2 0 2009 kro dru 0 journal Original Krol, O. V.[Olesya V.] Druzhinina, A. I.[Anna I.] Varushchenko, R. M.[Raisa M.] Reshetova, M. D.[Marina D.] Borisova, N. E.[Nataliya E.] Dorofeeva, O. V.[Olga V.] Troyanov, S. I.[Sergey I.] J. Chem. Eng. Data 2009 2009-02-25 Heat Capacities and Thermodynamic Functions of Propanoylferrocene and Propylferrocene The heat capacities of propanoylferrocene (POF), C5H5FeC5H4COC2H5, and propylferrocene (PF), C5H5FeC5- H4C3H7-n, were measured by vacuum adiabatic calorimetry in the temperature ranges from (10 and 7) K to 372 K. The temperatures and enthalpies of the phase transitions and the purity of the samples have been determined. The solid phase transition of PF was studied by single-crystal crystallography in the temperature range from (150 to 200) K. The thermodynamic functions (absolute entropies, changes of the enthalpy, and Gibbs energy) of POF and PF were calculated for the solid and liquid phases of the temperature intervals studied. The ideal gas thermodynamic functions were derived at T ) 298.15 K using the data on saturated vapor pressure and the enthalpies and entropies of vaporization. A reliability of the ideal gas thermodynamic functions was corroborated by the additive calculation method. A mutual congruence of the absolute entropies of alkylferrocenes and acylferrocenes studied in this work and available in the literature were critically analyzed. 10.1021/je800266e 54 263-271 1 propylferrocene C13H16Fe 1 Synthesized by the authors 1 99.24 4 Fraction melting in an adiabatic calorimeter 1 99.12 4 DSC 2 propanoylferrocene C13H14FeO 1 Synthesized by the authors 1 98.93 4 Fraction melting in an adiabatic calorimeter 1 98.95 4 DSC 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Triple point temperature, K Adiabatic calorimetry Crystal 2 Direct value, X 1 Author Crystal 2 Crystal 1 Gas 1 186.7 5 1 .3 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Triple point temperature, K Adiabatic calorimetry Crystal 1 Direct value, X 1 Author Crystal 1 Liquid Gas 1 311.62 5 1 .51 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Normal melting temperature, K DSC/DTA Crystal 1 Direct value, X Crystal 1 Liquid Air at 1 atmosphere 1 311.62 5 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy of transition or fusion, kJ/mol Adiabatic calorimetry Crystal 1 Direct value, X 1 Author Crystal 1 Liquid Gas 1 19.16 4 1 .12 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy of transition or fusion, kJ/mol DSC/DTA Crystal 1 Direct value, X Crystal 1 Liquid Air at 1 atmosphere 1 19.69 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy of transition or fusion, kJ/mol Adiabatic calorimetry Crystal 2 Direct value, X 1 Author Crystal 2 Crystal 1 Gas 1 1.23 3 1 .01 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar heat capacity at constant pressure, J/K/mol Small (less than 1 g) adiabatic calorimetry Crystal 2 Direct value, X Crystal 2 Pressure, kPa 101.325 6 1 Temperature, K 1 5 1 1 .5339 4 1 10 2 1 3.806 4 1 15 2 1 11.48 4 1 20 2 1 20.55 4 1 25 2 1 29.5 4 1 30 2 1 37.6 4 1 35 2 1 44.82 4 1 40 2 1 51.46 4 1 45 2 1 57.41 4 1 50 2 1 62.94 4 1 55 2 1 68.11 4 1 60 2 1 72.96 4 1 65 2 1 77.55 4 1 70 2 1 81.91 4 1 75 2 1 86.11 4 1 80 2 1 89.89 4 1 90 2 1 98.25 4 1 100 3 1 106.2 4 1 110 3 1 114.1 4 1 120 3 1 122 4 1 130 3 1 130.2 4 1 140 3 1 139.3 4 1 150 3 1 149.6 4 1 160 3 1 161.7 4 1 170 3 1 173.8 4 1 180 3 1 185.9 4 1 186.7 5 1 194 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy, kJ/mol Small (less than 1 g) adiabatic calorimetry Crystal 2 Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal 2 Crystal 2 Pressure, kPa 101.325 6 1 Temperature, K 1 5 1 1 .000668 3 1 10 2 1 .009802 4 1 15 2 1 .04748 4 1 20 2 1 .1273 4 1 25 2 1 .2527 4 1 30 2 1 .4209 4 1 35 2 1 .6272 4 1 40 2 1 .8683 4 1 45 2 1 1.14 4 1 50 2 1 1.441 4 1 55 2 1 1.769 4 1 60 2 1 2.122 4 1 65 2 1 2.498 4 1 70 2 1 2.897 4 1 75 2 1 3.317 4 1 80 2 1 3.758 4 1 90 2 1 4.699 4 1 100 3 1 5.721 4 1 110 3 1 6.823 4 1 120 3 1 8.003 4 1 130 3 1 9.263 4 1 140 3 1 10.61 4 1 150 3 1 12.05 4 1 160 3 1 13.61 4 1 170 3 1 15.29 4 1 180 3 1 17.08 4 1 186.7 5 1 18.36 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar entropy, J/K/mol Small (less than 1 g) adiabatic calorimetry Crystal 2 Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal 2 Crystal 2 Pressure, kPa 101.325 6 1 Temperature, K 1 5 1 1 .178 4 1 10 2 1 1.368 4 1 15 2 1 4.322 4 1 20 2 1 8.853 4 1 25 2 1 14.41 4 1 30 2 1 20.52 4 1 35 2 1 26.87 4 1 40 2 1 33.3 4 1 45 2 1 39.71 4 1 50 2 1 46.05 4 1 55 2 1 52.29 4 1 60 2 1 58.43 4 1 65 2 1 64.45 4 1 70 2 1 70.36 4 1 75 2 1 76.16 4 1 80 2 1 81.84 4 1 90 2 1 92.91 4 1 100 3 1 103.7 4 1 110 3 1 114.2 4 1 120 3 1 124.4 4 1 130 3 1 134.5 4 1 140 3 1 144.5 4 1 150 3 1 154.5 4 1 160 3 1 164.5 4 1 170 3 1 174.7 4 1 180 3 1 184.9 4 1 186.7 5 1 191.9 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar heat capacity at constant pressure, J/K/mol Small (less than 1 g) adiabatic calorimetry Crystal 1 Direct value, X Crystal 1 Pressure, kPa 101.325 6 1 Temperature, K 1 186.7 5 1 191.3 4 1 190 3 1 193.3 4 1 200 3 1 199.5 4 1 210 3 1 205.6 4 1 220 3 1 212.1 4 1 230 3 1 220.2 4 1 240 3 1 230.2 4 1 250 3 1 244.6 4 1 260 3 1 274.7 4 1 270 3 1 324 4 1 276.03 5 1 286.8 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy, kJ/mol Small (less than 1 g) adiabatic calorimetry Crystal 1 Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal 2 Crystal 1 Pressure, kPa 101.325 6 1 Temperature, K 1 186.7 5 1 19.59 4 1 190 3 1 20.22 4 1 200 3 1 22.19 4 1 210 3 1 24.21 4 1 220 3 1 26.3 4 1 230 3 1 28.46 4 1 240 3 1 30.71 4 1 250 3 1 33.08 4 1 260 3 1 35.65 4 1 270 3 1 38.64 4 1 276.03 5 1 40 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar entropy, J/K/mol Small (less than 1 g) adiabatic calorimetry Crystal 1 Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal 2 Crystal 1 Pressure, kPa 101.325 6 1 Temperature, K 1 186.7 5 1 198.5 4 1 190 3 1 201.9 4 1 200 3 1 211.9 4 1 210 3 1 221.8 4 1 220 3 1 231.5 4 1 230 3 1 241.1 4 1 240 3 1 250.7 4 1 250 3 1 260.4 4 1 260 3 1 270.4 4 1 270 3 1 281.7 4 1 276.03 5 1 286.6 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar heat capacity at constant pressure, J/K/mol Small (less than 1 g) adiabatic calorimetry Liquid Direct value, X Liquid Pressure, kPa 101.325 6 1 Temperature, K 1 276.03 5 1 305.9 4 1 280 3 1 308.4 4 1 290 3 1 314.9 4 1 298.15 5 1 319.5 4 1 300 3 1 320.5 4 1 310 3 1 325.8 4 1 320 3 1 331.8 4 1 330 3 1 338.2 4 1 340 3 1 344.4 4 1 350 3 1 350.7 4 1 360 3 1 356.6 4 1 370 3 1 361.5 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy, kJ/mol Small (less than 1 g) adiabatic calorimetry Liquid Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal 2 Liquid Pressure, kPa 101.325 6 1 Temperature, K 1 276.03 5 1 52.74 4 1 280 3 1 53.96 4 1 290 3 1 57.08 4 1 298.15 5 1 59.67 4 1 300 3 1 60.26 4 1 310 3 1 63.49 4 1 320 3 1 66.78 4 1 330 3 1 70.13 4 1 340 3 1 73.54 4 1 350 3 1 77.02 4 1 360 3 1 80.55 4 1 370 3 1 84.14 4 1 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar entropy, J/K/mol Small (less than 1 g) adiabatic calorimetry Liquid Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal 2 Liquid Pressure, kPa 101.325 6 1 Temperature, K 1 276.03 5 1 332.7 4 1 280 3 1 337.2 4 1 290 3 1 348.1 4 1 298.15 5 1 356.9 4 1 300 3 1 358.9 4 1 310 3 1 369.5 4 1 320 3 1 380 4 1 330 3 1 390.3 4 1 340 3 1 400.5 4 1 350 3 1 410.5 4 1 360 3 1 420.5 4 1 370 3 1 430.3 4 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Triple point temperature, K Adiabatic calorimetry Crystal Direct value, X 1 Author Crystal Liquid Gas 1 276.83 5 1 .5 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Normal melting temperature, K DSC/DTA Crystal Direct value, X Crystal Liquid Air at 1 atmosphere 1 278.2 5 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy of transition or fusion, kJ/mol Adiabatic calorimetry Crystal Direct value, X 1 Author Crystal Liquid Gas 1 12.74 4 1 .17 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy of transition or fusion, kJ/mol DSC/DTA Crystal Direct value, X Crystal Liquid Air at 1 atmosphere 1 14.67 4 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar heat capacity at constant pressure, J/K/mol Small (less than 1 g) adiabatic calorimetry Crystal Direct value, X Crystal Pressure, kPa 101.325 6 1 Temperature, K 1 10 2 1 4.607 4 1 15 2 1 11.25 4 1 20 2 1 18.61 4 1 25 2 1 26.27 4 1 30 2 1 34.16 4 1 35 2 1 42.07 4 1 40 2 1 49.63 4 1 45 2 1 56.35 4 1 50 2 1 61.76 4 1 55 2 1 66.08 4 1 60 2 1 70.11 4 1 65 2 1 74.36 4 1 70 2 1 79.11 4 1 75 2 1 84.35 4 1 80 2 1 89.8 4 1 90 2 1 99.79 4 1 100 3 1 108.7 4 1 110 3 1 116.7 4 1 120 3 1 124.2 4 1 130 3 1 131.6 4 1 140 3 1 138.9 4 1 150 3 1 146.4 4 1 160 3 1 154 4 1 170 3 1 161.9 4 1 180 3 1 170 4 1 190 3 1 178.3 4 1 200 3 1 186.8 4 1 210 3 1 195.4 4 1 220 3 1 204.1 4 1 230 3 1 212.9 4 1 240 3 1 221.9 4 1 250 3 1 231 4 1 260 3 1 240.3 4 1 270 3 1 250.1 4 1 280 3 1 260.5 4 1 290 3 1 271.7 4 1 298.15 5 1 280.7 4 1 300 3 1 282.7 4 1 310 3 1 293.8 4 1 311.13 5 1 295 4 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy, kJ/mol Small (less than 1 g) adiabatic calorimetry Crystal Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal Crystal Pressure, kPa 101.325 6 1 Temperature, K 1 10 2 1 .01261 4 1 15 2 1 .05079 4 1 20 2 1 .1253 4 1 25 2 1 .2374 4 1 30 2 1 .3884 4 1 35 2 1 .579 4 1 40 2 1 .8085 4 1 45 2 1 1.074 4 1 50 2 1 1.37 4 1 55 2 1 1.69 4 1 60 2 1 2.03 4 1 65 2 1 2.391 4 1 70 2 1 2.775 4 1 75 2 1 3.183 4 1 80 2 1 3.618 4 1 90 2 1 4.567 4 1 100 3 1 5.61 4 1 110 3 1 6.737 4 1 120 3 1 7.942 4 1 130 3 1 9.222 4 1 140 3 1 10.58 4 1 150 3 1 12 4 1 160 3 1 13.5 4 1 170 3 1 15.08 4 1 180 3 1 16.74 4 1 190 3 1 18.48 4 1 200 3 1 20.31 4 1 210 3 1 22.22 4 1 220 3 1 24.22 4 1 230 3 1 26.3 4 1 240 3 1 28.47 4 1 250 3 1 30.74 4 1 260 3 1 33.09 4 1 270 3 1 35.55 4 1 280 3 1 38.1 4 1 290 3 1 40.76 4 1 298.15 5 1 43.01 4 1 300 3 1 43.53 4 1 310 3 1 46.41 4 1 311.13 5 1 46.75 4 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar entropy, J/K/mol Small (less than 1 g) adiabatic calorimetry Crystal Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal Crystal Pressure, kPa 101.325 6 1 Temperature, K 1 10 2 1 1.703 4 1 15 2 1 4.709 4 1 20 2 1 8.946 4 1 25 2 1 13.92 4 1 30 2 1 19.4 4 1 35 2 1 25.27 4 1 40 2 1 31.38 4 1 45 2 1 37.63 4 1 50 2 1 43.86 4 1 55 2 1 49.95 4 1 60 2 1 55.87 4 1 65 2 1 61.65 4 1 70 2 1 67.33 4 1 75 2 1 72.97 4 1 80 2 1 78.59 4 1 90 2 1 89.75 4 1 100 3 1 100.8 4 1 110 3 1 111.5 4 1 120 3 1 122 4 1 130 3 1 132.2 4 1 140 3 1 142.2 4 1 150 3 1 152.1 4 1 160 3 1 161.8 4 1 170 3 1 171.3 4 1 180 3 1 180.8 4 1 190 3 1 190.2 4 1 200 3 1 199.6 4 1 210 3 1 208.9 4 1 220 3 1 218.2 4 1 230 3 1 227.5 4 1 240 3 1 236.7 4 1 250 3 1 246 4 1 260 3 1 255.2 4 1 270 3 1 264.4 4 1 280 3 1 273.7 4 1 290 3 1 283.1 4 1 298.15 5 1 290.7 4 1 300 3 1 292.5 4 1 310 3 1 301.9 4 1 311.13 5 1 303 4 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar heat capacity at constant pressure, J/K/mol Small (less than 1 g) adiabatic calorimetry Liquid Direct value, X Liquid Pressure, kPa 101.325 6 1 Temperature, K 1 311.13 5 1 347.6 4 1 320 3 1 353.3 4 1 330 3 1 359.7 4 1 340 3 1 365.7 4 1 350 3 1 372.9 4 1 360 3 1 378.5 4 1 370 3 1 381.9 4 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar enthalpy, kJ/mol Small (less than 1 g) adiabatic calorimetry Liquid Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal Liquid Pressure, kPa 101.325 6 1 Temperature, K 1 311.13 5 1 65.91 4 1 320 3 1 69.01 4 1 330 3 1 72.58 4 1 340 3 1 76.21 4 1 350 3 1 79.9 4 1 360 3 1 83.66 4 1 370 3 1 87.46 4 2 1 Principal objective of the work RDC TRC 2/24/2009 1 Molar entropy, J/K/mol Small (less than 1 g) adiabatic calorimetry Liquid Difference with the reference state, X-X(REF) Reference phase with the same composition at fixed temperature and pressure 0 0 101 3 Crystal Liquid Pressure, kPa 101.325 6 1 Temperature, K 1 311.13 5 1 364.6 4 1 320 3 1 374.4 4 1 330 3 1 385.4 4 1 340 3 1 396.2 4 1 350 3 1 406.9 4 1 360 3 1 417.5 4 1 370 3 1 427.9 4