Study on the Melting Mechanism of Maleic Anhydride

2020 ◽  
Vol 10 (1) ◽  
pp. 65-78
Author(s):  
Bratati Das ◽  
Ashis Bhattacharjee
Keyword(s):  
Phase Transition ◽  
Activation Energy ◽  
Maleic Anhydride ◽  
Temperature Dependence ◽  
Growth Models ◽  
Melting Process ◽  
Nucleation And Growth ◽  
Crystalline Solid ◽  
Scanning Calorimetry ◽  
Melting Mechanism

Background: Melting of a pure crystalline material is generally treated thermodynamically which disregards the dynamic aspects of the melting process. According to the kinetic phenomenon, any process should be characterized by activation energy and preexponential factor where these kinetic parameters are derivable from the temperature dependence of the process rate. Study on such dependence in case of melting of a pure crystalline solid gives rise to a challenge as such melting occurs at a particular temperature only. The temperature region of melting of pure crystalline solid cannot be extended beyond this temperature making it difficult to explore the temperature dependence of the melting rate and consequently the derivation of the related kinetic parameters. Objective: The present study aims to explore the mechanism of the melting process of maleic anhydride in the framework of phase transition models. Taking this process as just another first-order phase transition, occurring through the formation of nuclei of new phase and their growth, particular focus is on the nucleation and growth models. Methods: Non-isothermal thermogravimetry, as well as differential scanning calorimetry studies, has been performed. Using isoconversional kinetic analysis, temperature dependence of the activation energy of melting has been obtained. Nucleation and growth models have been utilized to obtain the theoretical temperature dependencies for the activation energy of melting and these dependencies are then compared with the experimentally estimated ones. Conclusion: The thermogravimetry study indicates that melting is followed by concomitant evaporation, whereas the differential scanning calorimetry study shows that the two processes appear in two different temperature regions, and these differences observed may be due to the applied experimental conditions. From the statistical analysis, the growth model seems more suitable than the nucleation model for the interpretation of the melting mechanism of the maleic anhydride crystals.

scholarly journals Differential Scanning Calorimetry of Metamict Pu-Substituted Zirconolite

1982 ◽  
Vol 15 ◽  
Author(s):  
Dean E. Peterson ◽  
Frank W. Clinard
Keyword(s):  
Activation Energy ◽  
Differential Scanning Calorimetry ◽  
Ambient Temperature ◽  
Total Energy ◽  
Temperature Dependence ◽  
Radiation Damage ◽  
Rate Constant ◽  
Stored Energy ◽  
Scanning Calorimetry ◽  
No Release

ABSTRACTSamples of CaPuTi2O7 were prepared by cold pressing and sintering. Plutonium was substituted for zirconium in order to characterize radiation damage effects. The energy stored in a sample which had reached saturation in swelling after storage at ambient temperature was measured with a differential scanning calorimeter. The total energy of 6.6±0.1 cal/g is released over the range 485–715° C. The activation energy of annealing of the damage is 1.22±0.05 eV. The temperature dependence of the rate constant is described by kT= 5.96E4 exp(−1.22/kBT) s−1 where kB and T are the Boltzmann's constant and temperature(K) respectively. A sample stored at 600°C was similarly evaluated and showed no release of stored energy to the precision of the apparatus (±0.1 cal/g). These results are applied to analysis of waste incorporation in Synroc and are correlated with analogous parameters for other materials.

scholarly journals Транспортные процессы с участием атомов углерода между поверхностью и объемом родия при образовании и разрушении графена

2020 ◽  
Vol 54 (6) ◽  
pp. 552
Author(s):  
Е.В. Рутьков ◽  
Е.Ю. Афанасьева ◽  
Н.Р. Галль
Keyword(s):  
Phase Transition ◽  
Activation Energy ◽  
Temperature Dependence ◽  
Atomic Carbon ◽  
Graphene Growth ◽  
Carbon Dissolution ◽  
The Difference ◽  
Kinetics Of

Equilibrium transport of atomic carbon between Rh surface and bulk has been studied. This transport controls the kinetics of the phase transition resulting in graphene growth or destruction. The difference ΔE=0.7 eV has been measured between the activation energy of atomic carbon dissolution E1s and that of its segregation from the bulk to the surface E1s. The temperature dependence of chemisorbed carbon critical cover Neq = Neq(T) has been measured, that is the cover when 2D phase transition takes place and graphene islands start to grow. E.g., Neq = 7.7•1014 cm-2 at T = 1800 K, and Neq = 3.1•1014 cm-2 at T = 1000 K.

scholarly journals Activation Energies and Temperature Dependencies of the Rates of Crystallization and Melting of Polymers

Polymers ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 1070 ◽  
Author(s):  
Sergey Vyazovkin
Keyword(s):  
Experimental Data ◽  
Phase Transition ◽  
Activation Energy ◽  
Temperature Dependence ◽  
Kinetic Analysis ◽  
Review Paper ◽  
Isoconversional Methods ◽  
Activation Energies ◽  
Phase Transition Kinetics ◽  
Kinetic Treatment

The objective of this review paper is to survey the phase transition kinetics with a focus on the temperature dependence of the rates of crystallization and melting, as well as on the activation energies of these processes obtained via the Arrhenius kinetic treatment, including the treatment by isoconversional methods. The literature is analyzed to track the development of the basic models and their underlying concepts. The review presents both theoretical and practical considerations regarding the kinetic analysis of crystallization and melting. Both processes are demonstrated to be kinetically complex, and this is revealed in the form of nonlinear Arrhenius plots and/or the variation of the activation energy with temperature. Principles which aid one to understand and interpret such results are discussed. An emphasis is also put on identifying proper computational methods and experimental data that can lead to meaningful kinetic interpretation.

Heat Capacity of K3LnCl6 Compounds with Ln = La, Ce, Pr, Nd

1999 ◽  
Vol 54 (3-4) ◽  
pp. 229-235 ◽  
Author(s):  
M. Gaune-Escard ◽  
L. Rycerz
Keyword(s):  
Experimental Data ◽  
Phase Transition ◽  
Differential Scanning Calorimetry ◽  
Heat Capacity ◽  
Phase Transitions ◽  
Liquid Phase ◽  
Temperature Dependence ◽  
Heat Capacities ◽  
Scanning Calorimetry ◽  
The Enthalpy Of Formation

The heat capacities of the solid and liquid K3LnCl6 compounds (Ln = La, Ce, Pr, Nd) have been determined by differential scanning calorimetry (DSC) in the temperature range 300 -1100 K. Their temperature dependence is discussed in terms of the phase transitions of these compounds as reported in literature. The heat capacity increases and decreases strongly in the vicinity of a phase transition but else varies smoothly. The Cp data were fitted by an equation which provides a satisfactory representation up to the temperatures of Cp discontinuity. The measured heat capacities were checked for consistency by calculating the enthalpy of formation of the liquid phase, which had been previously measured. The results obtained compare satisfactorily with these experimental data.

scholarly journals Voltammetric monitoring of a solid-liquid phase transition in N,N,N′,N′-tetraoctyl-2,6-diamino-9,10-anthraquinone (TODAQ)

2019 ◽  
Vol 24 (1) ◽  
pp. 11-16
Author(s):  
Sunyhik Ahn ◽  
Thomas R. Forder ◽  
Matthew D. Jones ◽  
Richard A. R. Blackburn ◽  
Paul S. Fordred ◽  
...  
Keyword(s):  
Phase Transition ◽  
Activation Energy ◽  
Differential Scanning Calorimetry ◽  
Liquid Phase ◽  
Apparent Activation Energy ◽  
Electrode Surface ◽  
Scanning Calorimetry ◽  
Liquid Phase Transition ◽  
Midpoint Potential ◽  
Solid Liquid

AbstractExploratory experiments on effects from a phase transition are reported for a low-melting microcrystalline anthraquinone (N,N,N′,N′-tetraoctyl-2,6-diamino-9,10-anthraquinone or TODAQ). Data for the solid-liquid phase transition are obtained by differential scanning calorimetry and then compared to data obtained by voltammetry. In preliminary electrochemical measurements, microcrystal deposits on a basal plane pyrolytic graphite electrode are shown to undergo a solid-state 2-electron 2-proton reduction in contact to aqueous 0.1 M HClO4 with a midpoint potential Emid,solid = − 0.24 V vs. SCE. The reduction mechanism is proposed to be limited mainly by the triple phase boundary line and some transport of TODAQ molecules towards the electrode surface for both solid and melt. A change in the apparent activation energy for this reduction is observed at 69 °C, leading to an enhanced increase in reduction current with midpoint potential Emid,liquid = − 0.36 V vs. SCE. A change of TODAQ transport along the crystal surface for solid microcrystalline material (for the solid) to diffusion within molten microdroplets (for the liquid) is proposed. Upon cooling, a transition at 60 °C back to a higher apparent activation energy is seen consistent with re-solidification of the molten phase at the electrode surface. Differential scanning calorimetry data for solid TODAQ dry and for TODAQ in contact to aqueous 0.1 M HClO4 confirm these transitions.

scholarly journals Thermal Analysis of Crystallization and Phase Transition in Novel Polyethylene Glycol Grafted Butene-1 Copolymers

Polymers ◽  
2019 ◽  
Vol 11 (5) ◽  
pp. 837 ◽  
Author(s):  
Chuanbin An ◽  
Yulian Li ◽  
Yahui Lou ◽  
Dongpo Song ◽  
Bin Wang ◽  
...  
Keyword(s):  
Phase Transition ◽  
Polyethylene Glycol ◽  
Crystallization Temperature ◽  
Isothermal Crystallization ◽  
Transition Rate ◽  
Average Molecular Weight ◽  
Melting Process ◽  
Scanning Calorimetry ◽  
Melting Temperatures ◽  
First Time

Copolymerization is an effective strategy to regulate the molecular structure and tune crystalline structures. In this work, novel butene-1 copolymers with different polyethylene glycol (PEG) grafts (number-average molecular weight Mn = 750, 2000, and 4000 g/mol) were synthesized, for the first time introducing long-chain grafts to the polybutene-1 main chain. For these PEG-grafted copolymers, crystallization, melting, and phase transition behaviors were explored using differential scanning calorimetry. With respect to the linear homopolymer, the incorporation of a trimethylsilyl group decreases the cooling crystallization temperature (Tc), whereas the presence of the long PEG grafts unexpectedly elevates Tc. For isothermal crystallization, a critical temperature was found at 70 °C, below which all polyethylene glycol-grafted butene-1 (PB-PEG) copolymers have faster crystallization kinetics than polybutene-1 (PB). The subsequent melting process shows that for the identical crystallization temperature, generated PB-PEG crystallites always have lower melting temperatures than that of PB. Moreover, the II-I phase transition behavior of copolymers is also dependent on the length of PEG grafts. When form II, obtained from isothermal crystallization at 60 °C, was annealed at 25 °C, PB-PEG-750, with the shortest PEG grafts of Mn = 750 g/mol, could have the faster transition rate than PB. However, PB-PEG-750 exhibits a negative correlation between transition rate and crystallization temperature. Differently, in PB-PEG copolymers with PEG grafts Mn = 2000 and 4000 g/mol, transition rates rise with elevating crystallization temperature, which is similar with homopolymer PB. Therefore, the grafting of the PEG side chain provides the available method to tune phase transition without sacrificing crystallization capability in butene-1 copolymers.

Differential Scanning Calorimetry and Guinier Camera/High-Temperature X-Ray Diffraction Studies of the Oxygen Sublattice Phase Transition in the Yba2Cu3O7−x System

1987 ◽  
Vol 99 ◽  
Author(s):  
David S. Lee ◽  
Zezhong Fu ◽  
Egon Hellstern ◽  
William L. Johnson ◽  
Paul Pietrokowsky ◽  
...  
Keyword(s):  
Phase Transition ◽  
Activation Energy ◽  
Differential Scanning Calorimetry ◽  
High Temperature ◽  
Chemical Potential ◽  
X Ray Diffraction ◽  
Oxygen Sublattice ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Xrd Techniques

ABSTRACTWe have studied the phase transition of the oxygen sublattice in the YBa2Cu3O7−x system by Differential Scanning Calorimetry (DSC), Guinier Camera, and high temperature x-ray diffraction (ht-xrd) techniques. The transition was examined under different thermodynamic constraints (constant oxygen partial pressure and constant oxygen concentration) and for a range of oxygen partial pressures. The variation of the endothermic peak temperature with DSC scanning rate was used to deduce an activation energy for the transition. The average activation energy for the process is between 38.7–75.0 kcal/mole(l:2:3) [mole], depending on the thermodynamic constraint imposed on the system.Pressure versus concentration isotherms (P(C)) were used to determine the chemical potential of the oxygen in this system.

scholarly journals Physical studies on phosphonium phosphatidylcholine. A unique [31P]phosphorus nuclear-magnetic-resonance probe for model and biological membranes

1975 ◽  
Vol 151 (3) ◽  
pp. 555-560 ◽  
Author(s):  
E Sim ◽  
P R Cullis ◽  
R E Richards
Keyword(s):  
Phase Transition ◽  
Nuclear Magnetic Resonance ◽  
Transition Temperature ◽  
Magnetic Resonance ◽  
Temperature Dependence ◽  
Phase Transition Temperature ◽  
Shift Reagent ◽  
Scanning Calorimetry ◽  
Distearoyl Phosphatidylcholine ◽  
Nuclear Magnetic

1. Distearoyl phosphatidylcholine and the phosphonium analogue, in which the nitrogen atom is replaced by phosphorus, show similar gel-liquid crystalline transition temperatures as detected by differential scanning calorimetry. 2. The temperature-dependence of the 31P n.m.r. (nuclear-magnetic-resonance) linewidths of the phosphate resonances of sonicated vesicles of distearoyl phosphatidylcholine and the phosphonium analogue are similar. Below the phase-transition temperature the linewidths decrease as the temperature is raised. Above the phase-transition temperature the phosphate resonances are relatively temperature-independent. The phosphonium 31P n.m.r. signal exhibits the same pattern of temperature-dependence. 3. The 31P n.m.r. phosphonium resonance is sensitive to the paramagnetic shift reagent, K3Fe(CN)6. Use of K3Fe(CN)6, together with Nd(NO3)3, enabled the determination of the trans-bilayer distribution of egg-yolk phosphatidylcholine and its phosphonium analogue in co-sonicated vesicles. Both are distributed comparably across the bilayer of the vesicles. 4. The phosphonium 31P n.m.r. signal is much sharper than the corresponding phosphate resonance in both sonicated and unsonicated dispersions of the phosphatidylcholine analogue. 5. The properties of the phosphonium analogue of phosphatidylcholine are discussed in terms of its suitability as a probe of membrane structure.

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