**1. Introduction**

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A comprehensive investigation of the phase equilibriums and determination of thermodynamic properties of pure substances is a significant object of the chemical thermodynamics. Data on the phase transitions, heat capacities, and saturation vapor pressure over the solid and liquid phases are used in many fields of science and technology, including calculations on the basis of the third law of thermodynamics. Theoretical and practical applications of thermodynamic data require verification of their reliability. The Clapeyron equation combines different properties of coexisting phases: temperature, vapor pressure, volume, enthalpy of the phase transitions, and caloric values*Cp* and*Cv* . Using this equation allows one to verify numerical data for thermodynamic concordance, to reveal unreliable quantities, and to predict failing thermodynamic properties. Mutual concordance and reliability of the calorimetric data on the heat capacity, the saturated vapor pressures, and the properties of phase transition can be verified by comparison of the absolute entropies determined from the experimental data by the third thermodynamic law, ( )( ) *o S g m* e x p t with those ones calculated by statistical thermodynamics, ( ) *o S stat m* . A congruence of these values within errors limits justifies their reliability. Critical analyses of the recent data on thermodynamic properties of some organic compounds are published by the National Institute of the Standards and Technology [NIST], USA. Literature data on the vapor pressures and the enthalpies of vaporization for *n*-alkanes C5 – C20 were reviewed and critically analyzed in the reference (Ruzicka & Majer, 1994). Thermodynamic properties of many classes of organic compounds were considered in monograph (Domalski & Hearing, 1993; Poling et al., 2001) that favoured the development of the Benson's calculation method. This chapter deals with reviewing and summarizing the data on the phase equilibriums carried out for some functional organic compounds by the low temperature adiabatic calorimetry, comparative ebulliometry, and vaporization calorimetry in the Luginin's Laboratory of Thermochemistry [LLT] of the Moscow State University [MSU] and other research centres. The numerous data on the heat capacity, the vapor pressure, enthalpies of the phase transitions, and derived thermodynamic functions were obtained for series of freons, cyclic hydrocarbons and fluorocarbons, and derivatives of ferrocene. A sufficient attention was given to the critical analyses of the thermodynamic data, their reliability, and

to interconnections between the properties and some structural parameters of the

Thermodynamics of the Phase Equilibriums of Some Organic Compounds 597

condensed states were calculated on the basis of the heat capacities and the properties of the

Part 4 deals with 1) determination of the ideal gas thermodynamic functions by experimental and theoretical methods, 2) verification of the thermodynamic functions by comparing the absolute entropies calculated on the basis of the third thermodynamic law and by statistical thermodynamics, and 3) the methods of extending the saturated vapor pressure of the "atmospheric" range of pressure to entire region of liquids from the triple to

Parts 5, 6, 7, and 8 present Conclusion, Acknowledgments, References, and Appendix,

The values of the vapor pressure of liquid substances are mostly determined by the static and dynamic (mainly ebulliometric) methods. A comparative ebulliometry is frequently employed due to its simpler technique and suitability for the series of determinations. The greatest number of saturated vapor pressure of organic compounds was obtained by this method in the moderate ("atmospheric") range of pressure 2-3 (, ) *p* k P a 100-150. The highest accurate of vapor pressure is usually attained in this range that makes it possible to obtain reliable derivative values, in particular, the enthalpies of vaporization. Few *pT* data are available in the literature for the entire region of liquid phase because of methodical difficulties and high errors of determination at low (<1 kPa) and high (>200 kPa) pressures.

Fig. 1 presents a schematic view of a setup designed for determinations of the temperature dependence of saturation vapor pressure by comparative ebulliometry (Varouchtchenko &

Fig. 1. The setup for determination of the *pT* parameters: DE, differential ebulliometer; MS, manometer system; (1) mercury-contact manometer; (2) electromagnetic valve; (3) roughing

**2. Temperature dependence of saturated vapor pressure**

**2.1 Experimental and mathematical processing**

pump; (4) ballast reservoir; (5) traps

solid-to-solid transitions and fusion.

the critical temperatures.

respectively.

Droujinina, 1995).

compounds. Experimental and calculation methods for determination of the properties rely mostly on the LLT-school.

Freons are halogen derivatives of ethane and propane which possess a unique combination of the useful properties: high volatility, high enthalpy of vaporization, no combustibility, biological inertness, etc. Due to these properties, freons have found a wide application in many areas of science, technology, and medicine (Varushchenko et. al., 2007).

Alkyl derivatives of adamantine, C10H16, , are of an interest due to tendency to form plastic crystals. Bicyclical *cis*- and *trans-* isomers of decaline, C10H18, , and hydrindane, C9H16, , have poor intermolecular interactions and also form plastic crystals. Their perfluoride counterparts exhibit high chemical stability, absolute biological inertness, and capacity for dissolving and transferring large amounts of gases, in particular, oxygen and carbon dioxide. Due to these properties, perfluorocarbons have found wide application in biology and medicine as effective gas-transferring media and artificial blood substitutes. A mixture of perfluorodecaline, C10F18, and perfluoro-N-(4-methylcyclohexyl)piperidine, C12F23N, forms of the "Ftorosan" blood substitute (Russia) (Ries*,* 1991). Bicyclical *cis*- and *trans-* isomers of decaline and hydrindane are of the interest in study of an interconnection between thermodynamic properties and the structure of the compounds when passing from perfluorocarbons to their hydrocarbon counterparts.

Alkyl- and acyl- ferrocene derivatives [FD] are the sandwich-type organometallic compounds discovered in the 50th years of the XX century. Owing to favourable conjunction of the chemical and physical properties, namely low toxicity, high thermal stability, and volatility, some FD has found ever-increasing application in technology (electric materials, regulators of fuel combustion etc.) and medicine (anti-cancer and blood-creating drugs).

This chapter is intended for researchers with an interest in measuring characteristics of the phase transitions and in determination of the equilibrium properties by experimental and theoretical methods. A number of relationships for practical use are represented with illustrative examples and necessary recommendations. The chapter contains main references to the literature used in reviewing and summarizing the numerous data on the properties of some functional organic compounds.

Part 2 deals with the ebulliometric and transpiration methods for determination of the saturation vapor pressure in dependence on the temperature. Design of devices and experimental techniques and mathematical processing of the vapor pressures are given. A modified ebulliometer of an original construction was given for determination of the *pT* parameters in moderate ("atmospheric") pressure region. The enthalpies of vaporization obtained by direct calorimetric method and those ones calculated from the vapor pressure are compared for justifying their reliability. An interconnection between the properties derived from the vapor pressure and some structural parameters of the substances are analyzed.

Part 3 considers the low-temperature adiabatic calorimetry for measuring the heat capacity and studying the properties of the phase transitions. Experimental technique has been presented by modern completely automated adiabatic calorimeter used in LLT. Experimental determination and mathematical processing of the phase transitions were given including an X-ray analysis of crystal structure and the infrared and Raman spectroscopy for interpretation of the processes occurring during the solid-phase transitions. Main thermodynamic functions (changes of the entropy, enthalpy, and Gibb's energy) in

compounds. Experimental and calculation methods for determination of the properties rely

Freons are halogen derivatives of ethane and propane which possess a unique combination of the useful properties: high volatility, high enthalpy of vaporization, no combustibility, biological inertness, etc. Due to these properties, freons have found a wide application in

Alkyl derivatives of adamantine, C10H16, , are of an interest due to tendency to form plastic crystals. Bicyclical *cis*- and *trans-* isomers of decaline, C10H18, , and hydrindane, C9H16, , have poor intermolecular interactions and also form plastic crystals. Their perfluoride counterparts exhibit high chemical stability, absolute biological inertness, and capacity for dissolving and transferring large amounts of gases, in particular, oxygen and carbon dioxide. Due to these properties, perfluorocarbons have found wide application in biology and medicine as effective gas-transferring media and artificial blood substitutes. A mixture of perfluorodecaline, C10F18, and perfluoro-N-(4-methylcyclohexyl)piperidine, C12F23N, forms of the "Ftorosan" blood substitute (Russia) (Ries*,* 1991). Bicyclical *cis*- and *trans-* isomers of decaline and hydrindane are of the interest in study of an interconnection between thermodynamic properties and the structure of the compounds when passing from

Alkyl- and acyl- ferrocene derivatives [FD] are the sandwich-type organometallic compounds discovered in the 50th years of the XX century. Owing to favourable conjunction of the chemical and physical properties, namely low toxicity, high thermal stability, and volatility, some FD has found ever-increasing application in technology (electric materials, regulators of fuel combustion etc.) and medicine (anti-cancer and blood-creating drugs). This chapter is intended for researchers with an interest in measuring characteristics of the phase transitions and in determination of the equilibrium properties by experimental and theoretical methods. A number of relationships for practical use are represented with illustrative examples and necessary recommendations. The chapter contains main references to the literature used in reviewing and summarizing the numerous data on the properties of

Part 2 deals with the ebulliometric and transpiration methods for determination of the saturation vapor pressure in dependence on the temperature. Design of devices and experimental techniques and mathematical processing of the vapor pressures are given. A modified ebulliometer of an original construction was given for determination of the *pT* parameters in moderate ("atmospheric") pressure region. The enthalpies of vaporization obtained by direct calorimetric method and those ones calculated from the vapor pressure are compared for justifying their reliability. An interconnection between the properties derived from the vapor pressure and some structural parameters of the substances are

Part 3 considers the low-temperature adiabatic calorimetry for measuring the heat capacity and studying the properties of the phase transitions. Experimental technique has been presented by modern completely automated adiabatic calorimeter used in LLT. Experimental determination and mathematical processing of the phase transitions were given including an X-ray analysis of crystal structure and the infrared and Raman spectroscopy for interpretation of the processes occurring during the solid-phase transitions. Main thermodynamic functions (changes of the entropy, enthalpy, and Gibb's energy) in

many areas of science, technology, and medicine (Varushchenko et. al., 2007).

perfluorocarbons to their hydrocarbon counterparts.

some functional organic compounds.

analyzed.

mostly on the LLT-school.

condensed states were calculated on the basis of the heat capacities and the properties of the solid-to-solid transitions and fusion.

Part 4 deals with 1) determination of the ideal gas thermodynamic functions by experimental and theoretical methods, 2) verification of the thermodynamic functions by comparing the absolute entropies calculated on the basis of the third thermodynamic law and by statistical thermodynamics, and 3) the methods of extending the saturated vapor pressure of the "atmospheric" range of pressure to entire region of liquids from the triple to the critical temperatures.

Parts 5, 6, 7, and 8 present Conclusion, Acknowledgments, References, and Appendix, respectively.


*Edited by Nodari Vakhania*

*and Mehmet Emin Aydin*

Optimization is a key subject in engineering and other real-world problems. Swarm intelligence has emerged as a novel and effective tool for solving optimization problems. This book introduces optimization techniques and approaches and demonstrates how optimization problems can be overcome with heuristic and swarm intelligence approaches. Chapters discuss Particle Swarm Optimization (PSO) and its applications in project management, convolutional neural networks, wave scattering problems, network efficiency, and multi-objective studies.

ISBN 978-1-83968-665-8

Optimisation Algorithms and Swarm Intelligence

Published in London, UK © 2022 IntechOpen © carloscastilla / iStock


Contents

Preface

A time series is a sequence of data points that are measured and ordered over uniform time intervals. Examples include: household energy consumption, heart rates, hourly air temperature measurements, daily company stock prices, monthly auto sales, and yearly sales figures. Time series analysis is a statistical technique that analyzes time series and then extracts meaningful statistics, characteristics, and insights from the data. Some applications include identifying cyclical changes in sales of a product, forecasting business budget based on historical trends, and studying employee turnover data and employee training data to determine if there is any dependence of employee training programs on employee turnover rates over time. Thus, analyzing time series data is an important topic that has gained significant interest in the past decade. However, due to the data pattern complexity in different domains and industries nowadays, time series analysis has become very challenging and this has inspired domain scientists and practitioners to develop and apply the updated methodologies and applications to solve real-world time series

problems such as forecasting, classification, and feature extraction.

Section 1: Mining Complex Patterns in Time Series Data

the content easily.

To address the above issues, the book editor has carefully selected a number of domain experts' papers that focus on data, methods, and applications on time series analysis that provide our readers with the latest information, developments, and trends in this research area. Specifically, this book is divided into three sections: (1) Mining complex patterns in time series data, (2) Deep neural networks for time series analytics, and (3) Time Series forecasting in real-world problems. Each section includes two chapters. Each chapter starts with motivational background, technical foundations, specific methodologies, and then ends with examples and case studies to explain the concepts and techniques that help our readers understand

• Process Fault Diagnosis for Continuous Dynamic Systems over Multivariate Time Series. Use grey level co-occurrence matrices and local binary patterns to

• Fuzzy Forecast Based on Fuzzy Time Series. Use fuzzy time series for interval

• Training Deep Neural Networks with Reinforcement Learning for Time Series Forecasting. Combine multiple restricted Boltzmann machines (RBMs) and multilayer perception (MLP) and use stochastic gradient ascent (SGA) training

• CNN Approaches for Time Series Classification. Use Convolutional Neural

extract features from time series for process fault diagnosis.

prediction and long-term significance level analysis.

Network (CNN) models for time series classification.

Section 2: Deep Neural Networks for Time Series Analytics

algorithm for time series forecasting.


**1. Introduction**

Pulsed laser deposition (PLD) is a popular application of laser ablation for making thin films. The technology in its variation of the matrix-assisted pulsed laser evaporation (MAPLE) has become a potent way of making polymer and other organic coatings. The chapter will describe a new method of making nano-composite films based on concurrent ablation/evaporation of more than one organic MAPLE and inorganic PLD targets with several laser beams. The advantage is an independent and optimized control of the deposition conditions for each target. The discussion will include the design of the multi-beam multi-target deposition system, examples of the deposited nano-composite films and their properties, the encountered problems/solutions, and the future trends.

For the last three decades, PLD technique has been intensively used for deposition of many kinds of oxides, nitrides, carbides, and metals and for fabrication of thin films including those composed of superconductors, electro-optic BaTi03, piezoelectric ZnO, electro-conductive TiO2, rare earth (RE) doped phosphate glasses, etc [1–14]. Those thin films had many deficiencies that had to be addressed before making them suitable for commercial applications. The technique was used by Smith and Turner [2] in 1965 for the preparation of semiconductor and dielectric thin films. They demonstrated the stoichiometry transfer between the target and the deposited film and high deposition rates of about 0.1 nm per pulse. The occurrence of the droplets of the target material on the substrate surface has been observed in [3]. Despite some encouraging results for single-component films, the conventional single-beam single-target PLD technique remains to be poorly suitable for composite films made of the materials of different nature: one of the reasons that a single laser beam cannot be always suitable for a wide spectrum of materials. Further improvement is a new variant of PLD called the concurrent multi-beam multi-target PLD that deposits different materials simultaneously with different laser beams producing overlapping plumes. In case of polymer nano-composite films at least one of the laser beams and the target must be suitable for the process of deposition of the polymer host, such as MAPLE.

In MAPLE, a frozen solution of a polymer in a volatile solvent becomes a laser target [15–54]. The solvent and concentration of the solution are chosen in such a way that first, the polymer dissolves completely and forms a dilute solution free of particulate; second, the main portion of the laser energy is absorbed by the solvent and not by the solute; and third, no photochemical reaction occurs between the solvent and the solute. The interaction between the laser radiation and matter in MAPLE is a photothermal process. The energy of the laser beam absorbed by the solvent is converted to thermal energy that heats the polymer but causes the solvent to vaporize. As the solvent molecules escape into the gas phase, the polymer molecules gain sufficient kinetic energy via collisions with the evaporating solvent molecules and enter the gas phase as well. Selection of the optimal MAPLE conditions (laser energy and wavelength, pulse repetition rate, type of solvent, concentration of the polymer solution, temperature, and background gas and its pressure) can result in the deposition process with no significant degradation of the polymer. The MAPLE deposition is carried on layer-by-layer, while the concentration of the polymer solution in the ablated target remains constant. When a substrate

is positioned directly in the path of the plume, a film starts forming from the evaporated polymer molecules on a substrate placed in the path of the plume. At the same time, the volatile solvent molecules are taken away from the chamber by the vacuum pump. In case of fabrication of polymer nano-composites, MAPLE targets are usually prepared as nano-colloids of the additives of interest in the initial polymer solutions. Combining the components of different nature, such as polymers and inorganic substances, in the same target and ablating them with the same laser beam rarely results in nano-composite films of fair quality. The laser beam energy and wavelength cannot fit all components in the mixture. Also, the proportion of the components in the film is dictated by the target and cannot be altered in the process. The improvements can be expected in the method of concurrent multi-beam and multi-target deposition using MAPLE polymer targets and inorganic PLD targets, each being concurrently ablated by laser beams of different wavelengths [55–64]. The method can be called as multibeam multi-target MAPLE and PLD or with acronym MBMT-MAPLE/PLD that is described below.


**3.** *Schistosoma mansoni* **life cycle and maintenance in the laboratory**

Schistosome species are dioecious (having male and female reproductive organs in separate individuals) platyhelminthes and have complex life cycles comprising multiple morphologically distinct phenotypes in definitive mammalian and intermediate snail hosts. *S. mansoni* is one of the most common etiological agents of human schistosomiasis and is the most widely used schistosome model for chemotherapeutic studies.Schistosome infection of humans (or another definitive host) occurs by direct contact with freshwater containing freeswimming larval forms of the parasite, known as cercariae. Cercariae penetrate the intact human skin and transform into schistosomula, which reside in the skin for up to 72 hours before entering a blood vessel. Within the vascular system, schistosomula migrate via complex routes to their nal venous destination, where they mature into male and female adults. The mature flukes dwell in the human portal vasculature, depositing eggs in the intestinal wall that either pass to the gut lumen and are expelled in the faeces or travel to the liver and trigger immune-mediated granuloma formation and peri-portal fibrosis. Egg production commences 5 to 6 weeks after infection and continues for the life of the worm. The life cycle is completed when the eggs passed in the faeces hatch in the water, releasing the larval form miracidia, which then infect freshwater snails of the *Biomphalaria* spp. The infected snails, bearing schistosomal sporocysts, release cercariae into the water, which in turn penetrate the skin of their denitive host (Gryseels et al., 2006).

To complete a life cycle in the laboratory, *S. mansoni* is commonly maintained using rodents, ranging from hamsters to mice, as the definitive hosts and *Biomphalaria glabrata* as the intermediate host snail species (Figure 1). Infections of rodents of the same gender, 3 to 4 weeks of age and weighing 18 to 25 g, with *S. mansoni* are commonly initiated by subcutaneous injection of 100 to 150 cercariae (infective larvae). At 42, 49 or 56 days postinfection, animals are sacrificed with CO2, dissected, and miracidia are hatched from *S. mansoni* eggs taken from animal livers. Each intermediate host snail is exposed to approximately 10 miracidia. All animals should be handled in strict accordance with good animal practice adhering to the institutional guidelines for animal husbandry. Thus, all studies should have a statement from their ethics committee or institutional review board indicating the approval of the research.

The use of *in vivo* animal models in drug discovery and the techniques used for these studies in the laboratory have recently been described in detail elsewhere by Keiser (2010) and Ramirez et al. (2007). This chapter will focus on the techniques used for *in vitro* studies. Many methods have been described that aim to determine the antischistosomal activity of drugs *in vitro*. The assessment of the viability of different stages of schistosome, tegumental changes, oviposition, toxicity in mammalian cells and other parameters are important in the search for antischistosomal substances. The techniques detailed here will be the key to better assess the methodology employed during screening tests.