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      Electrochemical routes for industrial synthesis

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          Abstract

          This review examines the reasons for increasing interest towards electrolyses by the chemical industry, reviews the electrochemical industries as most of them now exist, and provides a status report on the key technological advances which are occurring to meet present and future needs. Classical industries like those of chloroalkali, aluminium, p-aminophenol, adiponitrile, ethylene glycol, anthraquinone, perfluorinated products, glyoxylic acid and L-cysteine are initially covered. Considering the large amount of available publications in these topics of electrochemical engineering, the covered relevant information is treated at a scientific level, although in a simplified way. Then the paper deals with emerging inorganic and organic processes, e.g. electrosynthesis in ionic liquids and mediated electrochemical processes, and finishes by assessing what the future development trend might be given the electrochemical and non electrochemical competing influences. With this approach it is hoped to stimulate the interest of chemical engineers and scientists non-specialised in electrochemical routes, and to review some cutting edge research, particularly as far as electrosynthesis in ionic liquids is concerned.

          Translated abstract

          Esta revisão examina as razões que justificam um interesse crescente da indústria química pelos processos eletrolíticos. Reveem-se as indústrias químicas, nas quais compostos orgânicos e inorgânicos são processados e descrevem-se os avanços tecnológicos mais relevantes. Inicialmente, abordam-se processos bem estabelecidos, como as indústrias cloroalcalinas de produção de alumínio, p-aminofenol, adiponitrila, etileno glicol, antraquinona, produtos perfluorados, ácido glioxílico e L-cisteína. Face à grande quantidade de informação disponível, o assunto é tratado com base científica, mas de modo bastante simplificado. Posteriormente, descrevem-se processos orgânicos e inorgânicos emergentes, nomeadamente processos eletroquímicos mediados e síntese em líquidos iónicos. Estabelecem-se paralelos entre síntese química e síntese eletroquímica. Estimula-se o interesse nos processos de eletrossíntese, particularmente em líquidos iónicos, não desmerecendo a importância das vias puramente químicas de síntese orgânica e inorgânica.

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          Most cited references33

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          A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry

          We extend the spin-adapted density matrix renormalization group (DMRG) algorithm of McCulloch and Gulacsi [Europhys. Lett.57, 852 (2002)] to quantum chemical Hamiltonians. This involves two key modifications to the non-spin-adapted DMRG algorithm: the use of a quasi-density matrix to ensure that the renormalised DMRG states are eigenvalues of \(S^2\) , and the use of the Wigner-Eckart theorem to greatly reduce the overall storage and computational cost. We argue that the advantages of the spin-adapted DMRG algorithm are greatest for low spin states. Consequently, we also implement the singlet-embedding strategy of Nishino et al [Phys. Rev. E61, 3199 (2000)] which allows us to target high spin states as a component of a mixed system which is overall held in a singlet state. We evaluate our algorithm on benchmark calculations on the Fe\(_2\)S\(_2\) and Cr\(_2\) transition metal systems. By calculating the full spin ladder of Fe\(_2\)S\(_2\) , we show that the spin-adapted DMRG algorithm can target very closely spaced spin states. In addition, our calculations of Cr\(_2\) demonstrate that the spin-adapted algorithm requires only roughly half the number of renormalised DMRG states as the non-spin-adapted algorithm to obtain the same accuracy in the energy, thus yielding up to an order of magnitude increase in computational efficiency.
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            Electrochemical Aspects of Ionic Liquids

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              A survey of Ley's reactivity tuning in oligosaccharide synthesis.

              Ana Gomez (2011)
              This chapter summarizes the concepts and chemistry developed by Ley's group in relation to the relevance of reactivity tuning in oligosaccharide coupling reactions. The recognition that protecting groups affect the reactivity of glycosyl donors allowed Ley's group to make imaginative use of their 1,2-diacetal protecting groups. The combination of 1,2-diacetals with the presence of different anomeric leaving groups provides up to four different levels of reactivity. The exploitation of these reactivity levels in chemoselective glycosylation processes (reactivity tuning) has allowed the development of highly simplified routes to several complex oligosaccharides in step-wise or one-pot procedures.
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                Author and article information

                Journal
                jbchs
                Journal of the Brazilian Chemical Society
                J. Braz. Chem. Soc.
                Sociedade Brasileira de Química (São Paulo, SP, Brazil )
                0103-5053
                1678-4790
                2009
                : 20
                : 3
                : 387-406
                Affiliations
                [01] Lisboa orgnameTU Lisbon orgdiv1Instituto Superior Técnico orgdiv2DEQB Portugal
                Article
                S0103-50532009000300002 S0103-5053(09)02000302
                10.1590/S0103-50532009000300002
                41335ecd-822d-4246-9aba-0e5ea48992e6

                This work is licensed under a Creative Commons Attribution 4.0 International License.

                History
                : 22 April 2008
                : 06 February 2009
                Page count
                Figures: 0, Tables: 0, Equations: 0, References: 230, Pages: 20
                Product

                SciELO Brazil

                Categories
                Reviews

                electrochemical synthesis,emerging inorganic processes,scale-up electroorganic processes,organic chemicals,ionic liquids

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