Relaxation mapping analysis with an hyperbolic heating rate

2002 ◽  
Vol 754 ◽  
Author(s):  
C. J. Dias
Keyword(s):  
Activation Parameters ◽  
Activation Entropy ◽  
Relaxation Processes ◽  
Complex Materials ◽  
Cooperative Phenomena ◽  
Relaxation Parameters ◽  
A Value ◽  
Polarization Temperature ◽  
Free Activation Energy ◽  
Map Analysis

ABSTRACTThermally stimulated discharge currents (TSDC) together with the Relaxation Map Analysis (RMA) method is a convenient method to study relaxation processes in complex materials. In the RMA technique, one performs repeated TSDC runs while selecting polarization states through the use of a fixed polarization time schedule and a sucessively higher polarization temperature. Each peak has an associated polarization strength and a pair of activation parameters which can be the Gibbs free activation energy and the activation entropy. In the present paper we propose a different approach to RMA. It consists of a global heating of the sample in an hyperbolic manner to determine the activation parameters as a function of temperature. This determination is done by first selecting a value for the activation entropy for each temperature and then calculating the implied activation enthalpy or Gibbs free energy.We have reasoned that normal relaxation processes usually proceed with a null or close to zero activation entropy and that only relaxations associated to the glass transitionand/or cooperative phenomena involve large values of the activation entropy. In those cases and based on the curvature of the TSDC curve one can select a minimum activation entropy value which will fit the TSDC curve at a particular temperature. Using this data one determines the polarization strength associated to each pair of activation parameters. Results for the TSDC relaxation parameters spectra of a liquid crystal polymer will be presented together with comparisons between the thermal sampling method and the proposed method.

Diffusion Phenomena of the Oxygen and Nitrogen in Niobium by Mechanical Spectroscopy

2010 ◽  
Vol 297-301 ◽  
pp. 1346-1353
Author(s):  
Odila Florêncio ◽  
Paulo Sergio Silva ◽  
Carlos Roberto Grandini
Keyword(s):  
Diffusion Coefficients ◽  
Short Range ◽  
Annealed Sample ◽  
Relaxation Processes ◽  
Torsion Pendulum ◽  
Mechanical Spectroscopy ◽  
Interstitial Diffusion ◽  
Relaxation Parameters ◽  
Low Concentrations ◽  
Diffusion Phenomena

The short-range diffusion phenomenon (Snoek Effect) was investigated by mechanical spectroscopy measurements between 300 K and 650 K, in a polycrystalline niobium sample, containing oxygen and nitrogen, using a torsion pendulum. Experimental spectra of anelastic relaxation were obtained under three conditions: as-received sample; annealed sample and subsequently annealed in an oxygen atmosphere for three hours at 1170 K in partial pressure of 5x10-5mbar. The experimental spectra obtained were decomposed in elementary Debye peaks and the anelastic relaxation processes were identified. With anelastic relaxation parameters and the lattice parameters, the interstitial diffusion coefficients of the oxygen and nitrogen in niobium were calculated for each kind of preferential occupation (octahedral and tetrahedral). The results were compared with the literature data, and confirmed that the best adjustment is for the preferential occupation octahedral model for low concentrations of interstitial solutes, but at higher concentration of oxygen were observed deviations of experimental data for the interstitial diffusion coefficients of oxygen in niobium when compared with the literature data, this could be related to the possible occurrence of a double occupation of interstitial sites in the niobium lattice by oxygen interstitials.

Substituent Effects in Electron Transfer Reactions: The Preparation and Chromium(II) Reduction of 3-Formylpentane-2,4-dionatobis(ethylenediamine)cobalt(III). Preparation of the Linkage Isomer 2-Acetylbutane-1,3-dionatobis(ethylenediamine)cobalt(III)

1975 ◽  
Vol 53 (8) ◽  
pp. 1154-1164 ◽  
Author(s):  
Robert J. Balahura ◽  
N. A. Lewis
Keyword(s):  
Electron Transfer ◽  
Acidic Solution ◽  
Substituent Effects ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Linkage Isomers ◽  
A Value ◽  
Parent Complex ◽  
Kinetics Of ◽  
Sphere Mechanism

The preparation of the linkage isomers, 3-formylpentane-2,4-dionatobis(ethylenediamine)cobalt(III), (1), and 2-acetylbutane-1,3-dionatobis(ethylenediamine)cobalt(III), (2), are described. The kinetics of the reaction of Cr(OH2)62+ with 1 and the parent complex, 2,4-pentanedionatobis(ethylenediamine)cobalt(III), (3), have been studied spectrophotometrically in acidic solution. For 1, the reduction is described by the rate law −d ln [Co(III)complex]/dt = k[Cr2+], and k = 0.0863 M−1 s−1 at 25 °C, μ = 1.0 M (LiClO4). The activation parameters for this reaction were found to be ΔH≠ = 9.9 ± 0.5 kcal mol−1 and ΔS≠ = −30 ± 3 e.u. The reaction proceeded by an inner-sphere mechanism and the product of this reaction was isolated and characterized as 2-acetylbutane-1,3-dionatotetraaquochromium(III). The linkage isomer of this complex was also prepared. The parent complex (3) was not reduced by Cr(OH2)62+ at an observable rate and an upper limit for the rate constant of this reaction was assigned a value of 10−4–10−6M−1s−1 at 25 °C. The ability of the formyl group to enhance the rate of electron transfer is discussed, and the chromium(II) reduction studies of related chelated systems are compared with the results obtained in this investigation.

Adsorptive treatment via simultaneous removal of copper, lead and zinc from soil washing wastewater using spent coffee grounds

2019 ◽  
Vol 79 (6) ◽  
pp. 1029-1041 ◽  
Author(s):  
Cybelle M. Futalan ◽  
Jongsik Kim ◽  
Jurng-Jae Yee
Keyword(s):  
Heavy Metals ◽  
Soil Washing ◽  
Activation Parameters ◽  
Activation Entropy ◽  
Spent Coffee Grounds ◽  
Adsorptive Treatment ◽  
Potential Measurement ◽  
Coffee Grounds ◽  
Washing Wastewater ◽  
Soil Washing Wastewater

Abstract In the present work, the performance of spent coffee grounds (SCG) as an adsorbent in the treatment of real soil washing wastewater (SWW) was evaluated. Scanning electron microscopy, Fourier transform infrared spectroscopy, zeta potential measurement and Brunauer–Emmett–Teller analysis were utilized to determine the physicochemical characteristics of SCG. Maximum removal efficiency of 68.73% for Cu(II), 57.23% for Pb(II) and 84.55% for Zn(II) was attained at 2.5 g SCG, 300 min and 328 K. Error analysis was performed using root mean square error (RMSE) and sum of square error (SSE). Equilibrium data correlated well with the Langmuir isotherm for Pb(II) adsorption and Freundlich model for the removal of Cu(II) and Zn(II). The kinetic study shows that adsorption of the heavy metals using SCG can be satisfactorily described using the pseudo-second order equation (R2 ≥ 0.9901; RMSE ≤ 15.0539; SSE ≤ 145.1461). Activation parameters including activation energy, change in free energy of activation, activation entropy change (ΔS*) and activation enthalpy change (ΔH*) were determined using Arrhenius and Eyring equations. Thermodynamic studies show that adsorption of the heavy metals using SCG is spontaneous, endothermic (ΔH° ≥ 9.80 kJ/mol·K) and results in increased randomness at the solid/solution interface (ΔS° ≥ 2.28 J/mol).

Physical and Chemical Stress Relaxation of Elastomers

1977 ◽  
Vol 50 (5) ◽  
pp. 895-905 ◽  
Author(s):  
J. G. Curro ◽  
E. A. Salazar
Keyword(s):  
Stress Relaxation ◽  
Relaxation Modulus ◽  
Kinetic Mechanism ◽  
Chemical Kinetic ◽  
Relaxation Processes ◽  
Temperature Range ◽  
Kinetic Information ◽  
Relaxation Parameters ◽  
Chemically Reacting ◽  
Physical And Chemical

Abstract In this paper we have developed a method whereby physical and chemical relaxation processes can be distinguished, using stress relaxation experiments as a function of temperature. We assumed that there exists some temperature range above the glass transition temperature over which the chemical effects can be neglected for the time scale of the experiments. The data in this low temperature range were then used to determine the WLF constants and other physical relaxation parameters. The physical component of the stress relaxation could then be subtracted from high temperature experiments in order to extract chemical kinetic information. Based on certain reasonable assumptions, an equation was developed for the relaxation modulus of a chemically reacting system. This equation could be used to determine the time dependence of the crosslink density, or conversely could be used to predict the long-term relaxation modulus from an assumed kinetic mechanism. These calculations were demonstrated for ethylene-propylene and butyl elastomers.

Direct observation of dienols produced by photochemical enolisation of α,β-unsaturated ketones: rates and activation parameters for dienol reketonisation via a 1,5-hydrogen shift

1987 ◽  
Vol 65 (8) ◽  
pp. 1867-1872 ◽  
Author(s):  
Randy M. Duhaime ◽  
Alan C. Weedon
Keyword(s):  
Activation Energy ◽  
Low Temperatures ◽  
Nmr Spectra ◽  
Arrhenius Plot ◽  
Activation Parameters ◽  
Activation Entropy ◽  
Hydrogen Shift ◽  
Unsaturated Ketones ◽  
Ultraviolet Light Irradiation ◽  
Stable Solutions

The production of stable solutions of Z-dienols by ultraviolet light irradiation of α,β-unsaturated ketones at low temperatures (ca. −76 °C) in d4-methanol is reported. The rates of reketonisation of the dienols via a 1,5-sigmatropic hydrogen shift were determined at various temperatures between −43 °C and + 2 °C by monitoring the proton nmr spectra of the dienols. From the data the activation parameters for the reaction were calculated. For the dienol Z-2-hydroxy-4-methyl-2,4-pentadiene, 2, derived from photoenolisation of 4-methyl-3-penten-2-one, 1, the activation energy from the Arrhenius plot is 62 ± 4 kJ/mol, and the activation entropy and enthalpy from the Eyring plot are −87 ± 15 J/mol K and 60 ± 4 kJ/mol, respectively. For the dienol Z-4-tert-butyl-2-hydroxy-2,4-pentadiene, 4, obtained from photoenolisation of 4,5,5-trimethyl-3-hexen-2-one, 3, the activation energy, entropy, and enthalpy were found to be 47 ± 5 kJ/mol, −135 ± 19 J/mol K, and 45 ± 5 kJ/mol, respectively.

Plasma kinetic coefficients with account for relaxation processes

2015 ◽  
Vol 29 (32) ◽  
pp. 1550233 ◽  
Author(s):  
V. N. Gorev ◽  
A. I. Sokolovsky
Keyword(s):  
Homogeneous System ◽  
Distribution Functions ◽  
Relaxation Processes ◽  
Component Distribution ◽  
Relaxation Parameters ◽  
Ion Plasma ◽  
Kinetic Coefficients ◽  
Momentum Fluxes ◽  
Energy And Momentum ◽  
Component Temperature

The hydrodynamics of a completely ionized two-component electron–ion plasma is investigated on the basis of the Landau kinetic equation with account for component temperature and velocity relaxation. The term relaxation is understood here in a narrow sense as a process which can take place in a spatially homogeneous system. The investigation is made on the basis of a generalized Chapman–Enskog method. The relaxation is investigated in the vicinity of the standard hydrodynamic state of plasma: the deviations of the component temperatures and velocities from their standard hydrodynamic values are considered to be small. The integral equations for the component distribution functions are investigated in a perturbation theory in small gradients and small relaxation parameters. The component distribution functions of the first-order both in gradients and in relaxation parameters are calculated. Relaxation corrections to the energy and momentum fluxes and to the kinetic coefficients of the standard hydrodynamic state of the system are obtained.

scholarly journals Thermal inactivation studies of normal and variant human erythrocyte carbonic anhydrases by using a sulphonamide-binding assay

1974 ◽  
Vol 141 (1) ◽  
pp. 219-225 ◽  
Author(s):  
William R. A. Osborne ◽  
Richard E. Tashian
Keyword(s):  
Thermal Inactivation ◽  
Activation Parameters ◽  
Energy Of Activation ◽  
Heat Inactivation ◽  
Activation Entropy ◽  
Carbonic Anhydrases ◽  
Compensating Variation ◽  
Arrhenius Plots ◽  
Heat Stable ◽  
Free Energy Of Activation

Heat-inactivation studies were carried out on the two primary erythrocyte carbonic anhydrase isoenzymes, CA I and CA II, and the secondary isoenzyme of CA I, CA I (+1). In addition, two genetic variants of human isoenzyme CA I, CA Id Michigan (100 Thr→Lys) and CA If London (102 Glu→Lys), and one variant of isoenzyme CA II, CA IIh (251 Asn→Asp), were similarly analysed. The first-order rate constants and Arrhenius plots for these six enzyme forms showed that (1) isoenzyme CA II is more heat-stable than CA I, (2) isoenzyme CA I (+1) is less heat-stable than CA I, (3) the variants CA IIh and CA If London are less heat-stable than the normal enzymes, and (4) isoenzyme CA Id Michigan is more heat-stable than normal CA I. From the values of the slopes of the Arrhenius plots, the energy of activation (Ea) for each isoenzyme and isoenzyme variant was determined, and the following thermodynamic activation parameters were calculated at 55°C: the free energy of activation (ΔG‡), the activation enthalpy (ΔH‡) and the activation entropy (ΔS‡). The ΔG‡ for the enzymes shows a relative constancy with compensating variation in ΔH‡ and ΔS‡. When the values for ΔH‡ are plotted against ΔS‡, an increase in ΔH‡ involves a concomitant increase in ΔS‡.

Dielectric Relaxation of NaClO4Solutions in Formamide, N-Methylformamide, and N,N-Dimethylformamide

1995 ◽  
Vol 50 (1) ◽  
pp. 65-74 ◽  
Author(s):  
J. Barthel ◽  
K. Bachhuber ◽  
R. Büchner
Keyword(s):  
Average Length ◽  
Ion Pairs ◽  
Liquid Structure ◽  
Acceptor Site ◽  
Relaxation Processes ◽  
Hydrogen Bond Acceptor ◽  
Solvent Interactions ◽  
Structure And Dynamics ◽  
Relaxation Parameters ◽  
Diffusion Controlled

Complex permittivity spectra in the frequency range 0.95 ≤ v/[GHz] ≤ 89 for N,N-dimethylformamide (DMF), N-methylformamide (NMF), formamide (FA) and their solutions of NaClO4 are investigated to study the change of liquid structure and dynamics arising from the availability of one hydrogen-bond acceptor site together with no (DMF), one (NMF), or two (FA) donor sites on the same molecule. Three solvent relaxation processes are observed for NMF and two for FA and DMF. The relaxation parameters are used to determine solvation numbers. They show that ion-solvent interactions lead to a reduction of the average length of the H-bonded NMF chains but have only moderate influence on the FA structure. An additional solute relaxation process in DMF solutions is due to the diffusion-controlled formation and decomposition of solvent-shared ion pairs.

Relaxation Processes at High Temperature in TiAl-Nb-Mo Intermetallics

2012 ◽  
Vol 1516 ◽  
pp. 41-46 ◽  
Author(s):  
Pablo Simas ◽  
Thomas Schmoelzer ◽  
Svea Mayer ◽  
Maria L. Nó ◽  
Helmut Clemens ◽  
...  
Keyword(s):  
High Temperature ◽  
Relaxation Process ◽  
Activation Parameters ◽  
Relaxation Processes ◽  
Thermal Treatments ◽  
Intermetallic Alloys ◽  
Mechanical Spectroscopy ◽  
Responsible Mechanism ◽  
Defect Mobility

ABSTRACTIn the last decades there was a growing interest in developing new light-weight intermetallic alloys, which are able to substitute the heavy superalloys at a certain temperature range. At present a new Ti-Al-Nb-Mo family, called TNM™ alloys, is being optimized to fulfill the challenging requirements. The aim of the present work was to study the microscopic mechanisms of defect mobility at high temperature in TNM alloys in order to contribute to the understanding of their influence on the mechanical properties and hence to promote the further optimization of these alloys. Mechanical spectroscopy has been used to study the internal friction and the dynamic modulus up to 1460 K of a TNM alloy under different thermal treatments. These measurements allow to follow the microstructural evolution during in-situ thermal treatments. A relaxation process has been observed at about 1050 K and was characterized as a function of temperature and frequency in order to obtain the activation parameters of the responsible mechanism. In particular, the activation enthalpy has been determined to be H= 3 eV. The results are discussed and an atomic mechanism is proposed to explain the observed relaxation process.

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