Theoretical Calculations of Acid Dissociation Constants: A Review Article

Acid dissociation constants, or pKa values, are essential for understanding many fundamental reactions in chemistry. These values reveal the deprotonation state of a molecule in a particular solvent. There is great interest in using theoretical methods to calculate the pKa values for many different types of molecules. These include molecules that have not been synthesized, those for which experimental pKa determinations are difficult, and for larger molecules where the local environment changes the usual pKa values, such as for certain amino acids that are part of a larger polypeptide chain. Chemical accuracy in pKa calculations is difficult to achieve, because an error of 1.36 kcal/mol in the change of free energy for deprotonation in solvent results in an error of 1 pKa unit. In this review the most valuable methods for determining accurate pKa values in aqueous solution are presented for educators interested in explaining or using these methods for their students.

Comparative Analysis of Russian and French Prosodies: Theoretical, Experimental and Applied Aspects"

Experience shows that in teaching the pronunciation of a foreign language, it is the native syllable stereotype that resists correction most strongly. This is because the syllable is the basic unit of the perception and production of speech, and syllabic production is highly automatic and to some degree determines the prosody of speech at all levels: accent, rhythm, phrase, etc. The results of psycho-physiological studies show that the human acoustic analyser is a typical contemplator organ and new acoustic qualities are perceived through their inclusion into the already existing system of values characteristic to the mother tongue. This results in the adaptation of the perception and so production of foreign speech to native patterns. The less conscious the perception of the unit and the more 'primitive' its status, the greater the degree of its auditory assimilation, and the syllable is certainly among the less controllable linguistic units. The group carried out a complex investigation of the French and Russian languages at the level of syllable realisation, focusing on the stressed syllable of both open and closed types. The useful acoustic characteristics of the French/Russian syllable pattern were determined through identifying a typical syllable pattern within the system of each of the two languages, comparing these patterns to establish their contrasting features, and observing and systematising deviations from the pattern typical of the French/Russian language teaching situation. The components of the syllable pattern shown to need particular attention in teaching French pronunciation to Russian native speakers were intensity, fundamental frequency, and duration. The group then developed a method of correction which combines the auditory and visual canals of sound signal perception and tested this method with groups of Russian students of different levels.

The Function of Norms and Values in the Construction of Social Identity in Groups who experienced intergroup Conflicts

I present my explorative research about conflict and social identity. The Social Identity Approach of Henri Tajfel and John Turner is used as theoretical frame in the study. The main question is how the construction of social identity of group members is influenced by an inter-group conflict. The research project consists of two parts: 1. An empirical study conducted with qualitative research methods to investigate a today’s congregation of the Swiss reformed Church who experienced a conflict about twenty years ago. This conflict ended by the separation of a sub-group from the congregations. This group forms an independent community today. Members of both congregations where interviewed about the meaning which membership has for them and about their interpretation of the conflict. 2. An analysis of the Gospel of Matthew with questions who where developed out of the empirical study and the Social Identity Approach to better understand the separation conflict between the Matthean community and the synagogue.

Heat flow values in the Sea of Okhotsk region

Tectonic structure and anomalous distributions of geophysical fields of the Sea of Okhotsk region are considered; the lack of reliable data on age of the lithosphere beneath basins of various origin in the Sea of Okhotsk is noted. Model calculations based on geological and geophysical data yielded 65 Ma (Cretaceous-Paleocene boundary) age for the Central Okhotsk rise underlain by the continental lithosphere. This estimate agrees with the age (the end of Cretaceous) derived from seismostratigraphic data. A comparative analysis of theoretical and measured heat flows in the Akademii Nauk Rise, underlain by the thinned continental crust, is performed. The analysis points to a higher (by 20%) value of the measured thermal background of the rise, which is consistent with high negative gradient of gravity anomalies in this area. Calculations yielded 36 Ma (Early Oligocene) age and lithosphere thickness of 50 km for the South Okhotsk depression, whose seafloor was formed by processes of back-arc spreading. The estimated age of the depression is supported by kinematic data on the region; the calculated thickness of the lithosphere coincides with the value estimated from data of magnetotelluric sounding here. This indicates that formation time (36 Ma) of the South Okhotsk depression was estimated correctly. Numerical modeling performed for determination of the basement age of rifting basins in the Sea of Okhotsk gave the following estimates: 18 Ma (Early Miocene) for the Deryugin Basin, 12 Ma (Middle Miocene) for the TINRO Basin, and 23 Ma (Late Oligocene) for the West Kamchatka Trough. These estimates agree with formation time (Oligocene-Quaternary) of the sedimentary cover in rifting basins of the Sea of Okhotsk derived from geological and geophysical data. Model temperature estimates are obtained for lithologic and stratigraphic boundaries of the sedimentary cover in the Deryugin and TINRO Basins and the West Kamchatka Trough; the temperature analysis indicates that the latter two structures are promising for oil and hydrocarbon gas generation; the West Kamchatka Trough possesses better reservoir properties compared to the TINRO and Deryugin Basins. The latter is promising for generation of hydrocarbon gas. Paleogeodynamic reconstructions of the Sea of Okhotsk region evolution are obtained for times of 90, 66, and 36 Ma on the base of kinematic, geomagnetic, structural, tectonic, geothermal, and other geological and geophysical data.

Theoretical Transition Probabilities, Oscillator Strengths and Radiative Lifetimes Of Levels In Pb IV

Transitionprobabilities and oscillatorstrengths of 176 spectral lines with astrophysical interest arising from 5d10ns (n = 7,8), 5d10np (n = 6,7), 5d10nd (n = 6,7), 5d105f, 5d105g, 5d10nh (n = 6,7,8), 5d96s2, and 5d96s6p configurations, and radiativelifetimes for 43 levels of PbIV, have been calculated. These values were obtained in intermediate coupling (IC) and using relativistic Hartree–Fock calculations including core-polarization effects. For the IC calculations, we use the standard method of least-square fitting from experimental energy levels by means of the Cowan computer code. The inclusion in these calculations of the 5d107p and 5d105f configurations has facilitated a complete assignment of the energy levels in the PbIV. Transitionprobabilities, oscillatorstrengths, and radiativelifetimes obtained are generally in good agreement with the experimental data.

Dynamic Response of Wind Turbines to Theoretical 3D Seismic Motions Taking into Account the Rotational Component

We study the dynamic response of a wind turbine structure subjected to theoretical seismic motions, taking into account the rotational component of ground shaking. Models are generated for a shallow moderate crustal earthquake in the Madrid Region (Spain). Synthetic translational and rotational time histories are computed using the Discrete Wavenumber Method, assuming a point source and a horizontal layered earth structure. These are used to analyze the dynamic response of a wind turbine, represented by a simple finite element model. Von Mises stress values at different heights of the tower are used to study the dynamical structural response to a set of synthetic ground motion time histories

Theoretical Stark broadening parameters of Pb V spectral lines

In this paper, we report calculated values of the Stark widths and shifts for 72 spectral lines of Pb v. They were calculated using the Griem semi-empirical approach. A set of wavefunctions obtained from Hartree–Fock relativistic calculations including core polarization effects was used. Stark widths and shifts corresponding to lines arising from 5d9ns (n = 7, 8), 5d9 6p, 5d9 6d and 5d9 5f configurations of Pb v. Stark widths and shifts are presented for an electron density of 1017 cm−3 and temperatures T = 1.6–5.0 (104 K). The 2142.5, 2167.9 and 2278.6 Å lines of Pb v recently measured are included in our calculations. In this case, we have included for comparison calculations without core polarization effects. There is good agreement between our calculations and the above-cited experimental values.

Theoretical Stark broadening parameters for spectral lines arising from the 2p5ns, 2p5np and 2p5nd electronic configurations of MgIII

In the present work we report theoretical Stark widths and shifts calculated using the Griem semi-empirical approach, corresponding to 237 spectral lines of MgIII. Data are presented for an electron density of 1017 cm?3 and temperatures T = 0.5?10.0 (104 K). The matrix elements used in these calculations have been determined from 23 configurations of MgIII: 2s22p6, 2s22p53p, 2s22p54p, 2s22p54f and 2s22p55f for even parity and 2s22p5ns (n = 3?6), 2s22p5nd (n = 3?9), 2s22p55g and 2s2p6np (n = 3?8) for odd parity. For the intermediate coupling (IC) calculations, we use the standard method of least-squares fitting from experimental energy levels by means of the Cowan computer code. Also, in order to test the matrix elements used in our calculations, we present calculated values of 70 transition probabilities of MgIII spectral lines and 14 calculated values of radiative lifetimes of MgIII levels. There is good agreement between our calculations and experimental radiative lifetimes. Spectral lines of MgIII are relevant in astrophysics and also play an important role in the spectral analysis of laboratory plasma. Theoretical trends of the Stark broadening parameter versus the temperature for relevant lines are presented. No values of Stark parameters can be found in the bibliography.

Discourses and values underpin public debate on fracking in Spain: a case study at the crossroad

In the EU context extraction of shale and oil gas by hydraulic fracturing (fracking) differs from country to country in terms of legislation and implementation. While fossil fuel extraction using this technology is currently taking place in the UK, Germany and France have adopted respective moratoria. In between is the Spanish case, where hydrocarbon extraction projects through fracking have to undergo mandatory and routine environmental assessment in accordance with the last changes to environmental regulations. Nowadays Spain is at the crossroad with respect to the future of this technology. We presume a social conflictt in our country since the position and strategy of the involved and confronted social actors -national, regional and local authorities, energy companies, scientists, NGO and other social organization- are going to play key and likely divergent roles in its industrial implementation and public acceptance. In order to improve knowledge on how to address these controverted situations from the own engineering context, the affiliated units from the Higher Technical School of Mines and Energy Engineering at UPM have been working on a transversal program to teach values and ethics. Over the past seven years, this pioneering experience has shown the usefulness of applying a consequentialist ethics, based on a case-by-case approach and costs-benefits analysis both for action and inaction. As a result of this initiative a theoretical concept has arisen and crystallized in this field: it is named Inter-ethics. This theoretical perspective can be very helpful in complex situations, with multi-stakeholders and plurality of interests, when ethical management requires the interaction between the respective ethics of each group; professional ethics of a single group is not enough. Under this inter-ethics theoretical framework and applying content analysis techniques, this paper explores the articulation of the discourse in favour and against fracking technology and its underlying values as manifested in the Spanish traditional mass media and emerging social media such as Youtube. Results show that Spanish public discourse on fracking technology includes the costs-benefits analysis to communicate how natural resources from local communities may be affected by these facilities due to environmental, health and economic consequences. Furthermore, this technology is represented as a solution to the "demand of energy" according to the optimistic discourse while, from a pessimistic view, fracking is often framed as a source "environmental problems" and even natural disasters as possible earthquakes. In this latter case, this negative representation could have been influenced by the closure of a macro project to store injected natural gas in the Mediterranean Sea using the old facilities of an oil exploitation in Amposta (Proyecto Cástor). The closure of this project was due to the occurrence of earthquakes whose intensity was higher than the originally expected by the experts in the assessment stage of the project.

Cultural conflict: Conveyance of traditional Iranian values and the effects on sense of self of Iranian-American women

The literature on Iranians who immigrated to countries with modern cultures is sparse. This paper presents a theoretical understanding of the research with a particular appreciation on issues related to gender roles, sexuality, and acculturation within this population. In addition, treatment suggestions with this Iranian immigrant population will be presented through the lens of self psychology and a new perspective about the effects on the sense of self of young immigrant Iranian females will be discussed.

An observational and theoretical study of the structure and propagation of the Madden-Julian Oscillation

Thesis (Ph.D.)--University of Washington, 2016-06

Theoretical investigation of convective instability in inclined and fluid-saturated three-dimensional fault zones.

The convective instability of pore-fluid flow in inclined and fluid-saturated three-dimensional fault zones has been theoretically investigated in this paper. Due to the consideration of the inclined three-dimensional fault zone with any values of the inclined angle, it is impossible to use the conventional linear stability analysis method for deriving the critical condition (i.e., the critical Rayleigh number) which can be used to investigate the convective instability of the pore-fluid flow in an inclined three-dimensional fault zone system. To overcome this mathematical difficulty, a combination of the variable separation method and the integration elimination method has been used to derive the characteristic equation, which depends on the Rayleigh number and the inclined angle of the inclined three-dimensional fault zone. Using this characteristic equation, the critical Rayleigh number of the system can be numerically found as a function of the inclined angle of the three-dimensional fault zone. For a vertically oriented three-dimensional fault zone system, the critical Rayleigh number of the system can be explicitly derived from the characteristic equation. Comparison of the resulting critical Rayleigh number of the system with that previously derived in a vertically oriented three-dimensional fault zone has demonstrated that the characteristic equation of the Rayleigh number is correct and useful for investigating the convective instability of pore-fluid flow in the inclined three-dimensional fault zone system. The related numerical results from this investigation have indicated that: (1) the convective pore-fluid flow may take place in the inclined three-dimensional fault zone; (2) if the height of the fault zone is used as the characteristic length of the system, a decrease in the inclined angle of the inclined fault zone stabilizes the three-dimensional fundamental convective flow in the inclined three-dimensional fault zone system; (3) if the thickness of the stratum is used as the characteristic length of the system, a decrease in the inclined angle of the inclined fault zone destabilizes the three-dimensional fundamental convective flow in the inclined three-dimensional fault zone system; and that (4) the shape of the inclined three-dimensional fault zone may affect the convective instability of pore-fluid flow in the system. (C) 2004 Published by Elsevier B.V.

The valuation of travel time savings in least developed countries:theoretical and empirical challenges and results from a field study

In developed countries travel time savings can account for as much as 80% of the overall benefits arising from transport infrastructure and service improvements. In developing countries they are generally ignored in transport project appraisals, notwithstanding their importance. One of the reasons for ignoring these benefits in the developing countries is that there is insufficient empirical evidence to support the conventional models for valuing travel time where work patterns, particularly of the poor, are diverse and it is difficult to distinguish between work and non-work activities. The exclusion of time saving benefits may lead to a bias against investment decisions that benefit the poor and understate the poverty reduction potential of transport investments in Least Developed Countries (LDCs). This is because the poor undertake most travel and transport by walking and headloading on local roads, tracks and paths and improvements of local infrastructure and services bring large time saving benefits for them through modal shifts. The paper reports on an empirical study to develop a methodology for valuing rural travel time savings in the LDCs. Apart from identifying the theoretical and empirical issues in valuing travel time savings in the LDCs, the paper presents and discusses the results of an analysis of data from Bangladesh. Some of the study findings challenge the conventional wisdom concerning the time saving values. The Bangladesh study suggests that the western concept of dividing travel time savings into working and non-working time savings is broadly valid in the developing country context. The study validates the use of preference methods in valuing non-working time saving values. However, stated preference (SP) method is more appropriate than revealed preference (RP) method.

Leadership development: the role of developmental readiness, personality dispositions, and individual values

Increased awareness of the crucial role of leadership as a competitive advantage for organisations (McCall, 1998; Petrick, Scherer, Brodzinski, Quinn, & Ainina, 1999) has led to billions spent on leadership development programmes and training (Avolio & Hannah, 2008). However, research reports confusing and contradictory evidence regarding return on investment and developmental outcomes, and a lot of variance has been observed across studies (Avolio, Reichard, Hannah, Walumbwa, & Chan, 2009). The purpose of this thesis is to understand the mechanisms underlying this variability in leadership development. Of the many factors at play in the process, such as programme design and delivery, organisational support, and perceptions of relevance (Mabey, 2002; Day, Harrison, & Halpin, 2009), individual differences and characteristics stand out. One way in which individuals differ is in their Developmental Readiness (DR), a concept recently introduced in the literature that may well explain this variance and which has been proposed to accelerate development (Avolio & Hannah, 2008, 2009). Building on previous work, DR is introduced and conceptualised somewhat differently. In this study, DR is construed of self-awareness, self-regulation, and self-motivation, proposed by Day (2000) to be the backbones of leadership development. DR is suggested to moderate the developmental process. Furthermore, personality dispositions and individual values are proposed to be precursors of DR. The empirical research conducted uses a pre-test post-test quasi-experimental design. Before conducting the study, though, both a measure of Developmental Readiness and a competency profiling measure are tested in two pilot studies. Results do not find evidence of a direct effect of leadership development programmes on development, but do support an interactive effect between DR and leadership development programmes. Personality dispositions Agreeableness, Conscientiousness, and Openness to Experience and value orientations Conservation, Open, and Closed Orientation are found to significantly predict DR. Finally, the theoretical and practical implications of findings are discussed.