at x1 = 0.5 at different temperatures: ○,●, DPGMBE (1) + MA (2); △,▲, DPGMBE (1) + EA (2); □, ■, DPGMBE (1) + BA (2).

Figure 7. Deviations in isentropic compressibility Δκs (x1 = 0.5) for mixtures of alkoxypropanols + alkyl esters against m, the number of alkyl chain length in alkoxypropanols at 298.15 K: ⧫, MA (2); ■, EA (2); ▲, BA (2).

3.3. Deviation in Isentropic Compressibility. From Supporting Information, Table S1 and Figure 6, it is observed

bility of the mixture compared to pure liquids, which leads to lesser interactions. The sign and magnitude of ΔκS is vital in assessing the molecular rearrangement as a result of molecular interactions between the component molecules in the liquid mixtures. Strong molecular interactions occur through charge transfer, dipole induced-dipole, and dipole−dipole interactions, interstitial accommodation, and orientational ordering and all lead to a more compact structure which makes ΔκS negative. However, breakup of the alkoxypropanol structures tends to make ΔκS positive. The magnitude of the various contributions depends mainly on the relative molecular size of the components.

4. CONCLUSION An attempt is made to understand the mixing pattern of alkoxypropanols with n-alkyl esters in terms of excess molar volumes and isentropic compressibilities, which has been calculated from the experimental densities and ultrasonic speeds for the binary mixtures. The excess molar volumes are positive over the whole mole fraction range and at all temperatures and the magnitude of excess molar volumes decrease with an increase in the alkyl chain length of ester. The deviations in isentropic compressibilities for all mixtures are positive over the entire range of composition, and the magnitude decreases with the enlargement of the polar group of alkoxypropanols. Also, the values of deviations in isentropic compressibilities increase with decrease in chain length of ester. The results have been discussed in terms of interactions between molecules.

Figure 6. Deviations in isentropic compressibility Δκs vs volume fraction at 298.15 K for DPGMBE + ⧫, MA (2); ■, EA (2), and ▲, BA (2). Solid lines have been drawn from polynomial curve fitting.

that deviations in isentropic compressibilities for all mixtures are positive over the entire range of composition, indicating the disruption of molecular order existing between pure alkoxypropanol molecules. This behavior is similar to VEm at different temperatures for all the binaries studied. Also, this behavior may be compared with Δκs results for propylene glycol monoalkyl ether;36 the magnitude of Δκs decreases with the enlargement of the polar group of alkoxypropanols. It can be pointed out that the influence of the structure of the homologous series of esters on the isentropic compressibility behavior is very marked. An inspection of Figure 7 reveals that the ΔκS values become more positive with decreasing chain length of the ester, which indicates a significant decrease in van der Waal’s attractive forces. In Table S1 and Figure 7, a systematic increase in ΔκS (except with n-butyl acetate) with the rise in the alkyl chain length of alkoxyalkanols at all temperatures is noted for all binary mixtures at x1 = 0.5. The sign and magnitude of deviations in isentropic compressibilities make clear that fewer interactions are taking place between the binary liquid mixtures. The positive values for deviations in isentropic compressibilities suggest the increased compressi-

■

ASSOCIATED CONTENT

S Supporting Information *

Table containing excess molar volumes and isentropic compressibilitie for alkoxypropanols (1) + methyl acetate (2), + ethyl acetate (2), and + n-butyl acetate (2) at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K. This material is available free of charge via the Internet at http://pubs.acs.org.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest. 3199



■

Article

(19) Pal, A.; Kumar, H. Excess molar volumes and viscosities of binary liquid mixtures of (polyether + ester) systems at (298.15, 308.15, and 318.15) K. Fluid Phase Equilib. 2001, 181, 17−32. (20) Tower, C. A.; Carballo, E.; Cerdeirina, C. A.; Romani, L. Excess molar volumes and excess molar heat capacities of (2,5,8,11tetraoxadodecane + C4H8O2ester isomers) at several temperatures. J. Chem. Thermodyn. 1997, 29, 1353−1361. (21) Pal, A.; Sharma, S.; Gaba, R. Ultrasonic speeds and isentropic functions of (n- alkoxypropanol + n-alkanol) mixtures at 298.15 K. J. Mol. Liq. 2008, 137, 122−130. (22) Pal, A.; Gaba, R. Volumetric, acoustic, and viscometric studies of molecular interactions in binary mixtures of dipropylene glycol dimethyl ether with n-alkanols at 298.15 K. J. Chem. Thermodyn. 2008, 40, 818−828. (23) Pal, A.; Bhardwaj, R. K. Volumetric properties of some nalkoxyethanols with alkyl acetates at temperature 298.15 K. J. Indian Chem. 2001, 78, 18−22. (24) Rowlinson, J. S. Liquids and Liquid Mixtures; Butterworths: London, 1959. (25) Tu, C. H.; Peng, I. H.; Ku, S. C. Density and viscosity of mixtures of alkoxypropanols with ethanol at T = (298.15, 308.15, and 318.15) K. J. Chem. Eng. Data 2001, 46, 1392−1398. (26) Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents: Physical Properties and Methods of Purification, 3rd ed.; Wiley Interscience: New York, 1970. (27) Tangeda, S. J.; Nallani, S. N. Density and viscosity of binary liquid systems of N-methylacetamide with aromatic ketones at T = 308.15 K. J. Chem. Thermodyn. 2006, 38, 272−277. (28) Riddick, J. A.; Bunger, W. B. ; Sakano, T. K. Organic Solvents: Physical Properties and Methods of Purification, 4th ed.; John Wiley & Sons: New York, 1986. (29) Hasan, M.; Hiray, A. P.; Kadam, U. B.; Shirude, D. F.; Kurhe, K. J.; Sawant, A. B. Densities, viscosities, speeds of sound, FT-IR and 1HNMR studies of binary mixtures of n-butyl acetate with ethanol, propan-1-ol, butan-1-ol and pentan-1-ol at 298.15, 303.15, 308.15 and 313.15 K. J. Solution Chem. 2011, 40, 415−429. (30) Aminabhavi, T. M.; Raikar, S. K. Densities, viscosities, refractive indices, and speed of sound in methyl acetoacetate + methyl acetate, +n-butyl acetate,+methyl benzoate, and +ethyl benzoate at 298.15, 303.15 and 308.15 K. J. Chem. Eng. Data 1993, 38, 441−445. (31) Krishnam, K. M.; Raman, G. K. Excess volumes and speed of sound of ternary mixtures of 2-methoxyethanol (1) + butyl acetate (2) + aromatic hydrocarbons (3) at 303.15 K. J. Chem. Eng. Data 1995, 40, 128−131. (32) Rao, R. J.; Rao, C. V. Ternary liquid equilibria: Methanol− water−esters. J. Appl. Chem 1957, 7, 435−439. (33) Oswal, S. L.; Patel, N. B. Speeds of sound, isentropic compressibilities, and excess volumes of binary mixtures of acrylonitrile with organic solvents. J. Chem. Eng. Data 2000, 45, 225−230. (34) International Union of Pure and Applied Chemistry, Inorganic Chemistry Division, Commission on Atomic Weights and Isotopic Abundances.. Atomic Weights of the Elements 1985. Pure Appl. Chem. 1986, 58, 1677−1692. (35) Redlich, O.; Kister, A. T. Algebraic representation of thermodynamic properties and the classification of solutions. Ind. Eng. Chem. 1948, 40, 345−348. (36) Pal, A.; Kumar, H.; Maan, R.; Sharma, H. K. Densities and speeds of sound of binary liquid mixtures of some n-alkoxypropanols with methyl acetate, ethyl acetate and n-butyl acetate at T = (288.15, 293.15, 298.15, 303.15, and 308.15) K. J. Chem. Eng. Data 2012, 58, 225−239.

REFERENCES

(1) Nallini, S.; Boodida, S.; Tangeda, S. J. Density and speed of sound of binary mixtures of N-methylacetamide with ethyl acetate, ethyl chloroacetate, and cyanoacetate in the temperature interval (303.15 to 318.15) K. J. Chem. Eng. Data 2007, 52, 405−409. (2) Riemenschneider, W.; Bolt, H. M. Ullmann’s Encylopedia of Industrial Chemistry; Wiley-VCH: Weinheim, Germany, 2005. (3) Sastry, N. V.; Patel, M. C. Density, Excess molar volumes, viscosities, seed of sounds, excess isentropic compressibilities and relative permittivities for alkyl (methyl, ethyl, butyl and isoamly) acetates + glycols at different temperatures. J. Chem. Eng. Data 2003, 48, 1019−1027. (4) Aminabhavi, T. M.; Banarjee, K. Density, Viscosities, refractive index and speed of sound in binary mixtures of methyl acetate+ ethylene glycol or + poly (ethylene glycol) in the temperature interval (298.15−308.15) K. J. Chem. Eng. Data 1998, 43, 852−855. (5) Ortega, J.; Pena, J. A.; Paz Andrade, M. I. Excess molar volumes of binary mixtures of ethyl acetate and propyl acetate with normal alkanols. Aus. J. Chem. 1986, 39, 1685−1690. (6) Qin, A.; Hoffmann, D. E.; Munk, P. Excess volumes of mixtures of some alkyl esters with ketones with alkanols. Collect. Czech. Chem. Commun. 1993, 58, 2625−2641. (7) Nikam, P. S.; Mahale, T. R.; Hasan, M. Density and viscosity of binary mixtures of ethyl acetate with methanol, ethanol, propan-1-ol, propan-2-ol, 2-methylpropan-1-ol and 2-mehtyl propan-2-ol at (298.15, 303.15 and 308.15) K. J. Chem. Eng. Data 1996, 41, 1055− 1058. (8) Canosa, J.; Rodriguez, A.; Tojo, J. Dynamic viscosities of (methyl acetate or methanol) with (ethanol, 1-propanol, 2- propanol, 1butanol and 2- butanol) at 298.15 K. J. Chem. Eng. Data 1998, 43, 417−421. (9) Oswal, S. L.; Patel, N. B. Speed of sound, isentropic compressibility, viscosity and excess volumes of binary mixtures. I. Acetonitrile with alkyl acetate. J. Chem. Eng. Data 1995, 40, 840−844. (10) Aminabhavi, T. M.; Banerjee, K. Viscosity, refractive index and speed of sound in binary mixtures of acrylonitrile with methyl acetate, ethyl acetete, n-propyl acetate, n-butyl acetate and 3-methyl butyl 2acetate in the temperature interval (298.15−308.15) K. J. Chem. Eng. Data 1998, 43, 514−518. (11) Ortega, J.; Espiau, F.; Tojo, J.; Canosa, J.; Rodriguez, A. Isobaric vapor-liquid equilibria and excess properties for the binary systems of methyl esters + heptane. J. Chem. Eng. Data 2003, 48, 1183−1190. (12) Ortega, J.; Espiau, F.; Toledo, F. Thermodynamic properties of (an ester + an alkane). XVI. Experimental HE and VE values and a new correlation method for (an alkyl ethanoate + an alkane) at 318.15 K. J. Chem. Thermodyn. 2004, 36, 193−209. (13) Ortega, J.; Matos, J. S.; Paz-Andrade, M. I.; Fernandez, J. Excess molar volumes of ethyl formate or ethyl acetate + 1-chloroalkane at 298.15 K. J. Chem. Eng. Data 1987, 32, 464−466. (14) Aralaguppi, M. I.; Jadar, C. V.; Aminabhavi, T. M. Density, viscosity, refractive index, and speed of sound in binary mixtures of 2chloroethanol with methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate. J. Chem. Eng. Data 1999, 44, 441−445. (15) Fárková, J.; Wichterle, I. Vapor pressure of some ethyl and propyl esters of fatty acids. Fluid Phase Equilib. 1993, 90, 143−148. (16) Aminabhavi, T. M.; Phayde, H. T. S.; Khinnavar, R. S.; Bindu, G. Densities, refractive indices, speeds of sound, and viscosities of diethylene glycol dimethyl ether + butyl acetate at 298.15, 303.15, 308.15, 313.15, and 318.15 K. J. Chem. Eng. Data 1993, 38, 542−545. (17) Aminabhavi, T. M.; Phayde, H. T. S.; Khinnavar, R. S.; Bindu, G. Densities, refractive indices, speeds of sound, and shear viscosities of diethylene glycol dimethyl ether with ethyl acetate, methyl benzoate, ethyl benzoate, and diethyl succinate in the temperature range from 298.15 to 318.15 K. J. Chem. Eng. Data 1994, 39, 251−260. (18) Tovar, C. A.; Carballo, E.; Cerdeirina, C. A.; Romani, L. Excess molar volumes and excess molar heat capacities of mixtures containing (mono and poly) ethers + ethyl acetate. J. Chem. Eng. Data 1997, 42, 1085−1089. 3200


Volumetric and Ultrasonic Studies of Molecular Interactions in n

Recommend Documents