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Abstract  

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 1,10-phenanthroline (o-phenH2O) 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, Δr H m θ (sol), and the molar heat capacity of the complex, c m, 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, Δr H m θ(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, Δc U, 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, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16803.957.74 and –1115.428.94 kJ mol–1, respectively.

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Abstract  

A novel method for the determination of rate constants of reactions, the time-variable method, is proposed in this paper. The method needs only three time points (t), peak heights () and pre-peak areas (), obtained from the measured thermoanalytical curve. It does not require the thermokinetic reaction to be completed. It utilizes data-processing on a computer to give the rate constants. Four reaction systems, including a first-order reaction, second-order reactions (with equal concentrations and with unequal concentrations) and a third-order reaction, were studied with this method. The method was validated and its theoretical basis was verified by the experimental results.

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Abstract  

The heat capacities (C p,m) of 2-amino-5-methylpyridine (AMP) were measured by a precision automated adiabatic calorimeter over the temperature range from 80 to 398 K. A solid-liquid phase transition was found in the range from 336 to 351 K with the peak heat capacity at 350.426 K. The melting temperature (T m), the molar enthalpy (Δfus H m 0), and the molar entropy (Δfus S m 0) of fusion were determined to be 350.431±0.018 K, 18.108 kJ mol−1 and 51.676 J K−1 mol−1, respectively. The mole fraction purity of the sample used was determined to be 0.99734 through the Van’t Hoff equation. The thermodynamic functions (H T-H 298.15 and S T-S 298.15) were calculated. The molar energy of combustion and the standard molar enthalpy of combustion were determined, ΔU c(C6H8N2,cr)= −3500.15±1.51 kJ mol−1 and Δc H m 0 (C6H8N2,cr)= −3502.64±1.51 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. The standard molar enthalpy of formation of the crystalline compound was derived, Δr H m 0 (C6H8N2,cr)= −1.74±0.57 kJ mol−1.

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Abstract  

A solid complex Eu(C5H8NS2)3(C12H8N2) has been obtained from reaction of hydrous europium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen⋅H2O) in absolute ethanol. IR spectrum of the complex indicated that Eu3+ in the complex coordinated with sulfur atoms from the APDC and nitrogen atoms from the o-phen. TG-DTG investigation provided the evidence that the title complex was decomposed into EuS. The enthalpy change of the reaction of formation of the complex in ethanol, Δr H m θ(l), as –22.2140.081 kJ mol–1, and the molar heat capacity of the complex, c m, as 61.6760.651 J mol–1 K–1, at 298.15 K were determined by an RD-496 III type microcalorimeter. The enthalpy change of the reaction of formation of the complex in solid, Δr H m θ(s), was calculated as 54.5270.314 kJ mol–1 through a thermochemistry cycle. Based on the thermodynamics and kinetics on the reaction of formation of the complex in ethanol at different temperatures, fundamental parameters, including the activation enthalpy (ΔH θ), the activation entropy (ΔS θ), the activation free energy (ΔG θ), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained. The constant-volume combustion energy of the complex, Δc U, was determined as –16937.889.79 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16953.379.79 and –1708.2310.69 kJ mol–1, respectively.

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Abstract  

This paper presents a novel data processing method for thermokinetics of faster first-order reaction on the basis of the double-parameter theoretical model of a conduction calorimeter, in which the rate constant of a first-order reaction can be calculated from only four peak height data from the same thermoanalytical curve without using any peak-area. The saponifications of ethyl acetate and methyl acetate in aqueous solution and ethyl benzoate in aqueous alcohol have been studied to test the validity of this method. The rate constants calculated with this method are in fair agreement with those in literature; hence the validity of this method is demonstrated.

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Abstract  

On the basis of the theory of thermokinetics proposed in the literature, a novel thermokinetic method for determination of the reaction rate, the characteristic parameter method, is proposed in this paper. Mathematical models were established to determine the kinetic parameters and rate constants. In order to test the validity of this method, the saponifications of ethyl benzoate, ethyl acetate and ethyl propionate, and the formation of hexamethylenetetramine were studied with this method. The rate constants calculated with this method are in agreement with those in the literature, and the characteristic parameter method is therefore believed to be correct.In the light of the characteristic parameter method, we have developed further two thermo-kinetic methods, the thermoanalytical single and multi-curve methods, which are convenient for simultaneous determination of the reaction order and the rate constant. The reaction orders and rate constants of the saponifications of ethyl acetate and ethyl butyrate and the ring-opening reaction of epichlorohydrin with hydrobromic acid were determined with these methods, and their validity was verified by the experimental results.

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Acta Alimentaria
Authors:
J.J. Lin
,
Q.H. Meng
,
Z.F. Wu
,
S.Y. Pei
,
P. Tian
,
X. Huang
,
Z.Q. Qiu
,
H.J. Chang
,
C.Y. Ni
,
Y.Q. Huang
, and
Y. Li

Abstract

This paper explores the prediction of the soluble solid content (SSC) in the visible and near-infrared (400–1,000 nm) regions of Baise mango. Hyperspectral images of Baise mangoes with wavelengths of 400–1,000 nm were obtained using a hyperspectral imaging system. Multiple scatter correction (MSC) was chosen to remove the effect of noise on the accuracy of the partial least squares (PLS) regression model. On this basis, the characteristic wavelengths of mango SSC were selected using the competitive adaptive reweighted sampling (CARS), genetic algorithm (GA), uninformative variable elimination (UVE), and combined CARS + GA-SPA, CARS + UVE-SPA, and GA + UVE-SPA characteristic wavelength methods. The results show that the combined MSC-CARS + GA-SPA-PLS algorithm can reduce redundant information and improve the computational efficiency, so it is an effective method to predict the SSC of mangoes.

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Journal of Thermal Analysis and Calorimetry
Authors:
F. Xu
,
L. Sun
,
J. Zhang
,
Y. Qi
,
L. Yang
,
H. Ru
,
C. Wang
,
X. Meng
,
X. Lan
,
Q. Jiao
, and
F. Huang

Abstract  

Heat capacities of the carbon nanotubes (CNTs) with different sizes have been measured by modulated temperature differential scanning calorimetry (MDSC) and reported for the first time. The results indicated the values of C p increased with shortening length of CNTs when the diameters of CNTs were between 60 and 100 nm. However, the values of C p of CNTs were not affected by their diameter when the lengths of CNTs were 1–2 um, or not affected by the length of CNTs when their diameters were below 10 nm. The thermal stabilities of the CNTs have been studied by TG-DTG-DSC. The results of TG-DTG showed that thermal stabilities of CNTs were enhanced with their diameters increase. With lengths increase, the thermal stabilities of CNTs increased when their diameters were between 60 and 100 nm, but there is a slight decrease when their diameters were less than 60 nm. The further DSC analyses showed both released heat and T onset increased with the increase of CNTs diameters, which confirms the consistency of the results from both TG-DTG and DSC on CNTs thermal stability.

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Acta Alimentaria
Authors:
C.Y. Zhou
,
Q.W. Cheng
,
T. Chen
,
L.L. Meng
,
T.G. Sun
,
B. Hu
,
J. Yang
, and
D.Y. Zhang

Abstract

To study the feasibility of evaluating the quality characteristics of banana based on the browning area. The texture characteristics, total soluble solids (TSS), ascorbic acid, malondialdehyde (MDA) concentrations, relative conductivity, polyphenol oxidase, peroxidase, and phenylalanine ammonia-lyase (PAL) activities in banana peels were detected during storage. A linear model was made by principal component analysis and multiple linear regression between the banana browning area and characteristic indices. The results showed that the changes in the physiological characteristics of bananas were significantly different during different storage periods. The main factors that affected the banana browning area were relative conductivity, PAL, TSS, and MDA, indicating that lipid peroxidation, respiration, and metabolism of phenylpropanoids had significant influence on the banana browning area during storage. Thus, it is feasible to predict banana quality based on changes in browning area, which could be a rapid and non-destructive detection of banana quality during storage.

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