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DOI 10.1007/s11746-014-2450-1
ORIGINAL PAPER
Received: 25 October 2013 / Revised: 21 February 2014 / Accepted: 4 March 2014 / Published online: 2 April 2014
AOCS 2014
Abstract Densities q, ultrasonic speeds u and dynamic the communities in the Kalahari region of southern
viscosities g, of mixtures of morama, Tylosema esculen- Africa where it is extracted from the morama bean by
tum, seed oil with n-hexane, n-heptane, n-octane and traditional methods, e.g., by boiling the pounded seeds
n-nonane were determined over the entire composition in water and skimming the oil at the top. The oil is
range at 298.15 K and atmospheric pressure. Excess molar widely used for cooking and also for making butter.
volumes, VmE , excess molar free volumes VfE , deviations in Reported physicochemical parameters of the morama oil
isentropic compressibility, Djs, deviations in ultrasonic such as iodine value (IV), acid value (AV), and
speed, Du, deviations in viscosity, Dg, and the excess free saponification value (SV), peroxide value (PV), refrac-
energy of activation of viscous flow, DG*E, were calcu- tive index and density collectively described morama oil
lated therefrom and correlated by the RedlichKister as composed of medium chain-length fatty acids (C16/
equation for each of the [morama seed oil ? (n-hexane or C18) with medium unsaturation and favourable oxida-
n-heptane or n-octane or n-nonane)] mixtures. The results tive and hydrolytic stability [13]. Analysis of the lipid
have been discussed in terms of possible intermolecular classes showed the morama seed oil to be mainly made
interactions and structural effects. up of non-polar lipids, with triacylglycerol (TAG) being
the predominant lipid class [1]. GCMS determination
Keywords n-Alkanes Excess molar volume Excess of the fatty acid composition of morama oil showed
molar free volume Dynamic viscosity Isentropic morama oil to be typically oleic, with oleic acid content
compressibility Excess free energy of activation of in the range 4553 %. Other major fatty acid compo-
viscous flow Morama Tylosema esculentum nents are linoleic acid (2125 %), palmitic acid
(1216 %) and stearic acid (79 %) [1, 3, 4]. This fatty
acid composition of morama oil closely resembles that
Introduction of olive oil, both of which contain small but measurable
amounts of long chain fatty acids like C20:0, C22:0 and
The morama, Tylosema esculentum, seed oil is light C22:1. Analysis with a high resolution MS technique,
yellowish oil, which is much acclaimed due to its fine ESI-FTICR-MS, indicated that morama oil is made up
organoleptic properties and its good oxidative stability of seven major triacylglycerol classes, chief among
at ambient temperatures. The oil is highly cherished by which are C54:4, C54:3 and C52:3. The 13C NMR ana-
lysis revealed that the sn-2 position of the glycerol
backbone is 100 % occupied by oleoyl and linoleoyl
acyl chains [1, 2]. Thus, triacylglycerol molecules such
S. O. Yeboah (&) I. Oathotse W. A. A. Ddamba (&)
as triolein (OOO) will be predominantly present in the
Department of Chemistry, University of Botswana, Gaborone,
Botswana morama oil. This makes morama oil nutritionally a good
e-mail: yeboahso@mopipi.ub.bw monounsaturated oil, as the structure of the triacyl-
W. A. A. Ddamba glycerol molecules makes the unsaturated fatty acids
e-mail: ddambawa@mopipi.ub.bw readily available for metabolism.
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1066 J Am Oil Chem Soc (2014) 91:10651075
The socio-economic importance of the morama seed oil Materials and Methods
has attracted attention in the southern African region.
Currently a number of agricultural research groups are Materials
working on the domestication of the morama plant for
possible large scale production, whilst the quality, stability Analytical reagent grades of n-hexane, n-heptane,
and the chemistry of the morama seed oil is under intense n-octane and n-nonane were used, and were purchased
investigation in our laboratories. Oil yield from the mora- from Aldrich Chemicals. The n-alkanes were fractionally
ma bean has been reported to be 3648 % [1, 3], which is distilled and stored over 0.4 nm molecular sieves for
about two-fold higher than the oil output from soybean and, 60 h to remove any water content. The mass fraction
thus, makes morama oil an attractive candidate for com- purities that were tested by gas chromatography were: n-
mercial exploitation. hexane ([99 %), n-heptane ([99 %), n-octane
Morama oil contains modest amounts of phytosterols ([99.6 %) and n-nonane ([98.5). The purity of the four
and tocopherols, both being higher in morama oil than n-alkanes was tested by comparing their densities q,
in olive oil [2]. The total phytosterol content of the speeds of sound, u, and dynamic viscosities, g at
morama oil has been reported to be 150 lg/g, with 298.15 K, with reported literature data in Table 1, which
b-sitosterol, stigmasterol and campesterol being the also includes our measured values of these quantities. It
major phytosterols [2]. It is worth noting that these can be observed from Table 1 that the measured values
phytosterols have been attributed with favourable bio- of q, u and g were in good agreement with the literature
active properties such as prevention of cancer and data [712]. Benzene (Aldrich Chemicals, p.a.) used for
lowering of total plasma cholesterol [4, 5]. Total tocol the densimeter calibration was purified as reported
content of the morama oil has been reported as about elsewhere [7]. Water was first de-ionized by means of
200 lg/g, which is mainly made up of c-tocopherol and ion exchange resins and then triply distilled over KMnO4
a-tocopherol, both being strong antioxidants [2, 4]. under nitrogen. Its conductivity was always less than
Thus, overall, morama oil is nutritionally and health- 1.0 9 10-6 S cm-1. All purified organic solvents were
wise wholesome and, hence, the keen interest in trying stored in brown glass bottles and fractionally distilled
to develop it into a commercial commodity. and degassed immediately before preparation of binary
Edible oil processing widely applies organic solvents mixtures. The morama seed oils used in this investiga-
for different purification and treatment procedures such tion were obtained by solvent extraction [2], and were
as de-acidification and winterization. Despite their analyzed by means of a gas chromatograph Thermo-
application in various industrial scale purification pro- Quest Voyager capillary GCMS model coupled to a
cedures, experimental data on the physico-chemical and ThermoQuest Trace GC 2000 SERIES detector (San
thermodynamic properties of edible oil mixtures with Jose, California, USA). The details of the procedure for
potential separation solvents using environmentally the chromatographic analysis were described in previous
friendly procedures of extraction are rare in the litera- works [1]. The fatty acid composition obtained: oleic
ture. In our systematic investigation of the thermody- acid, 47.27 %; linoleic acid, 23.40 %; palmitic acid,
namic, acoustic and transport properties, we measured 12.93 %; stearic acid, 8.82 %; arachidic acid, 3.31 %;
density, q, ultrasonic speed u and dynamic viscosity g, erucic acid, 2.63 %; behenic acid, 1.03 % and arachi-
of binary systems of the morama seed oil with n-hexane, donic acid, 0.61 %; the uncertainty in mol % for these
n-heptane, n-octane and n-nonane at 298.15 K over the analyses were better than 0.06. The calculated average
entire mole fraction range of the mixtures investigated. molar mass of the morama seed oil used in this study
These experimental data have been used to calculate the was 850.34 g mol-1. The variation in the composition
excess molar volumes, VmE , excess molar free volume, between different oil samples affects mainly the mono-
VfE , deviations in ultrasonic speed, Du, deviations in unsaturated and polyunsaturated fatty acids, the change
isentropic compressibility, Djs, deviations in viscosity, in molar mass being lower than 3 g mol-1.
Dg, and the excess free energy of activation of viscous
flow, DG*E. The calculated excess or deviation func- Measurement of Physicochemical Properties
tions: (VmE , VfE , Djs, Du, Dg, DG*E), have been fitted to
the RedlichKister polynomial equation [6]. The varia- Solution Density
tion of these functions with composition at 298.15 K are
discussed in terms of non-specific molecular interaction Density measurements were performed at atmospheric
in the [morama seed oil ? (C6C9) n-alkane] binary pressure with an Anton Parr DMA 4500 vibrating-tube
systems. precision densimeter, thermostated at 298.15 K. The
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J Am Oil Chem Soc (2014) 91:10651075 1067
Table 1 Values of density q, ultrasonic velocities u, and dynamic viscosities g for pure liquids at T = 298.15 K
Liquid qexp (kg m-3) qlit (kg m-3) uexp (m s-1) ulit (m s-1) gexp (mPa s) glit (mPa s)
densimeter was first calibrated with ultra pure water and Ultrasonic Speeds
benzene [1315] as reference liquids. The [morama seed
oil ? (n-hexane or n-heptane, or n-octane or n-nonane)] The ultrasonic speeds were measured with an uncertainty
binary mixtures were prepared by weighing appropriate of 0.3 % using a single-crystal variable-path ultrasonic
amounts of the purified morama seed oil and n-alkane on interferometer (Mittal Enterprises, New Delhi, India),
a Sartorius Supermicro balance (Fabr.-Nr., Dm = 10-6 which was first calibrated with triply distilled water
g) by syringing each component into Teflon stoppered (Table 1). The temperature was maintained to with-
flasks in order to minimize preferential evaporation of the in 0.01 K by circulating thermostated water around a
alkane. Pure components were separately degassed by steel cell fitted with a quartz crystal of 1 MHz. In order to
ultrasound shortly before sample preparations. This pro- minimize the uncertainty in the wavelength measurements,
cedure eliminated possible changes in mixture composi- the number of measured maxima, n, was recorded against
tion that could occur during the degassing of already the total distance, d, covered by the reflector. Each maxi-
prepared binary mixtures. The uncertainty in solution mum was recorded with the highest swing of the needle on
composition expressed as mole fraction was found to be the micrometer scale for maximum sensitivity. The total
less than 8 9 10-5. A sample volume of not more than distance, d, is given by:
1.0 cm3 was needed to fill the densimeter cell, and ther- d nk=2; 1
mal equilibrium was attained quickly at each temperature.
The temperature of the sample was controlled electrically where k is the wavelength. All plots of d vs n generated
by means of a built-in thermostat (a semiconductor Peltier were linear (r2 = 1) with a slope of k/2. The frequency of
element and a resistance thermometer temperature control the cell single-crystal, m being accurately known (1 MHz),
system) and was measured with an accuracy of 0.01 K. the speed of sound, u, is calculated by using the relation:
The densimeter was calibrated after each set of four u km: 2
sample measurements to offset any problem of instrument
drift. There was, however, no noticeable drift in the Each ultrasonic speed value presented in Tables 1 and 2
density of the reference fluid and a linear relation between represents an average of u values deduced from four
the density of the fluid and the square of the vibrating independently determined k/2 values for pure components
period s, (q = A ? Bs2), was assumed. Buoyancy cor- and [MO ? n-alkane] binary compositions.
rections to the weight were made by taking into account
the air density, the barometric pressure, and the relative Dynamic Viscosity
humidity. Under such conditions quadruplet density
measurements of each sample were reproducible to Dynamic viscosity, g-values of the pure liquids and their
within 0.01 kg m-3. binary mixtures were measured at 298.15 K using an
123
1068 J Am Oil Chem Soc (2014) 91:10651075
Table 2 Densities, speeds of sound, deviation in speed of sound, of viscous flow and molar free volume for [(C6C9) n-alkane
deviation in isentropic compressibility, excess molar volumes, (1) ? MO (2)] binary systems at 298.15 K
deviation in dynamic viscosity, excess Gibbs free energy of activation
X2 q (kg m-3) u (m s-1) Du (m s-1) 1010 9 Djs (m2 N-1) 106 9 VmE (m3 mol-1) Dg (mPa s) DG*E (J mol-1) 106 9 VfE (m3 mol-1)
MO ? n-hexane
0.0040 662.71 1,093.8 10.59 -0.403 -0.1182 -0.1266 1,139 -0.0134
0.0062 667.11 1,100.0 15.95 -0.609 -0.2457 -0.1915 1,617 -0.0175
0.0081 670.70 1,106.2 21.45 -0.799 -0.3545 -0.2458 1,950 -0.0255
0.0106 675.48 1,112.2 26.50 -0.995 -0.5047 -0.3203 2,336 -0.0305
0.0142 681.57 1,117.0 29.93 -1.175 -0.6035 -0.4286 2,796 -0.0615
0.0164 685.31 1,124.2 36.31 -1.372 -0.7025 -0.4943 3,031 -0.0752
0.0211 692.68 1,129.8 41.26 -1.570 -0.8101 -0.6396 3,470 -0.0862
0.0252 698.92 1,132.8 43.11 -1.698 -0.9585 -0.7646 3,780 -0.0976
0.0313 707.60 1,147.5 53.98 -2.067 -1.1175 -0.9563 4,172 -0.1100
0.0359 713.88 1,152.5 57.22 -2.217 -1.2455 -1.1039 4,423 -0.1200
0.0407 720.10 1,158.4 61.33 -2.377 -1.3985 -1.2560 4,646 -0.1409
0.0499 730.95 1,182.0 81.45 -2.861 -1.5876 -1.5552 5,009 -0.1576
0.0601 741.84 1,192.9 88.48 -3.100 -1.7628 -1.8925 5,332 -0.1679
0.0714 752.77 1,205.4 96.71 -3.341 -1.9598 -2.2691 5,616 -0.1818
0.0807 760.92 1,212.6 100.42 -3.473 -2.1113 -2.5785 5,805 -0.1972
0.0899 768.39 1,228.7 113.02 -3.717 -2.2288 -2.8909 5,966 -0.2037
0.1021 777.24 1,242.7 122.42 -3.910 -2.3413 -3.3004 6,140 -0.2124
0.1526 805.81 1,274.3 134.96 -4.201 -2.5267 -4.9651 6,569 -0.2355
0.2025 826.06 1,310.9 152.69 -4.406 -2.6293 -6.4795 6,712 -0.2447
0.3004 852.35 1,354.2 158.99 -4.280 -2.5217 -8.7823 6,581 -0.2363
0.3993 869.33 1,390.4 157.84 -3.948 -2.3011 -9.9674 6,126 -0.2128
0.5088 882.19 1,411.4 137.47 -3.345 -2.0046 -9.9031 5,374 -0.1727
0.6013 890.05 1,422.3 113.44 -2.752 -1.6726 -8.8925 4,579 -0.1401
0.6991 896.50 1,431.8 85.98 -2.094 -1.3145 -7.1504 3,607 -0.1024
0.8046 902.01 1,439.0 53.31 -1.349 -0.9415 -4.8390 2,432 -0.0704
0.9023 906.02 1,448.7 26.11 -0.674 -0.4869 -2.5495 1,249 -0.0394
MO ? n-heptane
0.0041 685.99 1,137.8 1.36 -0.135 -0.1159 -0.0652 1,206 -0.0113
0.0062 689.01 1,141.5 4.39 -0.244 -0.1548 -0.0986 1,635 -0.0148
0.0081 691.68 1,145.9 8.19 -0.360 -0.1897 -0.1292 1,962 -0.0216
0.0105 695.01 1,149.4 10.89 -0.464 -0.2143 -0.1699 2,330 -0.0258
0.0142 699.88 1,153.5 13.78 -0.593 -0.2313 -0.2339 2,798 -0.0520
0.0162 702.54 1,155.7 15.34 -0.662 -0.2792 -0.2682 3,008 -0.0637
0.0183 705.43 1,159.8 18.76 -0.768 -0.3592 -0.3050 3,209 -0.0729
0.0211 708.92 1,163.3 21.34 -0.865 -0.3873 -0.3557 3,455 -0.0826
0.0304 719.97 1,186.8 41.84 -1.369 -0.5496 -0.5271 4,094 -0.0931
0.0352 725.31 1,192.5 45.98 -1.505 -0.6194 -0.6197 4,356 -0.1015
0.0403 730.61 1,196.6 48.44 -1.610 -0.6758 -0.7192 4,596 -0.1192
0.0506 740.56 1,208.5 56.97 -1.858 -0.7371 -0.9297 5,000 -0.1333
0.0601 749.03 1,217.9 63.30 -2.044 -0.8243 -1.1284 5,291 -0.1590
0.0702 757.43 1,227.6 69.66 -2.220 -0.9197 -1.3474 5,545 -0.1608
0.0803 765.08 1,240.1 78.94 -2.419 -0.9908 -1.5706 5,753 -0.1722
0.0901 771.96 1,253.7 89.36 -2.615 -1.0598 -1.7907 5,920 -0.1820
0.1035 780.90 1,272.7 104.01 -2.867 -1.2291 -2.0967 6,104 -0.1921
0.2013 825.04 1,321.5 121.11 -3.221 -1.5394 -4.3000 6,621 -0.2116
0.2964 850.20 1,356.5 125.23 -3.174 -1.5421 -6.0009 6,467 -0.2078
0.4012 868.22 1,387.6 122.35 -2.928 -1.4243 -6.9852 5,958 -0.1823
0.5020 880.20 1,410.4 112.47 -2.568 -1.2148 -6.9629 5,260 -0.1539
0.6029 889.19 1,423.8 93.10 -2.100 -1.0371 -6.1099 4,407 -0.1200
0.7004 895.86 1,434.7 72.39 -1.615 -0.8224 -4.7391 3,463 -0.0909
0.8002 901.26 1,443.7 49.01 -1.090 -0.4936 -3.0759 2,394 -0.0624
0.9001 905.66 1,448.7 21.61 -0.527 -0.2758 -1.4316 1,234 -0.0332
123
J Am Oil Chem Soc (2014) 91:10651075 1069
Table 2 continued
X2 q (kg m-3) u (m s-1) Du (m s-1) 1010 9 Djs (m2 N-1) 106 9 VmE (m3 mol-1) Dg (mPa s) DG*E (J mol-1) 106 9 VfE (m3 mol-1)
MO ? n-octane
0.0042 704.02 1,179.3 3.69 -0.143 -0.0902 -0.0491 1,080 -0.0077
0.0060 706.14 1,183.0 6.88 -0.228 -0.1082 -0.0701 1,417 -0.0101
0.0080 708.47 1,185.9 9.21 -0.300 -0.1251 -0.0941 1,744 -0.0147
0.0102 710.99 1,190.3 12.98 -0.398 -0.1436 -0.1207 2,058 -0.0176
0.0141 715.22 1,193.0 14.59 -0.481 -0.1681 -0.1679 2,514 -0.0355
0.0168 718.24 1,195.7 16.50 -0.552 -0.2061 -0.2023 2,790 -0.0434
0.0184 719.99 1,198.3 18.64 -0.610 -0.2272 -0.2229 2,938 -0.0497
0.0202 721.87 1,201.5 21.34 -0.677 -0.2505 -0.2455 3,088 -0.0563
0.0302 731.93 1,214.1 31.08 -0.952 -0.3647 -0.3773 3,773 -0.0635
0.0355 736.81 1,220.0 35.49 -1.075 -0.4100 -0.4485 4,053 -0.0692
0.0406 741.51 1,228.2 42.22 -1.226 -0.4740 -0.5204 4,291 -0.0813
0.0506 749.89 1,234.9 46.09 -1.370 -0.5617 -0.6623 4,672 -0.0909
0.0603 757.38 1,240.9 49.31 -1.489 -0.6071 -0.8061 4,972 -0.1084
0.0699 764.31 1,248.5 54.17 -1.620 -0.6655 -0.9517 5,214 -0.1164
0.0800 771.15 1,264.4 67.18 -1.850 -0.7392 -1.1083 5,425 -0.1311
0.0901 777.35 1,270.2 70.12 -1.935 -0.7714 -1.2668 5,600 -0.1477
0.1008 783.59 1,276.2 73.07 -2.017 -0.8219 -1.4389 5,755 -0.1554
0.1501 807.25 1,301.3 84.12 -2.280 -0.9580 -2.2486 6,188 -0.1687
0.2003 825.45 1,331.0 99.48 -2.495 -1.0534 -3.0634 6,337 -0.1758
0.3020 851.03 1,365.2 104.71 -2.499 -1.0991 -4.4730 6,176 -0.1652
0.4016 867.71 1,391.6 102.69 -2.333 -1.0551 -5.3094 5,691 -0.1458
0.5061 880.13 1,412.6 93.91 -2.045 -0.9584 -5.4352 4,978 -0.1227
0.6006 888.59 1,423.8 78.16 -1.694 -0.8574 -4.8731 4,207 -0.0993
0.7023 895.64 1,433.3 58.67 -1.280 -0.6758 -3.6789 3,271 -0.0728
0.8054 901.25 1,442.7 38.69 -0.847 -0.4109 -2.1305 2,224 -0.0495
0.9011 905.55 1,445.5 14.21 -0.394 -0.1887 -0.7799 1,170 -0.0268
MO ? n-nonane
0.0046 718.74 1,213.0 1.17 -0.079 -0.0527 -0.0545 852 -0.0051
0.0064 720.62 1,214.0 1.72 -0.111 -0.0857 -0.0763 1,118 -0.0067
0.0080 722.33 1,215.9 3.21 -0.156 -0.1169 -0.0964 1,337 -0.0098
0.0107 724.97 1,218.8 5.44 -0.222 -0.1468 -0.1292 1,652 -0.0117
0.0141 728.15 1,223.0 8.79 -0.311 -0.1590 -0.1712 1,998 -0.0237
0.0162 730.02 1,225.7 10.98 -0.366 -0.1707 -0.1963 2,180 -0.0289
0.0181 731.81 1,228.3 13.09 -0.418 -0.1843 -0.2208 2,342 -0.0331
0.0206 733.98 1,230.1 14.27 -0.461 -0.1878 -0.2518 2,530 -0.0376
0.0300 741.93 1,235.7 17.53 -0.596 -0.2296 -0.3706 3,116 -0.0423
0.0354 746.31 1,240.0 20.48 -0.685 -0.2659 -0.4399 3,387 -0.0461
0.0408 750.47 1,245.9 25.05 -0.792 -0.2971 -0.5093 3,621 -0.0542
0.0503 757.49 1,252.9 29.68 -0.924 -0.3664 -0.6331 3,969 -0.0606
0.0601 764.22 1,260.0 34.35 -1.049 -0.4287 -0.7619 4,262 -0.0723
0.0702 770.7 1,266.0 37.84 -1.151 -0.4845 -0.8961 4,512 -0.0776
0.0808 777.06 1,274.0 43.20 -1.271 -0.5411 -1.0378 4,730 -0.0874
0.0900 782.22 1,280.2 47.10 -1.359 -0.5812 -1.1613 4,891 -0.0978
0.1006 787.92 1,287.0 51.26 -1.451 -0.6596 -1.3036 5,048 -0.1059
0.1504 809.85 1,309.8 61.69 -1.697 -0.7941 -1.9613 5,514 -0.1238
0.1999 826.61 1,330.2 69.77 -1.840 -0.8803 -2.5751 5,700 -0.1372
0.3016 851.09 1,363.1 77.37 -1.907 -0.9158 -3.5906 5,627 -0.1321
0.4041 867.72 1,386.6 75.37 -1.786 -0.8507 -4.1383 5,207 -0.1172
0.5001 879.03 1,405.6 70.47 -1.600 -0.7449 -4.1435 4,626 -0.0988
0.6042 888.4 1,423.3 62.27 -1.345 -0.6518 -3.6109 3,853 -0.0816
0.7024 895.22 1,433.8 48.34 -1.036 -0.4798 -2.7044 3,018 -0.0638
0.8514 903.22 1,442.5 19.97 -0.495 -0.2157 -1.0404 1,592 -0.0355
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1070 J Am Oil Chem Soc (2014) 91:10651075
Ubbelohde viscometer. The viscometer was thoroughly Djs js x1 js;1 x2 js;2 4
cleaned, perfectly dried and filled with sample liquid and
its limbs closed to minimize partial evaporation of the n- where the subscripts 1 and 2 stand for the pure n-alkane
alkane. The apparatus was submerged in a transparent and MO, respectively. Assuming the absorption of the
walled thermostatic water-bath at 298.15 K with a resolu- acoustic wave is negligible, the value of js is calculated
tion of 0.05 K and allowed to stand for about 25 min to from the NewtonLaplace equation:
attain thermal equilibrium. The viscometer was calibrated 1
jS q u2 : 5
to determine the two viscometer constants A and B in the
equation g qAt B/t, by measuring efflux time t with The deviations of speed of sound, Du, were calculated
triply distilled water and cyclohexane. The efflux time for using the relation:
the flow of a finite volume of liquid through the capillary of Du u x1 u1 x2 u2 : 6
the viscometer was measured with an electronic digital
stopwatch with a precision of 0.1 s. Four repetitions of The deviations in dynamic viscosity, Dg, from linear
readings for the efflux time were measured for each pure dependence and excess free molar volume, VfE , were cal-
liquid or binary liquid mixture and the results were aver- culated by using the following relations:
aged. The obtained parameters were: A = 4.7706 m2 s-2 Dg g x1 g1 x2 g2 ; 7
and B = -1.9625 m2. The dynamic viscosity was repro-
ducible to within 2.0 9 10-3 mPa s. VfE Vf;m x1 Vf;1 x2 Vf;2 ; 8
where g is the dynamic viscosity of the binary mixture and
gi is the viscosity of pure component i, Vf,m and Vf,i rep-
Results and Discussion resent molar free volume of the mixture and pure compo-
nent i, respectively.
Experimental density, q, ultrasonic speed, u, and The molar free volume can be estimated using the
dynamic viscosity, g, for pure n-hexane, n-heptane, relation:
n-octane, n-nonane and the morama seed oil (MO) at
298.15 K are listed in Table 1, together with the liter- Vf; Mu = kg3=2 ; 9
ature data. The agreement, within the experimental 9
where k is a constant equal to 4.28 9 10 [16].
uncertainties, between the measured and the literature
On the basis of the theory of absolute reaction rates [17],
values confirmed the purity of the chemicals used as
the excess free energy of activation of viscous flow, DG*E,
well as the accuracy of the equipment and the experi-
was calculated by using the following equation:
mental procedure. The experimental values of q, u, and
g, with respect to the mole fraction x2 for the MO at DGE RT lngV x1 lng1 V1 x2 lng2 V2 ; 10
298.15 K and atmospheric pressure are listed in Table 2. where R is the universal constant of gases, T is the absolute
To the best of our knowledge, no data have been temperature, V and Vi are molar volumes of the binary
reported previously for the density, ultrasonic speeds or mixtures and pure component i, respectively.
dynamic viscosity for any of the binary systems in the
The values of the functions: VmE , VfE , Djs, Du, Dg and
present investigations.
DG*E (Table 2) for each of the [MO ? (C6C9) n-alkane]
Excess molar volumes, VmE , were calculated for each binary systems were least-squares fitted to the Redlich
[MO ? (C6C9) n-alkane] binary composition at 298.15 K Kister polynomial regressions [6]:
from density measurements using the following equation:
X n
VmE Vm Vmid M=q xi Mi =qi ; 3 wE x1 x2 R Ak 1 2x2 k ; 11
k0
where M is the molar mass of the mixture, which is the where WE = VmE , VfE , Djs, Du, Dg and DG*E.
mole fraction weighted adduct of the molar masses of the All points in the polynomial were weighted equally and
two pure components in each binary mixture. Vmid is the the regression coefficients Ak in Eq. (11) were evaluated by
ideal molar volume, q is the density of the mixture, and xi, the least-squares method. The estimated values of Ak
Mi and qi are, respectively, the mole fraction, the molar regression coefficients for the excess or deviation proper-
mass and the density of the pure liquid component i. ties: (VmE , VfE , Djs, Du, Dg or DG*E) for each of the
The values of the deviations in isentropic compress- [MO ? (C6C9) n-alkane] binary mixtures at 298.15 K are
ibility, Djs, for each binary system were calculated by listed in Table 3 along with the corresponding standard
using the following standard relation: deviations r(WE) defined by Eq. (12).
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J Am Oil Chem Soc (2014) 91:10651075 1071
Table 3 Least squares fitted Ak coefficients of the RedlichKister polynomial Eq. 11 and corresponding standard deviations of the fits, r (WE),
for the [(C6C9) n-alkane (1) ? MO (2)] binary systems at 298.15 K
Excess property A0 A1 A2 A3 A4 A5 A6 r (WE)
MO ? n-hexane
106 9 VmE (m3 mol-1) -8.122 6.765 -4.295 -0.203 -11.466 14.459 0.027
1010 9 DjS (m2 N-1) -13.403 12.523 -16.287 0.247 31.793 22.178 -54.860 0.080
Du (m s-1) 557.14 -443.08 193.88 39.92 -159.22 -503.96 686.63 3.32
Dg (mPa s) -39.823 11.430 12.014 -9.966 1.336 -1.760 -3.135 0.004
*E -1
DG (kJ mol ) 21.37 -20.08 47.40 118.81 -359.02 -953.21 113.83 0.15
106 9 VfE (m3 mol-1) -0.704 0.781 -0.764 -0.135 0.757 1.230 -2.008 0.006
MO ? n-heptane
106 9 VmE (m3 mol-1) -4.862 3.846 -6.919 3.067 12.104 0.607 -13.794 0.030
10 2 -1
10 9 DjS (m N ) -10.302 8.115 -4.813 5.404 -11.700 9.239 0.054
Du (m s-1) 455.18 -273.60 -206.33 -221.62 1,879.48 -244.32 -1,696.69 3.49
Dg (mPa s) -27.888 9.013 13.638 -7.762 0.003
DG*E (kJ mol-1) 20.61 -21.17 52.88 143.89 -416.91 -1,114.2 1,344.44 0.15
6 3 -1
10 9 VfE (m mol ) -0.613 0.666 -0.612 -0.104 0.316 1.180 -1.380 0.006
MO ? n-octane
106 9 VmE (m3 mol-1) -3.874 1.911 -2.786 3.578 4.412 0.378 -6.659 0.013
10 2 -1
10 9 DjS (m N ) -8.278 7.125 -3.259 -1.973 -7.410 13.327 0.030
Du (m s-1) 376.10 -268.29 54.02 71.84 303.52 -436.59 -195.58 2.03
Dg (mPa s) -21.800 4.400 14.800 0.009
DG*E (kJ mol-1) 19.74 -19.17 434.05 104.87 -308.19 -836.02 971.85 0.12
106 9 VfE (m3 mol-1) -0.495 0.448 -0.380 0.607 -0.585 0.005
MO ? n-nonane
106 9 VmE (m3 mol-1) -3.044 2.302 -1.576 1.855 -0.464 0.025
1010 9 DjS (m2 N-1) -6.427 4.558 -3.092 2.515 -2.984 4.160 0.016
Du (m s-1) 282.81 -129.32 113.35 -222.12 -56.10 1.23
Dg (mPa s) -16.575 5.050 9.725 0.002
DG*E (kJ mol-1) 185.78 -8.07 6.66 -96.91 52.84 318.91 -62.82 0.14
106 9 VfE (m3 mol-1) -0.769 0.219 -4.254 6.380 21.880 -10.003 -30.861 0.003
123
1072 J Am Oil Chem Soc (2014) 91:10651075
Table 4 Limiting excess molar volumes ViE;1 (m3 mol-1) for the
components in [(C6C9) n-alkane (1) ? MO (2)] binary systems at
298.15 K
n-hexane n-heptane n-octane n-nonane
(m3 mol-1)
-1
(m3 mol-1)
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J Am Oil Chem Soc (2014) 91:10651075 1073
u / (ms )
(mPa.s)
-1
X2 x2
Fig. 2 Deviations of speed of sound, Du vs X2 for the [(C6C9) Fig. 4 Deviations in dynamic viscosity, Dg vs X2 for the [(C6C9)
n-alkane (1) ? MO (2)] binary mixtures at 298.15 K. Symbols are n-alkane (1) ? MO (2)] binary mixtures at 298.15 K. Symbols are
same as in Fig. 1 same as in Fig. 1
123
1074 J Am Oil Chem Soc (2014) 91:10651075
4000
atmospheric pressure. The excess volume VmE , deviations in
3000
the speed of sound Du, deviations in isentropic compress-
E
-0.3
Acknowledgments Financial support from the Office of Research
X2 and Development, University of Botswana, is gratefully acknowledged.
Fig. 6 Excess free molar volume, VfE vs X2 for the [(C6C9) n-alkane
(1) ? MO (2)] binary mixtures at 298.15 K. Symbols are same as in
Fig. 1 References
123
J Am Oil Chem Soc (2014) 91:10651075 1075
6. Redlich O, Kister TA (1948) Algebraic representation of ther- 18. Acree WE Jr (1984) Thermodynamic properties of non-electro-
modynamic properties and the classification of solutions. Ind Eng lytes. Academic Press, Orlando
Chem 40(2):345348 19. Maham Y, Teng TT, Hepler LG, Mather AE (1994) Densities,
7. Riddick JA, Bunger WB, Sakano TK (1986) Organic solvents: excess molar volumes, and partial molar volumes for binary
physical properties and methods of purification, 4th edn. Wiley- mixtures of water with monoethanolamine, diethanolamine, and
Interscience, New York triethanolamine from 25 to 80 C. J Solution Chem
8. Dubey GP, Sharma M (2008) Study of molecular interactions in 23(2):195205
binary mixtures of 1-octanol with n-hexane, n-octane, and n- 20. Orge B, Iglesias M, Marino G, Tojo J (1999) Thermodynamic
decane using volumetric, viscometric, and acoustic properties. properties of (acetone methanol ? 2-butanol) at T = 298.15 K.
J Chem Thermodyn 40(6):9911000 J Chem Thermodyn 31(4):497512
9. Iloukhani H, Rezaei-Samet M, Basiri-Parsa J (2006) Excess 21. Lee B (1983) Partial molar volumes from the hard sphere mixture
molar volumes and dynamic viscosities for binary mixtures of model. J Phys Chem 87(1):112118
toluene ? n-alkanes (C5C10) at T = 298.15 Kcomparison 22. Lampreia IMS, Ferreira LAV (1997) Limiting partial molar
with PrigogineFloryPatterson theory. J Chem Thermodyn volumes an expansions for triethylamine in water and in aqueous
38(8):975982 tetraethylammonium chloride solutions from 15 to 35 C. J Chem
10. Gonzalez C, Iglesias M, Lanz J, Resa JM (1999) Temperature Soc Faraday Trans 93(13):22772281
dependence of excess molar volumes in (n-alkane (C6C9) or 23. Solimo HN, Riggio D, Davolio F, Katz M (1975) Thermody-
alcohol (C2C4)) ? olive oil mixtures. Thermochim Acta namic properties of binary liquid acidbase mixtures. Can J
328(12):277296 Chem 53(9):12581262
11. Gonzalez C, Resa JM, Lanz J, Iglesias M (2006) Intermolecular 24. Oswal SL, Desai HS (1998) Studies of viscosity and excess molar
interactions in soy bean oil ? different organic solvents by volume of binary mixtures: 1. Propylamine ? 1-alkanol mixtures
ultrasonic velocity measurements. J Food Eng 77(1):152161 at 303.15 and 313.15 K. Fluid Phase Equilib 149(12):359376
12. Nath J (2002) Speeds of sound and isentropic compressibilities of 25. Oswal SL, Desai HS (1999) Studies of viscosity and excess molar
(n-octanol ? n-hexane, or n-heptane or n-octane) at 298.15 K. volume of binary mixtures: 2. Butylamine ? 1-alkanol mixtures
Fluid Phase Equilib 203(12):261268 at 303.15 and 313.15 K. Fluid Phase Equlib 161(1):191204
13. Petek A, Dolecek V (1998) Excess molar volumes of binary 26. Oswal SL, Ghael NY, Prajapati KD (2004) Speeds of sound,
liquid mixtures of cyclohexane-carbon tetrachloride and toluene- isentropic compressibilities, viscosities and excess volumes of
benzene at various temperatures. Acta Chim Slov 45(2):153159 cyclohexanol ? cyclohexane at 303.15 K. Thermochim Acta
14. Haynes WM (ed) (20132014) CRC handbook of chemistry and 419(1):5965
physics, 94th edn. CRC Press, Boca Raton, pp 67 27. Oswal SL, Patel AT (1992) Viscosity of binary mixtures. II. n-
15. Anton Parr (2001) DMA 4500/5000 Instruction Manual, Graz, butyl, n-hexyl, n-octyl decyl, and n-dodecylamine with benzene
Austria, p 97 and n-hexyl, n-decyl, and n-dodecylamine with cyclohexane. Int J
16. Dubey GP, Sharma M (2008) Acoustic, thermodynamic, visco- Thermophys 13(4):629641
metric and volumetric studies in binary systems of 1-decanol with 28. Oswal SL, Patel AT (1991) Viscosity of binary mixtures. I.
n-hexane, n-octane and n-decade with respect to temperature. mono-, di-, and tri-n-butyl and -n-octylamine with cyclohexane.
J Mol Liq 143(23):109114 Int J Thermophys 12(5):821835
17. Glasstone S, Laidler KJ, Eyring H (1941) The theory of rate
process. McGraw-Hill, New York, pp 514516
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