Adjustment Of Constants Research Articles

Theoretical insight into key reactions in DME/NH3 co-firing: A detailed kinetic study and implications for rational combustion modelling

Dimethyl ether (DME) is promising as an additive for co-firing with ammonia (NH3) to solve the problem of its low reactivity combustion. However, the combustion modeling of blended fuels is challenging, and previous efforts primarily relied on the adjustment of rate constants for key reactions to bridge the gap between experiments and simulations. In the present work, ab initio kinetic studies were performed for the key reactions of OH/HO2/NH2 with DME in blended combustion. High-level theoretical calculations were carried out for all saddle points and a benchmark was implemented for accurate evaluation of the barrier heights. The direct dynamics calculations used variational transition state theory with interpolated single-point energies method. The kinetic studies took into account the small-curvature tunneling, low-pressure limit or pre-equilibrium model and the multistructural torsional anharmonicity effect. The calculated rate constants are in very good agreement with the available experimental kinetic data. The mechanism of Xiao et al. (Combust. Flame 245 (2022) 112372) was updated based on this kinetic study and the simulations of the ignition delay times with modified rate constants better agree with the measurements than with the original mechanism. Especially, the present model avoids decreasing the cross-reaction rate constants to improve the simulation results. This work provides detailed theoretical insights and updated models with good predictive performance based on ab initio kinetics, which have more rigorous theoretical significance.

A computer code for optimizing the neutronics model parameters based on results of reactor physics experiments

The paper describes in brief the functional capabilities of a computer code for optimizing the neutronics model parameters (neutron data, technological parameters, and their covariance matrices) based on results of reactor physics experiments using conditional nonlinear multi-parameter optimization algorithms. The code’s application scope includes adjustment of neutron constants, technological parameters and their covariance matrices based on integral measurement results, formulation of requiremen117198ts with respect to the neutron data uncertainties for achieving the target accuracies in calculation of the reactor functionals, and estimation of the reactor performance prediction accuracy, as well as the informativity and similarity metrics of reactor physics experiments with respect to each other and in relation to the target reactor system. The paper also considers some examples of using the code to refine the neutronics models of nuclear reactor and fuel cycle systems based on results of reactor physics experiments.

Bayesian model selection: Application to the adjustment of fundamental physical constants

Bayesian model selection: Application to the adjustment of fundamental physical constants

Calibration of Turbulent Model Constants Based on Experimental Data Assimilation: Numerical Prediction of Subsonic Jet Flow Characteristics

Experimental measurements and numerical simulations are two primary methods for studying turbulence. However, these methods often struggle to balance the accuracy and breadth of results. In order to accurately predict the flow characteristics of subsonic jet exhaust and provide a research foundation for the runway crossing operation after the takeoff point, this study utilizes the ensemble Kalman filter algorithm to recalibrate the SA turbulence model constants by integrating NASA’s experimental particle image velocimetry (PIV) data with a sample library generated using Latin hypercube sampling to obtain corresponding flow field calculations. The modified model constants effectively improve the prediction of jet flow characteristics, reducing the spatially averaged relative error along the horizontal axis behind the nozzle from 13.04% to 4.6%. This study focuses on enhancing the accuracy of numerical predictions for subsonic jet flows via the adjustment of turbulence model constants. The recalibrated model constants are then validated to improve the prediction of jet flows under various conditions. The findings have important implications for acquiring high-fidelity data on rear engine jet flows after takeoff, enabling precise determination of safety separation distances, and enhancing the operational efficiency of airports.

A combustion model for multi-component fuels based on relative reactivity and molecular structure

A reliable multi-component surrogate fuel model needs to be able to represent both physical properties and chemical kinetics of a real fuel. However, enhancing the fidelity of a model with detailed description of physical and chemical behavior of all fuel components found in real fuels is limited by the prohibitive computational load to calculate the combustion chemistry of the fuel. Hence, it is desirable to achieve computational efficiency by reducing the number of chemical surrogates at the minimum expense of prediction accuracy. The objective of this work is to develop a model that can simulate the oxidation of multi-component fuels by representing the ignition characteristics of physical surrogate components with fewer chemical surrogates and achieve both computational efficiency and prediction accuracy. The main advantage of the model, called the Reactivity-Adjustment (ReAd) combustion model, is to accurately predict the reactivity of the physical surrogate components that the reaction mechanisms of which are not included in the reaction kinetics model employed in the simulation. The reactivity variation of local mixtures with different compositions is modeled by adjusting the reaction rate constants of selected control-reactions in the reaction mechanism of the representative chemical surrogates. An initial version of the model has been developed employing a single chemical surrogate to represent the combustion of diesel fuel which is modeled as multiple surrogate components to capture the physical properties of the real fuel. The model was extended to consider two more chemical surrogate components to represent the ignition characteristics of other chemical families than n-alkanes. This enabled to avoid the excessive adjustment of reaction rate constants that were necessary when a single chemical surrogate is used to represent the oxidation kinetics of entire multi-component fuels. The model was extensively tested for simulating oxidation processes of many fuels with a variety of fuel reactivity and in various combustion regimes. The results demonstrated that excellent accuracy of the ignition/combustion prediction was achieved while ensuring computational efficiency.

Fission Yeast Polarization: Modeling Cdc42 Oscillations, Symmetry Breaking, and Zones of Activation and Inhibition.

Cells polarize for growth, motion, or mating through regulation of membrane-bound small GTPases between active GTP-bound and inactive GDP-bound forms. Activators (GEFs, GTP exchange factors) and inhibitors (GAPs, GTPase activating proteins) provide positive and negative feedbacks. We show that a reaction–diffusion model on a curved surface accounts for key features of polarization of model organism fission yeast. The model implements Cdc42 membrane diffusion using measured values for diffusion coefficients and dissociation rates and assumes a limiting GEF pool (proteins Gef1 and Scd1), as in prior models for budding yeast. The model includes two types of GAPs, one representing tip-localized GAPs, such as Rga3; and one representing side-localized GAPs, such as Rga4 and Rga6, that we assume switch between fast and slow diffusing states. After adjustment of unknown rate constants, the model reproduces active Cdc42 zones at cell tips and the pattern of GEF and GAP localization at cell tips and sides. The model reproduces observed tip-to-tip oscillations with periods of the order of several minutes, as well as asymmetric to symmetric oscillations transitions (corresponding to NETO “new end take off”), assuming the limiting GEF amount increases with cell size.

Improving double-ended transition state searches for soft-matter systems.

Transitions between different stable configurations of biomolecules are important in understanding disease mechanisms, structure-function relations, and novel molecular-scale engineering. The corresponding pathways can be characterized efficiently using geometry optimization schemes based on double-ended transition state searches. An interpolation is first constructed between the known states and then refined, yielding a band that contains transition state candidates. Here, we analyze an example where various interpolation schemes lead to bands with a single step transition, but the correct pathway actually proceeds via an intervening, low-energy minimum. We compare a number of different interpolation schemes for this problem. We systematically alter the number of discrete images in the interpolations and the spring constants used in the optimization and test two schemes for adjusting the spring constants and image distribution, resulting in a total of 2760 different connection attempts. Our results confirm that optimized bands are not necessarily a good description of the transition pathways in themselves, and further refinement to actually converge transition states and establish their connectivity is required. We see an improvement in the optimized bands if we employ the adjustment of spring constants with doubly-nudged elastic band and a smaller improvement from the image redistribution. The example we consider is representative of numerous cases we have encountered in a wide variety of molecular and condensed matter systems.

Adjustment of fundamental physical constant values using the interval fusion with preference aggregation

Abstract For adjustment of fundamental constants, the interval fusion with preference aggregation (IFP determines the profile consensus ranking; and the highest ranked consensus value is accepted as a fusion result x*. A nonlinear effect of the RAV partition norm on x* is studied. IF&PA, redesigned to obtain more accurate result x**, was experimentally tested when adjusting the Planck constant values on both random input data and real life values used in the CODATA adjustments 2006 and 2017. It is shown the IF&PA works well with no statistical assumptions and provides adjusted result x** with tangibly reduced uncertainty in contrast to traditional Birge ratio methods.

Quantification of drainable water storage volumes on landmasses and in river networks based on GRACE and river runoff using a cascaded storage approach – first application on the Amazon

Abstract. The knowledge of water storage volumes in catchments and in river networks leading to river discharge is essential for the description of river ecology, the prediction of floods and specifically for a sustainable management of water resources in the context of climate change. Measurements of mass variations by the GRACE gravity satellite or by ground-based observations of river or groundwater level variations do not permit the determination of the respective storage volumes, which could be considerably bigger than the mass variations themselves. For fully humid tropical conditions like the Amazon the relationship between GRACE and river discharge is linear with a phase shift. This permits the hydraulic time constant to be determined and thus the total drainable storage directly from observed runoff can be quantified, if the phase shift can be interpreted as the river time lag. As a time lag can be described by a storage cascade, a lumped conceptual model with cascaded storages for the catchment and river network is set up here with individual hydraulic time constants and mathematically solved by piecewise analytical solutions. Tests of the scheme with synthetic recharge time series show that a parameter optimization either versus mass anomalies or runoff reproduces the time constants for both the catchment and the river network τC and τR in a unique way, and this then permits an individual quantification of the respective storage volumes. The application to the full Amazon basin leads to a very good fitting performance for total mass, river runoff and their phasing (Nash–Sutcliffe for signals 0.96, for monthly residuals 0.72). The calculated river network mass highly correlates (0.96 for signals, 0.76 for monthly residuals) with the observed flood area from GIEMS and corresponds to observed flood volumes. The fitting performance versus GRACE permits river runoff and drainable storage volumes to be determined from recharge and GRACE exclusively, i.e. even for ungauged catchments. An adjustment of the hydraulic time constants (τC, τR) on a training period facilitates a simple determination of drainable storage volumes for other times directly from measured river discharge and/or GRACE and thus a closure of data gaps without the necessity of further model runs.

Efecto del patrón de flujo sobre las pérdidas de presión para flujo bifásico a través de lechos porosos bajo perspectiva fractal

La descripción del comportamiento de un flujo bifásico, a través de lechos porosos, por medio de modelos, basados en las ecuaciones de fenómenos de transporte, se dificulta debido a la irregularidad geométrica de los canales que se forman entre las partículas sólidas que constituyen el lecho. Los modelos deterministas desarrollados para flujos monofásicos requieren del ajuste de constantes empíricas y no pueden extrapolarse a flujos bifásicos, donde el patrón de flujo generado en el sistema influye significativamente sobre el comportamiento del flujo total y las pérdidas de presión por fricción. Por lo anterior, en este trabajo se presenta un modelo para describir el comportamiento del flujo bifásico en función del patrón de flujo y de la morfología, las dimensiones y las condiciones de operación del lecho poroso, cuya obtención se basó en un formalismo, empleando conjuntamente las ecuaciones de conservación de la cantidad de movimiento, la geometría fractal y el cálculo diferencial fraccional. El modelo predice que, para una misma composición del flujo bifásico, el patrón de flujo influye significativamente sobre las pérdidas de presión por fricción, habiendo un incremento cuando una de las fases se encuentra dispersa en el seno de la otra. Por otro lado, el incremento de la dimensión fractal de los poros causa a su vez un incremento de las pérdidas de presión por fricción. El modelo presenta limitaciones asociadas a las consideraciones establecidas durante su obtención, de tal manera que sólo es válido cuando los efectos de la tensión superficial son más significativos que los gravitatorios, despreciándose los efectos de esos últimos sobre el patrón de flujo, así como para el estado estacionario.

Finite Element Model Updating Combined with Multi-Response Optimization for Hyper-Elastic Materials Characterization.

The experimental stress-strain curves from the standardized tests of Tensile, Plane Stress, Compression, Volumetric Compression, and Shear, are normally used to obtain the invariant λi and constants of material Ci that will define the behavior elastomers. Obtaining these experimental curves requires the use of expensive and complex experimental equipment. For years, a direct method called model updating, which is based on the combination of parameterized finite element (FE) models and experimental force-displacement curves, which are simpler and more economical than stress-strain curves, has been used to obtain the Ci constants. Model updating has the disadvantage of requiring a high computational cost when it is used without the support of any known optimization method or when the number of standardized tests and required Ci constants is high. This paper proposes a methodology that combines the model updating method, the mentioned standardized tests and the multi-response surface method (MRS) with desirability functions to automatically determine the most appropriate Ci constants for modeling the behavior of a group of elastomers. For each standardized test, quadratic regression models were generated for modeling the error functions (ER), which represent the distance between the force-displacement curves that were obtained experimentally and those that were obtained by means of the parameterized FE models. The process of adjusting each Ci constant was carried out with desirability functions, considering the same value of importance for all of the standardized tests. As a practical example, the proposed methodology was validated with the following elastomers: nitrile butadiene rubber (NBR), ethylene-vinyl acetate (EVA), styrene butadiene rubber (SBR) and polyurethane (PUR). Mooney–Rivlin, Ogden, Arruda–Boyce and Gent were considered as the hyper-elastic models for modeling the mechanical behavior of the mentioned elastomers. The validation results, after the Ci parameters were adjusted, showed that the Mooney–Rivlin model was the hyper-elastic model that has the least error of all materials studied (MAEnorm = 0.054 for NBR, MAEnorm = 0.127 for NBR, MAEnorm = 0.116 for EVA and MAEnorm = 0.061 for NBR). The small error obtained in the adjustment of the Ci constants, as well as the computational cost of new materials, suggests that the methodology that this paper proposes could be a simpler and more economical alternative to use to obtain the optimal Ci constants of any type of elastomer than other more sophisticated methods.

Assessing accuracy in measurement: The dilemma of safety versus precision in the adjustment of the fundamental physical constants

Assessing accuracy in measurement: The dilemma of safety versus precision in the adjustment of the fundamental physical constants

Accurate Determination of the Values of Fundamental Physical Constants: The Basis of the New “Quantum” SI Units

The metric system appeared as the system of units designed for macroscopic (laboratory scale) measurements. The progress in accurate determination of the values of quantum constants (such as the Planck constant) in SI units shows that the capabilities in high-precision measurement of microscopic and macroscopic quantities in terms of the same units have increased substantially recently. At the same time, relative microscopic measurements (for example, the comparison of atomic transition frequencies or atomic masses) are often much more accurate than relative measurements of macroscopic quantities. This is the basis for the strategy to define units in microscopic phenomena and then use them on the laboratory scale, which plays a crucial role in practical methodological applications determined by everyday life and technologies. The international CODATA task group on fundamental constants regularly performs an overall analysis of the precision world data (the so-called Adjustment of the Fundamental Constants) and publishes their recommended values. The most recent evaluation was based on the data published by the end of 2014; here, we review the corresponding data and results. The accuracy in determination of the Boltzmann constant has increased, the consistency of the data on determination of the Planck constant has improved; it is these two dimensional constants that will be used in near future as the basis for the new definition of the kelvin and kilogram, respectively. The contradictions in determination of the Rydberg constant and the proton charge radius remain. The accuracy of determination of the fine structure constant and relative atomic weight of the electron has improved. Overall, we give a detailed review of the state of the art in precision determination of the values of fundamental constants. The mathematical procedure of the Adjustment, the new data and results are considered in detail. The limitations due to macroscopic properties of material standards (such as the International prototype of the kilogram) and the isotopic composition of substances involved in precision studies in general (as standard measures for the triple point of water) and, in particular, in the determination of the fundamental constants are discussed. The perspectives of the introduction of the new quantum units, which will be free from the mentioned problems, are considered. Many physicists feel no sympathy for the International system of units (SI), believing that it does not properly reflect the character of physical laws. In fact, there are three parallel systems, namely the systems of quantities, system of their units and the related standards. The definition of the units, in particular, the SI units, above all, reflects our ability to perform precision measurements of physical values under certain conditions, in particular, to create appropriate standards. This requirement is not related to the beauty of fundamental laws of nature. More accurate determination of the fundamental constants is one of the areas where we accumulate such experience.

The CODATA 2017 values of h, e, k, and NA for the revision of the SI

Sufficient progress towards redefining the International System of Units (SI) in terms of exact values of fundamental constants has been achieved. Exact values of the Planck constant h, elementary charge e, Boltzmann constant k, and Avogadro constant NA from the CODATA 2017 Special Adjustment of the Fundamental Constants are presented here. These values are recommended to the 26th General Conference on Weights and Measures to form the foundation of the revised SI.

New measurement of the Boltzmann constant k by acoustic thermometry of helium-4 gas

The SI unit of temperature will soon be redefined in terms of a fixed value of the Boltzmann constant k derived from an ensemble of measurements worldwide. We report on a new determination of k using acoustic thermometry of helium-4 gas in a 3 l volume quasi-spherical resonator. The method is based on the accurate determination of acoustic and microwave resonances to measure the speed of sound at different pressures. We find for the universal gas constant R = 8.314 4614(50) J·mol−1·K−1. Using the current best available value of the Avogadro constant, we obtain k = 1.380 648 78(83) × 10−23 J·K−1 with u(k)/k = 0.60 × 10−6, where the uncertainty u is one standard uncertainty corresponding to a 68% confidence level. This value is consistent with our previous determinations and with that of the 2014 CODATA adjustment of the fundamental constants (Mohr et al 2016 Rev. Mod. Phys. 88 035009), within the standard uncertainties. We combined the present values of k and u(k) with earlier values that were measured at LNE. Assuming the maximum possible correlations between the measurements, (kpresent/〈k〉 − 1) = 0.07 × 10−6 and the combined ur(k) is reduced to 0.56 × 10−6. Assuming minimum correlations, (kpresent/〈k〉 − 1) = 0.10 × 10−6 and the combined ur(k) is reduced to 0.48 × 10−6.

Determination of the Avogadro constant by the XRCD method using a 28Si-enriched sphere

To determine the Avogadro constant NA by the x-ray crystal density method, the density of a 28Si-enriched crystal was determined by absolute measurements of the mass and volume of a 1 kg sphere manufactured from the crystal. The mass and volume were determined by an optical interferometer and a vacuum mass comparator, respectively. The sphere surface was characterized by x-ray photoelectron spectroscopy and spectroscopic ellipsometry to derive the mass and volume of the Si core of the sphere excluding the surface layers. From the mass and volume, the density of the Si core was determined with a relative standard uncertainty of 2.3 × 10−8. By combining the Si core density with the lattice constant and the molar mass of the sphere reported by the International Avogadro Coordination (IAC) project in 2015, a new value of 6.022 140 84(15) × 1023 mol−1 was obtained for NA with a relative standard uncertainty of 2.4 × 10−8. To make the NA value determined in this work usable for a future adjustment of the fundamental constants by the CODATA Task Group on Fundamental Constants, the correlation of the new NA value with the NA values determined in our previous works was examined. The correlation coefficients with the values of NA determined by IAC in 2011 and 2015 were estimated to be 0.07 and 0.28, respectively. The correlation of the new NA value with the NA value determined by IAC in 2017 using a different 28Si-enriched crystal was also examined, and the correlation coefficient was estimated to be 0.21.

Electron counting capacitance standard and quantum metrology triangle experiments at PTB

This paper summarizes the final results of the electron counting capacitance standard experiment at the Physikalisch-Technische Bundesanstalt (PTB) achieved since the publication of a preliminary result in 2012. All systematic uncertainty contributions were experimentally quantified and are discussed. Frequency-dependent measurements on the 1 pF cryogenic capacitor were performed using a high-precision transformer-based capacitance bridge with a relative uncertainty of 0.03 µF F−1. The results revealed a crucial problem related to the capacitor, which hampered realizing the quantum metrology triangle with an accuracy corresponding to a combined total uncertainty of better than a few parts per million and eventually caused the discontinuation of the experiment at PTB. This paper provides a conclusion on the implications for future quantum metrology triangle experiments from the latest CODATA adjustment of fundamental constants, and summarizes perspectives and outlooks on future quantum metrology triangle experiments based on topical developments in small-current metrology.

Application of non-enzymatic browning of fructose for heating pattern determination in microwave assisted thermal pasteurization system

Various model foods and chemical markers have been used for the heating pattern determination in microwave processing at sterilization temperatures (110–130 °C). These chemical marker systems have slow reaction rates and are not useful at pasteurization temperatures (70–90 °C). In this study, non-enzymatic browning of fructose under alkaline conditions is investigated for its suitability to be used in the heating pattern determination for microwave assisted thermal pasteurization. Kinetics of browning of fructose in the mashed potato model food were studied. The model food samples were heated in a water bath at 60 °C, 70 °C, 80 °C and 90 °C for different time intervals and the browning kinetics were studied by spectrophotometric measurements at 420 nm. Reaction rate kinetics were fit to a linear first order kinetic model. Application of this model food to determine the heating pattern in the microwave assisted thermal pasteurization system was demonstrated. Dielectric properties of the mashed potato were measured to determine its suitability as a model food. Sucrose and salt were used as effective additives for the adjustment of the dielectric constants and loss factor respectively of the mashed potato. This system offers advantages of being cost-effective, opaque, homogeneous and easy to handle and thus provides an excellent system to locate the hot and cold spots of the food products.

Deuteron charge radius and Rydberg constant from spectroscopy data in atomic deuterium

We give a pedagogical description of the method to extract the charge radii and Rydberg constant from laser spectroscopy in regular hydrogen (H) and deuterium (D) atoms, that is part of the CODATA least-squares adjustment (LSA) of the fundamental physical constants. We give a deuteron charge radius from D spectroscopy alone of 2.1415(45) fm. This value is independent of the measurements that lead to the proton charge radius, and five times more accurate than the value found in the CODATA Adjustment 10. The improvement is due to the use of a value for the transition in atomic deuterium which can be inferred from published data or found in a PhD thesis.

Determination of the Side-Reaction Coefficient of Desferrioxamine B in Trace-Metal-Free Seawater

Electrochemical techniques like adsorptive cathodic stripping voltammetry with competitive ligand equilibration (ACSV-CLE) can determine total concentrations of marine organic ligands and their conditional binding constants for specific metals, but cannot identify them. Individual organic ligands, isolated from microbial cultures or biosynthesized through genomics, can be structurally characterized via NMR and tandem MS analysis, but this is tedious and time-consuming. A complementary approach is to compare known properties of natural ligands, particularly their conditional binding constants, with those of model organic ligands, measured under suitable conditions. Such comparisons cannot be meaningfully interpreted unless the side-reaction coefficient (SRC) of the model ligand in seawater is thoroughly evaluated. We conducted series of potentiometric titrations, in non-coordinating medium at seawater ionic strength (0.7 M NaClO4) over a range of metal:ligand molar ratios, to study complexation of the siderophore desferrioxamine B (DFOB) with Mg and Ca, for which it has the highest affinity among the major seasalt cations. From similar titrations of acetohydroxamic acid in the absence and presence of methanesulfonate (mesylate), it was determined that Mg and Ca binding to this common DFOB counter-ion is not strong enough to interfere with the DFOB titrations. Stability constants were measured for all DFOB complexes with Mg and Ca including, for the first time, the bidentate complexes. No evidence was found for Mg and Ca coordination with the DFOB terminal amine. From the improved DFOB speciation, we calculated five SRCs for each of the five (de)protonated forms of DFOB in trace-metal-free seawater, yet we also present a more convenient definition of a single SRC that allows adjustment of all DFOB stability constants to seawater conditions, no matter which of these forms is selected as the 'component' (reference species). An example of Cd speciation in seawater containing DFOB illustrates the non-trivial use of different SRCs for polyprotic, polydentate organic ligands.