Incommensurately modulated structure of morpholinium tetrafluoroborate and configurationalversuschemical entropies at the incommensurate and lock-in phase transitions

2017 ◽  
Vol 73 (5) ◽  
pp. 836-843
Author(s):  
Leila Noohinejad ◽  
Sander van Smaalen ◽  
Václav Petříček ◽  
Andreas Schönleber
Keyword(s):  
Phase Transitions ◽  
Conformational Changes ◽  
Ferroelectric Properties ◽  
Configurational Entropy ◽  
Chem Phys ◽  
Ambient Conditions ◽  
Disorder Phase Transition ◽  
The Difference ◽  
A Minor ◽  
Transition Entropy

Morpholinium tetrafluoroborate, [C4H10NO]+[BF4]−, belongs to a class of ferroelectric compoundsABX4. However, [C4H10NO]+[BF4]−does not develop ferroelectric properties because the incommensurate phase belowTc,I= 153 K is centrosymmetric with superspace groupPnam(σ100)00sand σ1= 0.42193 (12) atT= 130 K; the threefold superstructure belowTc,II= 117–118 K possesses the acentric but non-ferroelectric space groupP212121. At ambient conditions, [C4H10NO]+[BF4]−comprises orientationally disordered [BF4]−anions accommodated in cavities between four morpholinium cations. A structure model for the incommensurately modulated phase, which involves modulated orientational ordering of [BF4]−together with modulated distortions and displacements of the morpholinium ions is reported. A mechanism is proposed for the phase transitions, whereby at low temperatures morpholinium cations are shaped around the tetrafluoroborate anion in order to optimize the interactions with one orientation of this anion and, thus, forcing [BF4]−into this orientation. This mechanism is essentially different from a pure order–disorder phase transition. It is supported by consideration of the transition entropy. The difference in configurational entropy between the disordered and incommensurate phases has been computed from the structure models. It is shown to be much smaller than the experimental transition entropy reported by Owczareket al.[Chem. Phys.(2011),381, 11–20]. These features show that the order–disorder contribution is only a minor contribution to the transition entropy and that other factors, such as conformational changes, play a larger role in the phase transitions.

scholarly journals The effective volumes of waters of crystallization: general organic solids

2020 ◽  
Vol 76 (4) ◽  
pp. 650-653
Author(s):  
Leslie Glasser
Keyword(s):  
Conformational Changes ◽  
Coefficient Of Thermal Expansion ◽  
Chem Phys ◽  
Mean Value ◽  
Current Data ◽  
Linear Molecule ◽  
Supplementary File ◽  
Effective Volume ◽  
Organic Solids ◽  
The Difference

Using a list of compatible hydrate/anhydrate pairs prepared by van de Streek and Motherwell [CrystEngComm (2007), 9, 55–64], we have examined the effective volume per water of crystallization for 179 pairs of organic solids using current data from the Cambridge Crystallographic Structural Database (CSD). The effective volume is the difference per water molecule between the asymmetric unit volumes of the hydrate and parent anhydrate, and has the mean value 24 Å3. The conformational changes in the reference molecule between the hydrate and its anhydrate are shown in two figures: one for a relatively rigid standard organic molecule and (in the supplementary file) one for a more flexible linear molecule. Using data from Nyman and Day [Phys. Chem. Chem. Phys. (2016), 18, 31132–31143], we have also established a generic volumetric coefficient of thermal expansion of organic solids with a value of 147 ± 56 × 10−6 K−1. There is a significant number of outliers to the data, negative, near zero, and large and positive. Some explanation for the existence of these outliers is attempted.

Producing Steam by Spraying Water on a Heated Bed of Steel Spheres

2021 ◽  
pp. 1-42
Author(s):  
D. Jordan Bouchard ◽  
HengSheng Yang ◽  
Sanjeev Chandra
Keyword(s):  
Particle Size ◽  
Thermal Mass ◽  
Steam Generation ◽  
Bed Porosity ◽  
The Media ◽  
Effect Of Particle Size ◽  
The Difference ◽  
Rate Of Evaporation ◽  
A Minor ◽  
Counter Current

Abstract Steam generators used in industrial baking ovens operate by pouring or spraying water on a preheated thermal mass. This paper presents a methodology to quantify the amount of steam generated from a thermal mass along with experiments to determine the effect of particle size and porosity on steam generation. Three sizes of steel spheres, 0.6 mm, 8 mm, and 16 mm in diameter, were used to construct porous media beds that were preheated in an oven after which water was sprayed onto them from a full-cone nozzle for a fixed duration. The weight of the heated bed and the impinging water were recorded during spraying. The difference in weight change when spraying on heated and unheated beds gave the rate of evaporation. Thermocouples were used to record the internal temperature of the bed. Steam generation rate increased with particle size while bed porosity had only a minor influence. The counter-current flow of steam within the media bed disrupts the downward flow of water enough to leave pockets of hot material, reducing steam production. To maximize steam generation the media size, material, and spray time should be matched to ensure the surfaces of particles remain above the boiling point of water during spraying.

Sintering and Oxygen Ionic Conducting Properties of Bi2V0.9Co0.1O5.5-δ Derived from an EDTA-Citrate Precursor

2007 ◽  
Vol 124-126 ◽  
pp. 731-734
Author(s):  
Feng Zhang ◽  
Qing Xu ◽  
Duan Ping Huang ◽  
Wen Chen ◽  
Han Xing Liu ◽  
...  
Keyword(s):  
Sol Gel ◽  
Fine Powder ◽  
Synthesis Process ◽  
Complexing Agents ◽  
Aurivillius Phase ◽  
Disorder Phase Transition ◽  
Dense Microstructure ◽  
Ionic Conducting ◽  
Sintering Properties ◽  
The Difference

Bi2V0.9Co0.1O5.5-δ with a pure Aurivillius phase was synthesized by a sol-gel method using EDTA and citric as mixed complexing agents. It was found that homogeneous and fine powder (100-200 nm) with a pure Aurivillius phase can be produced by calcining the complex precursor at 450 °C for 1h in air. The sintering properties of Bi2V0.9Co0.1O5.5-δ were investigated in the range of 560-680 °C with respect to relativity density. Sintering at 640 °C was ascertained to be preferred for Bi2V0.9Co0.1O5.5-δ, producing a dense microstructure with uniform grains around 3-5 μm. The Bi2V0.9Co0.1O5.5-δ ceramic exhibits an oxygen ionic conductivity of 1.0×10-1 S·cm-1 at 600 °C. The difference between the activation energies for the ionic conducting in low and high temperature regions is qualitatively interpreted in terms of an order-disorder phase transition. This research demonstrates the advantage of the EDTA-citrate method in preparing Bi2V0.9Co0.1O5.5-δ with respect to the simplicity of synthesis process, desired morphology of synthesized powder, low sintering temperature and superior ionic conducting properties of ceramic specimen.

scholarly journals The mitochondrial ADP/ATP carrier exists and functions as a monomer

2020 ◽  
Vol 48 (4) ◽  
pp. 1419-1432 ◽  
Author(s):  
Edmund R.S. Kunji ◽  
Jonathan J. Ruprecht
Keyword(s):  
Conformational Changes ◽  
Membrane Vesicles ◽  
Native Mass Spectrometry ◽  
Published Data ◽  
Oligomeric State ◽  
Technical Errors ◽  
Density Maps ◽  
Mitochondrial Carrier Family ◽  
The Difference ◽  
And Function

For more than 40 years, the oligomeric state of members of the mitochondrial carrier family (SLC25) has been the subject of debate. Initially, the consensus was that they were dimeric, based on the application of a large number of different techniques. However, the structures of the mitochondrial ADP/ATP carrier, a member of the family, clearly demonstrated that its structural fold is monomeric, lacking a conserved dimerisation interface. A re-evaluation of previously published data, with the advantage of hindsight, concluded that technical errors were at the basis of the earlier dimer claims. Here, we revisit this topic, as new claims for the existence of dimers of the bovine ADP/ATP carrier have emerged using native mass spectrometry of mitochondrial membrane vesicles. However, the measured mass does not agree with previously published values, and a large number of post-translational modifications are proposed to account for the difference. Contrarily, these modifications are not observed in electron density maps of the bovine carrier. If they were present, they would interfere with the structure and function of the carrier, including inhibitor and substrate binding. Furthermore, the reported mass does not account for three tightly bound cardiolipin molecules, which are consistently observed in other studies and are important stabilising factors for the transport mechanism. The monomeric carrier has all of the required properties for a functional transporter and undergoes large conformational changes that are incompatible with a stable dimerisation interface. Thus, our view that the native mitochondrial ADP/ATP carrier exists and functions as a monomer remains unaltered.

scholarly journals Assessment of Conformational Changes in Low-Sulphur S-Carboxymethylkerateine from Wool

1967 ◽  
Vol 20 (4) ◽  
pp. 827 ◽  
Author(s):  
GM Bhatnagar ◽  
WG Crewther
Keyword(s):  
Absorption Spectrum ◽  
Conformational Changes ◽  
Guanidine Hydrochloride ◽  
Ultraviolet Absorption Spectrum ◽  
Spectral Measurements ◽  
Characteristic Difference ◽  
Concentrated Solutions ◽  
Difference Spectra ◽  
The Difference ◽  
Negative Difference

The effects of urea and guanidine hydrochloride on the ultraviolet absorption spectrum of the low-sulphur S-carboxymethylkerateine fraction of wool have been measured. In concentrated solutions of urea characteristic difference spectra were obtained with maxima of negative absorbance at 288, 280, and 240 miL. The addition of guanidine hydrochloride or an increase in temperature gave similar negative difference maxima at the higher wavelengths. Calculation of the extent of unfolding of the protein chains from the difference in absorbance at all three maxima showed that the unfolding was 50% complete at a urea concentration of about 1� 8M whereas a urea concep.tration of about 4� 3M was required to decrease the helix content by 50%. Similar measurements on components 7 and 8, the two major constituents of SCMKA, showed that a 50% decrease in helix content was obtained with 2�8M and O� 8M urea respectively whereas the corresponding values for 50 % unfolding assessed from difference spectral measurements were 2� 2M and 1� 2M urea respectively. It is suggested that the helical regions of components 7 and 8 aggregate specifically and that spectral measurements relate largely to non-helical portions of the chains.

Differential Scanning Calorimetry (DSC)

2008 ◽  
Author(s):  
José A. Martinho Simões ◽  
Manuel Minas da Piedade
Keyword(s):  
Differential Scanning Calorimetry ◽  
Phase Transitions ◽  
Small Samples ◽  
Calorimetric Data ◽  
Scanning Calorimetry ◽  
The Difference ◽  
Temperature Dependent Properties ◽  
Differential Scanning Calorimeters ◽  
New Applications ◽  
User Friendly

Physical and chemical changes may often be induced by raising or lowering the temperature of a substance. Typical examples are phase transitions, such as fusion, or chemical reactions, such as the solid state polymerization of sodium chloroacetate, which has an onset at 471 K: ClCH2COONa (cr) ⇋ NaCl (cr) + 1/n − (CH2COO)n − (pol) Differential scanning calorimetry (DSC) was designed to obtain the enthalpy or the internal energy of those processes and also to measure temperature-dependent properties of substances, such as the heat capacity. This is done by monitoring the change of the difference between the heat flow rate or power to a sample (S) and to a reference material (R), ΔΦ = ΦS − ΦR = (dQ/dt)S − (dQ/dt)R, as a function of time or temperature, while both S and R are subjected to a controlled temperature program. The temperature is usually increased or decreased linearly at a predetermined rate, but the apparatus can also be used isothermally. In some cases DSC experiments may provide kinetic data. According to Wunderlich, differential scanning calorimeters evolved from the differential thermal analysis (DTA) instruments built by Kurnakov at the beginning of the twentieth century. In these early DTA apparatus, the temperature difference between a sample and a reference, simultaneously heated by a single heat source, was measured as a function of time. No calorimetric data could be derived, and the instruments were used, for example, to determine the temperatures of phase transitions and to identify metals, oxides, minerals, soils, and foods. The attempts to obtain calorimetric data from DTA instruments eventually led to the development of DSC. The term differential scanning calorimetry and the acronym DSC were coined in 1963 when the first commercial instrument of this type became available. This apparatus was easy to operate, enabled fast experiments, and required only small samples (typically 5–10 mg). Its importance for materials characterization was immediately demonstrated and the DSC technique soon experienced a boom. New user-friendly commercial instruments were developed, and new applications were explored. It is, however, somewhat ironic that the method ows its still growing popularity to analytical rather than calorimetric uses.

Identification of the Minimum Number of Measurements Required for Thermal Comfort Assessment in Large Workplaces

2019 ◽  
Vol 63 (7) ◽  
pp. 729-742
Author(s):  
Paolo Lenzuni ◽  
Pierangelo Tura ◽  
Pierfrancesco Cervino
Keyword(s):  
Thermal Comfort ◽  
Thermal Environment ◽  
Significant Loss ◽  
Spatial Inhomogeneity ◽  
Main Window ◽  
Room Size ◽  
Synthetic Index ◽  
Minimum Number ◽  
The Difference ◽  
A Minor

Abstract Optimization of resources is the key to improve our ability to perform multiple tasks with limited time and money. In the context of thermal comfort assessment, optimization becomes important in large rooms where tens of individuals perform similar tasks. This work focuses on the identification of the minimum number of measurement points that allows an accurate description of the thermal environment. Accuracy of description is assumed if no significant loss of information is associated to the transition from the ‘primary’ thermal map based on all available measurement points to a ‘secondary’ thermal map based on a reduced set of measurement points. The concept of ‘no significant loss’ is quantified by requiring that the difference in PMV (Predicted Mean Vote) between the two maps is kept <0.1 in the vast majority (95%) of points. PMV is a standardized synthetic index that is used worldwide for quantifying thermal comfort (ISO 7730, 2005) taking into account both environmental (thermo-hygrometric) and personal (activity, clothing) quantities. We show that the uncertainty induced by the degraded resolution of the thermal map has a limited impact on the overall uncertainty on PMV. Application of the method to a few test environments shows that the room size perpendicular to the main window and the windows orientation play the largest role in determining spatial inhomogeneity in thermal maps. A minor concurring factor is the room area.

scholarly journals Elastic and Frictional Properties of Fault Zones in Reservoir-Scale Hydro-Mechanical Models—A Sensitivity Study

Energies ◽  
2020 ◽  
Vol 13 (18) ◽  
pp. 4606
Author(s):  
Torben Treffeisen ◽  
Andreas Henk
Keyword(s):  
Fault Zone ◽  
Sensitivity Study ◽  
Fault Zones ◽  
Small Scale ◽  
Fe Model ◽  
Angle Of Internal Friction ◽  
Fault Properties ◽  
Mechanical Models ◽  
The Difference ◽  
A Minor

The proper representation of faults in coupled hydro-mechanical reservoir models is challenged, among others, by the difference between the small-scale heterogeneity of fault zones observed in nature and the large size of the calculation cells in numerical simulations. In the present study we use a generic finite element (FE) model with a volumetric fault zone description to examine what effect the corresponding upscaled material parameters have on pore pressures, stresses, and deformation within and surrounding the fault zone. Such a sensitivity study is important as the usually poor data base regarding specific hydro-mechanical fault properties as well as the upscaling process introduces uncertainties, whose impact on the modelling results is otherwise difficult to assess. Altogether, 87 scenarios with different elastic and plastic parameter combinations were studied. Numerical modelling results indicate that Young’s modulus and cohesion assigned to the fault zone have the strongest influence on the stress and strain perturbations, both in absolute numbers as well as regarding the spatial extent. Angle of internal friction has only a minor and Poisson’s ratio of the fault zone a negligible impact. Finally, some general recommendations concerning the choice of mechanical fault zone properties for reservoir-scale hydro-mechanical models are given.

Development, Longevity and Fecundity of the False Wireworms Pterohelaeus-Darlingensis and Pterohelaeus-Alternatus (Coleoptera, Tenebrionidae) .4. Models for Larval and Pupal Development Under Fluctuating Temperatures

1986 ◽  
Vol 34 (6) ◽  
pp. 815 ◽  
Author(s):  
PG Allsopp
Keyword(s):  
Stochastic Model ◽  
Low Temperatures ◽  
Considerable Variability ◽  
Ambient Conditions ◽  
Pupal Development ◽  
Long Period ◽  
New Models ◽  
The Difference ◽  
Fluctuating Temperatures ◽  
Coleoptera Tenebrionidae

The usefulness of models derived from constant-temperature rearing in predicting development of larvae and pupae of Pterohelaeus darlingensis Carter and P, alternatus Pascoe under fluctuating temperature was determined. In general, these models underestimated development. The magnitude of the difference was proportional to the length of the development period and, by inference, negatively related to the temperatures experienced. New models were developed with data from individuals reared under fluctuating temperatures. The linear model gave better predictions of development under ambient conditions than did the curvilinear Stinner model for pupae of P. darlingensis, but both models gave similar predictions for larvae of both species. Development of P. alternatus pupae was still underestimated by both models. Substantial discrepancies between observed and expected development of individuals reared under a regimen incorporating a long period at low temperatures indicate that such a regimen is deleterious. Given the considerable variability in development rates between individuals, a stochastic model may predict development more accurately.

Sign in / Sign up

Export Citation Format

Share Document