The effect of flow regimes in the distillation of systems containing two liquid phases

Single phase solutions containing three components have been observed to exhibit foaminess near a single to two liquid phase boundary. It was seen, in a sintered plate column under mass transfer conditions, that distillation systems where the liquid appeared as one phase in one part of a column and two phases in another part, exhibited foaminess when the liquid concentration was near the one phase to two phase boundary. Various ternary systems have been studied in a 50 plate. 30mm i.d. Oldershaw column and it was observed that severe foaming occurred in the middle section of the column near the one liquid phase to two liquid phase boundary and no foaming occurred at the end of the column where liquid was either one phase or two phase. This is known as Ross type foam. Mass transfer experiments with Ross type ternary systems have been carried out in a perspex simulator with small and large hole diameter trays. It was observed that by removal of the more volatile component, Ross type foam did not build up on the tray. Severe entrainment of liquid was observed in all cases leading to a 'dry' tray, even with a low free area small diameter hole tray which was expected to produce a bubbly mixture. Entrainment was more severe for high gas superficial velocities and large hole diameters. This behaviour is quite different from the build up of foam observed when one liquid phase/two liquid phase Ross systems were contacted with air above a small sintered disc or with vapour in an Oldershaw distillation column. This observation explains why distillation columns processing mixtures which change from one liquid phase to two liquid phases (or vice versa) must be severely derated to avoid flooding. Single liquid phase holdups at the spray to bubbly transition were measured using a perspex simulator similar to that of Porter & Wong (17). i.e. with no liquid cross flow. A light transmission technique was used to measure the transition from spray regime to bubbly regime. The effect of tray thickness and the ratio of hole diameter to tray thickness on the transition was evaluated using trays of the same hole diameter and free area but having thickness of 2.38 mm, 4 mm, and 6.35 mm. The liquid holdup at the transition was less with the thin metal trays. This result may be interpreted by the theory of Lockett (101), which predicts the transition liquid holdup in terms of the angle of the gas iet leaving the holes in the sieve plate. All the existing correlations have been compared and none were found to be satisfactory and these correlations have been modified in view of the experimental results obtained. A new correlation has been proposed which takes into account the effect of the hole diameter to tray thickness ratio on the transition and good agreement was obtained between the experimental results and the correlated values of the liquid holdup at the transition. Results have been obtained for two immiscible liquids [kerosene and water] on trays to determine whether foaming can be eliminated by operating in the spray regime. Kerosene was added to a fixed volume of water or water was added to a fixed volume of kerosene. In both cases, there was a transition from spray to bubbly. In the water fixed system. the liquid holdup at the transition was slightly less than the pure kerosene system. Whilst for the kerosene fixed system, the transition occurred at much lower liquid holdups. Trends In the results were similar to those for single liquid phase. New correlations have been proposed for the two cases. It has been found that Ross type foams, observed in a sintered plate column and in the Oldershaw column can be eliminated by either carrying out the separation in a packed column or by the addition of defoaming additives.

Phase equilibrium studies at normal pressures

A total pressure apparatus has been developed to measure vapour-liquid equilibrium data on binary mixtures at atmospheric and sub-atmospheric pressures. The method gives isothermal data which can be obtained rapidly. Only measurements of total pressure are made as a direct function of composition of synthetic liquid phase composition, the vapour phase composition being deduced through the Gibbs-Duhem relationship. The need to analyse either of the phases is eliminated. As such the errors introduced by sampling and analysis are removed. The essential requirements are that the pure components be degassed completely since any deficiency in degassing would introduce errors into the measured pressures. A similarly essential requirement was that the central apparatus would have to be absolutely leak-tight as any leakage of air either in or out of the apparatus would introduce erroneous pressure readings. The apparatus was commissioned by measuring the saturated vapour pressures of both degassed water and ethanol as a function of temperature. The pressure-temperature data on degassed water measured were directly compared with data in the literature, with good agreement. Similarly the pressure-temperature data were measured for ethanol, methanol and cyclohexane and where possible a direct comparison made with the literature data. Good agreement between the pure component data of this work and those available in the literature demonstrates firstly that a satisfactory degassing procedure has been achieved and that secondly the measurements of pressure-temperature are consistent for any one component; since this is true for a number of components, the measurements of both temperature and pressure are both self-consistent and of sufficient accuracy, with an observed compatibility between the precision/accuracy of the separate means of measuring pressure and temperature. The liquid mixtures studied were of ethanol-water, methanol-water and ethanol-cyclohexane. The total pressure was measured as the composition inside the equilibrium cell was varied at a set temperature. This gave P-T-x data sets for each mixture at a range of temperatures. A standard fitting-package from the literature was used to reduce the raw data to yield y-values to complete the x-y-P-T data sets. A consistency test could not be applied to the P-T-x data set as no y-values were obtained during the experimental measurements. In general satisfactory agreement was found between the data of this work and those available in the literature. For some runs discrepancies were observed, and further work recommended to eliminate the problems identified.

Synthesis of triplex-forming oligonucleotide conjugates of the anticancer drug temodal

Covalent attachment of the anticancer drugs temozolomide (Temodal) and mitozolomide to triplex-forming oligonucleotides (TFOs) is a potential way of targeting these alkylating agents to specific gene sequences to maximise site-selectivity. In this work, polypyrimidine TFO conjugates of both drugs were synthesised and targeted to duplex DNA in an attempt to effect site-specific alkylation of guanine residues. Concurrently, in an attempt to enhance the triple helix stability of TFOs at neutral pH, the thermal stabilities of triplexes formed from TFOs containing isoguanine, 2-O-benzyl- and 2-O-allyl-adenine were evaluated. A novel cleavage and deprotection procedure was developed which allowed for the solid phase synthesis of the base-sensitive TFO-drug conjugates using a recently developed silyl-linked controlled pore glass (SLCPG) support. Covalent attachment of either temozolomide or mitozolomide at the 5'-end of TFO conjugates caused no destabilisation of the triplexes studied. The synthesis of a phosphoramidite derivative of mitozolomide enabled direct incorporation of this reagent into a model sequence during DNA synthesis. After cleavage and deprotection of the TFO-drug conjugate, the 5'-end mitozolomide residue was found to have decomposed presumably as a result of ring-opening of the tetrazinone ring. The base-sensitive antibacterial and antitumour agent, metronidazole, was also successfully incorporated at the 5'-end of the oligonucleotide d(T8) using conventional methods. Two C2-substituted derivatives of 2'-deoxyadenosine containing 2-O-benzyl and 2-O-allyl groups were synthesised. Hydrogenolysis of the 2-O-benzyl analogue provided a useful route, amenable to scale-up, for the synthesis of the rare nucleoside 2'-deoxyisoguanosine (isoG). Both the 2-O-allyl and 2-O-benzyl derivatives were incorporated into TFO sequences using phosphoramidite methodology. Thermal melting experiments showed that the 2-O-allyl and 2-O-benzyl groups caused marked destabilisation of the triple helices studied, in contrast to hexose-DNA duplexes, where aralkyl substituents caused significant stabilisation of duplexes. TFOs containing isoG were synthesised by Pd(O)-catalysed deallylation of 2-0-allyl adenine residues. These sequences containing isoG, in its N3- or 02-H tautomeric form, formed triple helices which were equally as stable as those containing adenine.

Solid-phase combinatorial chemistry and scintillation proximity assays

The Scintillation Proximity Assay (SPA) is a method that is frequently used to detect and quantify the strength of intermolecular interactions between a biological receptor and ligand molecule in aqueous media. This thesis describes the synthesis of scintillant-tagged-compounds for application in a novel cell-based SPA. A series of 4-functianlised-2,5-diphenyloxazole molecules were synthesised. These 4-functionalised-2,5-diphenyloxazoles were evaluated by Sense Proteomic Ltd. Accordingly, the molecules were evaluated for the ability to scintillate in the presence of ionising radiation. In addition, the molecules were incorporated into liposomal preparations which were subsequently evaluated for the ability to scintillate in the presence of ionising radiation. The optimal liposomal preparation was introduced into the membrane of HeLa cells that were used successfully in a cell-based SPA to detect and quantify the uptake of [14C]methionine. This thesis also describes the synthesis and subsequent polymerisation of novel poly(oxyethylene glycol)-based monomers to form a series of new polymer supports. These Poly(oxyethylene glycol)-polymer (POP) supports were evaluated for the ability to swell and mass-uptake in a variety of solvents, demonstrating that POP-supports exhibit enhanced solvent compatibilities over several commercial resins. The utility of POP-supports in solid-phase synthesis was also demonstrated successfully. The incorporation of (4’-vinyl)-4-benzyl-2,5-diphenyloxazole in varying mole percentage into the monomer composition resulted in the production of chemically functionalised scintillant-containing poly(oxyethylene glycol) polymer (POP-Sc) supports. These materials are compatible with both aqueous and organic solvents and scintillate efficiently in the presence of ionising radiation. The utility of POP-Sc supports in solid-phase synthesis and subsequent in-situ SPA to detect and quantify, in real-time, the kinetic progress of a solid-phase reaction was exemplified successfully.In addition, POP-Sc supports were used successfully both in solid-phase combinatorial synthesis of a peptide nucleic acid (PNA)-library and subsequent screening of this library for the ability to hybridise with DNA, which was labelled with a suitable radio-isotape. This data was used to identify the dependence of the number and position of complimentary codon pairs upon the extent of hybridisation. Finally, a further SPA was used to demonstrate the excellent compatibility of POP-Sc supports for use in the detection and quantification of enzyme assays conducted within the matrix of the POP-Sc support.

Thin film bearings with phase change of lubricant

The possible evaporation of lubricant in fluid film bearings has been investigated theoretically and by experiment using a radial flow hydrostatic bearing supplied with liquid refrigerant R114. Good correlation between measured and theoretical values was obtained using a bespoke computational fluid dynamic model in which the flow was assumed to be laminar and adiabatic. The effects of viscous dissipation and vapour generation within the fluid film are fully accounted for by applying a fourth order Runge-Kutta routine to satisfy the radial and filmwise transverse constraints of momentum, energy and mass conservation. The results indicate that the radial velocity profile remains parabolic while the flow remains in the liquid phase and that the radial rate of enthalpy generation is then constant across the film at a given radius. The results also show that evaporation will commence at a radial location determined by geometry and flow conditions and in fluid layers adjacent to the solid boundaries. Evaporation is shown to progress in the radial direction and the load carrying capacity of such a bearing is reduced significantly. Expressions for the viscosity of the liquid/vapour mixture found in the literature survey have not been tested against experimental data. A new formulation is proposed in which the suitable choice of a characteristic constant yields close representation to any of these expressions. Operating constraints imposed by the design of the experimental apparatus limited the extent of the surface over which evaporation could be obtained, and prevented clear identification of the most suitable relationship for the viscosity of the liquid/vapour mixture. The theoretical model was extended to examine the development of two phase flow in a rotating shaft face seal of uniform thickness. Previous theoretical analyses have been based on the assumption that the radial velocity profile of the flow is always parabolic, and that the tangential component of velocity varies linearly from the value at the rotating surface, to zero at the stationary surface. The computational fluid dynamic analysis shows that viscous shear and dissipation in the fluid adjacent to the rotating surface leads to developing evaporation with a consequent reduction in tangential shear forces. The tangential velocity profile is predicted to decay rapidly through the film, exhibiting a profile entirely different to that assumed by previous investigators. Progressive evaporation takes place close to the moving wall and does not occur completely at a single radial location, as has been claimed in earlier work.

Heterogeneous catalysis in an oscillatory baffled flow reactor

The first demonstration of heterogeneous catalysis within an oscillatory baffled flow reactor (OBR) is reported, exemplified by the solid acid catalysed esterification of organic acids, an important prototypical reaction for fine chemicals and biofuel synthesis. Suspension of a PrSOH-SBA-15 catalyst powder is readily achieved within the OBR under an oscillatory flow, facilitating the continuous esterification of hexanoic acid. Excellent semi-quantitative agreement is obtained between OBR and conventional stirred batch reaction kinetics, demonstrating efficient mixing, and highlighting the potential of OBRs for continuous, heterogeneously catalysed liquid phase transformations. Kinetic analysis highlights acid chain length (i.e. steric factors) as a key predictor of activity. Continuous esterification offers improved ester yields compared with batch operation, due to the removal of water by-product from the catalyst, evidencing the versatility of the OBR for heterogeneous flow chemistry and potential role as a new clean catalytic technology. © The Royal Society of Chemistry 2013.

Heterogeneous catalysts for clean technology:spectroscopy, design, and monitoring

Reactive, but not a reactant. Heterogeneous catalysts play an unseen role in many of today's processes and products. With the increasing emphasis on sustainability in both products and processes, this handbook is the first to combine the hot topics of heterogeneous catalysis and clean technology. It focuses on the development of heterogeneous catalysts for use in clean chemical synthesis, dealing with how modern spectroscopic techniques can aid the design of catalysts for use in liquid phase reactions, their application in industrially important chemistries - including selective oxidation, hydrogenation, solid acid- and base-catalyzed processes - as well as the role of process intensification and use of renewable resources in improving the sustainability of chemical processes. With its emphasis on applications, this book is of high interest to those working in the industry.

Room temperature electromechanical and magnetic investigations of ferroelectric Aurivillius phase Bi5Ti3(FexMn1−x)O15 (x = 1 and 0.7) chemical solution deposited thin films

Aurivillius phase thin films of Bi5Ti3(FexMn1−x)O15 with x = 1 (Bi5Ti3FeO15) and 0.7 (Bi5Ti3Fe0.7Mn0.3O15) on SiO2-Si(100) and Pt/Ti/SiO2-Si substrates were fabricated by chemical solution deposition. The method was optimized in order to suppress formation of pyrochlore phase Bi2Ti2O7 and improve crystallinity. The structuralproperties of the films were examined by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. Optimum crystallinity and pyrochlore phase suppression was achieved by the addition of 15 to 25 mol. % excess bismuth to the sols. Based on this study, 17.5 mol. % excess bismuth was used in the preparation of Bi2Ti2O7-free films of Bi5Ti3FeO15 on SrTiO3(100) and NdGaO3(001) substrates, confirming the suppression of pyrochlore phase using this excess of bismuth. Thirty percent of the Fe3+ ions in Bi5Ti3FeO15 was substituted with Mn3+ ions to form Bi2Ti2O7-free thin films of Bi5Ti3Fe0.7Mn0.3O15 on Pt/Ti/SiO2-Si, SiO2-Si(100), SrTiO3(100), and NdGaO3(001) substrates. Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films on Pt/Ti/SiO2-Si and SiO2-Si(100) substrates were achieved with a higher degree of a-axis orientation compared with the films on SrTiO3(100) and NdGaO3(001) substrates. Room temperature electromechanical and magnetic properties of the thin films were investigated in order to assess the potential of these materials for piezoelectric,ferroelectric, and multiferroic applications. Vertical piezoresponse force microscopy measurements of the films demonstrate that Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films are piezoelectric at room temperature. Room temperature switching spectroscopy-piezoresponse force microscopy measurements in the presence and absence of an applied bias demonstrate local ferroelectric switching behaviour (180°) in the films. Superconducting quantum interference device magnetometry measurements do not show any room temperature ferromagnetic hysteresis down to an upper detection limit of 2.53 × 10−3 emu; and it is concluded, therefore, that such films are not mutiferroic at room temperature. Piezoresponse force microscopy lithography images of Bi5Ti3Fe0.7Mn0.3O15thin films are presented.

Systematic characterization of thermodynamic and dynamical phase behavior in systems with short-ranged attraction

In this paper we demonstrate the feasibility and utility of an augmented version of the Gibbs ensemble Monte Carlo method for computing the phase behavior of systems with strong, extremely short-ranged attractions. For generic potential shapes, this approach allows for the investigation of narrower attractive widths than those previously reported. Direct comparison to previous self-consistent Ornstein-Zernike approximation calculations is made. A preliminary investigation of out-of-equilibrium behavior is also performed. Our results suggest that the recent observations of stable cluster phases in systems without long-ranged repulsions are intimately related to gas-crystal and metastable gas-liquid phase separation.

Evaporation maps for ternary non-ideal liquid mixtures

This thesis deals with the evaporation of non-ideal liquid mixtures using a multicomponent mass transfer approach. It develops the concept of evaporation maps as a convenient way of representing the dynamic composition changes of ternary mixtures during an evaporation process. Evaporation maps represent the residual composition of evaporating ternary non-ideal mixtures over the full range of composition, and are analogous to the commonly-used residue curve maps of simple distillation processes. The evaporation process initially considered in this work involves gas-phase limited evaporation from a liquid or wetted-solid surface, over which a gas flows at known conditions. Evaporation may occur into a pure inert gas, or into one pre-loaded with a known fraction of one of the ternary components. To explore multicomponent masstransfer effects, a model is developed that uses an exact solution to the Maxwell-Stefan equations for mass transfer in the gas film, with a lumped approach applied to the liquid phase. Solutions to the evaporation model take the form of trajectories in temperaturecomposition space, which are then projected onto a ternary diagram to form the map. Novel algorithms are developed for computation of pseudo-azeotropes in the evaporating mixture, and for calculation of the multicomponent wet-bulb temperature at a given liquid composition. A numerical continuation method is used to track the bifurcations which occur in the evaporation maps, where the composition of one component of the pre-loaded gas is the bifurcation parameter. The bifurcation diagrams can in principle be used to determine the required gas composition to produce a specific terminal composition in the liquid. A simple homotopy method is developed to track the locations of the various possible pseudo-azeotropes in the mixture. The stability of pseudo-azeotropes in the gas-phase limited case is examined using a linearized analysis of the governing equations. Algorithms for the calculation of separation boundaries in the evaporation maps are developed using an optimization-based method, as well as a method employing eigenvectors derived from the linearized analysis. The flexure of the wet-bulb temperature surface is explored, and it is shown how evaporation trajectories cross ridges and valleys, so that ridges and valleys of the surface do not coincide with separation boundaries. Finally, the assumption of gas-phase limited mass transfer is relaxed, by employing a model that includes diffusion in the liquid phase. A finite-volume method is used to solve the system of partial differential equations that results. The evaporation trajectories for the distributed model reduce to those of the lumped (gas-phase limited) model as the diffusivity in the liquid increases; under the same gas-phase conditions the permissible terminal compositions of the distributed and lumped models are the same.

Delivering enhanced efficiency in the synthesis of α-diazosulfoxides by exploiting the process control enabled in flow

Continuous-flow generation of α-diazosulfoxides results in a two- to three-fold increase in yields and decreased reaction times compared to standard batch synthesis methods. These high yielding reactions are enabled by flowing through a bed of polystyrene-supported base (PS-DBU or PS-NMe2) with highly controlled residence times. This engineered solution allows the α-diazosulfoxides to be rapidly synthesized while limiting exposure of the products to basic reaction conditions, which have been found to cause rapid decomposition. In addition to improved yields, this work has the added advantage of ease of processing, increased safety profile, and scale-up potential.

Design and Implementation of Tools for STM Studies in UHV and at the Solid-Liquid Interface

This thesis presents details of the design and development of novel tools and instruments for scanning tunneling microscopy (STM), and may be considered as a repository for several years' worth of development work. The author presents design goals and implementations for two microscopes. First, a novel Pan-type STM was built that could be operated in an ambient environment as a liquid-phase STM. Unique features of this microscope include a unibody frame, for increased microscope rigidity, a novel slider component with large Z-range, a unique wiring scheme and damping mechanism, and a removable liquid cell. The microscope exhibits a high level of mechanical isolation at the tunnel junction, and operates excellently as an ambient tool. Experiments in liquid are on-going. Simultaneously, the author worked on designs for a novel low temperature, ultra-high vacuum (LT-UHV) instrument, and these are presented as well. A novel stick-slip vertical coarse approach motor was designed and built. To gauge the performance of the motor, an in situ motion sensing apparatus was implemented, which could measure the step size of the motor to high precision. A new driving circuit for stick-slip inertial motors is also presented, that o ffers improved performance over our previous driving circuit, at a fraction of the cost. The circuit was shown to increase step size performance by 25%. Finally, a horizontal sample stage was implemented in this microscope. The build of this UHV instrument is currently being fi nalized. In conjunction with the above design projects, the author was involved in a collaborative project characterizing N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on Au(111) films. STM was used to characterize Au substrate quality, for both commercial substrates and those manufactured via a unique atomic layer deposition (ALD) process by collaborators. Ambient and UHV STM was then also used to characterize the NHC/Au(111) films themselves, and several key properties of these films are discussed. During this study, the author discovered an unexpected surface contaminant, and details of this are also presented. Finally, two models are presented for the nature of the NHC-Au(111) surface interaction based on the observed film properties, and some preliminary theoretical work by collaborators is presented.

Catalytic decomposition of formic acid using supported metal nanoparticles

Upgrade of hydrogen to valuable fuel is a central topic in modern research due to its high availability and low price. For the difficulties in hydrogen storage, different pathways are still under investigation. A promising way is in the liquid-phase chemical hydrogen storage materials, because they can lead to greener transformation processes with the on line development of hydrogen for fuel cells. The aim of my work was the optimization of catalysts for the decomposition of formic acid made by sol immobilisation method (a typical colloidal method). Formic acid was selected because of the following features: it is a versatile renewable reagent for green synthesis studies. The first aim of my research was the synthesis and optimisation of Pd nanoparticles by sol-immobilisation to achieve better catalytic performances and investigate the effect of particle size, oxidation state, role of stabiliser and nature of the support. Palladium was chosen because it is a well-known active metal for the catalytic decomposition of formic acid. Noble metal nanoparticles of palladium were immobilized on carbon charcoal and on titania. In the second part the catalytic performance of the “homemade” catalyst Pd/C to a commercial Pd/C and the effect of different monometallic and bimetallic systems (AuxPdy) in the catalytic formic acid decomposition was investigated. The training period for the production of this work was carried out at the University of Cardiff (Group of Dr. N. Dimitratos).

Kinetic study of solid phase demineralization by weak acids in one-step enzymatic bio-refinery of shrimp cuticles

We describe a one-step bio-refinery process for shrimp composites by-products. Its originality lies in a simple rapid (6 h) biotechnological cuticle fragmentation process that recovers all major compounds (chitins, peptides and minerals in particular calcium). The process consists of a controlled exogenous enzymatic proteolysis in a food-grade acidic medium allowing chitin purification (solid phase), and recovery of peptides and minerals (liquid phase). At a pH of between 3.5 and 4, protease activity is effective, and peptides are preserved. Solid phase demineralization kinetics were followed for phosphoric, hydrochloric, acetic, formic and citric acids with pKa ranging from 2.1 to 4.76. Formic acid met the initial aim of (i) 99 % of demineralization yield and (ii) 95 % deproteinization yield at a pH close to 3.5 and a molar ratio of 1.5. The proposed one-step process is proven to be efficient. To formalize the necessary elements for the future optimization of the process, two models to predict shell demineralization kinetics were studied, one based on simplified physical considerations and a second empirical one. The first model did not accurately describe the kinetics for times exceeding 30 minutes, the empirical one performed adequately.

Development of procedures for the triazole fungicides determination in fruits and liquid samples using microextraction techniques and chromatographic separation

Agricultural crops can be damaged by funguses, insects, worms and other organisms that cause diseases and decrease the yield of production. The effect of these damaging agents can be reduced using pesticides. Among them, triazole compounds are effective substances against fungus; for example, Oidium. Nevertheless, it has been detected that the residues of these fungicides in foods as well as in derivate products can affect the health of the consumers. Therefore, the European Union has established several regulations fixing the maximum residue of pesticide levels in a wide range of foods trying to assure the consumer safety. Hence, it is very important to develop adequate methods to determine these pesticide compounds. In most cases, gas or liquid chromatographic (GC, LC) separations are used in the analysis of the samples. But firstly, it is necessary to use proper sample treatments in order to preconcentrate and isolate the target analytes. To reach this aim, microextraction techniques are very effective tools; because allow to do both preconcentration and extraction of the analytes in one simple step that considerably reduces the source of errors. With these objectives, two remarkable techniques have been widely used during the last years: solid phase microextraction (SPME) and liquid phase microextraction (LPME) with its different options. Both techniques that avoid the use or reduce the amount of toxic solvents are convenient coupled to chromatographic equipments providing good quantitative results in a wide number of matrices and compounds. In this work simple and reliable methods have been developed using SPME and ultrasound assisted emulsification microextraction (USAEME) coupled to GC or LC for triazole fungicides determination. The proposed methods allow confidently determine triazole concentrations of μg L‐1 order in different fruit samples. Chemometric tools have been used to accomplish successful determinations. Firstly, in the selection and optimization of the variables involved in the microextraction processes; and secondly, to overcome the problems related to the overlapping peaks. Different fractional factorial designs have been used for the screening of the experimental variables; and central composite designs have been carried out to get the best experimental conditions. Trying to solve the overlapping peak problems multivariate calibration methods have been used. Parallel Factor Analysis 2 (PARAFAC2), Multivariate Curve Resolution (MCR) and Parallel Factor Analysis with Linear Dependencies (PARALIND) have been proposed, the adequate algorithms have been used according to data characteristics, and the results have been compared. Because its occurrence in Basque Country and its relevance in the production of cider and txakoli regional wines the grape and apple samples were selected. These crops are often treated with triazole compounds trying to solve the problems caused by the funguses. The peel and pulp from grape and apple, their juices and some commercial products such as musts, juice and cider have been analysed showing the adequacy of the developed methods for the triazole determination in this kind of fruit samples.