According to the theoretical basis of thermokinetics, the integral and differential thermokinetic equations of opposing reactions have been derived, and a novel thermokinetic research method, the characteristic parameter method for opposing reactions which taking place in a batch conduction calorimeter under isothermal condition, has been proposed in this paper. Only needing the characteristic thermoanalytical data corresponding to tm and 2tm from the same curve, the rate constants of forward and backward reactions and equilibrium constant can be calculated simultaneously with this method. In order to test the validity of this method, the proton-transfer reactions of nitroethane with ammonia at 15 and 25°C, and with trihydroxymethyl aminomethane (Tris) at 15 and 30°C have been studied, respectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in the literature. Therefore, the characteristic parameter method for opposing reaction is believed to be correct.
In order to enrich the thermokinetic research methods and enlarge the applicable range of the thermokinetic time-parameter
method, the integral and differential thermokinetic equations of consecutive first-order reaction have been deduced, and the
mathematical models of the time-parameter method for consecutive first-order reactions have been proposed in this paper. The
rate constants of two steps can be calculated from the same thermoanalytical curve measured in a batch conduction calorimeter
simultaneously with this method. The thermokinetics of saponifications of diester in aqueoushanol solvent has been studied.
The experimental results indicate that the time-parameter method for the consecutive first-order reaction is correct.
Authors:G. Xie, S. Chen, S. Gao, X. Meng, and Q. Shi
A novel solid complex, formulated as Ho(PDC)3
(o-phen), has been obtained from the reaction
of hydrate holmium chloride, ammonium pyrrolidinedithiocarbamate (APDC) and
in absolute ethanol, which was characterized by elemental analysis, TG-DTG
and IR spectrum. The enthalpy change of the reaction of complex formation
from a solution of the reagents, ΔrHmθ (sol), and the molar heat capacity of the complex, cm,
were determined as being –19.1610.051 kJ mol–1
and 79.2641.218 J mol–1 K–1
at 298.15 K by using an RD-496 III heat conduction microcalorimeter. The enthalpy
change of complex formation from the reaction of the reagents in the solid
phase, ΔrHmθ(s), was calculated as
being (23.9810.339) kJ mol–1 on the
basis of an appropriate thermochemical cycle and other auxiliary thermodynamic
data. The thermodynamics of reaction of formation of the complex was investigated
by the reaction in solution at the temperature range of 292.15–301.15
K. The constant-volume combustion energy of the complex, ΔcU, was determined as being –16788.467.74
kJ mol–1 by an RBC-II type rotating-bomb
calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHmθ, and standard enthalpy of formation,
ΔfHmθ, were calculated to be –16803.957.74 and –1115.428.94
kJ mol–1, respectively.
Authors:S. Chen, Sh Gao, X. Yang, R. Hu, and Q. Shi
Solid complexes of M(His)2Cl2nH2O (M=Mn, Co, Ni, Cu) of MnCl26H2O, CoCl26H2O, NiCl26H2O, CuCl22H2O and L-α-histidine (His) have been prepared in 95% ethanol solution and characterized by elemental analyses, chemical analyses,
IR and TG-DTG. The constant-volume combustion energies of the complexes have been determined by a rotating-bomb calorimeter.
And the standard enthalpies of formation of the complexes have been calculated as well.
This paper presents calorimeter measurement for the thermal decomposition of n-propyl nitrate (NPN), isopropyl nitrate (IPN) and 2-ethylhexyl nitrate (EHN). Similar experimental results of triethylene
glycol dinitrate (tri-EGDN) and tetraethylene glycol dinitrate (tetra-EGDN) are included for comparison. The potential energy
surfaces (PESs) along O-NO2 bond stretch are investigated using the DFT (B3P86, B3PW91 and B3LYP), ab initio Hartree-Fock and PM3 methods. The good coincidence
of experimental with theoretical results indicates that initial stage in the thermal decomposition of five nitrates is only
unimolecular homolytical dissociation of the O-NO2 bonds and the activation energies of thermolysis by DSC correspond to the energies of O-NO2 bond scission of nitrates.
DSC and TG-DTA techniques were used to investigate micro-sized silver powder particles and the adsorption of ethyl cellulose
on these particles in a solution of ethyl acetate. The apparent specific heat of the silver particles was determined, and
the kinetics of temperature-programmed desorption (TPD) of these adsorbed silver particles was investigated. Results show
that the apparent specific heat and desorption kinetic parameters obtained by thermal analysis techniques could be used to
characterize certain physico-chemical properties of such a particulate system.
Authors:C. Li, X. Ma, A. Wang, E. Nevo, and G. Chen
The aerial surface of land plants is protected by a cuticle against abiotic and biotic stresses. A better understanding of the determinants of cuticle formation and function has the potential to contribute to the breeding of more drought tolerant and disease resistant crop varieties. Two doubled haploid (DH) mapping populations, Steptoe × Morex populations and OWB-dominant × recessive populations were exploited to genetically position homologs of a set of known cuticle-associated genes. These genes were also placed on a consensus map, BinMap2005, which includes 27 eceriferum (cer) loci. Of the 49 known cuticle-associated genes, 21 identified a homolog in barley, and of these, 14 were mapped. There was a complete linkage between HvCER6 and cer-zg, suggesting the possibility that HvCER6 is the candidate gene of CER-ZG. Positioning known cuticle-associated genes on a consensus map containing cuticle mutant loci may guide the selection of candidate genes for cuticle mutants, and thus facilitate the isolation of cuticle-associated genes in barley.
Field cultivation practices affected soil temperature that influenced the crop development of winter crops. This study was undertaken to determine the effects of different mulch materials, tillage depths and planting methods on spike differentiation of winter wheat (
L.). The field experiment was consisted of three tests: (i) polythene mulch, straw mulch and no mulch; (ii) ridge planting and furrow planting; (iii) conventional tillage and shallow tillage. The results showed that soil temperature was affected by different practices. The higher soil temperature under polythene mulch resulted in the earlier initiation of spike differentiation, while straw mulch decreased soil temperature in spring that delayed the initiation compared with the non-mulch treatment. The spike initiation under ridge planting started earlier than that of furrow planting. Reduced tillage delayed the initiation compared with the conventional tillage. Duration of spike differentiation lasted longer under earlier starting of initiation that increased the grain numbers per spike. Other yield component characters were not affected by soil temperature. It was concluded that in the North China Plain where grain-filling duration of winter wheat was limited, agricultural practices that increased soil temperature in spring were favorable for grain production.
Gastrodia elata Blume polysaccharide (GEP) was extracted and then chemically characterised. Its antioxidant activity was evaluated in vitro and in vivo. The results of the in vitro investigation show that GEP consists of glucose with molecular weight of 875 185 Da and exhibits high hydroxyl radical scavenging, as well as 2,2-diphenyl-1- picrylhydrazyl activity and reducing capacity. For antioxidant activity in vivo, D-galactose-induced-aged mice were orally administered with three different doses of GEP over a period of 6 weeks. The administration of GEP dosedependently increased the body weight gain rates, liver and brain indices, superoxide dismutase and glutathione peroxidase activities, and malondialdehyde levels in the sera and brains of ageing mice. These results suggest that GEP exhibits high antioxidant activity and can retard human ageing associated with free radicals.