792 resultados para Interval exchange transformations


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The porous mixed oxide SiO2/TiO2/Sb2O5 obtained by the sol-gel processing method presented a good ion exchange property and a high exchange capacity towards the Li+, Na+ and K+ ions. In the H+/M+ ion exchange process, the H+ / Na+ could be described as presenting an ideal character. The ion exchange equilibria of Li+ and K+ were quantitatively described with the help of the model of fixed tetradentate centers. The results of simulation evidence that for the H+ / Li+ exchange the usual situation takes place: the affinity of the material to the Li+ ions is decreased with increasing the degree of ion exchange. On the contrary, for K+ the effects of positive cooperativity, that facilitate the H+ / K+ exchange, were revealed.

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Interest to hole-doped mixed-valence manganite perovskites is connected to the ‘colossal’ magnetoresistance. This effect or huge drop of the resistivity, ρ, in external magnetic field, B, attains usually the maximum value near the ferromagnetic Curie temperature, TC. In this thesis are investigated conductivity mechanisms and magnetic properties of the manganite perovskite compounds LaMnO3+, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1- xSrxMn1-yFeyO3. When the present work was started the key role of the phase separation and its influence on the properties of the colossal magnetoresistive materials were not clear. Our main results are based on temperature dependencies of the magnetoresistance and magnetothermopower, investigated in the temperature interval of 4.2 - 300 K in magnetic fields up to 10 T. The magnetization was studied in the same temperature range in weak (up to 0.1 T) magnetic fields. LaMnO3+δ is the parent compound for preparation of the hole-doped CMR materials. The dependences of such parameters as the Curie temperature, TC, the Coulomb gap, Δ, the rigid gap, γ, and the localization radius, a, on pressure, p, are observed in LaMnO3+δ. It has been established that the dependences above can be interpreted by increase of the electron bandwidth and decrease of the polaron potential well when p is increased. Generally, pressure stimulates delocalization of the electrons in LaMnO3+δ. Doping of LaMnO3 with Ca, leading to La1-xCaxMnO3, changes the Mn3+/Mn4+ ratio significantly and brings an additional disorder to the crystal lattice. Phase separation in a form of mixture of the ferromagnetic and the spin glass phases was observed and investigated in La1- xCaxMnO3 at x between 0 and 0.4. Influence of the replacement of Mn by Fe is studied in La0.7Ca0.3Mn1−yFeyO3 and La0.7Sr0.3Mn1−yFeyO3. Asymmetry of the soft Coulomb gap and of the rigid gap in the density of localized states, small shift of the centre of the gaps with respect to the Fermi level and cubic asymmetry of the density of states are obtained in La0.7Ca0.3Mn1−yFeyO3. Damping of TC with y is connected to breaking of the double-exchange interaction by doping with Fe, whereas the irreversibility and the critical behavior of the magnetic susceptibility are determined by the phase separation and the frustrated magnetic state of La0.7Sr0.3Mn1−yFeyO3.

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Växtoljor som utgör en förnybar naturresurs används som sådana eller i modifierade former i många industriella processer, som är av stor betydelse för vårt vardagliga liv. Växtoljor används i livsmedel, i kemiska och farmaceutiska produkter, i textilindustrin, för framställning av färgämnen och beläggningsmaterial samt som miljövänliga bränslekomponenter. Fetter och oljor hör till de äldsta kemiska komponenterna som utnyttjas av människan. De består huvudsakligen av glycerolestrar och fettsyror. Fetter och oljor har typiskt en kolkedja med kol-koldubbelbindningar samt karboxyl- och estergrupper, som kan genom hydrering eller dekarboxylering konverteras till nyttiga och miljövänliga produkter med hjälp av ädelmetallkatalysatorer. Aktivt kol (C) används som bärare på katalysatorerna. Väteaddition, d.v.s. hydrering av växtoljor har varit föremål för omfattande forskning i över hundra års tid. Hydreringen är en viktig process, för den tillämpas på produktion av fetter och margarin. Omättade fettsyror hydreras traditionellt på nickelbaserade heterogena katalysatorer. Samtidigt med en partiell hydrering av fettsyrorna och fettsyraestrarna som har två dubbelbindningar pågår också isomeringsreaktioner, vilka ger cis- och transisomerer av reaktantmolekylerna. Den största nackdelen med nickelkatalysatorerna är deras giftighet samt bildning av ohälsosamma transisomerer i reaktionsprodukterna. Dessutom deaktiveras nickelkatalysatorn snabbt p.g.a. att nickeltvålar bildas i reaktionsblandningen. Platinabaserade katalysatorer lider däremot inte av dessa begränsningar. Metaller i platinagruppen i det periodiska systemet studerades i detalj för att avslöja kinetiska effekter i hydreringen av cis-metyloleat. Palladium, rutenium, rhodium, platina och iridium användes som katalytiska metaller. Metallhalten på aktivkolbärare var 1 vikt-%. De olika platinametallerna undersöktes för att kartlägga konkurrerande hydrerings- och isomeringsrutter på metallerna. Det visade sig att metallerna i andra raden av det periodiska systemet (Ru, Rh, Pd) är aktivare i isomeringsprocesserna, medan metallerna i tredje raden (Ir, Pt) har en lägre aktivitet. Pd/C valdes bland platinametallerna, för att den är attraktiv ur ekonomisk synvinkel och den är mycket aktiv och selektiv, speciellt jämfört med nickel. Tyngdpunkten i arbetet var utvecklingen av en alternativ, palladiumbaserad hydreringsteknologi som skulle ersätta den traditionella teknologin som är baserad på användningen av nickelkatalysatorer. Palladiumbaserade katalysatorer kan återcirkuleras, de är aktivare och mera resistenta mot syror och de bildar mindre mängder av skadliga transisomerer. För att denna teknologi skall bli ekonomiskt hållbar och konkurrenskraftig, måste den basera sig på de bästa möjliga katalysatorerna, vilket innebär att en optimal kombination av hög aktivitet och selektivitet samt en lång livstid för katalysatorn krävs. Därför inkluderades teknologiska aspekter kraftigt i forskningen. Mycket arbete satsades på design av palladium på en mesoporös kolbärare och undersökning av korrelationerna mellan katalysatorns egenskaper och dess aktivitet i isomeriseringsreaktionerna och i hydreringen av kol-koldubbelbindningarna i reaktantmolekylen. Katalysatorerna karakteriserades med många fysikaliska och kemiska metoder (transmissionselektronmikroskopi (TEM), röntgendiffraktion (XRD), röntgenfotoelektronspektroskopi (XPS), temperaturprogrammerad reduktion (TPR), temperaturprogrammerad desorption (TPD) av kolmonoxid, kemisorption av kolmonoxid, fysisorption av kväve). Temperaturens, vätetryckets och katalysatorkoncentrationens inverkan på fettsyra- och isomersammansättningen hos de hydrerade oljorna bestämdes under kinetiska betingelser, i frånvaro av massöverföringseffekter. Syreavspjälkning genom fullständig dekarboxylering av karboxylgruppen i fettsyramolekylen är det hittills bästa sättet att framställa miljövänlig dieselolja, eftersom linjära paraffiner fås som reaktionsprodukter och en tillsats av dyr vätgas undviks. Deoxygeneringen undersöktes systematiskt på en Pd/C-katalysator (Sibunit) genom att använda mättade fettsyror C16-C20 och C22 som råvara. Produktmolekylen blev en dieselliknande kolvätemolekyl, med en kolatom färre än i utgångsmolekylen. Lika stora dekarboxyleringshastigheter observerades för rena, mättade fettsyror. En jämförelse av deoxygenereringshastigheterna för stearin-, olein- och linolsyra som råvara vid 300oC i närvaro av 1-volymprocent väte på mesoporös Pd/C (Sibunit) avslöjade att katalysatorns aktivitet och selektivitet ökade med en ökande mättningsgrad av reaktantmolekylen. Då stearinsyra användes som utgångsmolekyl, bestod huvudprodukterna av önskade C17-kolväten, medan mängden av aromatiska C17-komponenter ökade, då olein- och linolsyra användes som utgångsmolekyler. Katalysatordeaktiveringen var relativt påfallande vid deoxygeneringen av linolsyra så att endast 3% av fettsyrorna omsattes till produkter i 330 min. Deaktiveringen orsakades av aromatiska C17-komponenter samt av fettsyradimerer, som bildades via en Diels-Alderreaktion. Hydreringen av omättade fettsyror kan därför rekommenderas som ett primärt kemiskt steg i framställningen av miljövänliga dieselprodukter. Målet var också att öka förståelsen av palladiummetallernas roll i nanoskala, speciellt effekten av metallpartiklarna i katalytisk hydrering och deoxygenering. Pd/C-katalysatorer med lika stora halter av Pd syntetiserades och metallens dispersion på bärarmaterialet varierades systematiskt genom en kontrollerad uppväxt av palladiumnanopartiklar på aktiv kolbärare. Metalldispersionens effekt på hydrerings-hastigheten och cis-transförhållandet undersöktes i detalj. En optimal metalldispersion som gav den högsta dekarboxyleringshastigheten hittades. Massöverföringens inverkan på reaktionens hastighet studerades experimentellt och temperaturprogrammerad desorption av kolmonoxid från katalysatorytan undersöktes ingående. Hydrering av växtoljor genomfördes under satsvisa och kontinuerliga betingelser. Både finfördelat Pd/C och katalysatorgranulat användes i experimenten. Ett av målen med arbetet var uppskalningen av hydreringsprocesserna. Med tanke på stora produktionsvolymer var det logiskt att undersöka kontinuerliga hydrerings- och dekarboxyleringsteknologier. En kontinuerlig packad bäddreaktor studerades i laboratorieskala, vilket gav viktig information om katalysatorns långtidsstabilitet och deaktivering. Effekten av rena fettsyror och triglycerider som råvara samt metallpartikelstorleken och palladiumhalten studerades med hjälp av den kontinuerliga reaktorn. Produktionskapaciteten som erhölls med satsvis och kontinuerlig drift jämfördes. Dekarboxyleringen av stearinsyra undersöktes också i en kontinuerlig packad bädd. Omsättningsgraden blev 15% för en stabil katalysator.

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Ecophysiological studies under semi-controlled conditions in nurseries and greenhouses are essential to enable the use of native species to recover degraded areas and for commercial planting. Talisia subalbens (Mart) Radlk, 'cascudo', is a native fruiting species of the Cerrado on the verge of extinction. The ecophysiological performance of this species was evaluated in nursery conditions under different levels of shading (full sunshine, 30%, 50% and 70%). Initial growth, biomass allocation, gas exchange and chlorophyll content of the plants were analyzed. Full sunshine cultivated plants showed a higher accumulation of total, shoot, and root dry biomass. There was no significant difference in the root/shoot ratio among the treatments. Seedlings cultivated under full sunshine and 30% shading showed higher values for height, basal diameter, and leaf area. Differences in stomata conductance and photosynthesis rate were not observed among the different shading levels. Plants cultivated under 70% of shading had higher contents of chlorophyll a, b, and total. During the initial phase with higher levels of radiation were fundamental for the development of T. subalbens seedlings.

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ABSTRACT The Paratudo (Tabebuia aurea) is a species occurring in the Pantanal of Miranda, Mato Grosso do Sul, Brazil, an area characterized by seasonal flooding. To evaluate the tolerance of this plant to flooding, plants aged four months were grown in flooded soil and in non-flooded soil (control group). Stomatal conductance, transpiration and CO2 assimilation were measured during the stress (48 days) and recovery (11 days) period, totalling 59 days. The values of stomatal conductance of the control group and stressed plants at the beginning of the flooded were 0.33 mol m-2s-1 and reached 0.02 mol m-2 s-1 (46th day) at the end of this event. For the transpiration parameter, the initial rate was 3.1 mol m s-1, and the final rate reached 0.2 or 0.3 mol m-2 s-1 (47/48 th day). The initial photosynthesis rate was 8.9 mmol m-2s-1 and oscillated after the sixth day, and the rate reached zero on the 48th day. When the photosynthesis rate reached zero, the potted plants were dried, and the rate was analyzed (11th day). The following values were obtained for dried plants: stomatal conductance = 0.26 mol m-2 s-1, transpiration rate = 2.5 mol m-2 s-1 and photosynthesis rate = 7.8 mmol m-2 s-1. Flooded soil reduced photosynthesis and stomatal conductance, leading to the hypertrophy of the lenticels. These parameters recovered and after this period, and plants exhibited tolerance to flooding stress by reducing their physiological activities.

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Supply chains are becoming increasingly dependent on information ex-change in today’s world, and any disruption can cause severe repercus-sions to the flow of materials in the chain. The speed, accuracy and amount of information are key factors. The aim in this thesis is to address a gap in the research by focusing on information exchange and the risks related to it in a multimodal wood supply chain operating between the Baltic States and Finland. The study involved interviewing people engaged in logistics management in the supply chain in question. The main risk the interviewees identified arose from the sea logistics system, which held a lot of different kinds of information. The threat of breakdown in the Internet connection was also found to hinder the operations significantly. A vulnerability analysis was carried out in order to identify the main actors and channels of infor-mation flow in the supply chain. The analysis revealed that the most important and therefore most vulnerable information-exchange channels were those linking the terminal superintendent, the operative managers and the mill managers. The study gives a holistic picture of the investigated supply chain. Information-exchange-related risks varied greatly. One of the most frequently mentioned was the risk of information inaccuracy, which was usually due to the fact that those in charge of the various functions did not fully understand the consequences for the entire chain.

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The development of new technologies to supplement fossil resources has led to a growing interest in the utilization of alternative routes. Biomass is a rich renewable feedstock for producing fine chemicals, polymers, and a variety of commodities replacing petroleumderived chemicals. Transformation of biomass into diverse valuable chemicals is the key concept of a biorefinery. Catalytic conversion of biomass, which reduces the use of toxic chemicals is one of the important approaches to improve the profitability of biorefineries. Utilization of gold catalysts allows conducting reactions under environmentally-friendly conditions, with a high catalytic activity and selectivity. Gold-catalyzed valorization of several biomass-derived compounds as an alternative approach to the existing technologies was studied in this work. Isomerization of linoleic acid via double bond migration towards biologically active conjugated linoleic acid isomers (CLA) was investigated. The activity and selectivity of various gold catalysts towards cis-9,trans-11-CLA and trans-10,cis-12-CLA were investigated in a semi-batch reactor, showing that the yield of the desired products varied, depending on the catalyst support. The structure sensitivity in the selective oxidation of arabinose was demonstrated using a series of gold catalysts with different Au cluster sizes in a shaker reactor operating in a semibatch mode. The gas-phase selective oxidation of ethanol was studied and the influence of the catalyst support on the catalytic performance was investigated. The selective oxidation of the lignan hydroxymatairesinol (HMR), extracted from the Norway spruce (Picea abies) knots, to the lignan oxomatairesinol (oxoMAT) was extensively investigated. The influence of the reaction conditions and catalyst properties on the yield of oxoMAT was evaluated. In particular, the structure sensitivity of the reaction was demonstrated. The catalyst deactivation and regeneration procedures were studied. The reaction kinetics and mechanism were advanced.

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Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ≥ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore® membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

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This thesis examines the impact of foreign exchange rate volatility to the extent of use of foreign currency derivatives. Especially the focus is on the impacts of 2008 global financial crisis. The crisis increased risk level in the capital markets greatly. The change in the currency derivatives use is analyzed by comparing means between different periods and in addition, by linear regression that enables to analyze the explanatory power of the model. The research data consists of financial statements figures from fiscal years 2006-2011 published by firms operating in traditional Finnish industrial sectors. Volatilities of the chosen three currency pairs is calculated from the daily fixing rates of ECB. Based on the volatility the sample period is divided into three sub-periods. The results suggest that increased FX market volatility did not increase the use foreign currency derivatives. Furthermore, the increased foreign exchange rate volatility did not increase the power of linear regression model to estimate the use foreign currency derivatives compared to previous studies.

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The behavioural finance literature expects systematic and significant deviations from efficiency to persist in securities markets due to behavioural and cognitive biases of investors. These behavioural models attempt to explain the coexistence of intermediate-term momentum and long-term reversals in stock returns based on the systematic violations of rational behaviour of investors. The study investigates the anchoring bias of investors and the profitability of the 52-week momentum strategy (GH henceforward). The relatively highly volatile OMX Helsinki stock exchange is a suitable market for examining the momentum effect, since international investors tend to realise their positions first from the furthest security markets by the time of market turbulence. Empirical data is collected from Thomson Reuters Datastream and the OMX Nordic website. The objective of the study is to provide a throughout research by formulating a self-financing GH momentum portfolio. First, the seasonality of the strategy is examined by taking the January effect into account and researching abnormal returns in long-term. The results indicate that the GH strategy is subject to significantly negative revenues in January, but the strategy is not prone to reversals in long-term. Then the predictive proxies of momentum returns are investigated in terms of acquisition prices and 52-week high statistics as anchors. The results show that the acquisition prices do not have explanatory power over the GH strategy’s abnormal returns. Finally, the efficacy of the GH strategy is examined after taking transaction costs into account, finding that the robust abnormal returns remain statistically significant despite the transaction costs. As a conclusion, the relative distance between a stock’s current price and its 52-week high statistic explains the profits of momentum investing to a high degree. The results indicate that intermediateterm momentum and long-term reversals are separate phenomena. This presents a challenge to current behavioural theories, which model these aspects of stock returns as subsequent components of how securities markets respond to relevant information.

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The electrocardiography (ECG) QT interval is influenced by fluctuations in heart rate (HR) what may lead to misinterpretation of its length. Considering that alterations in QT interval length reflect abnormalities of the ventricular repolarisation which predispose to occurrence of arrhythmias, this variable must be properly evaluated. The aim of this work is to determine which method of correcting the QT interval is the most appropriate for dogs regarding different ranges of normal HR (different breeds). Healthy adult dogs (n=130; German Shepherd, Boxer, Pit Bull Terrier, and Poodle) were submitted to ECG examination and QT intervals were determined in triplicates from the bipolar limb II lead and corrected for the effects of HR through the application of three published formulae involving quadratic, cubic or linear regression. The mean corrected QT values (QTc) obtained using the diverse formulae were significantly different (ρ<0.05), while those derived according to the equation QTcV = QT + 0.087(1- RR) were the most consistent (linear regression). QTcV values were strongly correlated (r=0.83) with the QT interval and showed a coefficient of variation of 8.37% and a 95% confidence interval of 0.22-0.23 s. Owing to its simplicity and reliability, the QTcV was considered the most appropriate to be used for the correction of QT interval in dogs.

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Nowadays biomass transformation has a great potential for the synthesis of value-added compounds with a wide range of applications. Terpenoids, extracted from biomass, are inexpensive and renewable raw materials which often have a biological activity and are widely used as important organic platform molecules in the development of new medicines as well as in the synthesis of fine chemicals and intermediates. At the same time, special attention is devoted to the application of gold catalysts to fine chemical synthesis due to their outstanding activity and/or selectivity for transformations of complex organic compounds. Conversion of renewable terpenoids in the presence of gold nanoparticles is one of the new and promising directions in the transformation of biomass to valuable chemicals. In the doctoral thesis, different kinds of natural terpenoids, such as α-pinene, myrtenol and carvone were selected as starting materials. Gold catalysts were utilized for the promising routes of these compounds transformation. Investigation of selective α-pinene isomerization to camphene, which is an important step in an industrial process towards the synthesis of camphor as well as other valuable substrates for the pharmaceutical industry, was performed. A high activity of heterogeneous gold catalysts in the Wagner-Meerwein rearrangement was demonstrated for the first time. Gold on alumina carrier was found to reach the α-pinene isomerization conversion up to 99.9% and the selectivity of 60-80%, thus making this catalyst very promising from an industrial viewpoint. A detailed investigation of kinetic regularities including catalyst deactivation during the reaction was performed. The one-pot terpene alcohol amination, which is a promising approach to the synthesis of valuable complex amines having specific physiological properties, was investigated. The general regularities of the one-pot natural myrtenol amination in the presence of gold catalysts as well as a correlation between catalytic activity, catalyst redox treatment and the support nature were obtained. Catalytic activity and product distribution were shown to be strongly dependent on the support properties, namely acidity and basicity. The gold-zirconia (Au/ZrO2) catalyst pretreated under oxidizing atmosphere was observed to be rather active, resulting in the total conversion of myrtenol and the selectivity to the corresponding amine of about 53%. The reaction kinetics was modelled based on the mechanistic considerations with the catalyst deactivation step incorporated in the mechanism. Carvone hydrogenation over a gold catalyst was studied with the general idea of investigating both the activity of gold catalysts in competitive hydrogenation of different functional groups and developing an approach to the synthesis of valuable carvone derivatives. Gold was found to promote stereo- and chemoselective carvone hydrogenation to dihydrocarvone with a predominant formation of the trans-isomer, which generally is a novel synthetic method for an industrially valuable dihydrocarvone. The solvent effect on the catalytic activity as well as on the ratio between trans- and cis-dihydrocarvone was evaluated.