Improving hydrogen storage thermodynamics and kinetics of Ce-Mg-Ni-based alloy by mechanical milling with TiF_(3)

Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.

Two innovative equivalent statements of the third law of thermodynamics

It is found from textbooks and literature that there are three different statements for the third law of thermodynamics,i.e., the Nernst theorem, the unattainability statement of absolute zero temperature, and the heat capacity statement. It is pointed out that such three statements correspond to three thermodynamic parameters, which are, respectively, the entropy,temperature, and heat capacity, and can be obtained by extrapolating the experimental results of different parameters at ultralow temperatures to absolute zero. It is expounded that because there is no need for additional assumptions in the derivation of the Nernst equation, the Nernst theorem should be renamed as the Nernst statement. Moreover, it is proved that both the Nernst statement and the heat capacity statement are mutually deducible and equivalent, while the unattainability of absolute zero temperature is only a corollary of the Nernst statement or the heat capacity statement so that it is unsuitably referred to as one statement of the third law of thermodynamics. The conclusion is that the Nernst statement and the heat capacity statement are two equivalent statements of the third law of thermodynamics.

Thermodynamics in a quantum corrected Reissner-Nordstr?m-AdS black hole and its GUP-corrections

We calculate the thermodynamic quantities in the quantum corrected Reissner-Nordstr?m-AdS(RN-AdS)black hole,and examine their quantum corrections.By analyzing the mass and heat capacity,we give the critical state and the remnant state,respectively,and discuss their consistency.Then,we investigate the quantum tunneling from the event horizon of massless scalar particle by using the null geodesic method,and charged massive boson W^(±)and fermions by using the Hamilton-Jacob method.It is shown that the same Hawking temperature can be obtained from these tunneling processes of different particles and methods.Next,by using the generalized uncertainty principle(GUP),we study the quantum corrections to the tunneling and the temperature.Then the logarithmic correction to the black hole entropy is obtained.

Thermodynamics-directed bulk/grain-boundary engineering for superior electrochemical durability of Ni-rich cathode

Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the inferior rate capability originating from the hindered Li~+migration.Note that the non-magnetic Ti~(4+)ion can suppress Li/Ni disorder by removing the magnetic frustration in the transition metal layer.However,it is still challenging to directionally design expected Ta/Ti dual-modification,resulting from the complexity of the elemental distribution and the uncertainty of in-situ formed coating compounds by introducing foreign elements.Herein,a LiTaO_3 grain boundary(GB)coating and bulk Ti-doping have been successfully achieved in LiNi_(0.834)Co_(0.11)Mn_(0.056)O_(2) cathode by thermodynamic guidance,in which the structural formation energy and interfacial binding energy are employed to predict the elemental diffusion discrepancy and thermodynamically stable coating compounds.Thanks to the coupling effect of strengthened structural/interfacial stability and improved Li~+diffusion kinetics by simultaneous bulk/GB engineering,the Ta/Ti-NCM cathode exhibits outstanding capacity retention,reaching 91.1%after 400 cycles at 1 C.This elaborate work contributes valuable insights into rational dual-modification engineering from a thermodynamic perspective for maximizing the electrochemical performances of NCM cathodes.

Heart failure with preserved ejection fraction and the first law of thermodynamics

In heart failure with preserved ejection fraction,significant left ventricular diastolic abnormalities are present,despite a normal systolic ejection fraction.This article will consider whether this is consistent with the law of conservation of energy,also know as the first law of thermodynamics.

Dialectical Thermodynamics’Solution to the Conceptual Imbroglio That Is the Reversible Path

According to the second law of thermodynamics, as currently understood, any given transit of a system along the reversible path proceeds with a total entropy change equal to zero. The fact that this condition is also the identifier of thermodynamic equilibrium, makes each and every point along the reversible path a state of equilibrium, and the reversible path, as expressed by a noted thermodynamic author, “a dense succession of equilibrium states”. The difficulties with these notions are plural. The fact, for example, that systems need to be forced out of equilibrium via the expenditure of work, would make any spontaneous reversible process a consumer of work, this in opposition to common thermodynamic wisdom that makes spontaneous reversible processes the most efficient transformers of work-producing-potential into actual work. The solution to this and other related impasses is provided by Dialectical Thermodynamics via its previously proved notion assigning a negative entropy change to the energy upgrading process represented by the transformation of heat into work. The said solution is here exemplified with the ideal-gas phase isomerization of butane into isobutane.

Elimination, Kinetics and Thermodynamics of Fe(II) Ions by Adsorption in Static and Dynamic Conditions on Activated Carbons in Aqueous Media

This work investigated the removal, kinetics and thermodynamics of iron(II) ions (Fe(II)) by adsorption in static and dynamic conditions in aqueous media on activated carbons (AC-i30min, AC-i1h, and AC-i24h), prepared from palm nut shells collected in the city of Franceville to Gabon, using potassium hydroxide (KOH) as the activating agent. Results on the elimination of Fe(II) in static and dynamic adsorption on prepared activated carbons (ACs) showed that the AC-i24h adsorbent has the best Fe(II) adsorption capacities at saturation (Qsat). The Qsat obtained on AC-i24h in static and dynamic conditions (17.87 and 10.38 mg/g, respectively) were higher than those of AC-i30min (13.89 and 5.54 mg/g respectively) and AC-i1h (14.92 and 8.64 mg/g respectively). Moreover, the static adsorption was more effective in the removal of Fe(II) ions in aqueous media in our experimental conditions. The percentage removal (%E) of Fe(II) obtained on prepared activated carbons in static conditions was better than those obtained in dynamic conditions, especially on AC-i24h, where the %E was 89.27% in static and 61.56% in dynamic. In kinetics, results showed that the pseudo-second-order kinetic model best described the adsorption mechanisms of Fe(II) on prepared activated carbons in static adsorption, with mainly of chemisorption on the solid surfaces. However, in dynamic conditions, the pseudo-first-order kinetic model was more suitable. In addition to the weak interactions between Fe(II) and the activated carbon surfaces, strong interactions (chemisorption) were also observed. Also, thermodynamic data obtained on AC-i24h in static adsorption indicated that the adsorption of Fe(II) was spontaneous and increased with temperature (ΔG˚ H˚ = 503.54 KJ/mol).

Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents

2,4(5)-Dinitroimidazole(2,4(5)-DNI)is an important organic intermediate,and itself can also be used for energetic material.In this work,the solubility of 2,4(5)-DNI in(methanol+water,acetonitrile+water,acetone+water)binary solvents were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 k Pa.The Jouyban–Acree model,van't Hoff–Jouyban–Acree model,Apelblat–Jouyb an–Acree model,Ma model,and Sun model were used to correlate the experimental data.The values of relative average deviation(RAD)and root-mean-square deviation(RMSD)were very small,indicating that the error between the experimental value and the correlated value was very small.The thermodynamic parameters such as dissolution enthalpy,dissolution entropy and Gibbs energy were calculated based on solubility data.High-purity of 2,4(5)-DNI was efficiently obtained by using cooling and dilution crystallization method.

Removal of Organochlorine from Model Oil Using Mg-Modified ZSM-5 Zeolite:Dechlorination Performance,Regeneration,and Thermodynamics

Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.

Pseudo-rapidity distributions of charged particles in asymmetric collisions using Tsallis thermodynamics

The pseudo-rapidity distributions of the charged particles produced in the asymmetric collision systems p+Al,p+Au and ^(3)He+Au at√S_(NN)=200 GeV GeV are evaluated in the framework of a fireball model with Tsallis thermodynamics.The fireball model assumes that the experimentally measured particles are produced by fireballs following the Tsallis distribution and it can effectively describe the experimental data.Our results as well as previous results for d+Au collisions at√S_(NN)=200 GeV GeV and p+Pb collisions at√S_(NN)=5.02 TeV TeV validate that the fireball model based on Tsallis thermodynamics can provide a universal framework for pseudo-rapidity distribution of the charged particles produced in asymmetric collision systems.We predict the centrality dependence of the total charged particle multiplicity in the p+Al,p+Au and 3He+Au collisions.Additionally,the dependences of the fireball model parameters(y_(0a),y_(0A),σ_(a) and σ_(A))on the centrality and system size are studied.

Li^(+)-ion bound crown ether functionalization enables dual promotion of dynamics and thermodynamics for ambient ammonia synthesis

Electrosynthesis of ammonia from the reduction of nitrogen is still confronted with the limited supply of gas reactant in dynamics as well as high activation barrier in thermodynamics.Unfortunately,despite tremendous efforts devoted to electrocatalysts themselves,they still fail to tackle the above two challenges simultaneously.Herein,we employ a heterogeneous catalyst adlayer-composed of crown ethers associated with Li^(+)ions-to achieve the dual promotion of dynamics and thermodynamics for ambient ammonia synthesis.Dynamically,the bound Li^(+)ions interact with the strong quadrupole moment of nitrogen,and trigger considerable reactant flux toward the catalyst.Thermodynamically,Li^(+)associated with the oxygen of crown ether achieves a higher density of states at the Fermi level for the catalyst,enabling effortless electron transfer from the catalysts to nitrogen and thus greatly reducing the activation barrier.As expected,the proof-of-concept system achieves an ammonia yield rate of 168.5μg h^(-1)mg^(-1)and a Faradaic efficiency of 75.3%at-0.3 V vs.RHE.This system-level approach opens up pathways for tackling the two key challenges that have limited the field of ammonia synthesis.

Shadow thermodynamics of AdS black hole with the nonlinear electrodynamics term

We creatively employ the shadow radius to study the thermodynamics of a charged Ad S black hole with a nonlinear electrodynamics(NLED)term.First,the connection between the shadow radius and event horizon is constructed with the aid of the geodesic analysis.It turns out that the black hole shadow radius shows a positive correlation as a function of the event horizon radius.Then in the shadow context,we find that the black hole temperature and heat capacity can be presented by the shadow radius.Further analysis shows that the shadow radius can work similarly to the event horizon in revealing black hole phase transition process.In this sense,we construct the thermal profile of the charged Ad S black hole with inclusion of the NLED effect.In the P<Pc case,it is found that the N-type trend of the temperature given by the shadow radius is always consistent with that obtained by using the event horizon.Thus,we can conclude for the charged Ad S black hole that the phase transition process can be intuitively presented as the thermal profile in the shadow context.Finally,the effects of NLED are carefully analyzed.

Thermodynamics and Microphysical Characteristics of an Extreme Rainfall Event Under the Influence of a Low-level Jet over the South China Coast

In this paper,the data of Automatic Weather Stations(AWSs),ERA5 reanalysis,sounding,wind profile radar,and dual-polarization radar are used to study an extreme rainfall event in the south China Coast on 11 to 12 May 2022 from the aspects of thermodynamics and microphysical characteristics under the influence of low-level jets(LLJs).Results show that:(1)The extreme rainfall event can be divided into two stages:the first stage(S1)from 0000 to 0600 LST on May 12 and the second stage(S2)from 0700 to 1700 LST on the same day.During S1,the rainfall is mainly caused by the upper-level shortwave trough and the boundary layer jet(BLJ),characterized by strong upward motion on the windward side of mountains.In S2,the combined influence of the BLJ and synoptic-system-related low-level jet(SLLJ)increases the vertical wind shear and vertical vorticity,strengthening the rainstorm.In combination with the effect of topography,a warm and humid southwest flow continuously transports water vapor to farther north,resulting in a significant increase in rainfall over the study area(on the terrain’s windward slope).From S1 to S2,the altitude of a divergence center in the upper air decreases obviously.(2)The rainfalls in the two stages are both associated with the mesoscale convergence line(MCL)on the surface,and the wind field from the mesoscale outflow boundary(MOB)in S1 is in the same direction as the environmental winds.Due to a small area of convergence that is left behind the MOB,convection moves eastward quickly and causes a short duration of heavy rainfall.In S2,the convergence along the MOB is enhanced,which strengthens the rainfall and leads to strong outflows,further enhancing the surface convergence near the MOB and forming a positive feedback mechanism.It results in a slow motion of convection and a long duration of heavy rainfall.(3)In terms of microphysics,the center of a strong echo in S1 is higher than in S2.The warm-rain process of the oceanic type characterizes both stages,but the convective intensity in S2 is significantly stronger than that in S1,featuring bigger drop sizes and lower concentrations.It is mainly due to the strengthening of LLJs,which makes small cloud droplets lift to melting levels,enhancing the ice phase process(riming process),producing large amounts of graupel particles and enhancing the melting and collision processes as they fall,resulting in the increase of liquid water content(LWC)and the formation of large raindrops near the surface.

Thermodynamics of warm axionic Abelian gauge inflation

Inflationary spectral index from the Langevin equation is calculated under the frame of warm inflationary scenario with inflaton interacting with U(1) gauge fields through the Chern–Simons coupling ∝ФF_(μv)F^(μv). Under the strong dissipative condition, the spectral index is calculated in terms of the ratio of Hubble parameter to temperature H/T. Then relation between H/T and other cosmic parameters is analytically expressed, based on which a spectral index related to the Chern–Simons coupling strength is further obtained. Numerical results show that cosmic temperature T closes to a constant during inflation and decreases after inflation without a reheating process. Meanwhile, the ratio H/T tends to a constant if the gauged coupling constant is less than a threshold. This phenomenon shows that cosmic temperature may be an important physical parameter with a special value and adiabatic approximation still holds. We obtain the estimate H/T ≤ 0.3377 during inflation from Planck data and other constraint conditions.

Confirmation of the First Law of Thermodynamics in Theory and Extended Bernoulli Equation

The internal energy change of ideal gas does not depend on the volume and pressure. The internal energy change of real gas has not any relation with the volume and pressure, which had been proved. If the internal energy change had not any relation with the volume and pressure, we could confirm the first law of thermodynamics in theory. Simultaneously, the internal energy change is the state function that shall be able to be proved in theory. If the internal energy change depended on the volume and pressure, we could not prove that the internal energy change is the state function and the chemical thermodynamics theory is right. The extended or modified Bernoulli equation can be derived from the energy conservation law, and the internal energy change, heat, and friction are all considered in the derivation procedure. The extended Bernoulli equation could be applied to the flying aircraft and mechanical motion on the gravitational field, for instance, the rocket and airplane and so on. This paper also revises some wrong ideas, viewpoints, or concepts about the thermodynamics theory and Bernoulli equation.

A Computational Study of Microhydrated N-Acetyl-Phenylalaninylamide (NAPA): Kinetics and Thermodynamics

The formations of [NAPA-A(H2O)n (n = 1, 2, 3, 4)] complexes have been studied employing DFT/wB97XD/cc-pVTZ computational level to understand the kinetics and thermodynamics for the hydration reactions of N-acetyl-phenylalaninylamide (NAPA). Thermodynamic parameters such as reaction energy (E), enthalpy (H), Gibb’s free energy (G), specific heat capacity (Cv), entropy (S), and change of these parameters (ΔEr, ΔHr, ΔGr, ΔCr, and ΔSr) were studied using the explicit solvent model. The predicted values of H, G, C, and S increase with the sequential addition of water in NAPA-A due to the increase in the total number of vibrational modes. On the other hand, the value of ΔEr, ΔHr, and ΔGr increases (more negative to less negative) gradually for n = 1, 2, 3, and 4 that indicates an increase of hydration in NAPA-A makes exothermic to endothermic reactions. The barrier heights for the transition states (TS) of [NAPA-A(H2O)n (n = 1, 2, 3, 4)] complexes are predicted to lie at 4.41, 4.05, 3.72 and 2.26 kcal/mol respectively below the reactants. According to the calculations, the formations of [NAPA-A(H2O)1] and [NAPA-A(H2O)2] complexes are barrierless reactions because both water molecules are strongly bonded via two hydrogen bonds in the backbone of NAPA-A. On the contrary, the reactions of [NAPA-A(H2O)3] and [NAPA-A(H2O)4] complexation are endothermic and the barrier heights are predicted to stay at 6.30 and 10.54 kcal/mol respectively above the reactants. The free energy of activation (Δ‡G0) for the reaction of [NAPA-A(H2O)1], [NAPA-A(H2O)2], [NAPA-A(H2O)3], and [NAPA-A(H2O)4] complexation are 4.43, 4.28, 3.83 and 5.11 kcal/mol respectively which are very low. As well as the rates of reactions are 3.490 × 109 s-1, 4.514 × 109 s-1, 9.688 × 109 s-1, and 1.108 × 109 s-1 respectively which are very fast and spontaneous.

A Review of Recent Trends in Quantum Thermodynamics and a System’s Behavioural Analysis of the Universe Originating as a Quantum Energy System

This paper combines a review of recent advances in quantum thermodynamics, including work on objective collapse (Zurek’s quantum Darwinism) and quantum gravity (Verlinde’s quantum gravity explanation), with a redefinition of entropy generation as systems’ change process. These concepts are used as systems’ behaviour analysis tools to allow us to revisit Hartle and Hawking’s 1983 quantum universe and develop a hypothesis for how physically a universe starting in a quantum state could evolve into our current universe, based on systems analysis. The outcome of this analysis raises a question: do we already have the elements of a “theory of everything” hiding in plain sight within recent advances in quantum thermodynamics?

Quantum Gravity Based on Generalized Thermodynamics

This paper proposes a novel approach and simplified model of Quantum Gravity based on the unification framework of Generalized Thermodynamics which suggests cross-related terms and modified equations of General Relativity and Quantum Mechanics. To address the “background problem”, a metric tensor is introduced into stationary Schrödinger equations via curved coordinates yielding quantum spacetime variation term. Then quantum Lagrangian is added to Einstein-Hilbert functional yielding quantum stress-energy tensor. Obtained from one variational principle, two theories are linked by a common quantum spacetime field. The theory offers some interpretations of the quantum vacuum spacetime fluctuations, zero-point-fields, quantum fields shifting towards high spacetime densities, the quantum nature of spacetime, and black hole singularity.

Black Holes and the Third Law of Thermodynamics Revisited

Black holes contradict the Nernst-Planck (N/P) version of the 3rd law of thermodynamics, but agree with its unattainability (U) version. This happens without contradiction, because the N/P and U versions are not equivalent, namely, N/P implies U but U does not imply N/P. So, black holes obey the weaker version of the 3rd law, but not the stronger one.

钼精矿焙烧过程中杂质化合物对烧结行为的影响

在钼精矿焙烧过程中,伴生元素转化及其与二硫化钼的相互作用会引起粉体部分熔化、结块、团聚等烧结现象,严重影响钼焙砂质量和炉子寿命。本文研究了钼精矿焙烧时赋存的杂质(种类和含量)以及焙烧温度对其烧结行为的影响,对其烧结程度进行定量化计算,并观察烧结物中各成分黏结形态的微观形貌。结果表明:钼精矿中SiO_(2)和Al_(2)O_(3)对钼精矿焙烧烧结行为影响很小,而CaO、MgO、Fe_(2)O_(3)、CuO和K_(2)CO_(3)会强化烧结行为;增大反应温度达到MoO_(3)与钼酸盐共晶的临界温度后会加剧团聚现象;增大CaO、CuO和K_(2)CO_(3)含量,对钼精矿烧结行为影响最大。烧结物中各组分之间的黏结形态分为三类,即加SiO_(2)或Al_(2)O_(3)后呈孤立型,加CaO或MgO后呈交叉型,以及加Fe_(2)O_(3)、CuO或K_(2)CO_(3)后呈包裹型。