Sequential spectrofluorimetric determination of free and total glycerol in biodiesel in a multicommuted flow system

A new procedure for spectrofluorimetric determination of free and total glycerol in biodiesel samples is presented. It is based on the oxidation of glycerol by periodate, forming formaldehyde, which reacts with acetylacetone, producing the luminescent 3,5-diacetyl-1,4-dihydrolutidine. A flow system with solenoid micro-pumps is proposed for solution handling. Free glycerol was extracted off-line from biodiesel samples with water, and total glycerol was converted to free glycerol by saponification with sodium ethylate under sonication. For free glycerol, a linear response was observed from 5 to 70 mg L(-1) with a detection limit of 0.5 mg L(-1), which corresponds to 2 mg kg(-1) in biodiesel. The coefficient of variation was 0.9% (20 mg L(-1), n = 10). For total glycerol, samples were diluted on-line, and the linear response range was 25 to 300 mg L(-1). The detection limit was 1.4 mg L(-1) (2.8 mg kg(-1) in biodiesel) with a coefficient of variation of 1.4% (200 mg L(-1), n = 10). The sampling rate was ca. 35 samples h(-1) and the procedure was applied to determination of free and total glycerol in biodiesel samples from soybean, cottonseed, and castor beans.

Green Chemistry-Sensitive Analytical Procedure for Photometric Determination of Orthophosphate in River and Tap Water by Use of a Simple LED-Based Photometer

In the current work a Green Analytical Chemistry (GAC) procedure for photometric determination of orthophosphate in river water at mu g L-1 concentration level is described. The flow system module and the LED-based photometer were assembled together to constitute a compact unit in order to allow that a flow cell with optical path-length of 100mm was coupled to them. The photometric procedure based on the molybdenum blue method was implemented employing the multicommuted flow injection analysis approach, which provided facilities to allow reduction of reagent consumption and as well as waste generation. Aiming to prove the usefulness of the system, orthophosphate in river and tap waters was determined. Accuracy was ascertained by spiking samples with orthophosphate solution yielding recoveries ranging from 96% up to 107%. Other profitable features such as a wide linear response range between 10 to 800 mu g L-1 [image omitted]; a detection limit (3 sigma criterion) of 2.4 mu g L-1 [image omitted]; a relative standard deviation (n=7) of 2% using a typical water sample with concentration of 120 mu g L-1 [image omitted]; reagent consumption of 3.0mg ammonium molybdate, 0.3mg hydrazine sulfate, and 0.03mg stannous chloride per determination; a waste generation of 2.4mL per determination; and a sampling throughput of 20 determination per hours were also achieved.

Liquid-liquid microextraction without phase separation in a multicommuted flow system for diltiazem determination in pharmaceuticals

Liquid-liquid microextraction without phase segmentation was implemented in a multicommuted flow system for determination of the anti-hypertensive diltiazem. The procedure was based on ion pair formation between the drug and the dye bromothymol blue at pH 3.5. The detection was performed without phase separation in a glass tube coupled to a fiber-optics spectrophotometer. The total volume of chloroform was reduced to 50 mu L in comparison with 10 mL consumed in batch. A linear response was observed between 9 and 120 mu mol L(-1), with a detection limit of 0.9 mu mol L(-1) (99.7% confidence level). The coefficient of variation (n = 10), sampling rate and extraction efficiency were estimated as 0.6%, 78 determinations per hour and 61%, respectively. About 30 mu g of bromothymol blue was consumed and the waste volume was 380 mu L per determination. The results for pharmaceutical samples agreed with those obtained by the reference procedure at the 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.

A multicommuted flow system with solenoid micro-pumps for paraquat determination in natural waters

A flow system designed with solenoid micro-pumps is proposed for the determination of paraquat in natural waters. The procedure involves the reaction of paraquat with dehydroascorbic acid followed by spectrophotometric measurements. The proposed procedure minimizes the main drawbacks related to the standard chromatographic procedure and to flow analysis and manual methods with spectrophotometric detection based on the reaction with sodium dithionite, i.e. high solvent consumption and waste generation and low sampling rate for chromatography and high instability of the reagent in the spectrophotometric procedures. A home-made 10-cm optical-path flow cell was employed for improving sensitivity and detection limit. Linear response was observed for paraquat concentrations in the range 0.10-5.0 mg L-1. The detection limit (99.7% confidence level), sampling rate and coefficient of variation (n = 10) were estimated as 22 mu g L-1, 63 measurements per hour and 1.0%, respectively. Results of determination of paraquat in natural water samples were in agreement with those achieved by the chromatographic reference procedure at the 95% confidence level. (c) 2008 Elsevier B.V. All rights reserved.

An approach based on neural networks for estimation and generalization of crossflow filtration processes

The crossflow filtration process differs of the conventional filtration by presenting the circulation flow tangentially to the filtration surface. The conventional mathematical models used to represent the process have some limitations in relation to the identification and generalization of the system behaviour. In this paper, a system based on artificial neural networks is developed to overcome the problems usually found in the conventional mathematical models. More specifically, the developed system uses an artificial neural network that simulates the behaviour of the crossflow filtration process in a robust way. Imprecisions and uncertainties associated with the measurements made on the system are automatically incorporated in the neural approach. Simulation results are presented to justify the validity of the proposed approach. (C) 2007 Elsevier B.V. All rights reserved.

Phase fraction distribution measurement of oil-water flow using a capacitance wire-mesh sensor

In this paper, a novel wire-mesh sensor based on permittivity (capacitance) measurements is applied to generate images of the phase fraction distribution and investigate the flow of viscous oil and water in a horizontal pipe. Phase fraction values were calculated from the raw data delivered by the wire-mesh sensor using different mixture permittivity models. Furthermore, these data were validated against quick-closing valve measurements. Investigated flow patterns were dispersion of oil in water (Do/w) and dispersion of oil in water and water in oil (Do/w&w/o). The Maxwell-Garnett mixing model is better suited for Dw/o and the logarithmic model for Do/w&w/o flow pattern. Images of the time-averaged cross-sectional oil fraction distribution along with axial slice images were used to visualize and disclose some details of the flow.

Evaluation of flow patterns and elongated bubble characteristics during the flow boiling of halocarbon refrigerants in a micro-scale channel

In the present study, quasi-diabatic two-phase flow pattern visualizations and measurements of elongated bubble velocity, frequency and length were performed. The tests were run for R134a and R245fa evaporating in a stainless steel tube with diameter of 2.32 mm, mass velocities ranging from 50 to 600 kg/m(2) s and saturation temperatures of 22 degrees C, 31 degrees C and 41 degrees C. The tube was heated by applying a direct DC current to its surface. Images from a high-speed video-camera (8000 frames/s) obtained through a transparent tube just downstream the heated sections were used to identify the following flow patterns: bubbly, elongated bubbles, churn and annular flows. The visualized flow patterns were compared against the predictions provided by Barnea et al. (1983) [1], Felcar et al. (2007) [10], Revellin and Thome (2007) [3] and Ong and Thome (2009) [11]. From this comparison, it was found that the methods proposed by Felcar et al. (2007) [10] and Ong and Thome (2009) [1] predicted relatively well the present database. Additionally, elongated bubble velocities, frequencies and lengths were determined based on the analysis of high-speed videos. Results suggested that the elongated bubble velocity depends on mass velocity, vapor quality and saturation temperature. The bubble velocity increases with increasing mass velocity and vapor quality and decreases with increasing saturation temperature. Additionally, bubble velocity was correlated as linear functions of the two-phase superficial velocity. (C) 2010 Elsevier Inc. All rights reserved.

Film thickness measurement techniques applied to micro-scale two-phase flow systems

Recently semi-empirical models to estimate flow boiling heat transfer coefficient, saturated CHF and pressure drop in micro-scale channels have been proposed. Most of the models were developed based on elongated bubbles and annular flows in the view of the fact that these flow patterns are predominant in smaller channels. In these models, the liquid film thickness plays an important role and such a fact emphasizes that the accurate measurement of the liquid film thickness is a key point to validate them. On the other hand, several techniques have been successfully applied to measure liquid film thicknesses during condensation and evaporation under macro-scale conditions. However, although this subject has been targeted by several leading laboratories around the world, it seems that there is no conclusive result describing a successful technique capable of measuring dynamic liquid film thickness during evaporation inside micro-scale round channels. This work presents a comprehensive literature review of the methods used to measure liquid film thickness in macro- and micro-scale systems. The methods are described and the main difficulties related to their use in micro-scale systems are identified. Based on this discussion, the most promising methods to measure dynamic liquid film thickness in micro-scale channels are identified. (C) 2009 Elsevier Inc. All rights reserved.

Thermal characterization of a cross-flow heat exchanger with a new flow arrangement

The objective of the present paper is to thermally characterize a cross-flow heat exchanger featuring a new cross-flow arrangement, which may find application in contemporary refrigeration and automobile industries. The new flow arrangement is peculiar in the sense that it possesses two fluid circuits extending in the form of two tube rows, each with two tube lines. To assess the heat exchanger performance, it is compared against that for the standard two-pass counter-cross-flow arrangement. The two-part comparison is based on the thermal effectiveness and the heat exchanger efficiency for several combinations of the heat capacity rate ratio, C*, and the number of transfer units, NTU. In addition, a third comparison is made in terms of the so-called ""heat exchanger reversibility norm"" (HERN) through the influence of various parameters such as the inlet temperature ratio, T, and the heat capacity rate ratio, C*, for several fixed NTU values. The proposed new flow arrangement delivers higher thermal effectiveness and higher heat exchanger efficiency, resulting in lesser entropy generation over a wide range of C* and NTU values. These metrics are quantified with respect to the arrangement widely used in refrigeration industry due to its high effectiveness, namely, the standard two-pass counter-cross-flow heat exchanger. The new flow arrangement seems to be a promising avenue in situations where cross-flow heat exchangers for single-phase fluid have to be used in refrigeration units. (c) 2009 Elsevier Masson SAS. All rights reserved.

Stability analysis of core-annular flow and neutral stability wave number

A general transition criterion is proposed in order to locate the core-annular flow pattern in horizontal and vertical oil-water flows. It is based on a rigorous one-dimensional two-fluid model of liquid-liquid two-phase flow and considers the existence of critical interfacial wave numbers related to a non-negligible interfacial tension term to which the linear stability theory still applies. The viscous laminar-laminar flow problem is fully resolved and turbulence effects on the stability are analyzed through experimentally obtained shape factors. The proposed general transition criterion includes in its formulation the inviscid Kelvin-Helmholtz`s discriminator. If a theoretical maximum wavelength is considered as a necessary condition for stability, a stability criterion in terms of the Eotvos number is achieved. Effects of interfacial tension, viscosity ratio, density difference, and shape factors on the stability of core-annular flow are analyzed in detail. The more complete modeling allowed for the analysis of the neutral-stability wave number and the results strongly suggest that the interfacial tension term plays an indispensable role in the correct prediction of the stable region of core-annular flow pattern. The incorporation of a theoretical minimum wavelength into the transition model produced significantly better results. The criterion predictions were compared with recent data from the literature and the agreement is encouraging. (C) 2007 American Institute of Chemical Engineers.

Estimation of Mass Transfer Velocity Based on Measured Turbulence Parameters

The aim of this study is to quantify the mass transfer velocity using turbulence parameters from simultaneous measurements of oxygen concentration fields and velocity fields. The surface divergence model was considered in more detail, using data obtained for the lower range of beta (surface divergence). It is shown that the existing models that use the divergence concept furnish good predictions for the transfer velocity also for low values of beta, in the range of this study. Additionally, traditional conceptual models, such as the film model, the penetration-renewal model, and the large eddy model, were tested using the simultaneous information of concentration and velocity fields. It is shown that the film and the surface divergence models predicted the mass transfer velocity for all the range of the equipment Reynolds number used here. The velocity measurements showed viscosity effects close to the surface, which indicates that the surface was contaminated with some surfactant. Considering the results, this contamination can be considered slight for the mass transfer predictions. (C) 2009 American Institute of Chemical Engineers AIChE J, 56: 2005-2017; 2010

Slip ratio in dispersed viscous oil-water pipe flow

In this article, dispersed flow of viscous oil and water is investigated. The experimental work was performed in a 26.2-mm-i.d. 12-m-long horizontal glass pipe using water and oil (viscosity of 100 mPa s and density of 860 kg/m(3)) as test fluids. High-speed video recording and a new wire-mesh sensor based on capacitance (permittivity) measurements were used to characterize the flow. Furthermore, holdup data were obtained using quick-closing-valves technique (QCV). An interesting finding was the oil-water slip ratio greater than one for dispersed flow at high Reynolds number. Chordal phase fraction distribution diagrams and images of the holdup distribution over the pipe cross-section obtained via wire-mesh sensor indicated a significant amount of water near to the pipe wall for the three different dispersed flow patterns identified in this study: oil-in-water homogeneous dispersion (o/w H), oil-in-water non-homogeneous dispersion (o/w NH) and Dual continuous (Do/w & Dw/o). The phase slip might be explained by the existence of a water film surrounding the homogeneous mixture of oil-in-water in a hidrofilic-oilfobic pipe. (C) 2010 Elsevier Inc. All rights reserved.

Three-phase harmonic distortion state estimation algorithm based on evolutionary strategies

This paper presents a new methodology to estimate unbalanced harmonic distortions in a power system, based on measurements of a limited number of given sites. The algorithm utilizes evolutionary strategies (ES), a development branch of evolutionary algorithms. The problem solving algorithm herein proposed makes use of data from various power quality meters, which can either be synchronized by high technology GPS devices or by using information from a fundamental frequency load flow, what makes the overall power quality monitoring system much less costly. The ES based harmonic estimation model is applied to a 14 bus network to compare its performance to a conventional Monte Carlo approach. It is also applied to a 50 bus subtransmission network in order to compare the three-phase and single-phase approaches as well as the robustness of the proposed method. (C) 2010 Elsevier B.V. All rights reserved.

A novel approach for Modeling the steady-state VSC-based multiline FACTS controllers and their operational constraints

A new, simple approach for modeling and assessing the operation and response of the multiline voltage-source controller (VSC)-based flexible ac transmission system controllers, namely the generalized interline power-flow controller (GIPFC) and the interline power-flow controller (IPFC), is presented in this paper. The model and the analysis developed are based on the converters` power balance method which makes use of the d-q orthogonal coordinates to thereafter present a direct solution for these controllers through a quadratic equation. The main constraints and limitations that such devices present while controlling the two independent ac systems considered, will also be evaluated. In order to examine and validate the steady-state model initially proposed, a phase-shift VSC-based GIPFC was also built in the Alternate Transients Program program whose results are also included in this paper. Where applicable, a comparative evaluation between the GIPFC and the IPFC is also presented.

Debris flow affecting the Cubatauo Oil Refinery, Brazil

On February 6, 1994, a large debris flow developed because of intense rains in a 800-m-high mountain range called Serra do Cubatao, the local name for the Serra do Mar, located along the coast of the state of Sao Paulo, Brazil. It affected the Presidente Bernardes Refinery, owned by Petrobras, in Cubatao. The damages amounted to about US $40 million because of the muck cleaning, repairs, and 3-week interruption of the operations. This prompted Petrobras to conduct studies, carried out by the authors, to develop protection works, which were done at a cost of approximately US $12 million. The paper describes the studies conducted on debris flow mechanics. A new criteria to define rainfall intensities that trigger debris flows is presented, as well as a correlation of slipped area with soil porosity and rain intensity. Also presented are (a) an actual grain size distribution of a deposited material, determined by laboratory and a large-scale field test, and (b) the size distribution of large boulders along the river bed. Based on theory, empirical experience and back-analysis of the events, the main parameters as the front velocity, the peak discharge and the volume of the transported sediments were determined in a rational basis for the design of the protection works. Finally, the paper describes the set of the protection works built, emphasizing their concept and function. They also included some low-cost innovative works.