Geometrical study of the three-dimensional temperature–composition diagrams. An important aid to understand the behavior of the liquid–vapour equilibrium in ternary systems

In this work the usefulness of qualitatively studying and drawing three-dimensional temperature–composition diagrams for ternary systems is pointed out to understand and interpret the particular behavior of the liquid–vapour equilibrium of non-ideal ternary systems. Several examples have been used in order to highlight the interest and the possibilities of this tool, which should be an interesting support not only for lecturers, but also for researchers interested in experimental equilibrium data determination.

Gibbs Energy of Mixing Function: Topological Analysis in Azeotropic Systems

ESAT 2014. 27th European Symposium on Applied Thermodynamics, Eindhoven University of Technology, July 6-9, 2014.

A statistical approach to predict the effect of confinement on the detonation velocity of commercial explosives

Commercial explosives behave non-ideally in rock blasting. A direct and convenient measure of non-ideality is the detonation velocity. In this study, an alternative model fitted to experimental unconfined detonation velocity data is proposed and the effect of confinement on the detonation velocity is modelled. Unconfined data of several explosives showing various levels of nonideality were successfully modelled. The effect of confinement on detonation velocity was modelled empirically based on field detonation velocity measurements. Confined detonation velocity is a function of the ideal detonation velocity, unconfined detonation velocity at a given blasthole diameter and rock stiffness. For a given explosive and charge diameter, as confinement increases detonation velocity increases. The confinement model is implemented in a simple engineering based non-ideal detonation model. A number of simulations are carried out and analysed to predict the explosive performance parameters for the adopted blasting conditions.

Adsorption of N-2, Ar, acetone, chloroform and acetone-chloroform mixture on carbon black in the framework of molecular layer structure theory (MLST)

Adsorption of pure nitrogen, argon, acetone, chloroform and acetone-chloroform mixture on graphitized thermal carbon black is considered at sub-critical conditions by means of molecular layer structure theory (MLST). In the present version of the MLST an adsorbed fluid is considered as a sequence of 2D molecular layers, whose Helmholtz free energies are obtained directly from the analysis of experimental adsorption isotherm of pure components. The interaction of the nearest layers is accounted for in the framework of mean field approximation. This approach allows quantitative correlating of experimental nitrogen and argon adsorption isotherm both in the monolayer region and in the range of multi-layer coverage up to 10 molecular layers. In the case of acetone and chloroform the approach also leads to excellent quantitative correlation of adsorption isotherms, while molecular approaches such as the non-local density functional theory (NLDFT) fail to describe those isotherms. We extend our new method to calculate the Helmholtz free energy of an adsorbed mixture using a simple mixing rule, and this allows us to predict mixture adsorption isotherms from pure component adsorption isotherms. The approach, which accounts for the difference in composition in different molecular layers, is tested against the experimental data of acetone-chloroform mixture (non-ideal mixture) adsorption on graphitized thermal carbon black at 50 degrees C. (C) 2005 Elsevier Ltd. All rights reserved.

Noise in detection of qubit states using a quantum point contact

We present a model for detection of the states of a coupled quantum dots (qubit) by a quantum point contact. Most proposals for measurements of states of quantum systems are idealized. However in a real laboratory the measurements cannot be perfect due to practical devices and circuits. The models using ideal devices are not sufficient for describing the detection information of the states of the quantum systems. Our model therefore includes the extension to a non-ideal measurement device case using an equivalent circuit. We derive a quantum trajectory that describes the stochastic evolution of the state of the system of the qubit and the measuring device. We calculate the noise power spectrum of tunnelling events in an ideal and a non-ideal quantum point contact measurement respectively. We found that, for the strong coupling case it is difficult to obtain information of the quantum processes in the qubit by measurements using a non-ideal quantum point contact. The noise spectra can also be used to estimate the limits of applicability of the ideal model.

Advanced receivers for next generation wireless communication systems

Despite extensive progress on the theoretical aspects of spectral efficient communication systems, hardware impairments, such as phase noise, are the key bottlenecks in next generation wireless communication systems. The presence of non-ideal oscillators at the transceiver introduces time varying phase noise and degrades the performance of the communication system. Significant research literature focuses on joint synchronization and decoding based on joint posterior distribution, which incorporate both the channel and code graph. These joint synchronization and decoding approaches operate on well designed sum-product algorithms, which involves calculating probabilistic messages iteratively passed between the channel statistical information and decoding information. Channel statistical information, generally entails a high computational complexity because its probabilistic model may involve continuous random variables. The detailed knowledge about the channel statistics for these algorithms make them an inadequate choice for real world applications due to power and computational limitations. In this thesis, novel phase estimation strategies are proposed, in which soft decision-directed iterative receivers for a separate A Posteriori Probability (APP)-based synchronization and decoding are proposed. These algorithms do not require any a priori statistical characterization of the phase noise process. The proposed approach relies on a Maximum A Posteriori (MAP)-based algorithm to perform phase noise estimation and does not depend on the considered modulation/coding scheme as it only exploits the APPs of the transmitted symbols. Different variants of APP-based phase estimation are considered. The proposed algorithm has significantly lower computational complexity with respect to joint synchronization/decoding approaches at the cost of slight performance degradation. With the aim to improve the robustness of the iterative receiver, we derive a new system model for an oversampled (more than one sample per symbol interval) phase noise channel. We extend the separate APP-based synchronization and decoding algorithm to a multi-sample receiver, which exploits the received information from the channel by exchanging the information in an iterative fashion to achieve robust convergence. Two algorithms based on sliding block-wise processing with soft ISI cancellation and detection are proposed, based on the use of reliable information from the channel decoder. Dually polarized systems provide a cost-and spatial-effective solution to increase spectral efficiency and are competitive candidates for next generation wireless communication systems. A novel soft decision-directed iterative receiver, for separate APP-based synchronization and decoding, is proposed. This algorithm relies on an Minimum Mean Square Error (MMSE)-based cancellation of the cross polarization interference (XPI) followed by phase estimation on the polarization of interest. This iterative receiver structure is motivated from Master/Slave Phase Estimation (M/S-PE), where M-PE corresponds to the polarization of interest. The operational principle of a M/S-PE block is to improve the phase tracking performance of both polarization branches: more precisely, the M-PE block tracks the co-polar phase and the S-PE block reduces the residual phase error on the cross-polar branch. Two variants of MMSE-based phase estimation are considered; BW and PLP.

The effect of blending on selected physical properties of crude oils and their products

A study was made of the effect of blending practice upon selected physical properties of crude oils, and of various base oils and petroleum products, using a range of binary mixtures. The crudes comprised light, medium and heavy Kuwait crude oils. The properties included kinematic viscosity, pour point, boiling point and Reid vapour pressure. The literature related to the prediction of these properties, and the changes reported to occur on blending, was critically reviewed as a preliminary to the study. The kinematic viscosity of petroleum oils in general exhibited non-ideal behaviour upon blending. A mechanism was proposed for this behaviour which took into account the effect of asphaltenes content. A correlation was developed, as a modification of Grunberg's equation, to predict the viscosities of binary mixtures of petroleum oils. A correlation was also developed to predict the viscosities of ternary mixtures. This correlation showed better agreement with experimental data (< 6% deviation for crude oils and 2.0% for base oils) than currently-used methods, i.e. ASTM and Refutas methods. An investigation was made of the effect of temperature on the viscosities of crude oils and petroleum products at atmospheric pressure. The effect of pressure on the viscosity of crude oil was also studied. A correlation was developed to predict the viscosity at high pressures (up to 8000 psi), which gave significantly better agreement with the experimental data than the current method due to Kouzel (5.2% and 6.0% deviation for the binary and ternary mixtures respectively). Eyring's theory of viscous flow was critically investigated, and a modification was proposed which extends its application to petroleum oils. The effect of blending on the pour points of selected petroleum oils was studied together with the effect of wax formation and asphaltenes content. Depression of the pour point was always obtained with crude oil binary mixtures. A mechanism was proposed to explain the pour point behaviour of the different binary mixtures. The effects of blending on the boiling point ranges and Reid vapour pressures of binary mixtures of petroleum oils were investigated. The boiling point range exhibited ideal behaviour but the R.V.P. showed negative deviations from it in all cases. Molecular weights of these mixtures were ideal, but the densities and molar volumes were not. The stability of the various crude oil binary mixtures, in terms of viscosity, was studied over a temperature range of 1oC - 30oC for up to 12 weeks. Good stability was found in most cases.

Phase equilibrium studies at moderate pressures

The theory of vapour-liquid equilibria is reviewed, as is the present status or prediction methods in this field. After discussion of the experimental methods available, development of a recirculating equilibrium still based on a previously successful design (the modified Raal, Code and Best still of O'Donnell and Jenkins) is described. This novel still is designed to work at pressures up to 35 bar and for the measurement of both isothermal and isobaric vapour-liquid equilibrium data. The equilibrium still was first commissioned by measuring the saturated vapour pressures of pure ethanol and cyclohexane in the temperature range 77-124°C and 80-142°C respectively. The data obtained were compared with available literature experimental values and with values derived from an extended form of the Antoine equation for which parameters were given in the literature. Commissioning continued with the study of the phase behaviour of mixtures of the two pure components as such mixtures are strongly non-ideal, showing azeotopic behaviour. Existing data did not exist above one atmosphere pressure. Isothermal measurements were made at 83.29°C and 106.54°C, whilst isobaric measurements were made at pressures of 1 bar, 3 bar and 5 bar respectively. The experimental vapour-liquid equilibrium data obtained are assessed by a standard literature method incorporating a themodynamic consistency test that minimises the errors in all the measured variables. This assessment showed that reasonable x-P-T data-sets had been measured, from which y-values could be deduced, but that the experimental y-values indicated the need for improvements in the design of the still. The final discussion sets out the improvements required and outlines how they might be attained.

Possibilities and limitations of coded aperture imaging

We have simulated the performance of various apertures used in Coded Aperture Imaging - optically. Coded pictures of extended and continuous-tone planar objects from the Annulus, Twin Annulus, Fresnel Zone Plate and the Uniformly Redundant Array have been decoded using a noncoherent correlation process. We have compared the tomographic capabilities of the Twin Annulus with the Uniformly Redundant Arrays based on quadratic residues and m-sequences. We discuss the ways of reducing the 'd. c.' background of the various apertures used. The non-ideal System-Point-Spread-Function inherent in a noncoherent optical correlation process produces artifacts in the reconstruction. Artifacts are also introduced as a result of unwanted cross-correlation terms from out-of-focus planes. We find that the URN based on m-sequences exhibits good spatial resolution and out-of-focus behaviour when imaging extended objects.

Clogging in horizontal subsurface flow constructed wetlands

Horizontal Subsurface Flow Treatment Wetlands (HSSF TWs) are used by Severn Trent Water as a low-cost tertiary wastewater treatment for rural locations. Experience has shown that clogging is a major operational problem that reduces HSSF TW lifetime. Clogging is caused by an accumulation of secondary wastewater solids from upstream processes and decomposing leaf litter. Clogging occurs as a sludge layer where wastewater is loaded on the surface of the bed at the inlet. Severn Trent systems receive relatively high hydraulic loading rates, which causes overland flow and reduces the ability to mineralise surface sludge accumulations. A novel apparatus and method, the Aston Permeameter, was created to measure hydraulic conductivity in situ. Accuracy is ±30 %, which was considered adequate given that conductivity in clogged systems varies by several orders of magnitude. The Aston Permeameter was used to perform 20 separate tests on 13 different HSSF TWs in the UK and the US. The minimum conductivity measured was 0.03 m/d at Fenny Compton (compared with 5,000 m/d clean conductivity), which was caused by an accumulation of construction fines in one part of the bed. Most systems displayed a 2 to 3 order of magnitude variation in conductivity in each dimension. Statistically significant transverse variations in conductivity were found in 70% of the systems. Clogging at the inlet and outlet was generally highest where flow enters the influent distribution and exits the effluent collection system, respectively. Surface conductivity was lower in systems with dense vegetation because plant canopies reduce surface evapotranspiration and decelerate sludge mineralisation. An equation was derived to describe how the water table profile is influenced by overland flow, spatial variations in conductivity and clogging. The equation is calibrated using a single parameter, the Clog Factor (CF), which represents the equivalent loss of porosity that would reproduce measured conductivity according to the Kozeny-Carman Equation. The CF varies from 0 for ideal conditions to 1 for completely clogged conditions. Minimum CF was 0.54 for a system that had recently been refurbished, which represents the deviation from ideal conditions due to characteristics of non-ideal media such as particle size distribution and morphology. Maximum CF was 0.90 for a 15 year old system that exhibited sludge accumulation and overland flow across the majority of the bed. A Finite Element Model of a 15 m long HSSF TW was used to indicate how hydraulics and hydrodynamics vary as CF increases. It was found that as CF increases from 0.55 to 0.65 the subsurface wetted area increases, which causes mean hydraulic residence time to increase from 0.16 days to 0.18 days. As CF increases from 0.65 to 0.90, the extent of overland flow increases from 1.8 m to 13.1 m, which reduces hydraulic efficiency from 37 % to 12 % and reduces mean residence time to 0.08 days.

Mass transfer and chemical reaction on a distillation plate

A multistage distillation column in which mass transfer and a reversible chemical reaction occurred simultaneously, has been investigated to formulate a technique by which this process can be analysed or predicted. A transesterification reaction between ethyl alcohol and butyl acetate, catalysed by concentrated sulphuric acid, was selected for the investigation and all the components were analysed on a gas liquid chromatograph. The transesterification reaction kinetics have been studied in a batch reactor for catalyst concentrations of 0.1 - 1.0 weight percent and temperatures between 21.4 and 85.0 °C. The reaction was found to be second order and dependent on the catalyst concentration at a given temperature. The vapour liquid equilibrium data for six binary, four ternary and one quaternary systems are measured at atmospheric pressure using a modified Cathala dynamic equilibrium still. The systems with the exception of ethyl alcohol - butyl alcohol mixtures, were found to be non-ideal. Multicomponent vapour liquid equilibrium compositions were predicted by a computer programme which utilised the Van Laar constants obtained from the binary data sets. Good agreement was obtained between the predicted and experimental quaternary equilibrium vapour compositions. Continuous transesterification experiments were carried out in a six stage sieve plate distillation column. The column was 3" in internal diameter and of unit construction in glass. The plates were 8" apart and had a free area of 7.7%. Both the liquid and vapour streams were analysed. The component conversion was dependent on the boilup rate and the reflux ratio. Because of the presence of the reaction, the concentration of one of the lighter components increased below the feed plate. In the same region a highly developed foam was formed due to the presence of the catalyst. The experimental results were analysed by the solution of a series of simultaneous enthalpy and mass equations. Good agreement was obtained between the experimental and calculated results.

Hydro-physical characterization of media used in agricultural systems to develop the best management practices for operation of an environmentally sustainable agricultural enterprise

Florida is the second leading horticulture state in the United States with a total annual industry sale of over $12 Billion. Due to its competitive nature, agricultural plant production represents an extremely intensive practice with large amounts of water and fertilizer usage. Agrochemical and water management are vital for efficient functioning of any agricultural enterprise, and the subsequent nutrient loading from such agricultural practices has been a concern for environmentalists. A thorough understanding of the agrochemical and the soil amendments used in these agricultural systems is of special interest as contamination of soils can cause surface and groundwater pollution leading to ecosystem toxicity. The presence of fragile ecosystems such as the Everglades, Biscayne Bay and Big Cypress near enterprises that use such agricultural systems makes the whole issue even more imminent. Although significant research has been conducted with soils and soil mix, there is no acceptable method for determining the hydraulic properties of mixtures that have been subjected to organic and inorganic soil amendments. Hydro-physical characterization of such mixtures can facilitate the understanding of water retention and permeation characteristics of the commonly used mix which can further allow modeling of soil water interactions. The objective of this study was to characterize some of the locally and commercially available plant growth mixtures for their hydro-physical properties and develop mathematical models to correlate these acquired basic properties to the hydraulic conductivity of the mixture. The objective was also to model the response patterns of soil amendments present in those mixtures to different water and fertilizer use scenarios using the characterized hydro-physical properties with the help of Everglades-Agro-Hydrology Model. The presence of organic amendments helps the mixtures retain more water while the inorganic amendments tend to adsorb more nutrients due to their high surface area. The results of these types of characterization can provide a scientific basis for understanding the non-point source water pollution from horticulture production systems and assist in the development of the best management practices for the operation of environmentally sustainable agricultural enterprise

On the Regulation of Small Actors: Three Experimental Essays about Policies based on Voluntary Compliance and Decentralized Monitoring

Monitoring and enforcement are perhaps the biggest challenges in the design and implementation of environmental policies in developing countries where the actions of many small informal actors cause significant impacts on the ecosystem services and where the transaction costs for the state to regulate them could be enormous. This dissertation studies the potential of innovative institutions based on decentralized coordination and enforcement to induce better environmental outcomes. Such policies have in common that the state plays the role of providing the incentives for organization but the process of compliance happens through decentralized agreements, trust building, signaling and monitoring. I draw from the literatures in collective action, common-pool resources, game-theory and non-point source pollution to develop the instruments proposed here. To test the different conditions in which such policies could be implemented I designed two field-experiments that I conducted with small-scale gold miners in the Colombian Pacific and with users and providers of ecosystem services in the states of Veracruz, Quintana Roo and Yucatan in Mexico. This dissertation is organized in three essays.

The first essay, “Collective Incentives for Cleaner Small-Scale Gold Mining on the Frontier: Experimental Tests of Compliance with Group Incentives given Limited State Monitoring”, examines whether collective incentives, i.e. incentives provided to a group conditional on collective compliance, could “outsource” the required local monitoring, i.e. induce group interactions that extend the reach of the state that can observe only aggregate consequences in the context of small-scale gold mining. I employed a framed field-lab experiment in which the miners make decisions regarding mining intensity. The state sets a collective target for an environmental outcome, verifies compliance and provides a group reward for compliance which is split equally among members. Since the target set by the state transforms the situation into a coordination game, outcomes depend on expectations of what others will do. I conducted this experiment with 640 participants in a mining region of the Colombian Pacific and I examine different levels of policy severity and their ordering. The findings of the experiment suggest that such instruments can induce compliance but this regulation involves tradeoffs. For most severe targets – with rewards just above costs – raise gains if successful but can collapse rapidly and completely. In terms of group interactions, better outcomes are found when severity initially is lower suggesting learning.

The second essay, “Collective Compliance can be Efficient and Inequitable: Impacts of Leaders among Small-Scale Gold Miners in Colombia”, explores the channels through which communication help groups to coordinate in presence of collective incentives and whether the reached solutions are equitable or not. Also in the context of small-scale gold mining in the Colombian Pacific, I test the effect of communication in compliance with a collective environmental target. The results suggest that communication, as expected, helps to solve coordination challenges but still some groups reach agreements involving unequal outcomes. By examining the agreements that took place in each group, I observe that the main coordination mechanism was the presence of leaders that help other group members to clarify the situation. Interestingly, leaders not only helped groups to reach efficiency but also played a key role in equity by defining how the costs of compliance would be distributed among group members.

The third essay, “Creating Local PES Institutions and Increasing Impacts of PES in Mexico: A real-Time Watershed-Level Framed Field Experiment on Coordination and Conditionality”, considers the creation of a local payments for ecosystem services (PES) mechanism as an assurance game that requires the coordination between two groups of participants: upstream and downstream. Based on this assurance interaction, I explore the effect of allowing peer-sanctions on upstream behavior in the functioning of the mechanism. This field-lab experiment was implemented in three real cases of the Mexican Fondos Concurrentes (matching funds) program in the states of Veracruz, Quintana Roo and Yucatan, where 240 real users and 240 real providers of hydrological services were recruited and interacted with each other in real time. The experimental results suggest that initial trust-game behaviors align with participants’ perceptions and predicts baseline giving in assurance game. For upstream providers, i.e. those who get sanctioned, the threat and the use of sanctions increase contributions. Downstream users contribute less when offered the option to sanction – as if that option signal an uncooperative upstream – then the contributions rise in line with the complementarity in payments of the assurance game.

Design and implementation of generalized topologies of time-interleaved variable bandpass Σ−Δ modulators

In this thesis, novel analog-to-digital and digital-to-analog generalized time-interleaved variable bandpass sigma-delta modulators are designed, analysed, evaluated and implemented that are suitable for high performance data conversion for a broad-spectrum of applications. These generalized time-interleaved variable bandpass sigma-delta modulators can perform noise-shaping for any centre frequency from DC to Nyquist. The proposed topologies are well-suited for Butterworth, Chebyshev, inverse-Chebyshev and elliptical filters, where designers have the flexibility of specifying the centre frequency, bandwidth as well as the passband and stopband attenuation parameters. The application of the time-interleaving approach, in combination with these bandpass loop-filters, not only overcomes the limitations that are associated with conventional and mid-band resonator-based bandpass sigma-delta modulators, but also offers an elegant means to increase the conversion bandwidth, thereby relaxing the need to use faster or higher-order sigma-delta modulators. A step-by-step design technique has been developed for the design of time-interleaved variable bandpass sigma-delta modulators. Using this technique, an assortment of lower- and higher-order single- and multi-path generalized A/D variable bandpass sigma-delta modulators were designed, evaluated and compared in terms of their signal-to-noise ratios, hardware complexity, stability, tonality and sensitivity for ideal and non-ideal topologies. Extensive behavioural-level simulations verified that one of the proposed topologies not only used fewer coefficients but also exhibited greater robustness to non-idealties. Furthermore, second-, fourth- and sixth-order single- and multi-path digital variable bandpass digital sigma-delta modulators are designed using this technique. The mathematical modelling and evaluation of tones caused by the finite wordlengths of these digital multi-path sigmadelta modulators, when excited by sinusoidal input signals, are also derived from first principles and verified using simulation and experimental results. The fourth-order digital variable-band sigma-delta modulator topologies are implemented in VHDL and synthesized on Xilinx® SpartanTM-3 Development Kit using fixed-point arithmetic. Circuit outputs were taken via RS232 connection provided on the FPGA board and evaluated using MATLAB routines developed by the author. These routines included the decimation process as well. The experiments undertaken by the author further validated the design methodology presented in the work. In addition, a novel tunable and reconfigurable second-order variable bandpass sigma-delta modulator has been designed and evaluated at the behavioural-level. This topology offers a flexible set of choices for designers and can operate either in single- or dual-mode enabling multi-band implementations on a single digital variable bandpass sigma-delta modulator. This work is also supported by a novel user-friendly design and evaluation tool that has been developed in MATLAB/Simulink that can speed-up the design, evaluation and comparison of analog and digital single-stage and time-interleaved variable bandpass sigma-delta modulators. This tool enables the user to specify the conversion type, topology, loop-filter type, path number and oversampling ratio.

Properties of a composite material with mixed imperfect contact conditions

We present an analytical solution of a mixed boundary value problem for an unbounded 2D doubly periodic domain which is a model of a composite material with mixed imperfect interface conditions. We find the effective conductivity of the composite material with mixed imperfect interface conditions, and also give numerical analysis of several of their properties such as temperature and flux.