Excess Molar Volume along with Viscosity and Refractive Index for

Oct 8, 2013 - Science and Technology on Scramjet Laboratory, The 31st Research Institute of CASIC, Beijing 10074, China. •S Supporting Information...
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Excess Molar Volume along with Viscosity and Refractive Index for Binary Systems of Tricyclo[5.2.1.02.6]decane with Five Cycloalkanes Guangqian Li,† Hai Chi,† Yongsheng Guo,*,† Wenjun Fang,*,† and Shenlin Hu‡ †

Department of Chemistry, Zhejiang University, Hangzhou 310058, China Science and Technology on Scramjet Laboratory, The 31st Research Institute of CASIC, Beijing 10074, China

‡

S Supporting Information *

ABSTRACT: Densities, viscosities, and refractive indices have been measured for the binary system of tricyclo[5.2.1.02.6]decane with cyclohexane, methylcyclohexane, ethylcyclohexane, butylcyclohexane, or 1,2,4-trimethylcyclohexane at temperatures T = (293.15 to 318.15 K) and pressure p = 0.1 MPa. The excess molar volumes (VmE), the viscosity deviations (Δη), and the refractive index deviations (ΔnD) are then calculated. The changes of VmE and Δη with the composition are fitted to the Redlich−Kister equation. The values of density, viscosity, and refractive index increase continuously with the increase of mole fraction of tricyclo[5.2.1.02.6]decane and decrease with the rise of temperature. The VmE and Δη are all negative over the whole composition range for these five binary systems. The changes of VmE and Δη are discussed from the points of view of molecular interactions in the binary systems.

1. INTRODUCTION Aircrafts have been important for transportation not only in military but also in commercial aviation since the first flight of the Wright brothers on December 14, 1903, with an engine that could only generate slightly more than 578 N of thrust. With the improvement of the aircraft performance, high-speed flight attracts extensive attention.1 A big challenge of high-speed vehicles is that there is little existing material which can bear the high temperature from the hypersonic flight. Using the fuels brought on an aircraft to absorb the overmuch heat is considered to be one effective method to regeneratively cool the superheating components of the aircraft.2 Tricyclo[5.2.1.02.6]decane (C10H16), also called JP-10, is a synthetic high energy-density hydrocarbon fuel. JP-10 possesses many desirable properties, such as a suitable flash point, low freezing point,3 and high heat sink capacity. Hence, it can be used in the supersonic aircraft or hypersonic missile applications. An amount of work has been reported on the properties and reactions of JP-10.4−9 The investigations on the fundamental physicochemical properties, such as density, viscosity, and refractive index, of hydrocarbon fuels are of scientific and practical interest. The high density is favorable toward increasing the amount of a hydrocarbon fuel in a restricted space for long-distance flight aircraft. Since alkanes and cycloalkanes are the main components, they are usually used as the models of hydrocarbon fuels.10−13 Cycloalkanes have higher densities than alkanes with the same number of carbon, and they usually play an important role in the preparation of high-density hydrocarbon fuels. © 2013 American Chemical Society

For example, the high-density hydrocarbon JP-9 is the mixture of methylcyclohexane, JP-10, and endo-dihydrodinorbornadiene (RJ-5).14 Cyclohexane and its homologues, methylcyclohexane, ethylcyclohexane, butylcyclohexane, and 1,2,4-trimethylcyclohexane, are the candidates of single-ring cycloalkanes. Although the thermodynamic properties of JP-10 with a series of alkanes have been reported,15−17 there are few data about the systems of JP-10 with cycloalkanes. In this work, densities, viscosities, and refractive indices have been measured for the binary systems of JP-10 with a series of cycloalkanes (cyclohexane, methylcyclohexane, ethylcyclohexane, butylcyclohexane, and 1,2,4-trimethylcyclohexane) over the whole composition range at the temperatures T = (293.15 to 318.15 K) and pressure p = 0.1 MPa. The excess molar volumes (VmE), the viscosity deviations (Δη), and the refractive index deviations (ΔnD) of these five binary systems are then calculated and discussed on the basis of the molecular interactions. The results are expected to provide some useful information for the design and property optimization of new hydrocarbon fuels.

2. EXPERIMENTAL SECTION 2.1. Materials. JP-10 (CAS Registry No. 108-87-2), the molecular structure of which is given in Figure 1, is supplied by Liming Research Institute of Chemical Industry, and the mass fraction purity is better than 0.98. Cyclohexane (CAS Registry Received: June 4, 2013 Accepted: September 26, 2013 Published: October 8, 2013 3078

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double-distilled water. The apparatus can keep the temperature varying within ± 0.01 K and the efflux time within ± 0.001 s. The uncertainties of viscosity and viscosity deviation are ± 0.004 mPa·s and ± 0.006 mPa·s, respectively. A WAY-2S refractometer was used to measure the refractive index at T = (293.15, 303.15, and 313.15) K with a HAAKE circulator to maintain the constant temperature. The refractometer was calibrated with double-distilled water. The precision of the temperature is ± 0.01 K. The refractive index is present as the average of three times measurements for each sample. The uncertainties of the refractive indices are ± 0.0005.

Figure 1. Molecular structure of JP-10.

No. 108-91-8) and methylcyclohexane (CAS Registry No. 108-87-2) are obtained from Aladdin Chemical Regent Company, with the mass fraction purities better than 0.995, and 0.99, respectively. Ethylcyclohexane (CAS Registry No. 1678-91-7), butylcyclohexane (CAS Registry No. 1678-93-9), and 1,2,4-trimethylcyclohexane (CAS Registry No. 2234-75-5) are supplied by Tokyo Chemical Industry (TCI), with the mass fraction purities better than 0.98, 0.99, and 0.96, respectively. The components and purities of the samples are checked by an Agilent 7890A/5975C GC-MS. 1,2,4-Trimethylcyclohexane is treated with silica gel via solid-phase extraction to remove polar impurities. Other reagents are used without further purification. The specifications of these chemicals are listed in Table 1. The binary mixtures are prepared with a weighing method by using a Mettler balance with a precision of 0.0001 g. The uncertainties of mole fractions are estimated to be within ± 0.0001. 2.2. Methods. All of the densities of these pure liquids and binary mixtures were measured by an Anton Paar DMA 5000 M densimeter at a range of temperatures T = (293.15 to 318.15 K) and atmospheric pressure p = 0.1 MPa. The autocontrol apparatus could keep the temperature balance with a precision of 0.01 K. The atmospheric pressure is recorded once an hour from a Fortin barometer. The uncertainty of the pressure is 0.20 kPa. The densimeter was checked by itself; then it was calibrated with dried air and double-distilled water. The uncertainty of the density is less than ± 0.00005 g·cm−3, and the combined uncertainty of the corresponding excess volume, VmE, is less than ± 0.001 cm3·mol−1. The viscosities were measured by using an Anton Paar AMVn viscometer at the temperature T = (293.15 to 318.15 K) and pressure p = 0.1 MPa. The viscometer was calibrated with

3. RESULTS AND DISCUSSION The experimental values of density, viscosity, and refractive index for the pure compounds used in this work are compared with the corresponding literature data17−25 in Table 2, except those of 1,2,4-trimethylcyclohexane. The results show acceptable agreement. 3.1. Volumetric Properties. The measured densities (ρ) for the five binary systems over the whole composition range are listed in Table 3. It can be easily found that the density increases with increasing the mole fraction of JP-10 (x1) in each binary system of JP-10 (1) + cycloalkane (2) and decreases with the rise of temperature (T). The excess molar volumes (VmE) are calculated from the following equation: Vm E =

M1x1 + M 2x 2 ⎛ M1x1 Mx ⎞ − ⎜⎜ + 2 2 ⎟⎟ ρm ρ2 ⎠ ⎝ ρ1

(1)

where ρm is the density of the binary mixture; ρ1 and ρ2 are the densities of two components in the corresponding mixture, respectively; M1, M2 and x1, x2 are the molar masses and the mole fractions of the two components, respectively. The component 1 is JP-10, and the component 2 is cyclohexane, methylcyclohexane, ethylcyclohexane, butylcyclohexane, or 1,2,4-trimethylcyclohexane. The calculated values of VmE for the five binary

Table 1. Specification of Chemicals in This Work

a

chemical name

source

provided mass fraction purity

purification method

measured mass fraction purity

analysis method

tricycol[5.2.1.02.6]decane cyclohexane methylcyclohexane ethylcyclohexane butylcyclohexane 1,2,4-trimethylcyclohexane

LRICIa Aladdin Aladdin TCI TCI TCI

≥ 0.98 ≥ 0.995 ≥ 0.99 ≥ 0.98 ≥ 0.99 ≥ 0.96

none none none none none extraction

0.994 0.999 0.999 0.999 0.997 0.985

GC-MS GC-MS GC-MS GC-MS GC-MS GC-MS

LRICI is the abbreviation of Liming Research Institute of Chemical Industry, China.

Table 2. Densities (ρ), Viscosities (η), and Refractive Indices (nD) of Pure Compounds Used in This Work Compared with Literature Data at T = 293.15 K and p = 0.1 MPaa ρ/g·cm−3

η/mPa·s

nD

compound

exptl

lit.

exptl

lit.

exptl

lit.

JP-10 cyclohexane methylcyclohexane ethylcyclohexane butylcyclohexane

0.93572 0.77851 0.76935 0.78802 0.79947

0.935285b 0.7784c 0.76930e 0.788g 0.7992i

2.992 0.977 0.733 0.845 1.302

3.077b 0.968d 0.729e 0.842g 1.309j

1.4874 1.4256 1.4172 1.4276 1.4399

1.4877b 1.42638c 1.4192f 1.42865h 1.4408i

Standard uncertainties u(T) = 0.01 K, u(p) = 0.20 kPa, u(ρ) = 0.00005 g·cm−3, u(η) = 0.004 mPa·s, and u(nD) = 0.0005. bReference 17. cReference 18. dReference 19. eReference 20. fReference 21, T = 303.15 K. gReference 22. hReference 23, T = 303.15 K. iReference 24. jReference 25. a

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Table 3. Densities (ρ) at Different Mole Fractions (x1) for the Binary Systems of JP-10 (1) + Cycloalkane (2) at Temperatures T = (293.15 to 318.15) K and Pressure p = 0.1 MPaa ρ/g·cm−3 x1

293.15 K

298.15 K

0.0000 0.0998 0.2006 0.3003 0.3996 0.4987 0.6005 0.7002 0.8008 0.9000 1.0000

0.77851 0.79953 0.81911 0.83710 0.85382 0.86942 0.88443 0.89830 0.91150 0.92387 0.93572

0.77384 0.79492 0.81456 0.83265 0.84945 0.86515 0.88023 0.89420 0.90748 0.91992 0.93184

0.0000 0.1000 0.2009 0.3010 0.3999 0.4999 0.5992 0.7004 0.7995 0.9011 1.0000

0.76935 0.78879 0.80771 0.82581 0.84302 0.85994 0.87609 0.89198 0.90695 0.92182 0.93572

0.0000 0.0997 0.2006 0.3001 0.4003 0.5001 0.6011 0.7000 0.8001 0.8996 1.0000

0.78802 0.80352 0.81896 0.83408 0.84915 0.86399 0.87881 0.89321 0.90754 0.92166 0.93572

0.0000 0.1000 0.1993 0.2997 0.3991 0.5002 0.6005 0.7000 0.8004 0.8999 1.0000

0.79947 0.81106 0.82296 0.83542 0.84820 0.86166 0.87549 0.88972 0.90457 0.91980 0.93572

0.0000 0.1000 0.1996 0.3002 0.4009 0.5001 0.5992

0.79080 0.80462 0.81849 0.83273 0.84713 0.86144 0.87589

303.15 K

JP-10 (1) + Cyclohexane (2) 0.76911 0.79027 0.80999 0.82819 0.84507 0.86086 0.87606 0.89008 0.90343 0.91595 0.92794 JP-10 (1) + Methylcyclohexane (2) 0.76504 0.76071 0.78453 0.78025 0.80350 0.79926 0.82164 0.81746 0.83889 0.83475 0.85586 0.85175 0.87205 0.86799 0.88796 0.88394 0.90299 0.89901 0.91788 0.91394 0.93184 0.92794 JP-10 (1) + Ethylcyclohexane (2) 0.78401 0.77998 0.79947 0.79544 0.81495 0.81094 0.83007 0.82606 0.84518 0.84118 0.86001 0.85603 0.87485 0.87090 0.88926 0.88530 0.90361 0.89967 0.91775 0.91382 0.93184 0.9279 JP-10 (1) + Butylcyclohexane (2) 0.79571 0.79196 0.80731 0.80353 0.81919 0.81539 0.83163 0.82782 0.84439 0.84057 0.85783 0.85398 0.87164 0.86778 0.88586 0.88199 0.90070 0.89681 0.91595 0.91205 0.93184 0.92794 JP-10 (1) + 1,2,4-Trimethylcyclohexane 0.78692 0.78303 0.80071 0.79680 0.81461 0.81070 0.82884 0.82493 0.84321 0.83930 0.85751 0.85359 0.87198 0.86806 3080

308.15 K

313.15 K

318.15 K

0.76436 0.78560 0.80541 0.82369 0.84068 0.85656 0.87185 0.88597 0.89940 0.91198 0.92402

0.75957 0.78090 0.80082 0.81919 0.83628 0.85226 0.86763 0.88185 0.89535 0.90710 0.92011

0.75475 0.77618 0.79620 0.81468 0.83188 0.84796 0.86344 0.87772 0.89130 0.90402 0.91618

0.75636 0.77595 0.79501 0.81326 0.83060 0.84764 0.86393 0.87991 0.89501 0.91000 0.92402

0.75199 0.77164 0.79075 0.80905 0.82643 0.84353 0.85984 0.87588 0.89103 0.90604 0.92011

0.74760 0.76731 0.78648 0.80483 0.82226 0.83940 0.85575 0.87184 0.88703 0.90208 0.91618

0.77593 0.79140 0.80691 0.82204 0.83718 0.85203 0.86692 0.88134 0.89572 0.90989 0.92402

0.77186 0.78734 0.80287 0.81800 0.83314 0.84802 0.86292 0.87736 0.89176 0.90595 0.92011

0.76778 0.78325 0.79878 0.81396 0.82908 0.84399 0.85888 0.87335 0.88780 0.90199 0.91618

0.78820 0.79975 0.81160 0.82401 0.83673 0.85013 0.86392 0.87811 0.89292 0.90814 0.92402 (2) 0.77913 0.79290 0.80679 0.82101 0.83538 0.84967 0.86413

0.78443 0.79596 0.80779 0.82018 0.83289 0.84627 0.86005 0.87422 0.88902 0.90423 0.92011

0.78065 0.79217 0.80398 0.81635 0.82904 0.84241 0.85616 0.87032 0.88511 0.90032 0.91618

0.77523 0.78898 0.80287 0.81709 0.83145 0.84574 0.86020

0.77132 0.78506 0.79894 0.81316 0.82752 0.84180 0.85627

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Table 3. continued ρ/g·cm−3 x1 0.6998 0.7997 0.9001 1.0000

293.15 K

298.15 K

308.15 K

313.15 K

318.15 K

0.89070 0.90551 0.92061 0.93572

JP-10 (1) + 1,2,4-Trimethylcyclohexane (2) 0.88677 0.88285 0.87893 0.90161 0.89770 0.89378 0.91671 0.91281 0.90889 0.93184 0.92794 0.92402

303.15 K

0.87501 0.88985 0.90497 0.92011

0.87107 0.88592 0.90104 0.91618

a

x1 is the mole fraction of JP-10 in the binary systems. Standard uncertainties u are u(x) = 0.0001, u(T) = 0.01 K, u(p) = 0.20 kPa, and u(ρ) = 0.00005 g·cm−3.

Figure 2. Excess molar volumes (VmE) as a function of mole fraction of JP-10 (x1) for five binary systems (a, JP-10 + cyclohexane; b, JP-10 + methylcyclohexane; c, JP-10 + ethylcyclohexane; d, JP-10 + butylcyclohexane; e, JP-10 + 1,2,4-trimethylcyclohexane) at temperatures T = (293.15 to 318.15) K and pressure p = 0.1 MPa: ■, 293.15 K; ●, 298.15 K; ▲, 303.15 K; ▼, 308.15 K; ◆, 313.15 K; ◀, 318.15 K; ref 6: □, 303.15 K; ○, 308.15 K; △, 313.15 K; , the Redlich−Kister correlation. 3081

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systems at six different temperatures are listed in detail in Table S1 of the Supporting Information. The VmE values are fitted to the Redlich−Kister type polynomial equation. n

Y = x1(1 − x1) ·∑ Ai (2x1 − 1)i − 1

(2)

i=1

where Y and x1 are the excess molar volumes (VmE) and the mole fraction of JP-10, respectively. With the least-squares correlation and F-test, the values of the polynomial coefficients, Ai, can be obtained and are listed in Table S2 of the Supporting Information, along with the standard deviations (σ), Figure 3. Excess molar volume (VmE) as a function of mole fraction of JP-10 (x1) for five binary systems JP-10 + n-cycloalkanes at T = 298.15 K and pressure p = 0.1 MPa: (■, cyclohexane; ●, methylcyclohexane; ▲, ethylcyclohexane; ▼, butylcyclohexane; ◀, 1,2,4-trimethylcyclohexane); , the Redlich−Kister correlation.

σ = [∑ (Y − Ycal)2 /(n − k)]1/2

(3)

where n is the number of data points and k is the number of coefficients.

Table 4. Viscosities (η) at Different Mole Fractions (x1) for the Binary Systems of JP-10 (1) + Cycloalkane (2) at Temperatures T = (293.15 to 318.15) K and Pressure p = 0.1 MPaa η/mPa·s x1

293.15 K

298.15 K

0.0000 0.0998 0.2006 0.3003 0.3996 0.4987 0.6005 0.7002 0.8008 0.9000 1.0000

0.977 1.130 1.296 1.462 1.633 1.814 2.016 2.231 2.463 2.720 2.992

0.898 1.032 1.180 1.327 1.481 1.645 1.828 2.024 2.236 2.466 2.710

0.0000 0.1000 0.2009 0.3010 0.3999 0.4999 0.5992 0.7004 0.7995 0.9011 1.0000

0.733 0.842 0.959 1.102 1.267 1.454 1.670 1.925 2.220 2.582 2.992

0.687 0.785 0.892 1.023 1.171 1.340 1.534 1.762 2.026 2.347 2.710

0.0000 0.0997 0.2006 0.3001 0.4003 0.5001 0.6011 0.7000 0.8001 0.8996 1.0000

0.845 0.941 1.052 1.189 1.344 1.514 1.726 1.965 2.251 2.593 2.992

0.791 0.878 0.979 1.104 1.243 1.396 1.586 1.800 2.055 2.358 2.710

303.15 K JP-10 (1) + Cyclohexane (2) 0.828 0.948 1.080 1.212 1.351 1.500 1.668 1.846 2.037 2.248 2.467 JP-10 (1) + Methylcyclohexane (2) 0.646 0.735 0.833 0.952 1.087 1.239 1.416 1.621 1.857 2.146 2.467 JP-10 (1) + Ethylcyclohexane (2) 0.743 0.822 0.914 1.028 1.155 1.293 1.464 1.656 1.884 2.155 2.467 3082

308.15 K

313.15 K

318.15 K

0.766 0.874 0.993 1.113 1.239 1.375 1.528 1.691 1.866 2.056 2.255

0.712 0.808 0.917 1.026 1.141 1.267 1.407 1.555 1.715 1.888 2.069

0.664 0.751 0.848 0.949 1.055 1.169 1.298 1.435 1.581 1.741 1.907

0.609 0.692 0.781 0.890 1.013 1.151 1.312 1.497 1.709 1.967 2.255

0.576 0.652 0.733 0.834 0.947 1.074 1.218 1.388 1.579 1.810 2.069

0.546 0.616 0.691 0.783 0.887 1.003 1.135 1.290 1.463 1.672 1.907

0.700 0.772 0.856 0.960 1.076 1.202 1.356 1.530 1.735 1.976 2.255

0.661 0.727 0.804 0.900 1.005 1.120 1.261 1.417 1.602 1.820 2.069

0.626 0.687 0.758 0.845 0.942 1.047 1.175 1.317 1.485 1.682 1.907

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Table 4. continued η/mPa·s x1

293.15 K

0.0000 0.1000 0.1993 0.2997 0.3991 0.5002 0.6005 0.7000 0.8004 0.8999 1.0000

1.302 1.391 1.490 1.602 1.732 1.879 2.044 2.234 2.446 2.688 2.992

0.0000 0.1000 0.1996 0.3002 0.4009 0.5001 0.5992 0.6998 0.7997 0.9001 1.0000

0.886 0.986 1.101 1.230 1.381 1.562 1.759 2.008 2.277 2.609 2.992

298.15 K

303.15 K

308.15 K

JP-10 (1) + Butylcyclohexane (2) 1.200 1.111 1.032 1.279 1.181 1.096 1.367 1.261 1.168 1.467 1.351 1.249 1.584 1.456 1.344 1.715 1.574 1.451 1.863 1.707 1.571 2.032 1.858 1.707 2.224 2.031 1.862 2.438 2.223 2.036 2.710 2.467 2.255 JP-10 (1) + 1,2,4-Trimethylcyclohexane (2) 0.827 0.774 0.727 0.917 0.856 0.802 1.021 0.950 0.888 1.137 1.056 0.984 1.273 1.179 1.096 1.436 1.326 1.230 1.613 1.486 1.374 1.837 1.687 1.556 2.076 1.901 1.749 2.371 2.165 1.985 2.710 2.467 2.255

The excess molar volumes of the binary systems at different temperatures are visually shown in Figure 2, along with the reference data.6 It can be seen that all of the excess molar volumes for the five systems are negative. With the increase of temperature, the values of VmE change in decreasing trends. The data from ref 6 show the same trends, which is consistent with the results of this work. The maximum values of VmE of the five binary systems at a given temperature are at the mole fraction x1 from 0.4 to 0.6 of JP-10. As an example, the results at 298.15 K are shown in Figure 3. The absolute values of VmE are in the order: VmE(d) < VmE(a) < VmE(c) < VmE(e) < VmE(b), where d, a, c, e, or b denotes the binary system of JP-10 with butylcyclohexane, cyclohexane, ethylcyclohexane, 1,2,4-trimethylcyclohexane, or methylcyclohexane. These phenomena observed can be explained from the following aspects. Generally, the excess molar volumes should result from the chemical, physical, and structural effects. Considering the five binary systems are all nonpolar systems, there are no chemical interaction forces. Hence, the excess molar volume is the result of the balance between the physical intermolecular forces (mainly the dispersion force) and the structural effect. JP-10 is a cyclic alkane containing three rings, while cyclohexane, methylcyclohexane, ethylcyclohexane, butylcyclohexane, and 1,2,4-trimethylcyclohexane are single-ring cycloalkanes with no, one, or three side-chains. When different kinds of molecules contact with each other, the space of JP-10 may be aggregated with parts of cycloalkanes, and this can lead to a contraction in volume for each system of JP-10 + cycloalkane. The structural effect becomes different with the change of the

313.15 K

318.15 K

0.962 1.020 1.085 1.159 1.245 1.342 1.451 1.573 1.715 1.872 2.069

0.899 0.952 1.012 1.079 1.157 1.246 1.345 1.456 1.585 1.727 1.907

0.686 0.753 0.832 0.920 1.022 1.144 1.275 1.440 1.615 1.828 2.069

0.648 0.710 0.782 0.862 0.956 1.068 1.187 1.337 1.496 1.688 1.907

side-chain. On the other hand, the dispersion force shows intensive repulsive force with the contractible distance of two molecules, which can slow down the contraction in volume caused by the structural effect. With the increase of molecular mass, the dispersion force (repulsive force) becomes strongly, which causes the excess molar volume to be more positive. The balance of the dispersion force and the structural effect leads the excess molar volume to be negative, and the absolute value to be nearly in the order: VmE(d) < VmE(a) < VmE(c) < VmE(e) < VmE(b). 3.2. Viscometric Properties. The viscosities (η) of the five binary systems are listed in Table 4. It is found that the viscosity of each system becomes much smaller with increasing the temperature. With increasing the mole fraction of JP-10 at a given temperature, the value of viscosity becomes much larger. The viscosity deviation (Δη) calculation is proposed as the following equation: Δη = ηm − (x1η1 + x 2η2)

(4)

where ηm, η1, and η2 are the viscosities of the binary mixture, JP-10, and cycloalkane, respectively. The calculated values of Δη are listed in Table S3 of the Supporting Information. All of the viscosity deviations show negative values, and the maximum negative value for each binary system can be observed around the mole fraction of x1 = 0.6. The values of Δη can also be fitted to the Redlich−Kister type polynomial equation using eq 2, and the standard deviations (σ) can be calculated with eq 3. The correlation coefficients and standard deviations are listed in Table S4 of the Supporting Information. 3083

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Figure 4. Viscosity deviations (Δη) as a function of mole fraction of JP-10 (x1) for five binary systems (a, JP-10 + cyclohexane; b, JP-10 + methylcyclohexane; c, JP-10 + ethylcyclohexane; d, JP-10 + butylcyclohexane; e, JP-10 + 1,2,4-trimethylcyclohexane) at temperatures T = (293.15 to 318.15) K and pressure p = 0.1 MPa: ■, 293.15 K; ●, 298.15 K; ▲, 303.15 K; ▼, 308.15 K; ◆, 313.15 K; ◀, 318.15 K; ref 6: □, 303.15 K; ○, 308.15 K; △, 313.1 5 K; , the Redlich−Kister correlations.

JP-10 in the binary mixtures, while those become smaller with the rise of temperature. The trends also can be seen visually from Figure 5. The refractive index deviation (ΔnD) is calculated from the following equation:

The temperature is one of important factors to affect the viscosity deviations. As shown in Figure 4, it is indicated that the viscosity deviations of the five binary systems decrease obviously with the rise of temperature. The results from ref 6 show the same trends, which is consistent with this work. With the rise of temperature, the dispersion force becomes stronger and causes the value of Δη to be smaller at a certain mole fraction of the binary system. 3.3. Refractive Index. The experiment data of refractive indices of the five binary systems at temperature T = (293.15, 303.15, and 313.15) K are listed in Table S5 of the Supporting Information. The results show that the values of refractive indices become larger with increasing the mole fraction of

ΔηD = ηDm − (x1ηD1 + x 2ηD2)

(5)

where nDm, nD1, and nD2 are the refractive indices of the binary mixture, JP-10, and cycloalkane, respectively. All of the refractive index deviations are listed in Table S6 of the Supporting Information. The small values of ΔnD show slight deviations of the refractive indices from the ideal additions for these binary mixtures. No further correla3084

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Figure 5. Refractive indices (nD) as a function of mole fraction JP-10 (x1) for five binary systems (a, JP-10 + cyclohexane; b, JP-10 + methylcyclohexane; c, JP-10 + ethylcyclohexane; d, JP-10 + butylcyclohexane; e, JP-10 + 1,2,4-trimethylcyclohexane) at temperatures T = (293.15, 303.15, and 313.15) K and pressure p = 0.1 MPa: ■, 293.15 K; ●, 303.15 K; ▲, 313.15 K.

tions of ΔnD with the Redlich−Kister type equation are considered.

negative values, and the maximum absolute values of VmE at a given temperature are at the mole fraction x1 from 0.4 to 0.6 of JP-10. The different VmE values mainly result from the balance between the dispersion force and the structural effect (steric interaction) among the molecules of different binary systems. The viscosity deviations Δη of the binary mixtures are also negative over the whole composition range, and they show minimum value at the mole fraction x1 = 0.6. Both the negative excess molar volume and the viscosity deviation are valuable to the preparation of a hydrocarbon fuel for a high-speed flight aircraft.

4. CONCLUSION The experimental data of density (ρ), viscosity (η), and refractive index (nD) for binary systems of JP-10 with cyclohexane, methylcyclohexane, ethylcyclohexane, butylcyclohexane, and 1,2,4-trimethylcyclohexane over the entire composition range have been determined at temperatures T = (293.15 to 318.15 K) and pressure p = 0.1 MPa. Densities, viscosities, and refractive indices of these binary systems become smaller with the increase of temperature and become larger with increasing the mole fraction of JP-10. The excess molar volumes (VmE), the viscosity deviation (Δη), and the refractive index deviations (ΔnD) are calculated. It follows that all of excess molar volumes (VmE) show

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ASSOCIATED CONTENT

S Supporting Information *

Values of excess molar volumes (VmE), viscosity deviations (Δη), correlation coefficients (Ai) of the Redlich−Kister equation for 3085

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VmE and Δη, refractive indices (nD), and refractive index deviations (ΔnD). This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. Tel.: 86-571-88981416. Fax: +86571-88981416. *E-mail: [email protected]. Funding

This work was financially supported by the National Natural Science Foundation of China (grant nos. 21273201, 21173191). Notes

The authors declare no competing financial interest.

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