Authors:Y. Li, H. Xingen, L. Ruisen, and X. Guiying
Enthalpies of dilution of aqueous L-serine, pyridine and methylpyridine solutions and their enthalpies of mixing have been determined by a mixing-flow microcalorimeter
at 298.15 K. The data have been analyzed in terms of McMillan-Mayer formalism to fit to virial polynomials from which the
heterotactic enthalpic pairwise interaction coefficients, hxy, betweenL-serine and pyridine and methylpyridine isomers have been evaluated. The results obtained in the present paper are compared
with those reported in the earlier paper about glycine and L-alanine in the same organic solvent aqueous solutions, giving a global insight of the interaction mechanism between the a-amino
acids and pyridine and methylpyridine from the point of view of solute-solute interactions and substituent effects of methyl
groups introduced into the pyridine ring.
The dilution enthalpies of D-mannitol and D-sorbitol in aqueous sodium chloride solution at various concentrations have been determined by isothermal microcalorimetry
at 298.15 K. The homogeneous enthalpic interaction coefficients over a quite large range of concentration of aqueous sodium
chloride solutions have been calculated according to the excess enthalpy concept. The results show that enthalpic pairwise
interaction coefficients (h2) of D-mannitol and D-sorbitol are positive in aqueous sodium chloride solution and become more positive with increase of the concentration of
sodium chloride. The results are interpreted in terms of the different conformations of the two polyols, solute-solute and
solute-solvent interactions involved by solvent effects.
Conducting polyaniline/Cobaltosic oxide (PANI/Co3O4) composites were synthesized for the first time, by in situ deposition technique in the presence of hydrochloric acid (HCl)
as a dopant by adding the fine grade powder (an average particle size of approximately 80 nm) of Co3O4 into the polymerization reaction mixture of aniline. The composites obtained were characterized by infrared spectra (IR)
and X-ray diffraction (XRD). The composition and the thermal stability of the composites were investigated by TG-DTG. The
results suggest that the thermal stability of the composites is higher than that of the pure PANI. The improvement in the
thermal stability for the composites is attributed to the interaction between PANI and nano-Co3O4.
Authors:B. Tong, Z. Tan, Q. Shi, Y. Li, and S. Wang
The low-temperature heat capacity Cp,m of sorbitol was precisely measured in the temperature range from 80 to 390 K by means of a small sample automated adiabatic
calorimeter. A solid-liquid phase transition was found at T=369.157 K from the experimental Cp-T curve. The dependence of heat capacity on the temperature was fitted to the following polynomial equations with least square
method. In the temperature range of 80 to 355 K, Cp,m/J K−1 mol−1=170.17+157.75x+128.03x2-146.44x3-335.66x4+177.71x5+306.15x6, x= [(T/K)−217.5]/137.5. In the temperature range of 375 to 390 K, Cp,m/J K−1 mol−1=518.13+3.2819x, x=[(T/K)-382.5]/7.5. The molar enthalpy and entropy of this transition were determined to be 30.35±0.15 kJ mol−1 and 82.22±0.41 J K−1 mol−1 respectively. The thermodynamic functions [HT-H298.15] and [ST-S298.15], were derived from the heat capacity data in the temperature range of 80 to 390 K with an interval of 5 K. DSC and TG measurements
were performed to study the thermostability of the compound. The results were in agreement with those obtained from heat capacity
The decomposition kinetics of reference calcite and three ultra-fine samples with different morphologies are investigated.
The kinetic parameters and rate equation are obtained according to the methods reported in our previous studies. Compared
with the reference calcite, a considerable diminution of the activation energy Ea up to 70–80 kJ mol−1 is observed in the case of three ultra-fine samples. There are also some distinct differences concerning the activation energy
of each of the ultra-fine sample. This may have something to do with the particle morphology revealed by TEM and SEM measurements.
XRD measurements of four calcite samples show that large strain exists in the crystal lattice in the case of ultra-fine calcite
samples. This may give a reason to their abnormal decomposition behavior.
The molar heat capacities of the room temperature
ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4)
were measured by an adiabatic calorimeter in temperature range from 80 to
390 K. The dependence of the molar heat capacity on temperature is given as
a function of the reduced temperature X
by polynomial equations, CP,m
(J K–1 mol–1)=
195.55+47.230 X–3.1533 X2+4.0733 X3+3.9126 X4 [X=(T–125.5)/45.5] for the solid phase (80~171
K), and CP,m (J
378.62+43.929 X+16.456 X2–4.6684 X3–5.5876 X4 [X=(T–285.5)/104.5] for the liquid phase (181~390
K), respectively. According to the polynomial equations and thermodynamic
relationship, the values of thermodynamic function of the BMIBF4
relative to 298.15 K were calculated in temperature range from 80 to 390 K
with an interval of 5 K. The glass translation of BMIBF4
was observed at 176.24 K. Using oxygen-bomb combustion calorimeter, the molar
enthalpy of combustion of BMIBF4 was determined to
– 5335±17 kJ mol–1. The standard
molar enthalpy of formation of BMIBF4 was evaluated
to be ΔfHmo=
–1221.8±4.0 kJ mol–1 at T=298.150±0.001 K.
AP/HTPB based composite
propellants with additives such as ammonium oxalate (AO), mixture of ammonium
oxalate and strontium carbonate (SC) was investigated by burning rate, TG-DTG
and FTIR experiments. The results show that the burning rates of these propellants
are decreased significantly. TG-DTG experiments indicate that decomposition
temperatures of AP with these additives are increased. Furthermore, the activation
energy of the decomposition reaction of AP is also increased in the presence
of AO or AO/SC. These results show that AO or AO/SC restrains the decomposition
of AP. The burning rates of these propellants are decreased. The burning rate
temperature sensitivity of AP/HTPB based propellants is reduced significantly
by the addition of AO or AO/SC. But the effect of AO is less than that of
AO/SC. AO/SC is better effect to reduce temperature sensitivity and at the
same time, to reduce pressure exponent. The reduced heat release at the burning
surface of AP/HTPB/AO is responsible for the reduced temperature sensitivity.
Synergetic action is probably produced between AO and SC within AP/HTPB based
propellants in the pressure range tested. This synergetic effect causes the
heat release to reduce and the burning surface temperature to increase. Moreover,
it makes the net exothermal reaction of condensed phase become little dependent
on T0. Thus, the
burning rate temperature sensitivity is reduced.