Effect of chlorine on the adsorption of oxygen on Cu and Ag surfaces

Based on XPS and UVPS studies, it is shown that oxygen is preferentially adsorbed molecularly in the singlet state on Cu and Ag surfaces containing presorbed chlorine. Adsorption of chlorine on Cu and Ag surfaces containing presorbed atomic oxygen causes a disappearance of the oxygen. Extended Hückel calculations predict the observed behaviour.

Adsorption isotherms for neutral organic compounds-A hierarchy in modelling: Part II

A two-state model allowing for size disparity between the solvent and the adsorbate is analysed to derive the adsorption isotherm for electrosorption of organic compounds. Explicity, the organic adsorbate is assumed to occupy "n" lattice sites at the interface as compared to "one" by the solvent. The model parameters are the respective permanent and induced dipole moments apart from the nearest neighbour distance. The coulombic interactions due to permanent and induced dipole moments, discreteness of charge effects, and short-range and specific substrate interactions have all been incorporated. The adsorption isotherm is then derived using mean field approximation (MFA) and is found to be more general than the earlier multi-site versions of Bockris and Swinkels, Mohilner et al., and Bennes, as far as the entropy contributions are concerned. The role of electrostatic forces is explicity reflected in the adsorption isotherm via the Gibbs energy of adsorption term which itself is a quadratic function of the electrode charge-density. The approximation implicit in the adsorption isotherm of Mohilner et al. or Bennes is indicated briefly.

Adsorption isotherms for neutral organic compounds-A hierarchy in modelling: Part III

A simple three-state model permitting two different configurational states for the solvent, together with one for the organic adsorbate, is analysed to derive the adsorption isotherm. The implications of this model regarding pseudo-two-state and pseudo-Frumkin adsorption isotherms are indicated. A critique of the earlier theory of Bockris, Devanathan and Müller is presented in brief.

Adsorption isitherms for neutral organic compounds-A hierarchy in modelling: Part IV. Charge of maximum adsorption-Statistical mechanical basis

The charge at which adsorption of orgamc compounds attains a maximum ( \sigma MAX M) at an electrochenucal interface is analysed using several multi-state models in a hierarchical manner The analysis is based on statistical mechamcal results for the following models (A) two-state site parity, (B) two-state muhl-slte, and (C) three-state site parity The coulombic interactions due to permanent and reduced dipole effects (using mean field approximation), electrostatic field effects and specific substrate interactions have been taken into account. The simplest model in the hierarchy (two-state site parity) yields the exphcit dependence of ( \sigma MAX M) on the permanent dipole moment, polarizability of the solvent and the adsorbate, lattice spacing, effective coordination number, etc Other models in the baerarchy bring to hght the influence of the solvent structure and the role of substrate interactions, etc As a result of this approach, the "composition" of oM.x m terms of the fundamental molecular constants becomes clear. With a view to use these molecular results to maxamum advantage, the derived results for ( \sigma MAX M) have been converted into those involving experimentally observable parameters lake Co, C 1, E N, etc Wherever possible, some of the earlier phenomenologlcal relations reported for ( \sigma MAX M), notably by Parsons, Damaskm and Frumkln, and Trasattl, are shown to have a certain molecular basis, vlz a simple two-state sate panty model.As a corollary to the hxerarcbacal modelling, \sigma MAX M and the potential corresponding to at (Emax) are shown to be constants independent of 0max or Corg for all models The lmphcatlon of our analysis f o r OmMa x with respect to that predicted by the generalized surface layer equation (which postulates Om~ and Ema x varlaUon with 0) is discussed in detail Finally we discuss an passing o M. and the electrosorptlon valency an this context.

Adsorption isotherms for neutral organic compounds - A hierarchy in modelling: Part V. Models for the inner layer potential difference in the presence of dipolar adsorption

The relations for the inner layer potential &fference (E) in the presence of adsorbed orgamc molecules are derived for three hterarchlcal models, m terms of molecular constants like permanent &pole moments, polarlzablhtles, etc It is shown how the experimentally observed patterns of the E vs 0 plots (hnear m all ranges of $\sigma^M$, non-linear in one or both regions of o M, etc ) can be understood in a serm-quantltatlve manner from the simplest model in our hierarchy, viz the two-state site panty version Two-state multi-site and three-state (sxte panty) models are also analysed and the slope (3E/80),,M tabulated for these also The results for the Esm-Markov effect are denved for all the models and compared with the earlier result of Parsons. A comparison with the GSL phenomenologlcal equation is presented and its molecular basis, as well as the hmltatlons, is analysed. In partxcular, two-state multa-slte and three-state (site panty) models yield E-o M relations that are more general than the "umfied" GSL equation The posslblhty of vaewlng the compact layer as a "composite medium" with an "effective dlelectnc constant" and obtaimng novel phenomenological descnptions IS also indicated.

Adsorption isotherms-Microscopic modelling: Part II

A lattice formahsm using "spin variables" is employed to analyse multi-state models for the adsorption of neutral dipoles.In particular, a spin-1/2 (two-state) model incorporating permanent and reduced dipole moments of the solvent and the organic adsorbate,substrate interactions, and &screteness of charge effects is analysed The resulting Generalized Islng Hamaltonian is solved under mean field approximation (MFA) in order to derive the adsorption isotherm for organic molecules A few spin-1 (three-state) models are also analysed under MFA to describe the competitive adsorption of multi-state solvent and organic dipoles, and the appropriate equilibrium relations are derived The unification and isomorphism existing at the Hamlltonlan level for several diverse realizations, such as adsorption of ions and solvent/orgamc molecules, is indicated The possibility of analysing phase transitions using this generalized approach is briefly indicated.

Mean-field results of a lattice-gas model of multilayer adsorption

A lattice-gas model of multilayer adsorption has been solved in the mean-field approximation by a different numerical method. Earlier workers obtained a single solution for all values of temperature and pressure. In the present work, multiple solutions have been obtained in certain regions of temperature and pressure which give rise to bysteresis in the adsorption isotherm. In addition, we have obtained a parameter which behaves like an order parameter for the transition. The potential-energy function shows a double minimum in the region of bysteresis and a single maximum elsewhere.

Spontaneous symmetry breaking in twisted noncommutative quantum theories

We analyze aspects of symmetry breaking for Moyal spacetimes within a quantization scheme which preserves the twisted Poincare´ symmetry. Towards this purpose, we develop the Lehmann-Symanzik- Zimmermann (LSZ) approach for Moyal spacetimes. The latter gives a formula for scattering amplitudes on these spacetimes which can be obtained from the corresponding ones on the commutative spacetime. This formula applies in the presence of spontaneous breakdown of symmetries as well. We also derive Goldstone’s theorem on Moyal spacetime. The formalism developed here can be directly applied to the twisted standard model.

Methodological and Empirical Advances in the Quantitative Analysis of Spontaneous Responses in Psychophysiological Time Series

The aim of the present study was to advance the methodology and use of time series analysis to quantify dynamic structures in psychophysiological processes and thereby to produce information on spontaneously coupled physiological responses and their behavioral and experiential correlates. Series of analyses using both simulated and empirical cardiac (IBI), electrodermal (EDA), and facial electromyographic (EMG) data indicated that, despite potential autocorrelated structures, smoothing increased the reliability of detecting response coupling from an interindividual distribution of intraindividual measures and that especially the measures of covariance produced accurate information on the extent of coupled responses. This methodology was applied to analyze spontaneously coupled IBI, EDA, and facial EMG responses and vagal activity in their relation to emotional experience and personality characteristics in a group of middle-aged men (n = 37) during the administration of the Rorschach testing protocol. The results revealed new characteristics in the relationship between phasic end-organ synchronization and vagal activity, on the one hand, and individual differences in emotional adjustment to novel situations on the other. Specifically, it appeared that the vagal system is intimately related to emotional and social responsivity. It was also found that the lack of spontaneously synchronized responses is related to decreased energetic arousal (e.g., depression, mood). These findings indicate that the present process analysis approach has many advantages for use in both experimental and applied research, and that it is a useful new paradigm in psychophysiological research. Keywords: Autonomic Nervous System; Emotion; Facial Electromyography; Individual Differences; Spontaneous Responses; Time Series Analysis; Vagal System

The effect of interrogative function on intonation in spontaneous and read Finnish

Goals This study aims to map the effect of interrogative function on the intonation of spontaneous and read Finnish. Earlier research shows that the most prominent feature in Finnish question intonation is an appeal to the listener. Question word questions typically start with a high peak which is followed by falling intonation. In yes/no questions, F0 remains on a high level until the word carrying sentence stress and then falls. Final rises are mainly found in intonation clichés such as "Ai mitä?" ("What?") These earlier results are based on read speech and enacted dialogues. In this study, questions and statements found in spontaneous dialogues were compared. These utterances were also compared with read versions of the same utterances. Fundamental frequency values were compared using a mixed model. Contours were also grouped using auditory and visual inspection. Thus it was possible to compare frequencies of contour types according to utterance type and speech style. The position of questions in the F0 distribution of the whole material was also investigated in this study. Method The material consisted of four spontaneous dialogues and their read versions. The speakers were young adults from the Helsinki metropolitan area, four females and four males. The whole material was first divided into broad dialogue function categories arising from the material and F0 curves were calculated for each category. After this, 277 questions and 244 statements were selected for closer inspection. Values reflecting F0 distribution and contour shape were measured from the F0 contours of these utterances. A mixed model was used to analyse the differences. Utterance type, question type, speech style and speaker gender were used as fixed effects. The frequencies of F0 contour types were compared using a Chi square test. Additional material in this study came from eight young female speakers in central Finland. Results and conclusions In the mixed model analysis, significant differences were found both between questions and statements and between spontaneous and read speech. Generally, utterance type affected the variables reflecting contour type while speech style affected the variables reflecting F0 distribution. The effect of question type was not clearly visible. In read speech the contours resembled earlier results more closely. Speakers had different strategies in differentiating between questions and statements. In the whole material, F0 was slightly higher in questions than in statements. The effect of dialectal background could be seen in the contour types. The results show that interrogative function affects intonation in both spontaneous and read Finnish.

Spontaneous fermentation of traditional sago starch in Papua New Guinea

Sago starch is an important dietary carbohydrate in lowland Papua New Guinea (PNG). An investigation was conducted to determine whether microbes play a role in its preservation using traditional methods. In 12 stored sago samples collected from PNG villages, lactic acid bacteria (LAB) were present (>= 3.6 x 10(4) cfu/g) and pH ranged from 6.8 to 4.2. Acetic and propionic acids were detected in all samples, while butyric, lactic and valeric acids were present in six or more. In freshly prepared sago, held in sealed containers in the laboratory at 30 degrees C, spontaneous fermentation by endogenous microflora of sago starch was observed. This was evident by increasing concentrations of acetic, butyric and lactic acids over 4 weeks, and pH reducing from 4.9 to 3.1: both LAB and yeasts were involved. Survival of potential bacterial pathogens was monitored by seeding sago starch with similar to 10(4)/g of selected organisms. Numbers of Bacillus cereus, Listeria monocytogenes and Staphylococcus aureus fell to <30/g within 7 days. Salmonella sp. was present only in low numbers after 7 days (<36/g), but Escherichia coli was still detectable after three weeks (>10(2)/g). Fermentation appeared to increase the storability and safety of the product.

Adsorption Of Methanol On The Surfaces Of Copper-Alloys - Ups And Eels Studies

Methanol adsorbs molecularly on the surfaces of Cu–Pd alloys at low temperatures and transforms to CH3O or CO on warming, depending upon the alloy composition. On oxygen presorbed Cu–Pd alloy surfaces, adsorption of methanol gives rise to H2O and H2CO. CH3OH adsorbed molecularly on the surfaces of Cu–Au alloys and CH3O is formed only at relatively high temperatures.

Cellular and network mechanisms generating spontaneous population events in the immature rat hippocampus

Distinct endogenous network events, generated independently of sensory input, are a general feature of various structures of the immature central nervous system. In the immature hippocampus, these type of events are seen as "giant depolarizing potentials" (GDPs) in intracellular recordings in vitro. GABA, the major inhibitory neurotransmitter of the adult brain, has a depolarizing action in immature neurons, and GDPs have been proposed to be driven by GABAergic transmission. Moreover, GDPs have been thought to reflect an early pattern that disappears during development in parallel with the maturation of hyperpolarizing GABAergic inhibition. However, the adult hippocampus in vivo also generates endogenous network events known as sharp (positive) waves (SPWs), which reflect synchronous discharges of CA3 pyramidal neurons and are thought to be involved in cognitive functions. In this thesis, mechanisms of GDP generation were studied with intra- and extracellular recordings in the neonatal rat hippocampus in vitro and in vivo. Immature CA3 pyramidal neurons were found to generate intrinsic bursts of spikes and to act as cellular pacemakers for GDP activity whereas depolarizing GABAergic signalling was found to have a temporally non-patterned facilitatory role in the generation of the network events. Furthermore, the data indicate that the intrinsic bursts of neonatal CA3 pyramidal neurons and, consequently, GDPs are driven by a persistent Na+ current and terminated by a slow Ca2+-dependent K+ current. Gramicidin-perforated patch recordings showed that the depolarizing driving force for GABAA receptor-mediated actions is provided by Cl- uptake via the Na-K-C1 cotransporter, NKCC1, in the immature CA3 pyramids. A specific blocker of NKCC1, bumetanide, inhibited SPWs and GDPs in the neonatal rat hippocampus in vivo and in vitro, respectively. Finally, pharmacological blockade of the GABA transporter-1 prolonged the decay of the large GDP-associated GABA transients but not of single postsynaptic GABAA receptor-mediated currents. As a whole the data in this thesis indicate that the mechanism of GDP generation, based on the interconnected network of bursting CA3 pyramidal neurons, is similar to that involved in adult SPW activity. Hence, GDPs do not reflect a network pattern that disappears during development but they are the in vitro counterpart of neonatal SPWs.