Delineamentos experimentais eficientes para estudos de cinética química

In this paper we show how to obtain efficient designs of experiments for fitting Michaelis-Menten and Hill equations useful in chemical studies. The search of exact D-optimal designs by using local and pseudo-Bayesian approaches is considered. Optimal designs were compared to those commonly used in practice using an efficiency measure and theoretical standard errors of the kinetic parameter estimates. In conclusion, the D-optimal designs based on the Hill equation proved efficient for estimating the parameters of both models. Furthermore, these are promising with respect to practical issues, allowing efficient estimation as well as goodness-of-fit tests and comparisons between some kinetic models.

Polymeeripinnoitteen aiheuttamat itseherätteiset värähtelyt nipillisessä telasysteemissä

Lukuisissa teollisuussovelluksissa materiaalien, kuten paperin ja teräslevyjen, muokkaamiseen käytettävät pyörivät nippitelat kärsivät aina erilaisten herätteiden synnyttämistä mekaanisista värähtelyistä, jotka voivat aiheuttaa virheitä valmistettaviin tuotteisiin. Tässä työssä tutkittiin viskoelastisia polymeerejä ja polymeeripinnoitteen nipilliseen telasysteemiin synnyttämiä haitallisia itseherätteisiä värähtelyjä. Työn polymeerejä käsittelevässä kirjallisuusosassa luotiin katsaus amorfisten polymeerien fysikaalisiin ominaisuuksiin. Kokeellisessa osuudessa tutkittiin tarkemmin kahden amorfisen telapinnoitepolymeerin termoreologisia ja mekaanisia ominaisuuksia suoritettujen DMTA-mittausten perusteella. Sovittamalla toisen polymeerin master-käyrään yleistetty lineaarisen standardiaineen malli saatiin selville polymeerin mekaaniset parametrit ja approksimaatio sen relaksaatiospektrille. Telapinnoitteen nipilliseen systeemiin synnyttämiä itseherätteisiä värähtelyjä ja niiden seurauksia tarkasteltiin kahdelle telalle ja polymeeripinnoitteelle kehitetyn analyyttisen mallin ja numeeristen laskujen avulla. Pinnoite mallinnettiin lineaarisen standardiaineen mukaisesti. Telasysteemin parametrit määritettiin DMTA-mittaustuloksista ja systeemiä vastaavasta koelaitteesta kokeellisella moodianalyysillä ja elementtimenetelmällä. Numeerisesta stabiilisuusanalyysistä ja liikeyhtälöiden integroinneista saadut tulokset kertovat telapinnoitteen aaltomaisista deformaatiomuodoista ja niiden synnyttämistä taajuusalueittain esiintyvistä epästabiileista värähtelyistä. Telasysteemi on epästabiili pinnoitedeformaatiokuvion systeemiin aiheuttaman herätevoiman taajuuden ollessa lähellä systeemin korkeampaa ominaistaajuutta. Numeerisista tuloksista voitiin ennustaa nopean ja hitaan barringin olemassaolo.

Stability constants and thermodynamic parameters of cadmium complexes with sulfonamides and cephapirin

Stability constant (log beta) and thermodynamic parameters of Cd2+ complexes with sulfonamide and cephapirin were determined by Polarographic technique at pH = 7.30 ± 0.01 and µ = 1.0 M KNO3 at 250°C. The sulfonamides were sulfadiazine, sulfisoxazole, sulfamethaxazole, sulfamethazine, sulfathiazole, sulfacetamide and sulfanilamide used as primary ligands and cephapirin as secondary ligand. Cd2+ formed 1:1:1, 1:2:1 and 1:1:2 complexes. The nature of electrode processes were reversible and diffusion controlled. The stability constants and thermodynamic parameters (deltaG, deltaH and deltaS) were determined. The formation of the metal complexes has been found to be spontaneous, exothermic in nature, and entropically unfavourable at higher temperature.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Estimation of standard enthalpy of formation of alkanes in gaseous state by calculating size, structural and electronic parameters in the molecules

A quantitative analysis is made on the correlation ship of thermodynamic property, i.e., standard enthalpy of formation (ΔH fº) with Kier's molecular connectivity index(¹Xv),vander waal's volume (Vw) electrotopological state index (E) and refractotopological state index (R) in gaseous state of alkanes. The regression analysis reveals a significant linear correlation of standard enthalpy of formation (ΔH fº) with ¹Xv, Vw, E and R. The equations obtained by regression analysis may be used to estimate standard enthalpy of formation (ΔH fº) of alkanes in gaseous state.

Automated, adaptive methods for forest inventory

Forest inventories are used to estimate forest characteristics and the condition of forest for many different applications: operational tree logging for forest industry, forest health state estimation, carbon balance estimation, land-cover and land use analysis in order to avoid forest degradation etc. Recent inventory methods are strongly based on remote sensing data combined with field sample measurements, which are used to define estimates covering the whole area of interest. Remote sensing data from satellites, aerial photographs or aerial laser scannings are used, depending on the scale of inventory. To be applicable in operational use, forest inventory methods need to be easily adjusted to local conditions of the study area at hand. All the data handling and parameter tuning should be objective and automated as much as possible. The methods also need to be robust when applied to different forest types. Since there generally are no extensive direct physical models connecting the remote sensing data from different sources to the forest parameters that are estimated, mathematical estimation models are of "black-box" type, connecting the independent auxiliary data to dependent response data with linear or nonlinear arbitrary models. To avoid redundant complexity and over-fitting of the model, which is based on up to hundreds of possibly collinear variables extracted from the auxiliary data, variable selection is needed. To connect the auxiliary data to the inventory parameters that are estimated, field work must be performed. In larger study areas with dense forests, field work is expensive, and should therefore be minimized. To get cost-efficient inventories, field work could partly be replaced with information from formerly measured sites, databases. The work in this thesis is devoted to the development of automated, adaptive computation methods for aerial forest inventory. The mathematical model parameter definition steps are automated, and the cost-efficiency is improved by setting up a procedure that utilizes databases in the estimation of new area characteristics.

Field Weakening, Parameters and Operation Range of the Permanent Magnet Traction Motors

The main focus of this thesis is to define the field weakening point of permanent magnet synchronous machine with embedded magnets in traction applications. Along with the thesis a modelling program is made to help the designer to define the field weakening point in practical applications. The thesis utilizes the equations based on the current angle. These equations can be derived from the vector diagram of permanent magnet synchronous machine. The design parameters of the machine are: The maximum rotational speed, saliency ratio, maximum induced voltage and characteristic current. The main result of the thesis is finding out the rated rotational speed, from which the field weakening starts. The action of the machine is estimated at a wide speed range and the changes of machine parameters are examined.

NON-DESTRUCTIVE ANALYSIS OF THE ROOT SYSTEM AND TREE GROWTH PARAMETERS

ABSTRACT The productivity of Eucalyptus at plantations is increasing and has undergone a variety of research studies. Most research is dealing with simple dendrometric variables like the DBH (diameter at breast height) and tree height, or more complex variables including crown parameters or variables concerning photosynthesis. The root systems, however, have not been well analyzed yet. The objective of the study was to analyze the root system with a non-destructive method and to evaluate possible correlations with dendrometric variables of the tree (DBH, height, crown expansion). A small experimental plantation with 39 even-aged, 6-year-old trees of Eucalyptus grandis x urophylla has been investigated within this study. The results of the study show the highest correlation of the root areas with the crown expansion. In general, the root area shows a significantly bigger expansion in the eucalypt plantation than the tree crown, with a more homogeneous development.

Effects of thermal environment and supplementation levels on the physiological parameters of moxotó goats in confined and semi-confined rising systems

The objective of this work was to determine the effect of environmental variables and supplementation levels on physiological parameters of Moxotó goats in confined and semi-confined rising systems, in the Brazilian semi-arid region. The semi-confined individuals were kept on a grass based diet during the day and arrested in the end of the afternoon. The confined animals were kept in a management center, receiving two diets composed by forage cactus and maniçoba hay into two different levels (0.5 and 1.5% of the body weight). Inside the management center and in the external environment the environmental comfort parameters were set high during the afternoon period characterizing a situation of thermal discomfort for the animals. During the morning the semi-confined animals presented an average respiratory frequency (69.5 mov min-1) and rectal temperature (39.5 ºC) higher than the confined ones (62.6 mov min-1 and 39.0 ºC, respectively). The confined and semi-confined animals were able to maintain their rectal temperature within normal limits, with increase in the cardiac beatings rate and respiratory frequency. The greater percentage of the used supplementations (1.5%) seemed to increase rectal temperature in the two studied rising systems.

Application of simulated annealing in simulation and optimization of drying process of Zea mays malt

Kinetic simulation and drying process optimization of corn malt by Simulated Annealing (SA) for estimation of temperature and time parameters in order to preserve maximum amylase activity in the obtained product are presented here. Germinated corn seeds were dried at 54-76 °C in a convective dryer, with occasional measurement of moisture content and enzymatic activity. The experimental data obtained were submitted to modeling. Simulation and optimization of the drying process were made by using the SA method, a randomized improvement algorithm, analogous to the simulated annealing process. Results showed that seeds were best dried between 3h and 5h. Among the models used in this work, the kinetic model of water diffusion into corn seeds showed the best fitting. Drying temperature and time showed a square influence on the enzymatic activity. Optimization through SA showed the best condition at 54 ºC and between 5.6h and 6.4h of drying. Values of specific activity in the corn malt were found between 5.26±0.06 SKB/mg and 15.69±0,10% of remaining moisture.

Behavior, performance and physiological parameters of pigs reared in deep bedding

An experiment was conducted to evaluate the behavior, performance and physiological parameters of pigs in different production systems. Twenty four animals in the growth phase were distributed in a randomized block design in three treatments: T1 - concrete floor, T2 - deep bedding with wood shaving, and T3 - deep bedding with coffee husks. The behavioral study was carried out by observing the animal behavior for an uninterrupted period of eight hours throughout seven weeks. The proportions of time spent in each behavior were characterized using the frequency histogram composition. Environmental (IBGTH), physiological (rectal and skin temperature and respiratory rate) and performance (weight gain, feed intake and feed conversion) parameters were measured in animals during the period. The production systems of deep bedding showed higher values of IBGTH. There was no effect of production systems evaluated on the performance parameters. Rectal temperature was higher in animals reared on deep bedding with coffee husks in relation to the concrete floor. The use of deep bedding benefited the behavior of piglets in the growth phase and it reduced the agonistic behavior among individuals.

Spatial variability of yield and other parameters associated with pear trees

In the last few years, precision agriculture has become commonly used with many crops, particularly cereals, and there is also interest in precision horticulture. Pear is a seasonal fruit and well appreciated by Brazilian people, although it is mostly imported. Brazilian farmers are nowadays trying to increase pear production. Thus, this research aimed at mapping the yield of pear trees in order to study the spatial variability of yield as well as its comparison with spatial variability of soil and plant attributes. The experimental field had 146 pear trees, variety 'Pêra d'água', distributed on a 1.24 ha. Four harvests were performed according to the fruit ripening and from each tree; only the ripe fruits were harvested. In each harvest, all the fruits were weighed and the total yield was obtained based on the sum of each harvest. The soil attributes analyzed were P, K, Ca, Mg, pH in CaCl2, C, Cu, Zn, Fe, Mn and base saturation, and the plant attributes were fruit length, diameter and yield. Yield had low correlation with soil and plant attributes. An index of spatial variability was suggested in this study and helped in classifying levels of spatial dependence of the various soil and plant attributes: very low (fruit length); low (P, fruit diameter), medium (Mg, pH, Cu, Zn, Fe), high (Ca, K, base saturation and yield), and very high (Mn and C).