A micro-combustion calorimeter was developed. The small energy equivalent (ca. 68 JK–1) of this calorimeter makes it possible to measure combustion energies of very small samples. The energy equivalent was determined by burning 2 mg of benzoic acid. The standard deviation of the mean energy equivalent was reduced to 0.014% in 5 experiments. The standard massic energy of combustion of salicylic acid and the standard deviation of the mean were determined to be –21871±5 J g–1, which agrees well with the literature values. The standard molar enthalpy of formation of salicylic acid was derived as –591.2±1.7 kJ mol–1.
Summary The standard molar enthalpy of formation of methyl methylthiomethyl sulfoxide, CH3(CH3SCH2)SO, at T=298.15 K in the liquid state was determined to be -199.4±1.5 kJ mol-1 by means of oxygen rotating-bomb combustion calorimetry.
The energy of combustion of crystalline 3,4,5-trimethoxybenzoic acid in oxygen at T=298.15 K was determined to be -4795.91.3 kJ mol-1 using combustion calorimetry. The derived standard molar enthalpies of formation of 3,4,5-trimethoxybenzoic acid in crystalline
and gaseous states at T=298.15 K, ΔfHmΘ (cr) and ΔfHmΘ (g), were -852.91.9 and -721.72.0 kJ mol-1, respectively. The reliability of the results obtained was commented upon and compared with literature values.
The standard (p0=0.1
MPa) molar enthalpy of formation, ΔfH0m, for crystalline N-phenylphthalimide
was derived from its standard molar enthalpy of combustion, in oxygen, at
the temperature 298.15 K, measured by static bomb-combustion calorimetry,
as –206.03.4 kJ mol–1. The
standard molar enthalpy of sublimation, ΔgcrH0m
, at T=298.15 K, was derived, from high
temperature Calvet microcalorimetry, as 121.31.0 kJ mol–1.
The derived standard molar enthalpy of formation, in the gaseous state,
is analysed in terms of enthalpic increments and interpreted in terms of molecular
The standard (p0=0.1 MPa) molar enthalpy of formation of 1-cyanoacetylpiperidine, in the crystalline state, at T=298.15 K, has been derived from measurements of its standard massic energy of combustion, by static bomb combustion calorimetry,
as ΔfHm0=−217.1±1.4 kJ mol−1. The standard molar enthalpy of sublimation was measured, at T=298.15 K, by the microcalorimetric sublimation technique as ΔcrgHm0=103.5±1.9 kJ mol−1.
The standard (p0=0.1 MPa) molar enthalpy of formation, ΔfHm0(l)=169.8±2.6 kJ mol−1, of the liquid 3-bromoquinoline was derived from its standard molar energy of combustion, in oxygen, to yield CO2(g), N2(g) and HBr·600H2O(l), at T=298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was
used to measure the enthalpy of vaporization of the compound, Δ1gHm0=70.7±2.3 kJ mol−1. These two thermodynamic parameters yielded the standard molar enthalpy of formation, in the gaseous phase, at T=298.15 K, ΔfHm0(g)=240.5±3.5 kJ mol−1.
The thermal behaviour of salicylsalicylic acid (CAS number 552-94-3) was studied by differential scanning calorimetry (DSC).
The endothermic melting peak and the fingerprint of the glass transition were characterised at a heating rate of 10C min-1. The melting peak showed an onset at Ton = 144C (417 K) and a maximum intensity at Tmax = 152C (425 K), while the onset of the glass transition signal was at Ton = 6C. The melting enthalpy was found to be ΔmH = 28.90.3 kJ mol-1, and the heat capacity jump at the glass transition was ΔCP = 108.10.1 J K-1mol-1. The study of the influence of the heating rate on the temperature location of the glass transition signal by DSC, allowed
the determination of the activation energy at the glass transition temperature (245 kJ mol-1), and the calculation of the fragility index of salicyl salicylate (m = 45). Finally, the standard molar enthalpy of formation of crystalline monoclinic salicylsalicylic acid at T = 298.15 K, was determined as ΔfHmo(C14H10O5, cr) = - (837.63.3) kJ mol-1, by combustion calorimetry.
MPa) molar enthalpies of formation, ΔfHm0, for
crystalline phthalimides: phthalimide, N-ethylphthalimide
and N-propylphthalimide were derived from
the standard molar enthalpies of combustion, in oxygen, at the temperature
298.15 K, measured by static bomb-combustion calorimetry, as, respectively,
– (318.01.7), – (350.12.7) and – (377.32.2)
kJ mol–1. The standard molar enthalpies of
sublimation, ΔcrgHm0, at T=298.15
K were derived by the Clausius-Clapeyron equation, from the temperature dependence
of the vapour pressures for phthalimide, as (106.91.2) kJ mol–1
and from high temperature Calvet microcalorimetry for phthalimide, N-ethylphthalimide and N-propylphthalimide
as, respectively, (106.31.3), (91.01.2) and (98.21.4)
The derived standard molar enthalpies of formation,
in the gaseous state, are analysed in terms of enthalpic increments and interpreted
in terms of molecular structure.