Techniques for batch reinforcement learning in robotics

This thesis addresses the Batch Reinforcement Learning methods in Robotics. This sub-class of Reinforcement Learning has shown promising results and has been the focus of recent research. Three contributions are proposed that aim to extend the state-of-art methods allowing for a faster and more stable learning process, such as required for learning in Robotics. The Q-learning update-rule is widely applied, since it allows to learn without the presence of a model of the environment. However, this update-rule is transition-based and does not take advantage of the underlying episodic structure of collected batch of interactions. The Q-Batch update-rule is proposed in this thesis, to process experiencies along the trajectories collected in the interaction phase. This allows a faster propagation of obtained rewards and penalties, resulting in faster and more robust learning. Non-parametric function approximations are explored, such as Gaussian Processes. This type of approximators allows to encode prior knowledge about the latent function, in the form of kernels, providing a higher level of exibility and accuracy. The application of Gaussian Processes in Batch Reinforcement Learning presented a higher performance in learning tasks than other function approximations used in the literature. Lastly, in order to extract more information from the experiences collected by the agent, model-learning techniques are incorporated to learn the system dynamics. In this way, it is possible to augment the set of collected experiences with experiences generated through planning using the learned models. Experiments were carried out mainly in simulation, with some tests carried out in a physical robotic platform. The obtained results show that the proposed approaches are able to outperform the classical Fitted Q Iteration.

Thermodynamic efficiency of carbon capture and utilisation in anaerobic batch digestion process

Carbon capture and storage (CCS) in the oil and water industries is becoming common and a significant consumer of energy typically requiring 150–450 °C and or several hundred bar pressure [1] particularly in geological deposition. A biological carbon capture and conversion has been considered in conventional anaerobic digestion processes. The process has been utilised in biological mixed culture, where acetoclastic bacteria and hydrogenophilic methanogens play a major key role in the utilisation of carbon dioxide. However, the bio catalytic microorganisms, hydrogenophilic methanogens are reported to be unstable with acetoclastic bacteria. In this work the biochemical thermodynamic efficiency was investigated for the stabilisation of the microbial process in carbon capture and utilisation. The authors observed that a thermodynamic efficiency of biological carbon capture and utilisation (BCCU) had 32% of overall reduction in yield of carbon dioxide with complimentary increase of 30% in yield of methane, while the process was overall endothermic. Total consumption of energy (≈0.33 MJ l−1) was estimated for the carbonate solubility (0.1 mol l−1) in batched BCCU. This has a major influence on microbial composition in the bioreactor. This thermodynamic study is an essential tool to aid the understanding of the interactions between operating parameters and the mixed microbial culture.

Temperature regulation of a pilot-scale batch reaction system via explicit model predictive control

In this paper, the temperature of a pilot-scale batch reaction system is modeled towards the design of a controller based on the explicit model predictive control (EMPC) strategy -- Some mathematical models are developed from experimental data to describe the system behavior -- The simplest, yet reliable, model obtained is a (1,1,1)-order ARX polynomial model for which the mentioned EMPC controller has been designed -- The resultant controller has a reduced mathematical complexity and, according to the successful results obtained in simulations, will be used directly on the real control system in a next stage of the entire experimental framework

Topics in equilibrium and nonequilibrium thermodynamics: computing crystalline free energies and engineering Maxwell’s demon.

This dissertation covers two separate topics in statistical physics. The first part of the dissertation focuses on computational methods of obtaining the free energies (or partition functions) of crystalline solids. We describe a method to compute the Helmholtz free energy of a crystalline solid by direct evaluation of the partition function. In the many-dimensional conformation space of all possible arrangements of N particles inside a periodic box, the energy landscape consists of localized islands corresponding to different solid phases. Calculating the partition function for a specific phase involves integrating over the corresponding island. Introducing a natural order parameter that quantifies the net displacement of particles from lattices sites, we write the partition function in terms of a one-dimensional integral along the order parameter, and evaluate this integral using umbrella sampling. We validate the method by computing free energies of both face-centered cubic (FCC) and hexagonal close-packed (HCP) hard sphere crystals with a precision of $10^{-5}k_BT$ per particle. In developing the numerical method, we find several scaling properties of crystalline solids in the thermodynamic limit. Using these scaling properties, we derive an explicit asymptotic formula for the free energy per particle in the thermodynamic limit. In addition, we describe several changes of coordinates that can be used to separate internal degrees of freedom from external, translational degrees of freedom. The second part of the dissertation focuses on engineering idealized physical devices that work as Maxwell's demon. We describe two autonomous mechanical devices that extract energy from a single heat bath and convert it into work, while writing information onto memory registers. Additionally, both devices can operate as Landauer's eraser, namely they can erase information from a memory register, while energy is dissipated into the heat bath. The phase diagrams and the efficiencies of the two models are solved and analyzed. These two models provide concrete physical illustrations of the thermodynamic consequences of information processing.

Energy requirements for the continuous biohydrogen production from Spirogyra biomass in a sequential batch reactor

The current energy market requires urgent revision for the introduction of renewable, less-polluting and inexpensive energy sources. Biohydrogen (bioH2) is considered to be one of the most appropriate options for this model shift, being easily produced through the anaerobic fermentation of carbohydrate-containing biomass. Ideally, the feedstock should be low-cost, widely available and convertible into a product of interest. Microalgae are considered to possess the referred properties, being also highly valued for their capability to assimilate CO2 [1]. The microalga Spirogyra sp. is able to accumulate high concentrations of intracellular starch, a preferential carbon source for some bioH2 producing bacteria such as Clostridium butyricum [2]. In the present work, Spirogyra biomass was submitted to acid hydrolysis to degrade polymeric components and increase the biomass fermentability. Initial tests of bioH2 production in 120 mL reactors with C. butyricum yielded a maximum volumetric productivity of 141 mL H2/L.h and a H2 production yield of 3.78 mol H2/mol consumed sugars. Subsequently, a sequential batch reactor (SBR) was used for the continuous H2 production from Spirogyra hydrolysate. After 3 consecutive batches, the fermentation achieved a maximum volumetric productivity of 324 mL H2/L.h, higher than most results obtained in similar production systems [3] and a potential H2 production yield of 10.4 L H2/L hydrolysate per day. The H2 yield achieved in the SBR was 2.59 mol H2/mol, a value that is comparable to those attained with several thermophilic microorganisms [3], [4]. In the present work, a detailed energy consumption of the microalgae value-chain is presented and compared with previous results from the literature. The specific energy requirements were determined and the functional unit considered was gH2 and MJH2. It was possible to identify the process stages responsible for the highest energy consumption during bioH2 production from Spirogyra biomass for further optimisation.

Optimisation de l'extraction, en réacteur "batch", de biomasse énergétique à l'aide d'émulsions ultrasoniques de solvants verts

L’industrie des biocarburants de deuxième génération utilise, entre autre, la biomasse lignocellulosique issue de résidus forestiers et agricoles et celle issue de cultures énergétiques. Le sorgho sucré [Sorghum bicolor (L.) Moench] fait partie de ces cultures énergétiques. L’intérêt croissant de l’industrie agroalimentaire et des biocarburants pour cette plante est dû à sa haute teneur en sucres (jusqu’à 60% en masse sèche). En plus de se développer rapidement (en 5-6 mois), le sorgho sucré a l’avantage de pouvoir croître sur des sols pauvres en nutriments et dans des conditions de faibles apports en eau, ce qui en fait une matière première intéressante pour l’industrie, notamment pour la production de bioéthanol. Le concept de bioraffinerie alliant la production de biocarburants à celle de bioénergies ou de bioproduits est de plus en plus étudié afin de valoriser la production des biocarburants. Dans le contexte d’une bioraffinerie exploitant la biomasse lignocellulosique, il est nécessaire de s’intéresser aux différents métabolites extractibles en plus des macromolécules permettant la fabrication de biocarburants et de biocommodités. Ceux-ci pouvant avoir une haute valeur ajoutée et intéresser l’industrie pharmaceutique ou cosmétique par exemple. Les techniques classiques pour extraire ces métabolites sont notamment l’extraction au Soxhlet et par macération ou percolation, qui sont longues et coûteuses en énergie. Ce projet s’intéresse donc à une méthode d’extraction des métabolites primaires et secondaires du sorgho sucré, moins coûteuse et plus courte, permettant de valoriser économiquement l’exploitation industrielle du de cette culture énergétique. Ce travail au sein de la CRIEC-B a porté spécifiquement sur l’utilisation d’une émulsion ultrasonique eau/carbonate de diméthyle permettant de diminuer les temps d’opération (passant à moins d’une heure au lieu de plusieurs heures) et les quantités de solvants mis en jeu dans le procédé d’extraction. Cette émulsion extractive permet ainsi de solubiliser à la fois les métabolites hydrophiles et ceux hydrophobes. De plus, l’impact environnemental est limité par l’utilisation de solvants respectueux de l’environnement (80 % d’eau et 20 % de carbonate de diméthyle). L’utilisation de deux systèmes d’extraction a été étudiée. L’un consiste en la recirculation de l’émulsion, en continu, au travers du lit de biomasse; le deuxième permet la mise en contact de la biomasse et des solvants avec la sonde à ultrasons, créant l’émulsion et favorisant la sonolyse de la biomasse. Ainsi, en réacteur « batch » avec recirculation de l’émulsion eau/DMC, à 370 mL.min[indice supérieur -1], au sein du lit de biomasse, l’extraction est de 37,91 % en 5 minutes, ce qui est supérieur à la méthode ASTM D1105-96 (34,01 % en 11h). De plus, en réacteur « batch – piston », où la biomasse est en contact direct avec les ultrasons et l’émulsion eau/DMC, les meilleurs rendements sont de 35,39 % en 17,5 minutes, avec 15 psig de pression et 70 % d’amplitude des ultrasons. Des tests effectués sur des particules de sorgho grossières ont donné des résultats similaires avec 30,23 % d’extraits en réacteur « batch » avec recirculation de l’émulsion (5 min, 370 mL.min[indice supérieur -1]) et 34,66 % avec le réacteur « batch-piston » (30 psig, 30 minutes, 95 % d’amplitude).

Computational modelling of non-equilibrium condensing steam flows in low-pressure steam turbines

The steam turbines play a significant role in global power generation. Especially, research on low pressure (LP) steam turbine stages is of special importance for steam turbine man- ufactures, vendors, power plant owners and the scientific community due to their lower efficiency than the high pressure steam turbine stages. Because of condensation, the last stages of LP turbine experience irreversible thermodynamic losses, aerodynamic losses and erosion in turbine blades. Additionally, an LP steam turbine requires maintenance due to moisture generation, and therefore, it is also affecting on the turbine reliability. Therefore, the design of energy efficient LP steam turbines requires a comprehensive analysis of condensation phenomena and corresponding losses occurring in the steam tur- bine either by experiments or with numerical simulations. The aim of the present work is to apply computational fluid dynamics (CFD) to enhance the existing knowledge and understanding of condensing steam flows and loss mechanisms that occur due to the irre- versible heat and mass transfer during the condensation process in an LP steam turbine. Throughout this work, two commercial CFD codes were used to model non-equilibrium condensing steam flows. The Eulerian-Eulerian approach was utilised in which the mix- ture of vapour and liquid phases was solved by Reynolds-averaged Navier-Stokes equa- tions. The nucleation process was modelled with the classical nucleation theory, and two different droplet growth models were used to predict the droplet growth rate. The flow turbulence was solved by employing the standard k-ε and the shear stress transport k-ω turbulence models. Further, both models were modified and implemented in the CFD codes. The thermodynamic properties of vapour and liquid phases were evaluated with real gas models. In this thesis, various topics, namely the influence of real gas properties, turbulence mod- elling, unsteadiness and the blade trailing edge shape on wet-steam flows, are studied with different convergent-divergent nozzles, turbine stator cascade and 3D turbine stator-rotor stage. The simulated results of this study were evaluated and discussed together with the available experimental data in the literature. The grid independence study revealed that an adequate grid size is required to capture correct trends of condensation phenomena in LP turbine flows. The study shows that accurate real gas properties are important for the precise modelling of non-equilibrium condensing steam flows. The turbulence modelling revealed that the flow expansion and subsequently the rate of formation of liquid droplet nuclei and its growth process were affected by the turbulence modelling. The losses were rather sensitive to turbulence modelling as well. Based on the presented results, it could be observed that the correct computational prediction of wet-steam flows in the LP turbine requires the turbulence to be modelled accurately. The trailing edge shape of the LP turbine blades influenced the liquid droplet formulation, distribution and sizes, and loss generation. The study shows that the semicircular trailing edge shape predicted the smallest droplet sizes. The square trailing edge shape estimated greater losses. The analysis of steady and unsteady calculations of wet-steam flow exhibited that in unsteady simulations, the interaction of wakes in the rotor blade row affected the flow field. The flow unsteadiness influenced the nucleation and droplet growth processes due to the fluctuation in the Wilson point.

Quitosana imobilizada em suporte inerte para a adsorção de corantes alimentícios em coluna de leito fixo

O uso de corantes sintéticos na indústria de alimentos tem provocado transtornos à saúde humana e ao meio ambiente. A quitosana pode ser imobilizada em matrizes sólidas e aplicada na remoção de corantes em coluna de leito fixo. A análise da dinâmica de uma coluna de leito fixo é baseada na curva de ruptura, esta é dependente da geometria da coluna, das condições operacionais e dos dados de equilíbrio. Neste contexto, o objetivo deste trabalho foi estudar o recobrimento de esferas de vidro por quitosana e sua aplicação como adsorvente de corantes em coluna de leito fixo. No estudo do recobrimento avaliaram-se os efeitos da concentração de quitosana e dos métodos de cura. As esferas recobertas foram aplicadas em ensaios de adsorção estático e dinâmico. Inicialmente, avaliou-se o equilíbrio de adsorção através da construção de isotermas e ajuste de modelos, e após, avaliaram-se os efeitos do tipo de cura e do grau de desacetilação da quitosana. Em seguida, foram analisados os efeitos do tipo de corante e do pH, e o comportamento cinético da adsorção pela construção de curvas de ruptura e ajuste de modelos dinâmicos. A influência da altura do leito e da concentração inicial de corante sobre os parâmetros da adsorção em leito fixo foram analisados através da metodologia de superfície de resposta (MSR). Ao final, estudou-se a regeneração da coluna. Os resultados mostraram que os maiores percentuais de recobrimento foram obtidos pelos métodos físico e físico/químico, na concentração de quitosana de 0,5% (m/v). Nestas condições o percentual de recobrimento foi de 46%. Nas imagens da superfície das esferas (MEV) observou-se que as mesmas foram recobertas de forma homogênea pela quitosana. As isotermas de equilíbrio obtidas foram classificadas como do tipo V, sendo o modelo de Sips o mais adequado para representar os dados experimentais. As capacidades máximas de adsorção foram 337 mg g-1, 286 mg g-1 e 200 mg g-1 para os corantes amarelo tartrazina, amarelo crepúsculo e vermelho 40, respectivamente. A aplicação das esferas recobertas com quitosana em leito fixo mostrou-se mais adequada utilizando o método de cura físico/químico e quitosana com grau de desacetilação de 85%. A máxima capacidade de adsorção da coluna em função do corante e do pH variou de 13 a 108 mg g–1. Os modelos BDST (bed–depth–service–time), Thomas e Yoon–Nelson foram adequados para representar os dados experimentais. De acordo com a MSR, o melhor desempenho do leito foi com altura de 30 cm e concentração inicial de corante de 50 mg L-1. Nestas condições, obteve-se tempo de ruptura de 88 min, máxima capacidade da coluna de 108 mg g-1 e remoção de 86 %. Na regeneração da coluna observou-se que cerca de 75% da capacidade máxima da coluna foi mantida após cinco ciclos de adsorção–eluição. Diante do exposto, a coluna de leito fixo empacotada com esferas recobertas com quitosana mostrou-se promissora na remoção de corantes de soluções aquosas.

Banana peel: an effective biosorbent for aflatoxins

This work reports the application of banana peel as a novel bioadsorbent for in vitro removal of five mycotoxins (aflatoxins (AFB1, AFB2, AFG1, AFG2) and ochratoxin A). The effect of operational parameters including initial pH, adsorbent dose, contact time and temperature were studied in batch adsorption experiments. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and point of zero charge (pHpzc) analysis were used to characterise the adsorbent material. Aflatoxins’ adsorption equilibrium was achieved in 15 min, with highest adsorption at alkaline pH (6–8), while ochratoxin has not shown any significant adsorption due to surface charge repulsion. The experimental equilibrium data were tested by Langmuir, Freundlich and Hill isotherms. The Langmuir isotherm was found to be the best fitted model for aflatoxins, and the maximum monolayer coverage (Q0) was determined to be 8.4, 9.5, 0.4 and 1.1 ng mg−1 for AFB1, AFB2, AFG1 and AFG2 respectively. Thermodynamic parameters including changes in free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) were determined for the four aflatoxins. Free energy change and enthalpy change demonstrated that the adsorption process was exothermic and spontaneous. Adsorption and desorption study at different pH further demonstrated that the sorption of toxins was strong enough to sustain pH changes that would be experienced in the gastrointestinal tract. This study suggests that biosorption of aflatoxins by dried banana peel may be an effective low-cost decontamination method for incorporation in animal feed diets. © 2016 Informa UK Limited, trading as Taylor & Francis Group.

Adsorção de corantes têxteis aniônicos e catiônicos em resíduos do processamento de fios de algodão modificados quimicamente

The textile industry generates a large volume of high organic effluent loading whoseintense color arises from residual dyes. Due to the environmental implications caused by this category of contaminant there is a permanent search for methods to remove these compounds from industrial waste waters. The adsorption alternative is one of the most efficient ways for such a purpose of sequestering/remediation and the use of inexpensive materials such as agricultural residues (e.g., sugarcane bagasse) and cotton dust waste (CDW) from weaving in their natural or chemically modified forms. The inclusion of quaternary amino groups (DEAE+) and methylcarboxylic (CM-) in the CDW cellulosic structure generates an ion exchange capacity in these formerly inert matrix and, consequently, consolidates its ability for electrovalent adsorption of residual textile dyes. The obtained ionic matrices were evaluated for pHpcz, the retention efficiency for various textile dyes in different experimental conditions, such as initial concentration , temperature, contact time in order to determine the kinetic and thermodynamic parameters of adsorption in batch, turning comprehensive how does occur the process, then understood from the respective isotherms. It was observed a change in the pHpcz for CM--CDW (6.07) and DEAE+-CDW (9.66) as compared to the native CDW (6.46), confirming changes in the total surface charge. The ionized matrices were effective for removing all evaluated pure or residual textile dyes under various tested experimental conditions. The kinetics of the adsorption process data had best fitted to the model a pseudosecond order and an intraparticle diffusion model suggested that the process takes place in more than one step. The time required for the system to reach equilibrium varied according to the initial concentration of dye, being faster in diluted solutions. The isotherm model of Langmuir was the best fit to the experimental data. The maximum adsorption capacity varied differently for each tested dye and it is closely related to the interaction adsorbent/adsorbate and dye chemical structure. Few dyes obtained a linear variation of the balance ka constant due to the inversion of temperature and might have influence form their thermodynamic behavior. Dyes that could be evaluated such as BR 18: 1 and AzL, showed features of an endothermic adsorption process (ΔH° positive) and the dye VmL presented exothermic process characteristics (ΔH° negative). ΔG° values suggested that adsorption occurred spontaneously, except for the BY 28 dye, and the values of ΔH° indicated that adsorption occurred by a chemisorption process. The reduction of 31 to 51% in the biodegradability of the matrix after the dye adsorption means that they must go through a cleaning process before being discarded or recycled, and the regeneration test indicates that matrices can be reused up to five times without loss of performance. The DEAE+-CDW matrix was efficient for the removal of color from a real textile effluent reaching an UV-Visible spectral area decrease of 93% when applied in a proportion of 15 g ion exchanger matrix L-1 of colored wastewater, even in the case of the parallel presence of 50 g L-1 of mordant salts in the waste water. The wide range of colored matter removal by the synthesized matrices varied from 40.27 to 98.65 mg g-1 of ionized matrix, obviously depending in each particular chemical structure of the dye upon adsorption.

Effect of sea water level rise on sandy beach profile

Study of batch profile evolution and scouring effect due to the wave and current impacts in the coastal zone has been one of the most important issues in coastal engineering research projects during the past decades .to construct the coastal protective structures such piers, breakwaters and seawalls, it is necessary to estimate the scouring depth and bed level changes in the vicinity of such structures. Furthermore, the time - dependent changes in the equilibrium profile of the surf zone can be of great importance in designing coastal structures. Because of the importance of coastal engineering study in Iran due to the existence of two important coastal area located in the north and south parts of the country, and due to the lack of classified data in this respect (particularly the effect of sea level rise on coastal morphology) in the present study, based on the available data of Bandar Anzali region, an analysis of the coastal zone behavior is made. Bed level elevations are measured and compared with the theoretical equilibrium profile. It is shown that the behavior of the coastal zone in the region is consistent with the dean (equilibrium profile . In the next stage, following extensive investigations, the bed level changes due to a rise in sea level at different locations in the surf zone are estimated. Finally based on the results obtained for profile evolution due to sea level rise, the conclusion is made for design of coastal structures located in the study area. The results obtained from the present study indicate that the sea level rise can have a significant effect on beach profile and resulting erosion in the study area. The results are graphically presented with can be used for design purposes and establishing a data base for the coastal zone in the study region. It is believed that the present work can be regarded as a contribution to the existing knowledge of coast process in the study area and referred to as a basis for the future coastal research projects.

Other-Regarding Preferences in General Equilibrium

We study competitive market outcomes in economies where agents have other-regarding preferences. We identify a separability condition on monotone preferences that is necessary and sufficient for one’s own demand to be independent of the allocations and characteristics of other agents in the economy. Given separability, it is impossible to identify other-regarding preferences from market behavior: agents be- have as if they had classical preferences that depend only on own consumption in competitive equilibrium. If preferences, in addition, depend only on the final allocation of consumption in society, the Sec- ond Welfare Theorem holds as long as an increase in resources can be distributed such that all agents are better off. Nevertheless, the First Welfare Theorem generally does not hold. Allowing agents to care about their own consumption and the distribution of consump- tion possibilities in the economy, we provide a condition under which agents have no incentive to make direct transfers, and show that this condition implies that competitive equilibria are efficient given prices.

Rare sex or out of reach equilibrium? The dynamics of F-IS in partially clonal organisms

Background: Partially clonal organisms are very common in nature, yet the influence of partial asexuality on the temporal dynamics of genetic diversity remains poorly understood. Mathematical models accounting for clonality predict deviations only for extremely rare sex and only towards mean inbreeding coefficient (F-IS) over bar < 0. Yet in partially clonal species, both F-IS < 0 and F-IS > 0 are frequently observed also in populations where there is evidence for a significant amount of sexual reproduction. Here, we studied the joint effects of partial clonality, mutation and genetic drift with a state-and-time discrete Markov chain model to describe the dynamics of F-IS over time under increasing rates of clonality. Results: Results of the mathematical model and simulations show that partial clonality slows down the asymptotic convergence to F-IS = 0. Thus, although clonality alone does not lead to departures from Hardy-Weinberg expectations once reached the final equilibrium state, both negative and positive F-IS values can arise transiently even at intermediate rates of clonality. More importantly, such "transient" departures from Hardy Weinberg proportions may last long as clonality tunes up the temporal variation of F-IS and reduces its rate of change over time, leading to a hyperbolic increase of the maximal time needed to reach the final mean (F-IS,F-infinity) over bar value expected at equilibrium. Conclusion: Our results argue for a dynamical interpretation of F-IS in clonal populations. Negative values cannot be interpreted as unequivocal evidence for extremely scarce sex but also as intermediate rates of clonality in finite populations. Complementary observations (e.g. frequency distribution of multiloci genotypes, population history) or time series data may help to discriminate between different possible conclusions on the extent of clonality when mean (F-IS) over bar values deviating from zero and/or a large variation of F-IS over loci are observed.

In situ differentiation of labile/inert metal species in Brazilian tropical rivers by means of a time-controlled batch-procedure based on TEPHA resin

The present study deals with a new analytical procedure based on a cellulose diffusion membrane and immobilised tetraethylene-pentamine-hexaacetate chelator (DM-TEPHA) for an in situ differentiation of labile and inert metal species in aquatic systems. The DM-TEPHA system was prepared by placing TEPHA chelator in pre-purified cellulose bags and in situ applied immersing the system in two Brazilian rivers to study the relative lability of metal species (Cu, Pb, Fe, Mn and Ni) as a function of the time and the quantity of exchanger, respectively. The procedure is simple and enables a new perspective for understanding the complexation, transport, stability and lability of metal species in aquatic systems rich in organic matter.

Vapor–liquid equilibrium of binary mixtures containing isopropyl acetate and alkanols at 101.32 kPa

Isobaric vapor-liquid equilibria of binary mixtures of isopropyl acetate plus an alkanol (1-propanol, 2-propanol, 1-butanol, or 2-butanol) were measured at 101.32 kPa, using a dynamic recirculating still. An azeotropic behavior was observed only in the mixtures of isopropyl acetate + 2-propanol and isopropyl acetate + 1-propanol. The application of four thermodynamic consistency tests (the Herington test, the Van Ness test, the infinite dilution test, and the pure component test) showed the high quality of the experimental data. Finally, both NRTL and UNIQUAC activity coefficient models were successfully applied in the correlation of the measured data, with the average absolute deviations in vapor phase composition and temperature of 0.01 and 0.16 K, respectively.