Reversible Diffusion-Limited Reactions: "Chemical Equilibrium" State and the Law of Mass Action Revisited

The validity of two fundamental concepts of classical chemical kinetics - the notion of "Chemical Equilibrium" and the "Law of Mass Action" - are re-examined for reversible \textit{diffusion-limited} reactions (DLR), as exemplified here by association/dissociation $A+A \rightleftharpoons B$ reactions. We consider a general model of long-ranged reactions, such that any pair of $A$ particles, separated by distance $\mu$, may react with probability $\omega_+(\mu)$, and any $B$ may dissociate with probability $\omega_-(\lambda)$ into a geminate pair of $A$s separated by distance $\lambda$. Within an exact analytical approach, we show that the asymptotic state attained by reversible DLR at $t = \infty$ is generally \textit{not a true thermodynamic equilibrium}, but rather a non-equilibrium steady-state, and that the Law of Mass Action is invalid. The classical picture holds \text{only} in physically unrealistic case when $\omega_+(\mu) \equiv \omega_-(\mu)$ for any value of $\mu$.Comment: 4 page

Some thoughts about nonequilibrium temperature

The main objective of this paper is to show that, within the present framework of the kinetic theoretical approach to irreversible thermodynamics, there is no evidence that provides a basis to modify the ordinary Fourier equation relating the heat flux in a non-equilibrium steady state to the gradient of the local equilibrium temperature. This fact is supported, among other arguments, through the kinetic foundations of generalized hydrodynamics. Some attempts have been recently proposed asserting that, in the presence of non-linearities of the state variables, such a temperature should be replaced by the non-equilibrium temperature as defined in Extended Irreversible Thermodynamics. In the approximations used for such a temperature there is so far no evidence that sustains this proposal.Comment: 13 pages, TeX, no figures, to appear in Mol. Phy

General Non-equilibrium Theory of Colloid Dynamics

A non-equilibrium extension of Onsager's canonical theory of thermal fluctuations is employed to derive a self-consistent theory for the description of the statistical properties of the instantaneous local concentration profile n(r,t) of a colloidal liquid in terms of the coupled time evolution equations of its mean value n(r,t) and of the covariance {\sigma}(r,r';t) \equiv of its fluctuations {\delta}n(r, t) = n(r, t) - n(r, t). These two coarse-grained equations involve a local mobility function b(r, t) which, in its turn, is written in terms of the memory function of the two-time correlation function C(r, r' ; t, t') \equiv <{\delta}n(r, t){\delta}n(r',t')>. For given effective interactions between colloidal particles and applied external fields, the resulting self-consistent theory is aimed at describing the evolution of a strongly correlated colloidal liquid from an initial state with arbitrary mean and covariance n^0(r) and {\sigma}^0(r,r') towards its equilibrium state characterized by the equilibrium local concentration profile n^(eq)(r) and equilibrium covariance {\sigma}^(eq)(r,r'). This theory also provides a general theoretical framework to describe irreversible processes associated with dynamic arrest transitions, such as aging, and the effects of spatial heterogeneities

Towards a new understanding of cohabitation: Insights from focus group research across Europe and Australia

Background: Across the industrialized world, more couples are living together without marrying. Although researchers have compared cohabitation cross-nationally using quantitative data, few have compared union formation using qualitative data. Objective: We use focus group research to compare social norms of cohabitation and marriage in Australia and nine countries in Europe. We explore questions such as: what is the meaning of cohabitation? To what extent is cohabitation indistinguishable from marriage, a prelude to marriage, or an alternative to being single? Are the meanings of cohabitation similar across countries? Methods: Collaborators conducted seven to eight focus groups in each country using a standardized guideline. They analyzed the discussions with bottom-up coding in each thematic area. They then collated the data in a standardized report. The first and second authors systematically analyzed the reports, with direct input from collaborators. Results: The results describe a specific picture of union formation in each country. However, three themes emerge in all focus groups: commitment, testing, and freedom. The pervasiveness of these concepts suggests that marriage and cohabitation have distinct meanings, with marriage representing a stronger level of commitment. Cohabitation is a way to test the relationship, and represents freedom. Nonetheless, other discourses emerged, suggesting that cohabitation has multiple meanings. Conclusions: This study illuminates how context shapes partnership formation, but also presents underlying reasons for the development of cohabitation. We find that the increase in cohabitation has not devalued the concept of marriage, but has become a way to preserve marriage as an ideal for long-term commitment

Possible experiment to check the reality of a nonequilibrium temperature

An experiment is proposed to check the physical reality of a nonequilibrium absolute temperature previously proposed from theoretical grounds in the framework of extended irreversible thermodynamics

Tunable Pinning of Burst-Waves in Extended Systems with Discrete Sources

We study the dynamics of waves in a system of diffusively coupled discrete nonlinear sources. We show that the system exhibits burst waves which are periodic in a traveling-wave reference frame. We demonstrate that the burst waves are pinned if the diffusive coupling is below a critical value. When the coupling crosses the critical value the system undergoes a depinning instability via a saddle-node bifurcation, and the wave begins to move. We obtain the universal scaling for the mean wave velocity just above threshold.Comment: 4 pages, 5 figures, revte

Magnetic Field Effects on Neutron Diffraction in the Antiferromagnetic Phase of UPt3UPt_3

We discuss possible magnetic structures in UPt$_3$ based on our analysis of elastic neutron-scattering experiments in high magnetic fields at temperatures $T<T_N$. The existing experimental data can be explained by a single-{\bf q} antiferromagnetic structure with three independent domains. For modest in-plane spin-orbit interactions, the Zeeman coupling between the antiferromagnetic order parameter and the magnetic field induces a rotation of the magnetic moments, but not an adjustment of the propagation vector of the magnetic order. A triple-{\bf q} magnetic structure is also consistent with neutron experiments, but in general leads to a non-uniform magnetization in the crystal. New experiments could decide between these structures.Comment: 5 figures included in the tex

Awake craniotomy versus craniotomy under general anesthesia for the surgical treatment of insular glioma: choices and outcomes

Objective: To investigate differences in outcomes in patients who underwent surgery for insular glioma using an awake craniotomy (AC) vs. a craniotomy under general anesthesia (GA). Methods: Data from patients treated at our hospital between 2005 and 2015 were analyzed retrospectively. The preoperative, intraoperative, postoperative, and longer term follow-up characteristics and outcomes of patients who underwent surgery for primary insular glioma using either an AC or GA were compared. Results: Of the 52 identified patients, 24 had surgery using an AC and 28 had surgery under GA. The extent of resection was similar for the two anesthesia techniques: the median extent of resection was 61.4% (IQR: 37.8–74.3%) in the WHO grade <4 AC group vs. 50.5% (IQR: 35.0–71.2%) in the grade <4 GA group and 73.4

Superconductivity in heavy-fermion U(Pt,Pd)3 and its interplay with magnetism

The effect of Pd doping on the superconducting phase diagram of the unconventional superconductor UPt3 has been measured by (magneto)resistance, specific heat, thermal expansion and magnetostriction. Experiments on single- and polycrystalline U(Pt1-xPdx)3 for x<= 0.006 show that the superconducting transition temperatures of the A phase, Tc+, and of the B phase, Tc-, both decrease, while the splitting DTc increases at a rate of 0.30(2)K/at.%Pd. We find that DTc(x) correlates with an increase of the weak magnetic moment m(x) upon Pd doping. This provides further evidence for Ginzburg-Landau scenarios with magnetism as the symmetry breaking field, i.e. the 2D E representation and the 1D odd parity model. Only for small splittings DTc is proportional to m^2(Tc+) (DTc<= 0.05 K) as predicted. The results at larger splittings call for Ginzburg-Landau expansions beyond 4th order. The tetracritical point in the B-T plane persists till at least x= 0.002 for B perpendicular to c, while it is rapidly suppressed for B||c. Upon alloying the A and B phases gain stability at the expense of the C phase.Comment: 25 pages text (PS), 8 pages with 14 figures (PS), submitted to Phys.Rev.