scholarly journals Estimating the activation energy of bond hydrolysis by time-resolved weighing of dissolving crystals

2021 ◽  
Vol 5 (1) ◽  
Author(s):  
Philippe Ackerer ◽  
Arnaud Bouissonnié ◽  
Raphael di Chiara Roupert ◽  
Damien Daval
Keyword(s):  
Activation Energy ◽  
Crystal Surface ◽  
Calibration Method ◽  
Solute Concentration ◽  
Bond Breaking ◽  
Dissolution Rates ◽  
Experimental Conditions ◽  
Time Resolved ◽  
Crystal Dissolution ◽  
Dissolution Model

AbstractBond-breaking activation energy EB is nowadays a key parameter for understanding and modeling crystal dissolution processes. However, a methodology to estimate EB based on classical dissolution experiments still does not exist. We developed a new method based on the calibration of a Kossel type dissolution model on measured dissolution rates obtained by mass (or volume) variations over time. The dissolution model does not depend on the geometry of the crystal surface but only on the density of the different types of sites (kink, step, terrace, bulk). The calibration method was applied to different experimental setups (flow through and batch) with different ways of estimating the dissolution rates (solute concentration in the fluid, surface topography) for calcite crystals. Despite the variety of experimental conditions, the estimated bond-breaking activation energies were very close to each other (between 31 and 35 kJ/mol) and in good agreement with ab initio calculations.

The effect of pH on kaolinite dissolution rates and on activation energy

1995 ◽  
Vol 59 (6) ◽  
pp. 1037-1052 ◽  
Author(s):  
Jiwchar Ganor ◽  
Jose Luis Mogollón ◽  
Antonio C. Lasaga
Keyword(s):  
Activation Energy ◽  
Dissolution Rates ◽  
Effect Of Ph

Diffusion in Biological Systems

Drug Delivery ◽  
2001 ◽  
Author(s):  
W. Mark Saltzman
Keyword(s):  
Diffusion Coefficient ◽  
Diffusion Coefficients ◽  
Molecular Diffusion ◽  
Biological Systems ◽  
Biological Tissues ◽  
Solute Concentration ◽  
Diffusion Resistance ◽  
Experimental Conditions ◽  
Composition Structure ◽  
Reliable Mechanism

Drug diffusion is an essential mechanism for drug dispersion throughout biological systems. Diffusion is fundamental to the migration of agents in the body and, as we will see in Chapter 9, diffusion can be used as a reliable mechanism for drug delivery. The rate of diffusion (i.e., the diffusion coefficient) depends on the architecture of the diffusing molecule. In the previous chapter a hypothetical solute with a diffusion coefficient of 10-7 cm2/s was used to describe the kinetics of diffusional spread throughout a region. Therapeutic agents have a multitude of sizes and shapes and, hence, diffusion coefficients vary in ways that are not easily predictable. Variability in the properties of agents is not the only difficulty in predicting rates of diffusion. Biological tissues present diverse resistances to molecular diffusion. Resistance to diffusion also depends on architecture: tissue composition, structure, and homogeneity are important variables. This chapter explores the variation in diffusion coefficient for molecules of different size and structure in physiological environments. The first section reviews some of the most important methods used to measure diffusion coefficients, while subsequent sections describe experimental measurements in media of increasing complexity: water, membranes, cells, and tissues. Diffusion coefficients are usually measured by observing changes in solute concentration with time and/or position. In most situations, concentration changes are monitored in laboratory systems of simple geometry; equally simple models (such as the ones developed in Chapter 3) can then be used to determine the diffusion coefficient. However, in biological systems, diffusion almost always occurs in concert with other phenomena that also influence solute concentration, such as bulk motion of fluid or chemical reaction. Therefore, experimental conditions that isolate diffusion—by eliminating or reducing fluid flows, chemical reactions, or metabolism—are often employed. Certain agents are eliminated from a tissue so slowly that the rate of elimination is negligible compared to the rate of dispersion. These molecules can be used as “tracers” to probe mechanisms of dispersion in the tissue, provided that elimination is negligible during the period of measurement. Frequently used tracers include sucrose [1, 2], iodoantipyrene [3], inulin [1], and size-fractionated dextran [3, 4].

scholarly journals Modeling and thermodynamic properties of ‘bacaba’ pulp drying

2019 ◽  
Vol 23 (9) ◽  
pp. 702-708 ◽  
Author(s):  
Maria F. de Morais ◽  
José R. O. dos Santos ◽  
Marisângela P. dos Santos ◽  
Dyego da C. Santos ◽  
Tiago N. da Costa ◽  
...  
Keyword(s):  
Activation Energy ◽  
Thermodynamic Properties ◽  
Diffusion Coefficients ◽  
Effective Diffusion ◽  
Thermal Conditions ◽  
Drying Process ◽  
Experimental Conditions ◽  
Effective Diffusion Coefficients ◽  
Drying Rates ◽  
Increasing Temperature

ABSTRACT This study aimed to dry ‘bacaba’ (Oenocarpus bacaba Mart.) pulp under different thermal conditions, fit different mathematical models to the dehydration curves, and calculate the diffusion coefficients, activation energy and thermodynamic properties of the process. ‘Bacaba’ fruits were meshed to obtain the pulp, which was dried at temperatures of 40, 50 and 60 °C and with thickness of 1.0 cm. Increase in drying temperature reduced the dehydration times, as well as the equilibrium moisture contents, and drying rates of 0.65, 1.04 and 1.25 kg kg min-1 were recorded at the beginning of the process for temperatures of 40, 50 and 60 °C, respectively. The Midilli’s equation was selected as the most appropriate to predict the drying phenomenon, showing the highest R2, lowest values of mean square deviation (MSD) and χ2 under most thermal conditions, and random distribution of residuals under all experimental conditions. The effective diffusion coefficients increased with increasing temperature, with magnitudes of the order of 10-9 m2 s-1, being satisfactorily described by the Arrhenius equation, which showed activation energy (Ea) of 37.01 kJ mol-1. The drying process was characterized as endergonic, in which enthalpy (ΔH) and entropy (ΔS) reduced with the increment of temperature, while Gibbs free energy (ΔG) was increased.

scholarly journals Metatranscriptomic reconstruction reveals RNA viruses with the potential to shape carbon cycling in soil

2019 ◽  
Vol 116 (51) ◽  
pp. 25900-25908 ◽  
Author(s):  
Evan P. Starr ◽  
Erin E. Nuccio ◽  
Jennifer Pett-Ridge ◽  
Jillian F. Banfield ◽  
Mary K. Firestone
Keyword(s):  
Carbon Cycling ◽  
Temporal Dynamics ◽  
Rna Viruses ◽  
Marker Genes ◽  
Experimental Conditions ◽  
Time Resolved ◽  
Host Cell Death ◽  
Root Litter ◽  
Viral Communities ◽  
Microbial Systems

Viruses impact nearly all organisms on Earth, with ripples of influence in agriculture, health, and biogeochemical processes. However, very little is known about RNA viruses in an environmental context, and even less is known about their diversity and ecology in soil, 1 of the most complex microbial systems. Here, we assembled 48 individual metatranscriptomes from 4 habitats within a planted soil sampled over a 22-d time series: Rhizosphere alone, detritosphere alone, rhizosphere with added root detritus, and unamended soil (4 time points and 3 biological replicates). We resolved the RNA viral community, uncovering a high diversity of viral sequences. We also investigated possible host organisms by analyzing metatranscriptome marker genes. Based on viral phylogeny, much of the diversity wasNarnaviridaethat may parasitize fungi orLeviviridae, which may infect Proteobacteria. Both host and viral communities appear to be highly dynamic, and rapidly diverged depending on experimental conditions. The viral and host communities were structured based on the presence of root litter. Clear temporal dynamics byLeviviridaeand their hosts indicated that viruses were replicating. With this time-resolved analysis, we show that RNA viruses are diverse, abundant, and active in soil. When viral infection causes host cell death, it may mobilize cell carbon in a process that may represent an overlooked component of soil carbon cycling.

Delamination-induced dielectric breakdown in Cu/low-k interconnects

2008 ◽  
Vol 23 (6) ◽  
pp. 1802-1808 ◽  
Author(s):  
T.L. Tan ◽  
C.L. Gan ◽  
A.Y. Du ◽  
Y.C. Tan ◽  
C.M. Ng
Keyword(s):  
Activation Energy ◽  
Failure Mechanism ◽  
Thermal Process ◽  
Dielectric Breakdown ◽  
Time Dependent ◽  
Bond Breaking ◽  
Capping Layer ◽  
Time Dependent Dielectric Breakdown ◽  
Potential Failure ◽  
Low K

Delamination at an interface with the weakest adhesion strength, which is found to be between the SiC(N) capping layer and the SiOCH low-k dielectric, is a potential failure mechanism contributing to time-dependent dielectric breakdown (TDDB) reliability. Bond breaking at that interface is believed to be driven by a field-enhanced thermal process and catalyzed by leakage current through the capping layer based on physical analyses and TDDB measurements. Delamination is found to be easier in terminated tips and corners than in parallel comb lines due to the layout orientation of the Cu lines. Moreover, TDDB activation energy Ea can be an indicator of the ease of delamination, whereby a lower Ea corresponds to an easier delamination.

The growth of crystals and the equilibrium structure of their surfaces

1951 ◽  
Vol 243 (866) ◽  
pp. 299-358 ◽  
Keyword(s):  
Activation Energy ◽  
Transition Temperature ◽  
Crystallographic Orientation ◽  
Crystal Surface ◽  
Equilibrium Structure ◽  
Surface Melting ◽  
Atomic Scale ◽  
Nearest Neighbour ◽  
Two Dimensional ◽  
Rate Of Growth

Parts I and II deal with the theory of crystal growth, parts III and IV with the form (on the atomic scale) of a crystal surface in equilibrium with the vapour. In part I we calculate the rate of advance of monomolecular steps (i.e. the edges of incomplete monomolecular layers of the crystal) as a function of supersaturation in the vapour and the mean concentration of kinks in the steps. We show that in most cases of growth from the vapour the rate of advance of monomolecular steps will be independent of their crystallographic orientation, so that a growing closed step will be circular. We also find the rate of advance for parallel sequences of steps. In part II we find the resulting rate of growth and the steepness of the growth cones or growth pyramids when the persistence of steps is due to the presence of dislocations. The cases in which several or many dislocations are involved are analysed in some detail; it is shown that they will commonly differ little from the case of a single dislocation. The rate of growth of a surface containing dislocations is shown to be proportional to the square of the supersaturation for low values and to the first power for high values of the latter. Volmer & Schultze’s (1931) observations on the rate of growth of iodine crystals from the vapour can be explained in this way. The application of the same ideas to growth of crystals from solution is briefly discussed. Part III deals with the equilibrium structure of steps, especially the statistics of kinks in steps, as dependent on temperature, binding energy parameters, and crystallographic orientation. The shape and size of a two-dimensional nucleus (i.e. an ‘island* of new monolayer of crystal on a completed layer) in unstable equilibrium with a given supersaturation at a given temperature is obtained, whence a corrected activation energy for two-dimensional nucleation is evaluated. At moderately low supersaturations this is so large that a crystal would have no observable growth rate. For a crystal face containing two screw dislocations of opposite sense, joined by a step, the activation energy is still very large when their distance apart is less than the diameter of the corresponding critical nucleus; but for any greater separation it is zero. Part IV treats as a ‘co-operative phenomenon’ the temperature dependence of the structure of the surface of a perfect crystal, free from steps at absolute zero. It is shown that such a surface remains practically flat (save for single adsorbed molecules and vacant surface sites) until a transition temperature is reached, at which the roughness of the surface increases very rapidly (‘ surface melting ’). Assuming that the molecules in the surface are all in one or other of two levels, the results of Onsager (1944) for two-dimensional ferromagnets can be applied with little change. The transition temperature is of the order of, or higher than, the melting-point for crystal faces with nearest neighbour interactions in both directions (e.g. (100) faces of simple cubic or (111) or (100) faces of face-centred cubic crystals). When the interactions are of second nearest neighbour type in one direction (e.g. (110) faces of s.c. or f.c.c. crystals), the transition temperature is lower and corresponds to a surface melting of second nearest neighbour bonds. The error introduced by the assumed restriction to two available levels is investigated by a generalization of Bethe’s method (1935) to larger numbers of levels. This method gives an anomalous result for the two-level problem. The calculated transition temperature decreases substantially on going from two to three levels, but remains practically the same for larger numbers.

Hydrothermal Transformation of Inorganic and Biogenic Silica as Studied Using in Situ Hydrothermal Infrared Microspectroscopy

2018 ◽  
Vol 72 (10) ◽  
pp. 1487-1497
Author(s):  
Naoto Morifuji ◽  
Satoru Nakashima
Keyword(s):  
Activation Energy ◽  
Rate Constants ◽  
Biogenic Silica ◽  
Zero Order ◽  
Silica Gels ◽  
Dissolution Rates ◽  
First Order ◽  
Order Rate ◽  
Hydrothermal Transformation

Infrared (IR) spectral changes with time of biogenic and inorganic silica have been examined using in situ IR micro-spectroscopy by using an original hydrothermal diamond cell. Centric diatoms (diameters = 100–350 µm) and silica gels (C-300, Wako Chemicals) were heated at 125–185 ℃ range with a pressure of 3 MPa. Decreases of 950 cm−1 (Si–OH) peak heights could be fitted by a combination of exponential and linear decreases (y = A1 exp (−k1t) − k0 t + A0). The first-order rate constants k1 [s−1] for Si–OH decreases of diatoms and silica gels are similar but the activation energy was lower for diatoms (61 kJċmol−1 < 106 kJċmol−1). The first-order rate constants k1 [s−1] for Si–OH decreases of diatoms and silica gels are much faster than reported hydrothermal transformation rates of silica (Opal A to Opal CT and Opal CT to quartz). These results indicate that the exponential Si–OH decreases observed in biogenic and inorganic silica during hydrothermal reactions are considered to correspond to dehydration–condensation reactions in the amorphous states (Si–OH + HO–Si → Si–O–Si). In fact, band area ratios 1220 cm−1/1120 cm−1 increased exponentially indicating more bridging of Si–O–Si. On the other hand, the linear decreases of Si–OH of silica gels (k0 [s−1]) were considered to be due to dissolution of silica. By using the grain size and density of silica gels, the zero-order dissolution rate constants k0* [molċm−2ċs−1] were calculated from k0 [s−1]. The obtained dissolution rates k0* are larger than reported values for silica glass and quartz. The zero-order dissolution rates k0 [s−1] for diatoms are similar to those for silica gels but with a lower activation energy (32 kJċmol−1 < 60 kJċmol−1). The smaller activation energy values for diatoms than silica gels both for the first and zero-order decrease rates of Si–OH might indicate catalytic effects of organic components bound to biogenic silica for the dehydration–condensation reaction and dissolution. The present in situ hydrothermal IR micro-spectroscopy is useful for characterizing transformation of amorphous materials including inorganic–organic composites.

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