5,871 research outputs found
Open access self-archiving: An author study
No full textThis, our second author international, cross-disciplinary study on open access had 1296 respondents. Its focus was on self-archiving. Almost half (49%) of the respondent population have self-archived at least one article during the last three years. Use of institutional repositories for this purpose has doubled and usage has increased by almost 60% for subject-based repositories. Self-archiving activity is greatest amongst those who publish the largest number of papers. There is still a substantial proportion of authors unaware of the possibility of providing open access to their work by self-archiving. Of the authors who have not yet self-archived any articles, 71% remain unaware of the option. With 49% of the author population having self-archived in some way, this means that 36% of the total author population (71% of the remaining 51%), has not yet been appraised of this way of providing open access. Authors have frequently expressed reluctance to self-archive because of the perceived time required and possible technical difficulties in carrying out this activity, yet findings here show that only 20% of authors found some degree of difficulty with the first act of depositing an article in a repository, and that this dropped to 9% for subsequent deposits. Another author worry is about infringing agreed copyright agreements with publishers, yet only 10% of authors currently know of the SHERPA/RoMEO list of publisher permissions policies with respect to self-archiving, where clear guidance as to what a publisher permits is provided. Where it is not known if permission is required, however, authors are not seeking it and are self-archiving without it. Communicating their results to peers remains the primary reason for scholars publishing their work; in other words,
researchers publish to have an impact on their field. The vast majority of authors (81%) would willingly comply with a mandate from their employer or research funder to deposit copies of their articles in an institutional or subject-based repository. A further 13% would comply reluctantly; 5% would not comply with such a mandate
Progress of international hydrogen production network for the thermochemical Cu–Cl cycle
No full textThis paper presents recent advances by an international team which is developing the thermochemical copper–chlorine (Cu–Cl) cycle for hydrogen production. Development of the Cu–Cl cycle has been pursued by several countries within the framework of the Generation IV International Forum (GIF) for hydrogen production with the next generation of nuclear reactors. Due to its lower temperature requirements in comparison with other thermochemical cycles, the Cu–Cl cycle is particularly well matched with Canada's Generation IV reactor, SCWR (Super-Critical Water Reactor), as well as other heat sources such as solar energy or industrial waste heat. In this paper, recent developments of the Cu–Cl cycle are presented, specifically involving unit operation experiments, corrosion resistant materials and system integration.Atomic Energy of Canada LimitedOntario Research Excellence FundNatural Sciences and Engineering Research Council of CanadaUniversity Network of Excellence in Nuclear Engineering (UNENE)Canada Research Chairs progra
ŻYCIE UKRYTE W SŁOWIE. "BEKSIŃSCY. PORTRET PODWÓJNY" MAGDALENY GRZEBIAŁKOWSKIEJ W ŚWIETLE POSTSTRUKTURALIZMU
No full textLife Hidden in Words. Magdalena Grzebiałkowska\u27s "Beksińscy. Portret podwójny" and Poststructuralism
The article analyzes Magdalena Grzebiałkowska\u27s biographical "Beksińscy. Portret podwójny" which focuses on the lives of Zdzisław Beksiński and Tomasz Beksiński. The author looks at the construction of the biography and its relationship to poststructuralism, which allows for an appreciation of the literary features of the book. He points to how the specificity of the content, language, a mode of narration in Grzebiałkowska\u27s book make it a full-fledged literary work itself. As such the book departs from a typical biographical scheme. Juxtaposing the book with poststructural ideas leads to the reconsideration of the role of the author in the process of shaping of a biographical narrative
Study of the Square Planar Methylpalladium (II) Complexes Bearing Unsymmetrical α-Aminoaldimine Bidentate Ligands of Hetero Functionalities: Synthesis, Geometrical Isomerism and Reactivity
No full text一系列含胺-亞胺不對稱異官能雙牙配位基，R1R2NCMe2CH=NR (R1, R2 = Me, Et, c-C4H8 or R1 = iPr, tBu, R2 = H; R = Me, Et, iPr, tBu)，成功地藉由二甲基胺異丁醛和胺類的縮合反應製備而成。中性胺-亞胺鈀(II)金屬錯合物可以藉由上述配位基置換起始物((COD)Pd(Me)Cl)中的1,5-環辛二烯合成獲得。晶體結構分析顯示產物之胺-亞胺鈀金屬錯合物為平面四邊形的結構，並且只有單一的幾何異構物。晶體之構形取決於溶液中反式和順式異構物之相對含量；倘若順式異構物於溶液狀態下比例具有優勢，獲得晶體之構型即為順式，反之亦然。錯和物於溶液中有幾何異構化的現象。胺-亞胺鈀金屬錯合物之幾何異構物相對比例可以藉由胺-亞胺上的取代基之立體效應微調控制，其幾何異構化的動力學和反應機構的研究是以變溫氫譜核磁共振儀作為輔助工具。不同溫度下的幾何異構物速率常數分別為：6.97 × 10-5 s-1 (-10℃)、5.29 × 10-4 s-1 (0.0℃)和3.49 × 10-3 s-1 (10℃)，反應之活化能為120 kJ/mol。活化焓和活化熵的數值證明幾何異構化的反應機構乃是經由亞胺的解離以及重新配位。CO-和CNR-對於胺-亞胺鈀金屬錯合物的嵌入反應之產物依然具有幾何異構物。幾何異構物的反應活性差異乃是研究丁炔二酸二甲酯(DMAD)的嵌入反應。順式和反式幾何異構物的反應速率、反應機構和反應產物之差異於本文中清楚地呈現。A series of unsymmetrical bidentate ligands of α-aminoaldimines in the form of R1R2NCMe2CH=NR (R1, R2 = Me, Et, c-C4H8 or R1 = iPr, tBu, R2 = H; R = Me, Et, iPr, tBu) have been synthesized using condensation of 2,2-aminoethylpropanal with such ligands can replace COD in (COD)PdMeCl to give neutral methylchloropalladium complexes contain geometrical isomers with square planar configuration, and cis-trans isomerism was observed in solutions. However, it is interested that crystallographic analysis gives only single form crystal. Which geometrical isomers could be available depending on the relative stability in solution. The equilibrium constant of the isomerization may be fine-tuned in terms of the variation of the ligand substituents. Kinetic and mechanistic studies for the substitution and isomerization reactions are investigated by varied temperature 1H NMR. The rate constant of isomerization is 6.97 × 10-5 s-1 at -10℃, 5.29 × 10-4 s-1 at 0℃, and 3.49 × 10-3 s-1 at 10℃, and the activation energy is 120 kJ/mol. The geometrical isomerization is proposed to proceed via an imine dissociation and re-coordination. The CO- and CNR- inserted products of [R1R2NCMe2CH=NR]PdMeCl also contain geometrical isomers, and the reactivity is differentiated toward DMAD. Here we report the variation in insertion rate constant and proposed mechanism between cis and trans form.1. Introductions 1-1. Unsymmetrical Bidentate Chelating Nitrogen Ligands and Unsymmetrical Bidentate Palladium (II) Complexes 1-1-I Characteristic of Bidentate Nitrogen Ligands and Unsymmetrical Bidentate Palladium (II) Complexes 1-1-II Application of Unsymmetrical Bidentate Palladium (II) Complexes with Nitrogen donors 5-2. Geometrical isomers of Unsymmetrical Bidentate Pd (II) complexes: Isomerization, Thermodynamic and Kinetic Behaviors 7-2-I Variation in Ratio of Geometrical Isomers of Unsymmetrical Bidentate Pd (II) Complexes Controlled by Steric or Electronic Factor 7-2-II Temperature dependence of Geometrical Isomerism: Determination of Thermodynamic Parameters by Van’t Hoff Equation 10-2-III Kinetic Behavior of Geometrical Isomerism: Determination of Rate Activation Parameters by Arrhenius and Eyring equation 12-2-IV Kinetic Behavior of Geometrical Isomerism: Determination of Mechanism of Geometrical Isomerism by Activation Parameters 15-3. Insertion of Unsaturated Molecules into Pd-C Bond: Kinetic Behavior, Mechanism and Reactivity difference between Geometrical Isomers 16-3-I CO Insertion Reaction of Palladium (II) Complexes with Unsymmetrical Bidentate Ligands 16-3-II Alkyne Insertion Reaction of Palladium (II) Complexes with Unsymmetrical bidentate ligands 19-3-III Variation in Reactivity between Geometrical Isomers of Palladium (II) Complexes 20-4. Goal and Experimental Design of This Thesis 23-4-I Synthessis for the Bidentate Nitrogen Ligands and Unsymmetrical C2-Bidentate Palladium (II) Complexes with Nitrogen donors 23-4-II Thermodynamic and Kinetic Behavior of Unsymmetrical C2-Bidentate Palladium (II) Complexes: Mechanism of Geometrical Isomerization 25-4-III Insertion Reaction of CO, CNR, Alkene and Alkyne toward to Pd (II) complexes: Insertion products, Reaction Rate, Mechanism and Different Reactivity of Geometrical Isomers 26. Synthesis and Characterization of Palladium (II) Complexes with Bidentate σ-Aminoaldimine Ligands 28-1. Synthesis and Characterization of Bidentate σ-Aminoaldimine Ligands 28-1-I Characterization of Bidentate σ-Aminoaldimine Ligands 28-1-II Variation in Two Nitrogen Atoms of Bidentate σ-Aminoaldimine 29-1-III Synthesis for Bidentate σ-Aminoaldimine Ligands 30-2. Synthesis and Characterization of Neutral Bidentate σ-Aminoaldimine Palladium (II) Complexes [(N^N′)Pd(Me)Cl] 34-2-I Character of Bidentate Palladium (II) Complexes [(N^N′)Pd(Me)Cl 34-2-II Synthesis of Bidentate Palladium (II) Complexes [(N^N′)Pd(Me)Cl] 36-3. Crystallographic Analysis of Neutral Palladium (II) Complexes [N^N′]Pd(Me)Cl 40-3-I Bond lengths and Bond Angles of Neutral Palladium (II) Complexes [(N^N′)Pd(Me)Cl 41-3-II Torsion angles and Intramolecular Distances of Neutral Palladium (II) Complexes [(N^N′)Pd(Me)Cl 45-3-III X-ray Crystal Structure Determination of Palladium (II) Complexes 48-3-IV Isomerization with Crystal of Pure Geometrical Isomer 55. Kinetic and Mechanism Understanding with Isomerism of Bidentate (σ-Aminoaldimine)Pd(Me)Cl (II) Complexes 58-1. Fine-Tuned Geometrical Isomers Ratio of [(N^N′)Pd(Me)Cl] with Controlling the Steric Effect of Unsymmetrical Bidentate σ-Aminoaldimine Ligands 58-1-I Fine-tuned Geometrical Isomerism of [(N^N′)Pd(Me)Cl] 58-1-II Characteristic of Geometrical Isomerism of [(N^N′)Pd(Me)Cl] 60-2. Gibbs Free Energy Dependence of Temperature for Isomerism of Palladium (II) Complexes Bearing Unsymmetrical Bidentate σ-Aminoaldimine Ligands 64-2-I Temperature Dependence of Geometrical Isomerism [(N^N′)Pd(Me)Cl] 64-2-II ΔG° Dependence of Temperature for Isomerism of [(N^N′)Pd(Me)Cl] 66-3. Kinetic Study for Isomerism of Neutral Palladium (II) 71omplexes with σ-Aminoaldimine Ligands 71-3-I Kinetic Study for Isomerism of [(N^N′)Pd(Me)Cl] 71-3-II Activation Parameters and Activation Energy of [(N^N′)Pd(Me)Cl] 77-4. Mechanism Study for Isomerism of Neutral Palladium (II) Complexes [(N^N′)Pd(Me)Cl] 81-4-I Different Isomerization Rate Causing from Variation in Functionality between Amine and Imine 81-4-II Proposed mechanism of Isomerization of [(N^N′)Pd(Me)Cl] 84. Reactivity and Insertion Reaction of Bidentate (σ-Aminoaldimine)Pd(Me)Cl (II) Complexes 88-1. CO- and CNR- Insertion in Neutral Palladium (II) Complexes [(N^N′)Pd(Me)Cl] 88-1-I CO- Insertion in Neutral Palladium (II) Complexes Bearing Unsymmetrical Bidentate σ-Aminoaldimine Ligands 88-1-II Thermodynamic Characteristics for CO- Insertion Products 91-1-III The Other Synthetic Strategy for CO- Insertion Products 96-1-IV Fine-tuned Geometrical Isomerism of [(N^N′)Pd(C=OMe)Cl] 101-1-V CNR- Insertion in Neutral Palladium (II) Complexes Bearing Unsymmetrical Bidentate σ-Aminoaldimine Ligands 103-2. Alkene- and Alkyne- Insertion in Neutral Palladium (II) Complexes [(N^N′)Pd(Me)Cl] 107-2-I Alkyne Insertion in Neutral Palladium (II) Complexes Bearing Unsymmetrical Bidentate σ-Aminoaldimine Ligands 107-2-II Alkene- Insertion in Neutral Palladium (II) Complexes Bearing Unsymmetrical Bidentate σ-Aminoaldimine Ligands 111-3. Kinetics and Mechanisms Study for Insertion Reaction of Neutral Palladium (II) Complexes [(N^N′)Pd(Me)Cl]: Reactivity Difference between Geometrical Isomers 113-3-I Proposed Mechanism of CO- insertion of [(N^N′)Pd(Me)Cl] 114-3-II Variation in reactivity for CO- insertion of [(N^N′)Pd(Me)Cl] 120-3-III Proposed Mechanism of DMAD insertion of [(N^N′)Pd(Me)Cl] 125-3-IV Variation in reactivity for DMAD insertion of [(N^N′)Pd(Me)Cl] 129. Conclusions 139. Experimental Section 144eneral Considerations 144eagents and Materials 145ynthesis and Characterization 145hermodynamic Measurement: Temp dependence of ΔG° 187inetic Measurement: cis-trans isomerism 188inetic Measurement: DMAD Insertion 188eneral Procedure for Measuring the Variation in Reactivity between cis-trans [(N^N′)Pd(Me)Cl] Complexes of CO Insertion 189eneral Procedure for Measuring the Variation in Reactivity between cis-trans [(N^N′)Pd(Me)Cl] Complexes of t-Butyl Isocyanide Insertion 190-ray Crystallographic Analysis 191eferences 193ppendix 207RTEP Drawing of (N^N’)Pd(Me)Cl (II) and (N^N’)PdCl2 (II) Complexes 20
Systems, methods and devices for the capture and hydrogenation of carbon dioxide with thermochemical Cu—Cl and Mg—Cl—Na/K—CO2 cycles
No full textSystems, methods, and devices for producing hydrogen and capturing CO2 from emissions combine both H2 production and CO2 capture processes in forms of thermochemical cycles to produce useful products from captured CO2. The thermochemical cycles are copper-chlorine (Cu—Cl) and magnesium-chlorine-sodium/potassium cycles (Mg—Cl—Na/K—CO2). One system comprises a Cu—Cl cycle, a CO2 capture loop, and a hydrogenation cycle. Another system comprises an Mg—Cl—Na/K—CO2 cycle and a hydrogenation cycle. Devices for hydrogen production, CO2 capture, hydrogenation, and process and equipment integration include a two-stage fluidized/packed bed, hybrid two-stage spray-fluidized/packed bed reactor, a two-stage wet-mode absorber, a hybrid two-stage absorber, and a catalyst packed/fluidized bed reactor
Clean hydrogen production with the Cu–Cl cycle – Progress of international consortium, I: Experimental unit operations
No full textAdvancement of the thermochemical copper–chlorine (Cu–Cl) cycle for hydrogen production is reviewed and discussed in this paper. Individual unit operations and their linkage into an integrated cycle are being developed by a Canadian consortium, as part of the Generation IV International Forum (GIF) for hydrogen production with the next generation of nuclear reactors. This paper focuses on the consortium’s latest advances on the Cu–Cl cycle, particularly with respect to hydrogen production with Canada’s Generation IV reactor, called SCWR (Super-Critical Water Reactor). Other heat sources may also be utilized for the Cu–Cl cycle, such as solar energy or industrial waste heat. In this first of two companion papers, recent developments in Canada’s nuclear hydrogen program are reported, specifically unit operation experiments of the Cu–Cl cycle and system integration. The following second companion paper will present system modeling with Aspen Plus, corrosion resistant materials, thermochemistry, safety, and reliability aspects of the Cu–Cl cycle.Atomic Energy of Canada LimitedOntario Research Excellence FundNatural Sciences and Engineering Research Council of CanadaUniversity Network of Excellence in Nuclear Engineering (UNENE)Canada Research Chairs progra
Canada’s program on nuclear hydrogen production and the thermochemical Cu–Cl cycle
No full textThis paper presents an overview of the status of Canada’s program on nuclear hydrogen production and the thermochemical copper–chlorine (Cu–Cl) cycle. Enabling technologies for the Cu–Cl cycle are being developed by a Canadian consortium, as part of the Generation IV International Forum (GIF) for hydrogen production with the next generation of nuclear reactors. Particular emphasis in this paper is given to hydrogen production with Canada’s Super-Critical Water Reactor, SCWR. Recent advances towards an integrated lab-scale Cu–Cl cycle are discussed, including experimentation, modeling, simulation, advanced materials, thermochemistry, safety, reliability and economics. In addition, electrolysis during off-peak hours, and the processes of integrating hydrogen plants with Canada’s nuclear plants are presented.Atomic Energy of Canada LimitedOntario Research Excellence FundArgonne National Laboratory (International Nuclear Energy Research Initiative; U.S. Department of Energy)Natural Sciences and Engineering Research Council of Canada (NSERC)University Network of Excellence in Nuclear Engineering (UNENE)Canada Research Chairs (CRC
K-shell Photoionization of Atomic Cl
No full textRecent measurements of the photoionization of atomic Cl in the vicinity of the 1s thresholds have motivated the present R-matrix calculation which takes into account relativistic effects via the Breit-Pauli operator. The computer code CIV3 of Hibbert and Glass and Hibbert, which also includes relativistic effects, is used to obtain the discrete wavefunctions. These are constructed with orbitals generated from a carefully-chosen large scale configuration interaction expansion. The open-shell nature of the Cl atom translates into the existence of actually four 1s thresholds, 3Po 0,1,2 and 1P 1. The results are analyzed with particular focus on the resonances leading up to the four thresholds, and the various effects that dominate the cross sections in this energy range are unraveled
Integrated gasification and Cu–Cl cycle for trigeneration of hydrogen, steam and electricity
No full textThis paper develops and analyzes an integrated process model of an Integrated Gasification Combined Cycle (IGCC) and a thermochemical copper–chlorine (Cu–Cl) cycle for trigeneration of hydrogen, steam and electricity. The process model is developed with Aspen HYSYS software. By using oxygen instead of air for the gasification process, where oxygen is provided by the integrated Cu–Cl cycle, it is found that the hydrogen content of produced syngas increases by about 20%, due to improvement of the gasification combustion efficiency and reduction of syngas NOx emissions. Moreover, about 60% of external heat required for the integrated Cu–Cl cycle can be provided by the IGCC plant, with minor modifications of the steam cycle, and a slight decrease of IGCC overall efficiency. Integration of gasification and thermochemical hydrogen production can provide significant improvements in the overall hydrogen, steam and electricity output, when compared against the processes each operating separately and independently of each other.Natural Sciences and Engineering Research Council of Canada (NSERC
JPL Author Database
No full textA viewgraph presentation describing the background, goals, implementation, uses and future development of JPL's author database is shown
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