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Density and viscosity of hydrazinesubstited aqueous solutions under various temperature and pressures. Equation state
High temperature high pressure (2008)
  • Mohira Abdusalomovna Zaripova
  • Tahmina Rustamovna Tilloeva
  • Hikmatullo Abdukholikovich Zoirov
  • Mahmadali Mahmadievich Safarov
  • Shamsullo Asoevich Aminov
Abstract
The results of experimental research on the density and viscosity of hydra-zinesubstituted aqueous solutions (hydrazine, hydrazinehydrate, phenylhydrazine, ethylhydrazine, aerozine, and dimethylhydrazine) in the temperature range 293.1-551.2K, and pressure range 0.101-98.1MPa, with concentration 0.1-0.9 mass. H2O, are presented. A generalized aqueous solution has been developed. The common relative errors of measurement in density and viscosity under a coef-ficient of confidence, a, of 0.95 are respectively 0.1 and 2.6%. For the calculation of heat and mass exchange and the development of a mathematical model of the processes taking place in different reactors, we need data on the thermodynamics properties (energy Gibbs, energy Hellholes, density and viscosity) of hydrazine substituted aqueous solutions in a wide range of temperatures and pressures. The current relevance of the problem is demonstrated by the continuous growth of the needs of science, technology, and leading branches of industry for reliable data on thermo physical properties of techno-logically important liquids, gases, and their solutions. A radical in crease of the efficiency of power systems requires the development and introduction of the technology. The solutions of this problem is impossible without reliable the- oretically grounded methods of calculation of the thermo physical properties of the prospective hydrazine-substituted aqueous solutions which are used in power and technological constructions. The lack of data (in the literature) on the thermo physical properties of hydrazine, hydrazinehydrate, phenylhydrazine, ethylhyd-razine, dimethylhydrazine and aerozine in the pure state as well as with the ad-dition of water as functions of temperature and pressure makes it difficult to use reactors rationally. With the temperature, pressure, and mole concentration of water, the thermo physical properties of the solutions change, thus influencing the way it can be exploited. Investigation of the thermo physical properties of hydrazine-substituted aqueous solutions in the wide range of temperatures and pressures is currently relevant, represents great scientific interest, and is of practical value as well. Therefore we investigated the thermo physical properties (density and viscosity) of the fluids in the temperature range 293-573K and pressure range 0.101-98.1 MPa. 1 Introduction The overall development of industry creates shortage of energy resources and causes various environmental problems. The necessity of use of sustainable energy resources such as solar energy increased whiling previous years'. Solar collectors play the most important role for the collection of solar rays. They are heat by heat transfer. Heat transfers are used for heating systems in various purposes. Therefore efficiency of installations more depends on thermodynamic properties of heat transfers. It is vital to note, that they should be environmentally safe and clean, with good heat producing capacity, fluidity, viscosity etc. However, thermodynamic properties, in particular density, temperature of boiling at various pressures, should be considered. In the solar ray collectors water are basically used as the heat transferor. Recently it became more popular to use aqueous solutions with aliphatic alcohols. In this work the thermodynamic properties of one of these solutions (cartamus tingtorius oil+n-hexan) was investigated. The thermodynamic properties, molar excess volumes, properties in the "liquid -vapor" phase transition line and etc. of methanol + water solutions have been reported in several papers [1-38]. A lot of papers from these include small range of state parameters (basically in the low temperatures). To understand the properties of cartamus tingtorius oil+n-hexan solutions and to provide accurate data for the design of processes and plants, it is necessary to investigate these solutions in the wide range of state parameters. This paper presents the results of experimental measurements to determine P-p-T and Ps-ps-Ts properties and calculated V values of cartamus tingtorius oil+n-hexan solutions in the temperature range from 298.15 to 473.15 K, in the 25, 50, 75 % concentrations of methanol and at pressures from the "liquid -vapor" phase transition line up to 60 MPa. This heater used for creating necessary temperature range and used periodically with help of the regulation of temperature VRT-2. 2 Experimental The measurements were carried out using the experimental installation realizing the method of constant volume piezometer (Figura 1) [1]. The developed experi-mental installation enables one to derive P-ρ-T and Ps-ρs-Ts properties with high accuracy, as well as to perform experiments on isotherms, isochors, and isobars. The piezometer volume was determined at room temperature by the mass of water filling it at an exactly measured temperature and moderate (of the order of 1 to 1.5 MPa) pressure, that is with parameters for which the density of ordinary water is known with high accuracy (0.001-0.003%) from the International Backbone Table for water [37] and was equal to 350.13 10 -6 m3. A spherical, thick walled, high pressure vessel manufactured of ICrl8Ni9Ti grade stainless steel was used as the measuring device. The constant volume of the piezometer filled with liquid under investigation was maintained by a mercury seal under visual observation. The piezometer ballast volume could be substantially reduced owing to the use of sinalldiame Lear capillaries and a valve of special design intended for injecting and tapping the liquid to be tested. The piezometer ballast volume was determined both experimentally and by computation, and its value amounted to 0.1% of the working volume of the piezometer . The thermostatic control of the piezometer was carried out by means of a liquid-filled thermostat. The different heat-transfer substances was used with due regard for the temperature range. The water was used from 298.15 to 348,15 K; me glycerin was used from 348.15 K to 423.15 K and the nitrous mixture (45% KNO3 and 55% NaNO2) was used from 423.15 K to 523.15 K temperatures. An axial pump was used to circulate the heat-transfer agent on the contour of the thermostat. The temperature was regulated by a VRT-2 thermoregulator and measured by a two TSN-25 platinum resistance thermometers. The thermometers in special cases were immersed into the thermostat so that their sensitive elements were level with the piezometer midline. The one thermometer worked during all experiment period, and the second thermometer used for compare the temperature. The difference of values of two different thermometer was ±1 mK. The pressure in the experiments was built up and measured by MP-6, MP-60 and MP-600 deadweight pressure gages of 0.05 accuracy class. Figure 1. Constant volume piezometer installation. 1, piezometer; 2,3, capillary Lube; 4, TSN-25 platinum resistance thermometer; 5,6,7,8,9, heaters; 10, coolers; 11,12, valves; 13, tee; 14,tube; 15, axial pump; 16, access hole; 17, separator tube.[1] The thermostat was made from two different cylinders with inside diameters 0.24 m and 0.09 m and connected with two tubes: one from up in the centers of tubes, second in the tangential form in the down of tubes for creating of rotational heater fluid motion. The thermostat was heating with the help of five heaters. The all heaters was made from nickel and chrome mixtures and the four from these have diameters of wire 0.0009 m. The two heaters (5th and 6th in the figure 1) tie up to the big cylinder in the twice form, one heating thermostat from down (7th in the figure 1), other one tic up to the small cylinder. The fifth heater have diameter of wire 0.0003 m. 3 RESULTS The experiments for temperature between 298.3 K and 473.2 K at intervals of 25 K temperatures and pressures from the “liquid-vapor” phase transition line up 60 MPa were carried out. In the near of phase transition line the step of pressure was diminished and approximately after the every 0.5 MPa interval of pressures was measured the P-ρ-T properties and by this way was obtained the phase transition line. Internal mature consistency of the obtained results was tested in the P-ρ, T-ρ, X-ρ and Ps-Tsthermodynamic cross sections. The scattering of experimental data around the corresponding smooth curves is within the experimental deviation. The P-ρ-T, Ps-ρs-Ts , thermodynamics properties and values are described in table 1-4. Table 1 Experimetal data density (ρ,kg.m-3) systems aerozine,dependence tempe-rature and concentrations water n,% Т,К 0 10 20 30 40 50 60 70 80 90 293 1091.2 1080 1064.9 1060.9 1057.3 1056.5 1046.2 1025.2 1009.3 999.6 303 1084.1 1074 1062.3 1054.9 1054.6 1052.3 1038.5 1018.3 1005.6 997.3 313 1078.8 1068 1056.2 1048.2 1045.9 1043.7 1031.8 1013.9 1001.2 994.7 323 1072.7 1061 1049.7 1040.5 1038.1 1035.2 1024.3 1010.5 998.3 992.1 333 1066.0 1054 1044.3 1034.6 1029.2 1026.4 1016.7 1006.7 993.4 988.7 343 1059.3 1048 1037.1 1027.9 1024.5 1019.3 1012.3 1001.4 988.9 984.3 353 1052.6 1041 1030.7 1020.3 1015.4 1010.3 1005.3 998.2 984.2 977.5 Table 2 Experimental Ps-ρs-Ts values of methylhydrazine water solutions T,K Ps, MPa Ps, kg/m3 X=25% X=50% X=75% X=25% X=50% X=75% 373.15 0.1907 0.2631 0.3143 876.8 810.4 757.8 398.15 0.4167 0.5594 0.6547 850.2 782.9 726.3 423.15 0.8103 1.0521 1.2331 827.2 752.3 6942 448.15 1.3391 1.7323 2.0912 793.9 717.9 658.1 473.15 2.6043 3.1184 3.4907 760.1 679.4 606.5 498.15 4.1130 5.1621 5.4913 718.3 628.8 552.6 X - concentration of water Table 3 Experimental data density (ρ,kg.m-3) systems phenilhydrazine (40%C6H8N2 + 60%H2O) mass. dependence temperature and pressures Т, К Pressures Р, МPa 0.101 4.91 9.81 29.43 49.05 68.81 88.29 98.10 290.1 1047.0 1051.6 1058.4 1073.0 1087.6 1103.0 1121.0 1131.0 318.4 1028.5 1033.4 1040.7 1057.4 1075.0 1089.2 1105.3 1115.1 340.5 1011.0 1017.1 1024.0 1042.8 1058.7 1075.6 1090.0 1110.4 355.1 1001.6 1005.0 1013.5 1033.0 1053.6 1066.5 1082.4 1091.5 376.8 990.4 999.6 1020.0 1035.8 1056.0 1070.5 1077.6 403.4 970.6 980.9 995.7 1018.7 1039.3 1053.6 1061.7 437.5 945.7 958.1 980.0 998.5 1020.7 1033.7 1040.2 456.7 930.4 942.0 967.2 984.8 1007.2 1020.0 1028.0 490.2 905.0 916.8 944.1 964.9 987.6 999.8 1008.0 510.7 888.4 903.0 930.0 951.7 976.1 987.9 994.3 536.4 870.6 883.9 914.4 934.0 960.9 971.1 978.8 549.0 864.8 875.4 905.6 928.1 953.5 963.0 970.0 Table 4 The calculated meanings of thermodynamic properties of system (60%N2H4+ 40%H2O) mass. depending on temperature and pressure Т, К Thermodynamics properties ΔН,J/kg ΔS, J/kg К ,J/kg ,J/kg , J/kg Р=0.101 МPа 313 7620 233.05 -65324.7 -65420.2 7524.4 333 141240 451.97 -9266.1 -9364.1 141141.9 373 282480 854.50 -36248.5 -36348.5 282380 473 635580 1691.35 -164428.6 - - P=4.91 МPа 313 70220 231.73 -2311.5 -7019.1 65512.4 333 140440 449.41 -9380.0 -13989.8 135663.7 373 280880 849.66 -36043.0 -36043.2 275970.0 473 631980 1681.8 -163497.2 -163511.4 626689.1 Р=9,81МPа 313 70000 231 -2303.0 -11744.8 60558.2 333 140000 448 -9184.0 -18754.7 130429.3 373 280000 847 -35931.0 -467333.1 270190 473 630000 1676,5 -16298.5 -173567 619417.5 Р=29,43 МPа 313 69300 228.69 -2279.9 -29911.8 41588.1 333 138600 443.52 -8759.2 -9092.2 138600.0 373 277200 838.53 -35571.9 -64424.6 248347.1 473 623700 1659.74 -161357.0 -192336.0 592721.0 Р=49,1 МPа 313 68600 226.38 -2256.9 -47719.8 23137.1 333 137200 439.04 -9001.7 -54845.3 91355 373 274400 830.06 -68390.0 -8242.9 227188.5 473 617400 1642.9 -159691.7 -210414.8 566676.9 4 THEORETICAL INVESTIGATIONS Using standard thermodynamic analysis programs equation of state (ES) was constructed in following form: P = Ap2+Bp8+Cp12 (1) where: A, B and C are coefficients of the equation (1) and both are functions of temperature and concentration in following form: (2) where: aij, bij and сij are the coefficients of polynomial. The ES (1) with (2) was described experimental values with deviations in max. 0,1%. The deviation between experimental and calculated by ES (1) with (2) values of density was defined by (3) The Pa-ps-Ts value of investigated solutions was calculated by the following ES in polynomial form: (4) The mean relative deviation between experimental and calculated by (3) bubble pressure defined by (5) The excess volume of investigated solutions was calculated from experi-mental values of solutions with below mentioned equation (6) The values of hydrazine from [38] and water from [37] was used for creation of concentration dependence. (7) The meanings of factors ki, ci, li and di for water solutions aerozine are given in table.5. Table 5 Data coefficients кi , ci , li и di equation (7) k0 k . 10-2 k . 10-4 c0 c1 c2 3.5289 - 1.9543 1.2536 0.3302353 0.728159 -0.054124 l0 . 10-18 L1 .10-19 l2 . 10-21 d0 d1 d2 7.7487 - 1.6083 1.2059 0.8672 - 2.14 2.2151 The check of the equation (7) for water solutions aerozine has shown, that it with an error 0.2 % describes experimental data. At processing experimental data on above-stated methods have received the equations of a condition for water solutions hydrazinehydrate in the following kind: (8) The meanings of factors for water solutions hydrazinehydrate are given in table 6. Table 6 Data coefficients fi , νi , ri , и hi equation (8) f0 f1 . 10-4 f2 . 10-5 ν0 ν1 ν2 - 3.343 - 3.36 1.89 0.417 0.315 0.249 r0 r1 . 10-3 r2 . 10-6 h0 h1 h2 0.545 - 1.35 3.16 1.01 - 2.76 2.79 For water solutions ethylhydrazine: (9) For water solutions dimethylhydrazine: (10) The received equations are described experimental data on density of water solutions ethylhydrazine and dimethylhydrazine in an interval by temperature Т = 290-550 K and pressure Р = 9.8 - 98.1 МPа with average 0.5 - 3.2 %. 5 Discussion The investigation substances was compared with various literature values. Kubota el al.,[30] investigated these solution in the 283-348K, and 0.1-208 MPa state parameters by a modified. Adams piezometer and high pressure burette method. The comparison of present values with this showed low deviations. Approximately with 0.05% deviations present values compared with values of [30]. Maximum deviation was obtained in the concentration of methanol in the 75%, in the 20 MPa pressure, and in the 348.15 K temperature. This deviation is +0.13%. Approximately the present values lower than values [30]. Xiao el al., [34] give the excess molar volumes and densities of these solutions in the 323 K and 573 K temperatures, and in the 7.0 MPa and 13.5 MPa pressures. Measurements were carried out in a vibrating-tube dens meter. The present values was compared with this values and was obtained good results. Basically values of present work lower than values of [34]. The maximum deviation was obtained in the X=75%; T=423.15 K and P=13.5 MPa. This value is +0.12 %. The middle deviation of the result of comparison is ±0.15 %. The data by Osada et a/., [35] was presented from the 320 K to 420 K temperature interval up to 200 MPa. The metal-bellows volumomеtеr was used as experi-mental installation. This data agrees with the corresponding density measu-rement in present work with a middle deviation ±0.1%. The Ps-ρs-Ts values of investigated solutions was published by Griswold and Wong [8] between 373.15 K and 523.15 K, by Schroder [10] at 413.15 K, by Hirata and Suda [11] and Hirata et al. [13] at pressures of 0.3 MPa and 0.5 MPa. Also Mc Glashan and Williamson [15], Kurihara et al [31] Bao et al. [32], Osada et al. [35] measured bubble point pressure of investigated solutions. In general, these works carried out in the little interval of phase transition line. In present work the Ps-ρs-Ts values was investigated in large interval of phase transition line (from bubble temperature in the atmosphere pressure up to 523.15 K). The present work was compared with below-mentioned literatures and obtained good results. REFERENCE 1. Shakhverdiev A N, Naziev Ya. M, Safarov J. T. Zh.Fiz.K.hi.m, Russian Journal of Physical Chemistry, Moscow, Russia, 1992, 66, p 454-458. 2. Duffie, J. A.; Beckman W. A. Solar Engineering of Thermal Processes, 2nd Edition , John Wiley & Sons, New York. 1992, 919 pp. 3 Amagat, E. H. Ann. Chim. Phys. 1893,29, 508. 4 Bridgman, P. W. Proc. Am. Acad. Arts Sci. 1913,49, 3. 5 Moesveld, A. L. Z. Phys, Chem. 1923, 105,450. 6. Gibson, R. E. /. Am. Chem. Soc. 1935, 37, 1551-1557. 7 Newitt, D. M.; Weal, K. E. J. Chem. Soc. 1951, 3092. 8 Griswold, J.; Wong, S. Y. Chem. Eng. Prog. Symp. Ser. 1952, 48-3, 18-34. 9 Stutchbury, J. E. Ausl. J. Chem. 1956,9, 536. 10 Schroder, W. Chem.-Ing.-Tech. 1958, 30, 523-525. 11 Hirata, M.; Suda, S. Kagaflu. Kogaku 1967, 31, 339-341. 12 Grandjan, V.A. Dep. V1NITI, Moscow, USSR. 1973, No 7670-73. 13 Hirata, M.; Qhe, S.; Nagahama, K. Computer aided data of VLE; Elsevier: Amsterdam, 1975. 14 Kubota, H,; Tanaka, Y.; Makita, T. Kagaku Kogaku Ronbunshu 1975, 1,176. 15 McGlashan, M. L.; Williamson, A. G. J. Chem. Eng. Data 1976,21-2, 196-199. 16 Yusa, M.; Malhur, G. P.; Stage, R. A. J. Chem. Eng. 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J. Thermophysics 1987, 8,47-70. 31 Kurihara, K.; Minoura, T.; Kojima, K. J. Chem. Eng. Data 1995,40, 679-684. 32 Bao, Z.; Liu, M.; Yang, J.; Wang, N. J. Chem. Ind. Eng. (China) 1995,46, 230-233. 33 Chen, C. Y.; Eng, Y. W; Eu. K. S. J. Chem. Eng. Data 1995, 40, 1001-1004. 34 Xiao, C.; Bianchi, H.; Tremain, P. R. J. Chem. Thermodynamics 1997,29, 261-286. 35 Osada, O.; Sato, M.; Uematsu, M. /. Chem. Thermodynamics 1999, 31, 451-464. 36 Kuroki, T., Kagawa, N., Endo, H., Tsuruno, S., and Magee, J., W. Paper in XIVInternational Symposium of Thermophysical Properties. Colorado, USA, 2000, 19 pp. 37 Rivkin, S.L., Aleksandrov, A.A. Tertnodinamicheskie svoistva vody i vodyanogo para(The thermodynamic properties of water and water vapor), Energiya: Moscow, USSR.1975, 80 pp. (in Russian). 38 Rabinovich S.G. Pogreshnosti izmerenii (Measuring Errors), Energiya: Leningrad,USSR. 1978, 261 pp. (In Russian).
Keywords
  • density,
  • viscosity,
  • temperature,
  • hydrazine,
  • water,
  • concentration
Publication Date
Winter December, 2008
Citation Information
Mohira Abdusalomovna Zaripova, Tahmina Rustamovna Tilloeva, Hikmatullo Abdukholikovich Zoirov, Mahmadali Mahmadievich Safarov, et al.. "Density and viscosity of hydrazinesubstited aqueous solutions under various temperature and pressures. Equation state" High temperature high pressure (2008)
Available at: http://works.bepress.com/mahmadali_mahmadievich_safarov/4/