Det 19. Landsmøte i kjemi

Posterforedrag


Oversikt


P1-H: Femti år med organisk kjemi på NTH, Trondheim 1910-1960
Elisabeth Jacobsen

P2-Ka: Computational study of zeolite dealumination and formation of silanol nests
Stian Svelle, University of Oslo

P3-Ka: H-SAPO-5 as model catalyst in methanol-to-hydrocarbons (MTH) research: Does lower acid strength cause a shift in olefin formation mechanisms?
Marius Westgård Erichsen, University of Oslo

P4-Ka: Investigation of Reaction Network in Ethanol Steam Reforming over Ni/Mg-Al Catalyst: The Intermediates
Guangming Zeng, University of Oslo

P5-Ka: Synthesis and characterization of platinum-containing UiO-67 Zr-based metal organic framework
Sigurd Øien, University of Oslo

P6-Ka: Zeolite membranes for selective CO2-separation
Nelli Pfaff, University of Oslo

P7-Ka: A study of chain termination and propagation on 20%Co/CNT Fischer Tropsch catalyst
Jia Yang, NTNU

P8-Ka: Two step low temperature methanol synthesis
Klaus-J.Jens, Høgskolen i Telemark

P9-Ka: Synthetic Methods in Gold(III) Chemistry
Eirin Langseth, University of Oslo

P10-Km: A systematic approach to the calculation of Rydberg states
Clemens Woywod, University of Tromso, Chemistry Department, CTCC

P11-Km: First principles theory for the material constants
Anelli Marco, University of Tromsø

P12-O: Carotenoid as antireductants
Muhammad Zeeshan, Institute of Chemistry, Norwegian University of Science and Technology (NTNU)

P13-O: Synthesis of longest polyene with 27 double bonds
Muhammad Zeeshan, Institute of Chemistry, Norwegian University of Science and Technology (NTNU)

P14: Faggruppe for kjemiundervisning - Norsk kjemilærerforening
Kirsten Fiskum, Nasjonalt senter for naturfag i opplæringen - Naturfagsenteret

P15: Kjemifestival
Norsk Teknisk Museum/Universitetet i Oslo


Poster abstracts


P1-H

Femti år med organisk kjemi på NTH, Trondheim 1910-1960

Elisabeth Jacobsen

 I forbindelse med feiringen av professor Nils Andreas Sørensens 100-års fødselsdag 8. desember 2009 skrev noen av hans elever en minnebok, redigert av professorene Synnøve Liaaen Jensen, Ketil Motzfeldt og Thorleif Anthonsen. Boken ble lansert under en mottakelse i Realfagbiblioteket hvor en utstilling av instrumenter og gjenstander fra perioden også ble presentert. Utstillingen skal nå tas ned, og vi har gleden av å presentere litt av denne historien på Landsmøtet i kjemi 2011. Da undervisningen startet ved den nyopprettede Norges Tekniske Høyskole høsten 1910 var kjemiavdelingen organisert i fire institutter: Lab A Uorganisk kjemi, Lab B Organisk kjemi, Lab C Teknisk-uorganisk kjemi og Lab D Teknisk-organisk kjemi. Den første professor i organisk kjemi var Claus Nissen Riiber. Han var professor fra 1911 til 1936 og også rektor i perioden 1923-1925. Riiber som var utdannet ved Universitetet i Oslo, hadde arbeidet i industriell forskning i flere år. Hans forskning omfatter både teoretisk og praktisk virksomhet. Blant annet var han opptatt av optisk spaltning av threo- og erythro-3-fenyl-2,3-dihydroksipropansyre, og av alle isomerene av brom hydroksi-3-fenylpropansyre. I 1939 ble Nils Andreas Sørensen ansatt som meget ung professor (30 år) i organisk kjemi. Sørensen var utdannet på NTH (1933) og ble Dr. Techn. i 1937. I sine tidligste år som forsker var han opptatt av fargestoffer i marine organismer og av mutarotasjon i karbohydrater. Dette siste var temaet for hans doktorgrad. I en periode arbeidet han hos professor Richard Kuhn i Heidelberg med studier av fargestoffer i hummer, astaxanthin. Kuhn fikk Nobelprisen i kjemi, 1938, for sitt arbeide med karotenoider og vitaminer. Sørensen beholdt gjennom hele forskningskarrieren interessen for naturstoffkjemi, og er blitt mest kjent for sine studier av acetylenforbindelser i kurvblomster. Torger Bruun var også knyttet til instituttet som dosent. Han var også naturstoffkjemiker med terpenoider i lavarter som forskningsområde.


P2-Ka

Computational study of zeolite dealumination and formation of silanol nests

Stian Svelle

University of Oslo

Zeolites are porous catalytic materials - marvelous for the needs of petrochemical industry. In zeolites, aluminum will form both framework Brønsted and extra-framework Lewis acid sites and is thus responsible for the catalytic behavior of the material. Importantly, the distribution and density of the acid sites can be guided by steaming at high temperature, under which hydration reactions weaken the bonding between aluminum and the framework, eventually leading to the detachment of atoms creating vacancies like silanol nests. This process is referred to as dealumination, and plays a pivotal role in the practical application of zeolites as catalysts. For example, zeolite Y, which is employed in the catalytic cracking of heavy oil fractions, is typically dealuminated by steaming to reduce the density of acid sites before application. Herein, we present a detailed reaction mechanism for the dealumination process. The results are compared to the analogous process where silicon is removed from the framework (desilication).


P3-Ka

H-SAPO-5 as model catalyst in methanol-to-hydrocarbons (MTH) research: Does lower acid strength cause a shift in olefin formation mechanisms?

Marius Westgård Erichsen

University of Oslo 

As world oil reserves are decreasing, interest in utilisation of alternative feedstocks, such as natural gas and biomass, for production of petrochemicals is increasing. The conversion of methanol to hydrocarbons (MTH) represent a family of flexible processes for production of either light olefins or gasoline, depending on catalyst used and conditions employed. As methanol production from a variety of sources is well established, commercial interest in its conversion to higher value products is on the rise. A key issue in this family of processes, as in other catalytic processes, is product selectivity. While a large number of products can be produced from methanol over acidic catalysts, tuning the process to provide only a select group of products is highly desirable. This requires a high degree of insight into the reaction mechanisms and how it correlates with catalyst parameters. It has previously been found that MTH is an autocatalytic reaction. Olefin formation from methanol in wide-pore zeolites proceeds via continuous addition of methanol to an adsorbed pool of hydrocarbons, and subsequent elimination of olefins. In previously studied wide-pore zeolites, the dominant hydrocarbon pool species have been identified as methylbenzenes. In the present study, a wide-pore H-SAPO-5 material has been studied as an MTH catalyst. While co-feeding of benzene and methanol showed that some olefins can be produced from methylbenzene intermediates, transient isotopic labelling studies indicated that the reaction mechanism in this catalyst is shifted in favour of an alkene-based hydrocarbon pool. These findings hint at a significant shift in reaction mechanism when the acid strength of the catalyst is decreased, providing a vital piece for unravelling the puzzle of methanol conversion mechanisms over acidic catalysts.


P4-Ka

Investigation of Reaction Network in Ethanol Steam Reforming over Ni/Mg-Al Catalyst: The Intermediates

Guangming Zeng

University of Oslo

Catalytic steam reforming of ethanol is being considered as a promising and feasible process for renewable H2 (or syngas) production and facilitates the low carbon economy with the long-term potential to reduce pollutant emissions. Although the thermodynamics of ethanol steam reforming makes it appear as a simple reaction with very few side products, in kinetically controlled regimes, the reaction network can be quite complicated and heavily dependent on the catalyst system employed. Since the contribution of different reactions not only determines the selectivity and H2 yield that can be obtained but also directly impacts the catalyst stability (coking), it is critical to gain a comprehensive understanding of the reaction pathway involved. In this preliminary work, the possible by-products/intermediates involved in the ethanol steam reforming have been investigated as a function of temperature, H2O/C2H5OH molar ratio and time-on-stream through ethanol decomposition and steam reforming with/without catalyst. The results point to a complex reaction system that various previously proposed by-products/intermediates, such as C2H2, CH2O, C3H8, C6H6, in ethanol steam reforming were verified. Furthermore, TPO experiments of the spent catalysts demonstrate that at least two types of carbon, H-rich amorphous carbon and filamentous carbon, were deposited on the supported Ni catalyst, being governed by the temperature range as well as the H2O/C2H5OH molar ratio. Based on the extensive studies reported during the past decade, a reassessment was contributed to improve the possible reaction pathway.


P5-Ka

Synthesis and characterization of platinum-containing UiO-67 Zr-based metal organic framework

Sigurd Øien

University of Oslo

Metal organic frameworks (MOFs) are steadily becoming more attractive and promising materials for heterogeneous catalysis, due to their high internal surface area, stability and diversity[1]. The isoreticular Zr-based MOFs (the UiO-series) are among the most stable of these compounds, and has been shown to exhibit catalytic activity on modified linkers[2]. In this work, UiO-67 has been modified with bipyridine linkers and doped with K2PtCl4 and K2PtCl6 in a one-step synthesis to yield a crystalline product with a high surface area that is also stable in air after solvent removal. We are able to reduce platinum with hydrogen in the structure, as indicated by IR and UV/visible spectroscopies. This material is now characterized to establish whether the platinum is dispersed randomly in the pores or aligned to bipyridine. They will also be tested for catalytic/photocatalytic activity in processes such as CO oxidation, C-H bond activation and others. The synthesis method is currently being applied to other metal salts such as RuCl3 and RhCl3.

  1. J. Hafizovic et.al., Journal of the American Chemical Society 2008 130 (42), 13850-13851
  2. C. Wang et.al., Journal of the American Chemical Society 2011 133 (34), 13445-13454


P6-Ka

Zeolite membranes for selective CO2-separation

Nelli Pfaff

University of Oslo

 In order to reduce the anthropogenic emission of CO2, for instance in the coal-fired power plants, development of specific CO2 separation and capture technologies are required. A continuous separation process is the most convenient way, and also the most ecological method, especially if it can be carried out at the prevailing temperature and pressure. Membranes made of high thermal and chemical resistant materials, such as zeolites can work under these conditions. In addition zeolites have a well-defined pore size which makes them highly selective towards the diffusing molecules. Ultra-thin membranes with a high selectivity and high permeance can even be used for gas separation of CO2 from CH4. The scope of this project is to gain knowledge of diffusion, separation, and synthesis of membranes by using the CHA-type zeolite SSZ-13 with an estimated pore diameter of 3.7 × 4.2 Å (hydrated). For this application a clear solution will be used to obtain nanosized zeolite crystals, which are then going to be used for a two-step membrane preparation.


P7-Ka

A study of chain termination and propagation on 20%Co/CNT Fischer Tropsch catalyst

Jia Yang

NTNU

Fischer-Tropsch Synthesis aims at converting syngas to clean liquid fuel and therefore requires catalysts with high C5+ selectivity. At industry conditions, the C5+ selectivity may be influenced by several parameters due to the presence of liquid phases, for instance, α-olefin re-adsorption, diffusion effect for reactants and products and water partial pressure etc. [1-2] To study the intrinsic chain propagation/termination probability without the influence of above mentioned parameters, a catalyst consisting of 20%Co supported on carbon nanotubes (CNT) with a cobalt particle size at around 18 nm was chosen and tested under methanation conditions. The mechanism of chain initiation, propagation and termination will be analyzed, and the chain growth intermediates will be specially addressed.


P8-Ka

Two step low temperature methanol synthesis

Klaus-J. Jens

Høgskolen i Telemark

Methanol has been considered as one of the promising alternative fuels to petroleum[1]. Current methanol synthesis is the second largest scale process world-wide involving catalysis at high pressure and temperature. Methanol synthesis at low temperature would allow the

 process to be operated at lower pressure[2]. Low temperature methanol synthesis (LTMS) is reported for two catalyst systems, Ni carbonyl and Raney Ni based[3-5] and Cu chromite based[6]. LTMS based on biomass derived syn-gas feedstock requires the catalyst to be stable in the presence of feedstock byproducts such as water. This project is focusing on exploratory research to find water resistant LTMS catalyst. So far this target has not been reached. The LTMS reaction which proceeds through synthesis of Methyl formate (MF) as an intermediate employs alkali alkoxide as a catalyst in the first carbonylation step. Trial reactions based on Ni(CO)4 and Raney copper have been performed. Since Ni(CO)4 is very poisonous, we have set-up a closed system synthesizing Ni(CO)4 in situ using NiSO4 as precursor[7]. Another system based on Raney copper[8] is being investigated for hydrogenation of MF to methanol. Key words: low temperature methanol synthesis; Ni(CO)4; Raney copper; alkali alkoxide

  1. George A. Olah, «Beyond Oil and Gas: The Methanol Economy», Angewandte Chemie International Edition 44 (18) 2005.
  2. Jacob A. Moulijn et al., Chemical process technology, Chichester : Wiley, 2001.
  3. K. Li, D, Jiang, Journal of Molecular Catalysis A: Chemical 147 (1999) 125-130.
  4. S. Ohyama, Appl. Catal. A 313(2006) 58-62.
  5. E.S. Lee, K. Aika, Journal of Molecular Catalysis A: Chemical 141 (1999) 241-248.
  6. S.Ohyama, Topics in Catalysis Vol. 22, Nos. 3-4 2003.
  7. W.Manchot, H.Gall, Chem. Ber. 62, 678(1929).
  8. Y. Kokubu, K. Fujiwara, H. Ono, H. Sugawara, US Patent 6,028,119(2000).



P9-Ka

Synthetic Methods in Gold(III) Chemistry

Eirin Langseth

University of Oslo

The interest in organo-gold compounds continues to grow. Gold(III) complexes are being investigated as catalysts for organic transformations as well as tested as potential anti-cancer drugs [Arcadi Chem. Rev. 2008, 108, 3266, Gabbiani, Casini, Messori Gold Bulletin 2007, 40, 73]. Despite this wide-ranging interest in the properties of such complexes, the synthetic methods for preparing them are underdeveloped. AuCl2(tpy) (tpy=2-(4'-tolyl)pyridine) is an example of a compound that previously required the use of an organomercury reagent to achieve an acceptable yield with respect to gold [Parish, Wright, Pritchard J. Organomet. Chem. 2000, 596, 165]. Several gold(III) complexes with different bipyridine and pyridine ligands have now been prepared in our group using microwave heating and mercury-free conditions [Shaw, Tilset, Heyn, Jakobsen J. Coord. Chem. 2011, Accepted, Shaw, Ghosh, Törnroos, Wragg, Tilset, Swang, Heyn, Jakobsen Submitted].


P10-Km

A systematic approach to the calculation of Rydberg states

Clemens Woywod

University of Tromso, Chemistry Department, CTCC

The description of Rydberg states by the complete active space self-consistent field (CASSCF) electronic structure method is known to be a tricky business. In particular two problems are frequently encountered: (1) The simultaneous presence of valence and Rydberg excited states in the same energy region can potentially lead to artificial valence-Rydberg mixing in the electronic wave functions. (2) Rydberg states have a tendency to be difficult to converge. A successful wave function optimization requires a good starting guess and a well defined active orbital space. On the energy surface spanned by the configuration interaction (CI) and molecular orbital (MO) parameters, a Rydberg state often corresponds to a pronounced, but highly localized minimum. Therefore, in many cases the Rydberg orbitals will be undesirably eliminated from the active space during the CASSCF iterations. Only if the initial wave function represents a sufficiently good approximation of the target state and if the correct Rydberg functions are included in the active space will the designated solution be obtained. The questions are now how to provide an accurate starting wave function and how to derive the information for a selection of the active orbitals. A newly developed systematic approach for a consistent description of both valence and Rydberg excited states within the CASSCF electronic structure model is presented. By employing multiconfigurational second- and third-order perturbation theory methods based on CASSCF reference wave functions, the procedure is verified by comparison with spectroscopic results for the example molecules pyrazine [1], pyridine and butadiene. Particular attention is paid the to the relevance of valence excitations for the description of Rydberg states.

  1.  Woywod, C. and Papp, A. and Halasz, G. J. and Vibok, A., Theor. Chem. Acc. 125, 521 (2010).



P11-Km

First principles theory for the material constants

Anelli Marco

University of Tromsø

The interactions between matter and electromagnetic fields are commonly analyzed using the constitutive relations, which relate the applied electric and magnetic fields (E,B) to the response fields (D,H) through the material constants. Therefore, material constants (also known as constitutive tensors) describe the response of the matter to the external fields. In the case of a static perturbation, material constants are observable/measurable quantities, and they can been defined using multipole theory. In contrast, when a dynamic field is considered, multipole theory leads to origin-dependent expressions for the material constants, and thus do not correspond to physically acceptable observable quantities. There is therefore a need for origin-independent definitions of the material constants. Origin-independent expressions of the material constants have been derived by Raab and de Lange applying a transformed multipole theory. They have also derived expressions for the material constants based on a covariant formulation of the constitutive relations. Both these theories provide expressions of the material constants which are covariant, origin-independent and preserve the spatial invariance of the wave equations. In the dynamic case, a unique definitions of the material constants still do not exist, and the possibility of deriving unique definitions for these quantities is still unresolved. We will discuss our recent analysis of the problem, focusing on the pure electric and magnetic material constants, namely the electric permittivity and the inverse permeability. In particular, we will provide arguments in order to distinguish between the two possible definitions of the material constants proposed so far. An important part of our analysis will be how to relate the material constants to well-known measurable quantities. We propose that the absorption coefficient and the scattering amplitude, as defined in QED, can be expressed in terms of the electric permittivity, consistently with the definition provided by transformed multipole theory.


P12-O

Carotenoid as antireductants

Muhammad Zeeshan

Institute of Chemistry, Norwegian University of Science and Technology (NTNU)

The electron-rich carotenoids are prime examples for their electron donor property to reactive radicals. The reverse reaction, the uptake of electrons by Car, has not yet been observed in nature and is difficult to perform in the laboratory. Cyclic polyenes easily take up electrons (Birch reduction), but chain polyenes resist in electron transfer reactions. Carotenoids were forced to take up electrons by difficult chemical procedures (Na in high vacuum) or with methods requiring special instruments (electrochemistry, flash photolysis, pulse radiolysis). Nevertheless, it has been predicted theoretically that carotenoids could act favorably as electron acceptors. Recently, crocetindial has been reacted in a simple procedure with the electron donator alkaline DMSO = H3C(S=O)CH2– = DMSO– [1]. An immediate two-electron uptake reaction to crocetin dienolate was observed by a color change to blue.   We present now the synthesis of a series of dialdehydes (C10:3 to C50:19) and describe their electron uptake properties with regard to the chain length. Carbonyl carotenoids, like any other carotenoid, may act as antioxidants by releasing electrons. We demonstrate that carbonyl carotenoids also easily accept electrons; therefore, these carotenoids react as antireductants.    Acknowledgments:   This project is financially supported by the Higher Education Commission Pakistan (HEC) and the Norwegian Centre for International Cooperation in Higher Education (SIU).

  1. Øpstad CL, Sliwka HR, Partali V. Facile electron uptake by carotenoids under mild, non-radiative conditions: formation of carotenoid anions. European Journal of Organic Chemistry 2010; 4637–4641.



P13-O

Synthesis of longest polyene with 27 double bonds

Muhammad Zeeshan

Institute of Chemistry, Norwegian University of Science and Technology (NTNU)

 

Most carotenoids have 11 C=C bonds; the natural maxima is reached with 14 C=C bonds. Notwithstanding extending the π-system by increasing the number of double bonds beyond the natural boundary is a goal for theoretical and practical consideration. The λmax of polyenes increase asymptotically to the limiting value λ∞; in spite of many calculations λ∞ is still unknown. Polymer polyenes only show a partial conjugation of double bonds. Synthetic chain elongation is therefore the only way to sustain molecular calculations.  The synthesis of long-chain carotenoids under classical Wittig conditions is always accompanied with substantial decomposition. The purity of previously synthesized C60:19 can be questioned [1], a supposed C70:23 carotenoid decomposed at low temperatures under argon [2]. It is therefore likely that the limit for the classical carotenoid syntheses is reached with C60 or C70.  We have now found that the synthesis of long chain carotenoids can substantially be improved, when the Wittig reaction is performed under microwave irradiation. The microwave variant of the Wittig reaction allowed us to synthesize the longest carotenoid ever synthesized, the zeaxanthin derivate C80 with 27 double bonds. The synthesis, purity and spectroscopic properties of the zeaxanthin series will be presented from natural C40 to C50, C60, C70 and ultimate C80.

  1. Andersson PO, Gillbro T, Photophysics and dynamics of the lowest excited singlet state in long substituted polyenes with implications to the very long-chain limit. J. Chem. Phys. 1995; 103: 2509-2519.
  2. Broszeit G, Diepenbrock F, Hecht D, Martin HD, Strehblow HH, Vinylogous p-carotenes: generation, storage, and delocalization of charge in carotenoids. Liebigs Ann./Recueil  1997; 2205-2213.


P14

Faggruppe for kjemiundervisning - Norsk kjemilærerforening

Kirsten Fiskum

Nasjonalt senter for naturfag i opplæringen - Naturfagsenteret

For å styrke kjemifaget i norsk skole ønsker vi å etablere "Faggruppe for kjemiundervisning". Vårt mål er at dette skal bli en faggruppe i Norsk kjemisk selskap der hovedmålgruppen er de som er interesserte i formidling av kjemi.


P15

Kjemifestival

Kjemiåret

Norsk Teknisk Museum/Universitetet i Oslo

Fra 21.-29. november avholdes det Kjemifestival på Teknisk Museum i Oslo. Arrangementet er et samarbeid mellom Kjemiåret og Teknisk Museum, med finansiell støtte fra Forskningsrådet. I løpet av festivalen vil det avholdes et stort antall ulike aktiviteter myntet på skoleklasser, barnefamilier og generelt publikum.