Calorimetric study and thermal analysis of crystalline nicotinic acid

As one primary component of Vitamin B-3, nicotinic acid [pyridine 3-carboxylic acid] was synthesized, and calorimetric study and thermal analysis for this compound were performed. The low-temperature heat capacity of nicotinic acid was measured with a precise automated adiabatic calorimeter over the temperature rang from 79 to 368 K. No thermal anomaly or phase transition was observed in this temperature range. A solid-to-solid transition at T-trs = 451.4 K, a solid-to-liquid transition at T-fus = 509.1 K and a thermal decomposition at T-d = 538.8 K were found through the DSC and TG-DTG techniques. The molar enthalpies of these transitions were determined to be Delta(trs)H(m =) 0.81 kJ mol(-1), Delta(fus)H(m) 27.57 kJ mol(-1) and Delta(d)H(m) = 62.38 kJ mol(-1), respectively, by the integrals of the peak areas of the DSC curves.

Heat capacity and enthalpy of fusion of penconazole (C13H15C12N3)

Low-temperature heat capacities of penconazole (C13H15Cl2N3) were precisely measured with an automated adiabatic calorimeter over the temperature rang from 78 to 364 K. The sample was observed to melt at 332.38 +/- 0.06 K. The molar enthalpy and entropy of fusion of the compound were determined to be 33580 +/- 11 J mol(-1), 101.03 +/- 0.02 J mol(-1) K-1, respectively. Further research of the melting process for this compound was carried out by means of differential scanning calorimetry (DSC) technique. The result was in agreement with that obtained from the measurements of heat capacities. (C) 2003 Elsevier B.V. All rights reserved.

Thermodynamic study of ibuprofen by adiabatic calorimetry and thermal analysis

Molar heat capacities of ibuprofen were precisely measured with a small sample precision automated adiabatic calorimeter over the temperature range from 80 to 400 K. The polynomial functions of C-p,C-m (J K-1 mol(-1)) versus T were established on the heat capacity measurements by means of the least fitting square method. The functions are as follows: for solid ibuprofen, at the temperature range of 79.105 K less than or equal to T less than or equal to 333.297 K, C-p,C-m = 144.27 + 77.046X + 3.5171X(2) + 10.925X(3) + 11.224X(4), where X = (T - 206.201)/127.096; for liquid ibuprofen, at the temperature range of 353.406 K less than or equal to T less than or equal to 378.785 K, C-p,C-m = 325.79 + 8.9696X - 1.6073X(2) - 1.5145 X-3, where X = (T - 366.095)/12.690. A fusion transition at T = 348.02 K was found from the C-p-T curve. The molar enthalpy and entropy of the fusion transition were determined to be 26.65 kJ mol(-1) and 76.58 J mol(-1) K-1, respectively. The thermodynamic functions on the base of the reference temperature of 298.15 K, (H-T - H-298.15) and (S-T - S-298.15), were derived. Thermal characteristic of ibuprofen was studied by thermo-gravimetric analysis (TG-DTG) and differential scanning calorimeter (DSC). The temperature of fusion, the molar enthalpy and entropy of fusion obtained by DSC were well consistent with those obtained by adiabatic calorimeter. The evaporation process of ibuprofen was investigated further by TG and DTG, and the activation energy of the evaporation process was determined to be 80.3 +/- 1.4 kJ mol(-1). (C) 2003 Elsevier B.V. All rights reserved.

Low-temperature heat capacity and standard molar enthalpy of formation of 9-fluorenemethanol (C14H12O)

Low-temperature heat capacities of the 9-fluorenemethanol (C14H12O) have been precisely measured with a small sample automatic adiabatic calorimeter over the temperature range between T = 78 K and T = 390 K. The solid-liquid phase transition of the compound has been observed to be T-fus = (376.567 +/- 0.012) K from the heat-capacity measurements. The molar enthalpy and entropy of the melting of the substance were determined to be Delta(fus)H(m) = (26.273 +/- 0.013) kJ (.) mol(-1) and Delta(fus)S(m) = (69.770 +/- 0.035) J (.) K-1 (.) mol(-1). The experimental values of molar heat capacities in solid and liquid regions have been fitted to two polynomial equations by the least squares method. The constant-volume energy and standard molar enthalpy of combustion of the compound have been determined, Delta(c)U(C14H12O, s) = -(7125.56 +/- 4.62) kJ (.) mol(-1) and Delta(c)H(m)degrees(C14H12O, s) = -(7131.76 +/- 4.62) kJ (.) mol(-1), by means of a homemade precision oxygen-bomb combustion calorimeter at T = (298.15 +/- 0.001) K. The standard molar enthalpy of formation of the compound has been derived, Delta(f)H(m)degrees (C14H12O, s) = -(92.36 +/- 0.97) kJ (.) mol(-1), from the standard molar enthalpy of combustion of the compound in combination with other auxiliary thermodynamic quantities through a Hess thermochemical cycle. (C) 2004 Elsevier Ltd. All rights reserved.

Heat capacity and enthalpy of fusion of pyrimethanil laurate (C24H37N3O2)

Low-temperature heat capacities of pyrimethanil laurate (C24H37N3O2) were precisely measured with an automated adiabatic calorimeter over the temperature range between T = 78 K and T = 340 K. The sample was observed to melt at (321.52 +/- 0.04) K. The molar enthalpy and entropy of fusion as well as the chemical purity of the compound were determined to be (67244 +/- 11) J (.) mol(-1), (209.28 +/- 0.02) J (.) mol(-1) (.) K-1, (0.9943 +/- 0.0004) mass fraction, respectively. The extrapolated melting temperature for the absolutely pure compound obtained from fractional melting experiments was (322.264 +/- 0.006) K. (C) 2004 Elsevier Ltd. All rights reserved.

Calorimetric study and thermal analysis of berberine sulphate

The heat capacities of berberine sulphate [(C20H18NO4)(2)SO4.3H(2)O] were measured from 80 to 390 K by means of an automated adiabatic calorimeter. Smoothed heat capacities,{H-T-H-298.15} and {S-T-S-298.15} were calculated. The loss of crystalline water started at about 339.3+/-0.2 K, and its peak temperature was 365.8+/-0.6 K. The peak temperature of decomposition for berberine sulphate was at about 391.4+/-0.4 K by DSC curve. TG-DTG analysis of this material was carried out in temperature range from 310 to 970 K. TG and DSC curves show that there is no melting in the whole heating process.

Low temperature heat capacity and thermal stability of nanocrystalline nickel

The heat capacity (C-p) of nanocrystalline nickel (nc-Ni, 40 mn crystallite size) has been measured over the temperature range of 78-370 K with a high-resolution automated adiabatic calorimeter. The measured results are compared with the C-p values of the corresponding coarse-grained crystal, and an enhancement of heat capacity of the nanocrystalline nickel was observed to be 2-4% in the temperature range between 100 and 370 K. The thermal stability of the nanocrystalline nickel sample was determined by a differential scanning calorimeter and a thermogravimetric system. The melting point of nc-Ni is the same as that of the corresponding coarse-grained crystalline nickel and the sample is stable at temperature lower than 500 K. (C) 2002 Elsevier Science B.V. All rights reserved.