Internal standard versus external standard calibration: an uncertainty case study of a liquid chromatography analysis

Traditionally, in the cigarettes industry, the determination of ammonium ion in the mainstream smoke is performed by ion chromatography. This work studies this determination and compares the results of this technique with the use of external and internal standard calibration. A reference cigarette sample presented measurement uncertainty of 2.0 μg/cigarette and 1.5 μg/cigarette, with external and internal standard, respectively. It is observed that the greatest source of uncertainty is the bias correction factor and that it is even more significant when using external standard, confirming thus the importance of internal standardization for this correction.

Estimation of surface area and pore volume of activated carbons by methylene blue and iodine numbers

Data of methylene blue number and iodine number of activated carbons samples were calibrated against the respective surface area, micropore volume and total pore volume using multiple regression. The models obtained from the calibrations were used in predicting these physical properties of a test group of activated carbon samples produced from several raw materials. In all cases, the predicted values were in good agreement with the expected values. The method allows extracting more information from the methylene blue and iodine adsorption studies than normally obtained with this type of material.

Indomethacin solubility estimation in 1,4-dioxane + water mixtures by the extended hildebrand solubility approach

Extended Hildebrand Solubility Approach (EHSA) was successfully applied to evaluate the solubility of Indomethacin in 1,4-dioxane + water mixtures at 298.15 K. An acceptable correlation-performance of EHSA was found by using a regular polynomial model in order four of the W interaction parameter vs. solubility parameter of the mixtures (overall deviation was 8.9%). Although the mean deviation obtained was similar to that obtained directly by means of an empiric regression of the experimental solubility vs. mixtures solubility parameters, the advantages of EHSA are evident because it requires physicochemical properties easily available for drugs.

Organic and total mercury determination in sediments by cold vapor atomic absorption spectrometry: methodology validation and uncertainty measurements

The purpose of the present study was to validate a method for organic Hg determination in sediment. The procedure for organic Hg was adapted from literature, where the organomercurial compounds were extracted with dichloromethane in acid medium and subsequent destruction of organic compounds by bromine chloride. Total Hg was performed according to 3051A USEPA methodology. Mercury quantification for both methodologies was then performed by CVAAS. Methodology validation was verified by analyzing certified reference materials for total Hg and methylmercury. The uncertainties for both methodologies were calculated. The quantification limit of 3.3 µg kg-1 was found for organic Hg by CVAAS.

Estimativa da incerteza de medição: estudo de caso no ensaio de migração de ε-caprolactama com determinação por CG-DIC

The estimation of measurement uncertainty of an analytical result is an important tool to be applied for compliance to ISO IEC 17025. Through the available guides it is possible to establish procedures and criteria for the estimation of measurement uncertainty. This paper presents a case study on the estimation of measurement uncertainty in migration the test of ε-caprolactam from the polyamide 6 packages to fatty foods with determination by GC-FID. The calculation methodology used for the estimation of measurement uncertainty for the migration test was developed based on the guides EURACHEM / CITAC and ISO GUM, taking into account relevant aspects of the migration test. The expanded uncertainty estimated was approximately 23% of the concentration of migration.

Estimation of phenotypic diversity in field populations of Magnaporthe grisea from two upland rice cultivars

The phenotypic diversity of Magnaporthe grisea was evaluated based on leaf samples with blast lesions collected from eight commercial fields of the upland rice cultivars 'BRS Primavera' and 'BRS Bonança', during the growing seasons of 2001/2002 and 2002/2003, in Goias State. The number of M. grisea isolates from each field utilized for virulence testing varied from 28 to 47. Three different indices were used based on reaction type in the eight standard international differentials and eight Brazilian differentials. The M. grisea subpopulations of ´Primavera' and 'Bonança', as measured by Simpson, Shannon and Gleason indices, showed similar phenotypic diversities. The Simpson index was more sensitive relation than those of Shannon and Gleason for pathotype number and standard deviation utilizing Brazilian differentials. However, the Gleason index was sensitive to standard deviation for international differentials. The sample size did not significantly influence the diversity index. The two sets of differential cultivars used in this study distinguished phenotypic diversity in different ways in all of the eight subpopulations analyzed. The phenotypic diversity determined based on eight differential Brazilian cultivars was lower in commercial rice fields of 'Primavera' than in the fields of 'Bonança,' independent of the diversity index utilized, year and location. Considering the Brazilian differentials, the four subpopulations of 'BRS Primavera' did not show evenness in distribution and only one pathotype dominated in the populations. The even distribution of pathotype was observed in three subpopulations of 'BRS Bonança'. The pathotype diversity of M. grisea was determined with more precision using Brazilian differentials and Simpson index.

Mobile system for pump working point estimation

In the current economy situation companies try to reduce their expenses. One of the solutions is to improve the energy efficiency of the processes. It is known that the energy consumption of pumping applications range from 20 up to 50% of the energy usage in the certain industrial plants operations. Some studies have shown that 30% to 50% of energy consumed by pump systems could be saved by changing the pump or the flow control method. The aim of this thesis is to create a mobile measurement system that can calculate a working point position of a pump drive. This information can be used to determine the efficiency of the pump drive operation and to develop a solution to bring pump’s efficiency to a maximum possible value. This can allow a great reduction in the pump drive’s life cycle cost. In the first part of the thesis, a brief introduction in the details of pump drive operation is given. Methods that can be used in the project are presented. Later, the review of available platforms for the project implementation is given. In the second part of the thesis, components of the project are presented. Detailed description for each created component is given. Finally, results of laboratory tests are presented. Acquired results are compared and analyzed. In addition, the operation of created system is analyzed and suggestions for the future development are given.

Estimation of existing cable systems in generator-busbar unit and choice the optimal solution for its modernization

The aim of this master’s thesis is to develop an algorithm to calculate the cable network for heat and power station CHGRES. This algorithm includes important aspect which has an influence on the cable network reliability. Moreover, according to developed algorithm, the optimal solution for modernization cable system from economical and technical point of view was obtained. The conditions of existing cable lines show that replacement is necessary. Otherwise, the fault situation would happen. In this case company would loss not only money but also its prestige. As a solution, XLPE single core cables are more profitable than other types of cable considered in this work. Moreover, it is presented the dependence of value of short circuit current on number of 10/110 kV transformers connected in parallel between main grid and considered 10 kV busbar and how it affects on final decision. Furthermore, the losses of company in power (capacity) market due to fault situation are presented. These losses are commensurable with investment to replace existing cable system.

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.

Development and validation of spectroscopic methods for simultaneous estimation and dissolution of ofloxacin and ornidazole in tablet dosage forms

The aim of this work was to develop and validate simple, accurate and precise spectroscopic methods (multicomponent, dual wavelength and simultaneous equations) for the simultaneous estimation and dissolution testing of ofloxacin and ornidazole tablet dosage forms. The medium of dissolution used was 900 ml of 0.01N HCl, using a paddle apparatus at a stirring rate of 50 rpm. The drug release was evaluated by developed and validated spectroscopic methods. Ofloxacin and ornidazole showed 293.4 and 319.6nm as λmax in 0.01N HCl. The methods were validated to meet requirements for a global regulatory filing. The validation included linearity, precision and accuracy. In addition, recovery studies and dissolution studies of three different tablets were compared and the results obtained show no significant difference among products.

Loviisan ydinvoimalaitoksen todennäköisyyspohjaisen riskianalyysin tason 2 epävarmuustarkastelut

Diplomityössä tarkastellaan Loviisan ydinvoimalaitoksen todennäköisyyspohjaisen riskianalyysin tason 2 epävarmuuksia. Tason 2 riskitutkimuksissa tutkitaan ydinvoimalaitosonnettomuuksia, joiden seurauksena osa reaktorin radioaktiivisista aineista vapautuu ympäristöön. Näiden tutkimuksien päätulos on suuren päästön vuotuinen taajuus ja se on pääosin todelliseen laitoshistoriaan perustuva tilastollinen odotusarvo. Tämän odotusarvon uskottavuutta voidaan parantaa huomioimalla merkittävimmät laskentaan liittyvät epävarmuudet. Epävarmuuksia laskentaan aiheutuu muiden muassa vakavan reaktorionnettomuuden ilmiöistä, turvallisuusjärjestelmien laitteista, inhimillisistä toiminnoista sekä luotettavuusmallin määrittelemättömistä osista. Diplomityössä kuvataan, kuinka epävarmuustarkastelut integroidaan osaksi Loviisan ydinvoimalaitoksen todennäköisyyspohjaisia riskianalyysejä. Tämä toteutetaan diplomityössä kehitetyillä apuohjelmilla PRALA:lla ja PRATU:lla, joiden avulla voidaan lisätä laitoshistorian perusteella muodostetut epävarmuusparametrit osaksi riskianalyysien luotettavuusdataa. Lisäksi diplomityössä on laskettu laskentaesimerkkinä Loviisan ydinvoimalaitoksen suuren päästön vuotuisen taajuuden vaihtelua kuvaava luottamusväli. Tämä laskentaesimerkki pohjautuu pääosin konservatiivisiin epävarmuusarvioihin, ei todellisiin tilastollisiin epävarmuuksiin. Laskentaesimerkin tulosten perusteella Loviisan suuren päästön taajuudella on laaja vaihteluväli; virhekertoimeksi saatiin 8,4 nykyisillä epävarmuusparametreilla. Suuren päästön taajuuden luottamusväliä voidaan kuitenkin tulevaisuudessa supistaa, kun hyödynnetään todelliseen laitoshistoriaan perustuvia epävarmuusparametreja.

MCMC Analysis for Optimization of Stochastic Models

In any decision making under uncertainties, the goal is mostly to minimize the expected cost. The minimization of cost under uncertainties is usually done by optimization. For simple models, the optimization can easily be done using deterministic methods.However, many models practically contain some complex and varying parameters that can not easily be taken into account using usual deterministic methods of optimization. Thus, it is very important to look for other methods that can be used to get insight into such models. MCMC method is one of the practical methods that can be used for optimization of stochastic models under uncertainty. This method is based on simulation that provides a general methodology which can be applied in nonlinear and non-Gaussian state models. MCMC method is very important for practical applications because it is a uni ed estimation procedure which simultaneously estimates both parameters and state variables. MCMC computes the distribution of the state variables and parameters of the given data measurements. MCMC method is faster in terms of computing time when compared to other optimization methods. This thesis discusses the use of Markov chain Monte Carlo (MCMC) methods for optimization of Stochastic models under uncertainties .The thesis begins with a short discussion about Bayesian Inference, MCMC and Stochastic optimization methods. Then an example is given of how MCMC can be applied for maximizing production at a minimum cost in a chemical reaction process. It is observed that this method performs better in optimizing the given cost function with a very high certainty.