HPLC in photokinetics: Determination of reaction mechanism and photochemical quantum yields of (E)-1-phenylpropene

1987 ◽  
Vol 23 (6) ◽  
pp. 395-400 ◽  
Author(s):  
G. Gauglitz ◽  
W. Schmid
Author(s):  
John Ross ◽  
Igor Schreiber ◽  
Marcel O. Vlad

In a chemical system with many chemical species several questions can be asked: what species react with other species: in what temporal order: and with what results? These questions have been asked for over one hundred years about simple and complex chemical systems, and the answers constitute the macroscopic reaction mechanism. In Determination of Complex Reaction Mechanisms authors John Ross, Igor Schreiber, and Marcel Vlad present several systematic approaches for obtaining information on the causal connectivity of chemical species, on correlations of chemical species, on the reaction pathway, and on the reaction mechanism. Basic pulse theory is demonstrated and tested in an experiment on glycolysis. In a second approach, measurements on time series of concentrations are used to construct correlation functions and a theory is developed which shows that from these functions information may be inferred on the reaction pathway, the reaction mechanism, and the centers of control in that mechanism. A third approach is based on application of genetic algorithm methods to the study of the evolutionary development of a reaction mechanism, to the attainment given goals in a mechanism, and to the determination of a reaction mechanism and rate coefficients by comparison with experiment. Responses of non-linear systems to pulses or other perturbations are analyzed, and mechanisms of oscillatory reactions are presented in detail. The concluding chapters give an introduction to bioinformatics and statistical methods for determining reaction mechanisms.


1980 ◽  
Vol 45 (12) ◽  
pp. 3313-3319 ◽  
Author(s):  
Josef Komárek ◽  
Dalibor Kolčava ◽  
Lumír Sommer

The effect of chelating agents on the determination of cobalt in various flames, in a graphite cuvette and tantalum boat was studied considering the expected reaction mechanism of the atomization of cobalt and the reagent donor atom. A marked increase in the sensitivity of the determination of cobalt was observed in the presence of 1-(2-pyridylazo)-2-naphthol, pyrrolidinedithiocarboxylate, diethyldithiocarbamate, 8-mercaptoquinoline, 8-hydroxyquinoline and thenoyltrifluoroacetone for atomization from a tantalum boat. The optimum conditions for the determination of cobalt in the presence of 1-(2-pyridylazo)-1-naphthol are given.


Materials ◽  
2018 ◽  
Vol 11 (10) ◽  
pp. 1990 ◽  
Author(s):  
Md. Hoque ◽  
Marcelo Guzman

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic light. In this regard, an astonishing number of recent research articles include claims of highly efficient (photo)catalysts or similar terms about materials with superior or enhanced efficiency for a given reaction without proper experimental support. Consequently, the comparison of the efficiencies of photocatalysts may result as being meaningless, especially when reports are only based on expressions determining (1) a reaction rate per weight of catalyst or its surface area, (2) quantum efficiencies or quantum yields, and (3) turnover frequencies or turnover numbers. Herein, we summarize the standards needed for reporting valuable data in photocatalysis and highlight some common discrepancies found in the literature. This work should inform researchers interested in reporting photocatalysis projects about the correct procedures for collecting experimental data and properly characterizing the materials by providing examples and key supporting literature.


ChemPhysChem ◽  
2015 ◽  
Vol 16 (9) ◽  
pp. 1861-1862 ◽  
Author(s):  
John E. T. Corrie ◽  
Jack H. Kaplan ◽  
Biff Forbush ◽  
David C. Ogden ◽  
David R. Trentham
Keyword(s):  

1999 ◽  
Vol 71 (2) ◽  
pp. 321-335 ◽  
Author(s):  
Angela Salinaro ◽  
Alexei V. Emeline ◽  
Jincai Zhao ◽  
Hisao Hidaka ◽  
Vladimir K. Ryabchuk ◽  
...  

In the preceding article [Serpone and Salinaro, Pure Appl. Chem., 71(2), 303-320 (1999)] we examined two principal features of heterogeneous photocatalysis that demanded scrutiny: (i) description of photocatalysis and (ii) description of process efficiencies. For the latter we proposed a protocol relative photonic efficiency which could subsequently be converted to quantum yields. A difficulty in expressing a quantum yield in heterogeneous photochemistry is the very nature of the system, either solid/liquid or solid/gas, which places severe restrictions on measurement of the photon flow absorbed by the light harvesting component, herein the photocatalyst TiO2, owing to non-negligible scattering by the particulates. It was imperative therefore to examine the extent of this problem. Extinction and absorption spectra of TiO2 dispersions were determined at low titania loadings by normal absorption spectroscopy and by an integrated sphere method, respectively, to assess the extent of light scattering. The method is compared to the one reported by Grela et al. [J. Phys. Chem., 100, 16940 (1996)] who used a polynomial extrapolation of the light scattered in the visible region into the UV region where TiO2 absorbs significantly. This extrapolation underestimates the scattering component present in the extinction spectra, and will no doubt affect the accuracy of the quantum yield data. Further, we report additional details in assessing limiting photonic efficiencies and quantum yields in heterogeneous photocatalysis.


2012 ◽  
Vol 13 (1) ◽  
pp. 1-12 ◽  
Author(s):  
Inova Putri Carera ◽  
I Wayan Dasna

This study was aimed to develop teaching materials about chemical reaction rate which covered materials adapted to A-Level High School students of grade XI in Pioneer International Standard High School (RSMA-BI). The developmental research was adopting the instructional development model 4D which include four stages of development, namely define, design, develop, and disseminate. Instructional materials were written in English consist of seven topics titled: Reaction Rate Concept, The Exchange's Expressions, Rate Law and Reaction Order, Experimental Determination of a Rate Law, Reaction Mechanism, Theories of Reaction Rate, Factors Affecting Reaction Rate. Results of content validation from content experts obtained the average score of 3. 56 of 14 range of scores which means valid / good / decent. Test limited to high school students of RSBI obtained an average score of 3.35 (valid / good / decent). The results of the use of teaching materials obtained a score of 77.8 which is above the minimal passing grade (75). Therefore it can be concluded that the materials were feasible to be used in the classroom.Penelitian ini bertujuan untuk mengembangkan bahan ajar laju reaksi dengan cakupan materi yang disesuaikan dengan A-Level untuk siswa kelas XI Rintisan Sekolah Menengah Atas Bertaraf Internasional (RSMA-BI. Rancangan penelitian pengembangan mengadaptasi model pengembangan bahan ajar Model 4D yang meliputi empat tahap pengembangan, yaitu define, design, develop dan disseminate. Produk pengembangan adalah bahan ajar kimia RSMA-BI kelas XI materi laju reaksi yang ditulis dalam bahasa Inggris menggunakan pendekatan kontekstual. Bahan ajar terdiri atas empat bagian utama yaitu pendahuluan, materi, evaluasi dan penutup. Materi tersusun atas tujuh sub materi yaitu Reaction Rate Concept, The Rates Expressions, Rate Law and Reaction Order, Experimental Determination of a Rate Law, Reaction Mechanism, Theories of Reaction Rate, Factors Affecting Reaction Rate. Hasil validasi isi dari ahli materi diperoleh nilai rata-rata 3,56 dari rentang skor 1-4 dengan kriteria valid/baik/layak. Hasil uji terbatas pada siswa SMA RSBI diperoleh nilai rata-rata 3,35 dari rentang skor 1-4 dengan kriteria valid/baik/layak. Hasil uji penggunaan bahan ajar diperoleh skor sebesar 77,8. Skor ini diatas SKM (Skor Kelulusan Minimal) yaitu 75 sehingga dapat disimpulkan bahwa bahan ajar telah layak dan dapat digunakan dalam pembelajaran di kelas.


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