Search results for: solvent relaxation

Authors: S. Toufigh Bararpour, Davood Karami, Nader Mahinpey

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Dependence of global economics on fossil fuels has led to a large growth in the emission of greenhouse gases (GHGs). Among the various GHGs, carbon dioxide is the main contributor to the greenhouse effect due to its huge emission amount. To mitigate the threatening effect of CO₂, carbon capture and sequestration (CCS) technologies have been studied widely in recent years. For the combustion processes, three main CO₂ capture techniques have been proposed such as post-combustion, pre-combustion and oxyfuel combustion. Post-combustion is the most commonly used CO₂ capture process as it can be readily retrofit into the existing power plants. Multiple advantages have been reported for the post-combustion by solid sorbents such as high CO₂ selectivity, high adsorption capacity, and low required regeneration energy. Chemical adsorption of CO₂ over alkali-metal-based solid sorbents such as K₂CO₃ is a promising method for the selective capture of diluted CO₂ from the huge amount of nitrogen existing in the flue gas. To improve the CO₂ capture performance, K₂CO₃ is supported by a stable and porous material. Al₂O₃ has been employed commonly as the support and enhanced the cyclic CO₂ capture efficiency of K₂CO₃. Different phases of alumina can be obtained by setting the calcination temperature of boehmite at 300, 600 (γ-alumina), 950 (δ-alumina) and 1200 °C (α-alumina). By increasing the calcination temperature, the regeneration capacity of alumina increases, while the surface area reduces. However, sorbents with lower surface areas have lower CO₂ capture capacity as well (except for the sorbents prepared by hydrophilic support materials). To resolve this issue, a highly efficient alumina-aerogel support was synthesized with a BET surface area of over 2000 m²/g and then calcined at a high temperature. The synthesized alumina-aerogel was impregnated on K₂CO₃ based on 50 wt% support/K₂CO₃, which resulted in the preparation of a sorbent with remarkable CO₂ capture performance. The effect of synthesis conditions such as types of alcohols, solvent-to-co-solvent ratios, and aging times was investigated on the performance of the support. The best support was synthesized using methanol as the solvent, after five days of aging time, and at a solvent-to-co-solvent (methanol-to-toluene) ratio (v/v) of 1/5. Response surface methodology was used to investigate the effect of operating parameters such as carbonation temperature and H₂O-to-CO₂ flowrate ratio on the CO₂ capture capacity. The maximum CO₂ capture capacity, at the optimum amounts of operating parameters, was 7.2 mmol CO₂ per gram K₂CO₃. Cyclic behavior of the sorbent was examined over 20 carbonation and regenerations cycles. The alumina-aerogel-supported K₂CO₃ showed a great performance compared to unsupported K₂CO₃ and γ-alumina-supported K₂CO₃. Fundamental performance analyses and long-term thermal and chemical stability test will be performed on the sorbent in the future. The applicability of the sorbent for a bench-scale process will be evaluated, and a corresponding process model will be established. The fundamental material knowledge and respective process development will be delivered to industrial partners for the design of a pilot-scale testing unit, thereby facilitating the industrial application of alumina-aerogel.

Keywords: alumina-aerogel, CO₂ capture, K₂CO₃, optimization

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Authors: Alessandra Pardu, Elena Curti, Marco Caredda, Alessio Dedola, Margherita Addis, Massimo Pes, Antonio Pirisi, Tonina Roggio, Sergio Uzzau, Roberto Anedda

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Some of the artisanal cheeses products of European Countries certificated as PDO (Protected Designation of Origin) are made from raw milk. To recognise potential frauds (e.g. pasteurisation or thermisation of milk aimed at raw milk cheese production), the alkaline phosphatase (ALP) assay is currently applied only for pasteurisation, although it is known to have notable limitations for the validation of ALP enzymatic state in nonbovine milk. It is known that frauds considerably impact on customers and certificating institutions, sometimes resulting in a damage of the product image and potential economic losses for cheesemaking producers. Robust, validated, and univocal analytical methods are therefore needed to allow Food Control and Security Organisms, to recognise a potential fraud. In an attempt to develop a new reliable method to overcome this issue, Time-Domain Nuclear Magnetic Resonance (TD-NMR) spectroscopy has been applied in the described work. Daily fresh milk was analysed raw (680.00 µL in each 10-mm NMR glass tube) at least in triplicate. Thermally treated samples were also produced, by putting each NMR tube of fresh raw milk in water pre-heated at temperatures from 68°C up to 72°C and for up to 3 min, with continuous agitation, and quench-cooled to 25°C in a water and ice solution. Raw and thermally treated samples were analysed in terms of 1H T2 transverse relaxation times with a CPMG sequence (Recycle Delay: 6 s, interpulse spacing: 0.05 ms, 8000 data points) and quasi-continuous distributions of T2 relaxation times were obtained by CONTIN analysis. In line with previous data collected by high field NMR techniques, a decrease in the spin-spin relaxation constant T2 of the predominant 1H population was detected in heat-treated milk as compared to raw milk. The decrease of T2 parameter is consistent with changes in chemical exchange and diffusive phenomena, likely associated to changes in milk protein (i.e. whey proteins and casein) arrangement promoted by heat treatment. Furthermore, experimental data suggest that molecular alterations are strictly dependent on the specific heat treatment conditions (temperature/time). Such molecular variations in milk, which are likely transferred to cheese during cheesemaking, highlight the possibility to extend the TD-NMR technique directly on cheese to develop a method for assessing a fraud related to the use of a milk thermal treatment in PDO raw milk cheese. Results suggest that TDNMR assays might pave a new way to the detailed characterisation of heat treatments of milk.

Keywords: cheese fraud, milk, pasteurisation, TD-NMR

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Authors: Lenuta Kloetzer, Alexandra C. Blaga, Dan Cascaval, Alexandra Tucaliuc, Anca I. Galaction

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Rosmarinic acid, an ester of caffeic acid and 3-(3,4-dihydroxyphenyl) lactic acid, is considered a valuable compound for the pharmaceutical and cosmetic industries due to its antimicrobial, antioxidant, antiviral, anti-allergic, and anti-inflammatory effects. It can be obtained by extraction from vegetable or animal materials, by chemical synthesis and biosynthesis. Indifferent of the method used for rosmarinic acid production, the separation and purification process implies high amount of raw materials and laborious stages leading to high cost for and limitations of the separation technology. This study focused on separation of rosmarinic acid by synergic reactive extraction with a mixture of two extractants, one acidic (acid di-(2ethylhexyl) phosphoric acid, D2EHPA) and one with basic character (Amberlite LA-2). The studies were performed in experimental equipment consisting of an extraction column where the phases’ mixing was made by mean of a perforated disk with 45 mm diameter and 20% free section, maintained at the initial contact interface between the aqueous and organic phases. The vibrations had a frequency of 50 s⁻¹ and 5 mm amplitude. The extraction was carried out in two solvents with different dielectric constants (n-heptane and dichloromethane) in which the extractants mixture of varying concentration was dissolved. The pH-value of initial aqueous solution was varied between 1 and 7. The efficiency of the studied extraction systems was quantified by distribution and synergic coefficients. For calculating these parameters, the rosmarinic acid concentration in the initial aqueous solution and in the raffinate have been measured by HPLC. The influences of extractants concentrations and solvent polarity on the efficiency of rosmarinic acid separation by synergic extraction with a mixture of Amberlite LA-2 and D2EHPA have been analyzed. In the reactive extraction system with a constant concentration of Amberlite LA-2 in the organic phase, the increase of D2EHPA concentration leads to decrease of the synergic coefficient. This is because the increase of D2EHPA concentration prevents the formation of amine adducts and, consequently, affects the hydrophobicity of the interfacial complex with rosmarinic acid. For these reasons, the diminution of synergic coefficient is more important for dichloromethane. By maintaining a constant value of D2EHPA concentration and increasing the concentration of Amberlite LA-2, the synergic coefficient could become higher than 1, its highest values being reached for n-heptane. Depending on the solvent polarity and D2EHPA amount in the solvent phase, the synergic effect is observed for Amberlite LA-2 concentrations over 20 g/l dissolved in n-heptane. Thus, by increasing the concentration of D2EHPA from 5 to 40 g/l, the minimum concentration value of Amberlite LA-2 corresponding to synergism increases from 20 to 40 g/l for the solvent with lower polarity, namely, n-heptane, while there is no synergic effect recorded for dichloromethane. By analysing the influences of the main factors (organic phase polarity, extractant concentration in the mixture) on the efficiency of synergic extraction of rosmarinic acid, the most important synergic effect was found to correspond to the extractants mixture containing 5 g/l D2EHPA and 40 g/l Amberlite LA-2 dissolved in n-heptane.

Keywords: Amberlite LA-2, di(2-ethylhexyl) phosphoric acid, rosmarinic acid, synergic effect

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Authors: S. S. Patil, R. M. Mhetre, S. V. Patil

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Lisinopril is an angiotensin converting enzyme inhibitor used in the treatment of hypertension and heart failure in prophylactic treatment after myocardial infarction and in diabetic nephropathy. However, it is very poorly absorbed from gastro-intestinal tract. Intranasal administration is an ideal alternative to the parenteral route for systemic drug delivery. Formulating multiparticulate system with mucoadhesive polymers provide a significant increase in the nasal residence time. The aim of the present approach was to overcome the drawbacks of the conventional dosage forms of lisinopril by formulating intranasal microspheres with Carbopol 974P NF and HPMC K4 M along with film forming polymer ethyl cellulose.The microspheres were prepared by emulsion solvent evaporation method. The prepared microspheres were characterized for encapsulation efficiency, drug loading, particle size, and surface morphology, degree of swelling, ex vivo mucoadhesion, drug release, ex vivo diffusion studies. All formulations has shown entrapment efficiency between 80 to more than 95%, mucoadhesion was more than 80 % and drug release up to 90 %. Ex vivo studies revealed tht the improved bioavailability of drug compared to oral drug administration. Both in vitro and in vivo studies conclude that combination of Carbopol and HPMC based microspheres shown better results than single carbopol based microspheres for the delivery of lisinopril.

Keywords: microspheres, lisinopril, nasal delivery, solvent evaporation method

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Authors: Lamzira Ebralidze, Aleksandre Tsertsvadze, Dali Berashvili, Aliosha Bakuridze

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Nowadays, there is an increasing demand for biologically active substances from vegetable, animal, and mineral resources. In terms of the use of natural compounds, pharmaceutical, cosmetic, and nutrition industry has big interest. The biggest drawback of conventional extraction methods is the need to use a large volume of organic extragents. The removal of the organic solvent is a multi-stage process. And their absolute removal cannot be achieved, and they still appear in the final product as impurities. A large amount of waste containing organic solvent damages not only human health but also has the harmful effects of the environment. Accordingly, researchers are focused on improving the extraction methods, which aims to minimize the use of organic solvents and energy sources, using alternate solvents and renewable raw materials. In this context, green extraction principles were formed. Green Extraction is a need of today’s environment. Green Extraction is the concept, and it totally corresponds to the challenges of the 21st century. The extraction of biologically active compounds based on green extraction principles is vital from the view of preservation and maintaining biodiversity. Novel technologies of green extraction are known, such as "cold methods" because during the extraction process, the temperature is relatively lower, and it doesn’t have a negative impact on the stability of plant compounds. Novel technologies provide great opportunities to reduce or replace the use of organic toxic solvents, the efficiency of the process, enhance excretion yield, and improve the quality of the final product. The objective of the research is the development of green technologies of flavonoids containing preparations. Methodology: At the first stage of the research, flavonoids containing preparations (Tincture Herba Leonuri, flamine, rutine) were prepared based on conventional extraction methods: maceration, bismaceration, percolation, repercolation. At the same time, the same preparations were prepared based on green technologies, microwave-assisted, UV extraction methods. Product quality characteristics were evaluated by pharmacopeia methods. At the next stage of the research technological - economic characteristics and cost efficiency of products prepared based on conventional and novel technologies were determined. For the extraction of flavonoids, water is used as extragent. Surface-active substances are used as co-solvent in order to reduce surface tension, which significantly increases the solubility of polyphenols in water. Different concentrations of water-glycerol mixture, cyclodextrin, ionic solvent were used for the extraction process. In vitro antioxidant activity will be studied by the spectrophotometric method, using DPPH (2,2-diphenyl-1- picrylhydrazyl) as an antioxidant assay. The advantage of green extraction methods is also the possibility of obtaining higher yield in case of low temperature, limitation extraction process of undesirable compounds. That is especially important for the extraction of thermosensitive compounds and maintaining their stability.

Keywords: extraction, green technologies, natural resources, flavonoids

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Authors: Martin Botz, Michael Kraus, Geralt Siebert

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The use of laminated glass gains increasing importance in structural engineering. For safety reasons, at least two glass panes are laminated together with a polymeric interlayer. In case of breakage of one or all of the glass panes, the glass fragments are still connected to the interlayer due to adhesion forces and a certain residual load-bearing capacity is left in the system. Polymer interlayers used in the laminated glass show a viscoelastic material behavior, e.g. stresses and strains in the interlayer are dependent on load duration and temperature. In the intact stage only small strains appear in the interlayer, thus the material can be described in a linear way. In the broken stage, large strains can appear and a non-linear viscoelasticity material theory is necessary. Relaxation tests on two different types of polymeric interlayers are performed at different temperatures and strain amplitudes to determine the border to the non-linear material regime. Based on the small-scale specimen results further tests on broken laminated glass panes are conducted. So-called ‘through-crack-bending’ (TCB) tests are performed, in which the laminated glass has a defined crack pattern. The test set-up is realized in a way that one glass layer is still able to transfer compressive stresses but tensile stresses have to be transferred by the interlayer solely. The TCB-tests are also conducted under different temperatures but constant force (creep test). Aims of these experiments are to elaborate if the results of small-scale tests on the interlayer are transferable to a laminated glass system in the broken stage. In this study, limits of the applicability of linear-viscoelasticity are established in the context of two commercially available polymer-interlayers. Furthermore, it is shown that the results of small-scale tests agree to a certain degree to the results of the TCB large-scale experiments. In a future step, the results can be used to develop material models for the post breakage performance of laminated glass.

Keywords: glass breakage, laminated glass, relaxation test, viscoelasticity

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Authors: L. Heidari, M. Jalili Ghazizade

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In recent years, different petrochemical complexes have been established to produce aromatic compounds. Among them, Nouri Petrochemical Complex (NPC) is the largest producer of aromatic raw materials in the world, and is located in south of Iran. Environmental concerns have been raised in this region due to generation of different types of solid waste generated in the process of aromatics production, and subsequently, industrial waste characterization has been thoroughly considered. The aim of this study is qualitative and quantitative characterization of industrial waste generated in the aromatics production process and determination of the best method for industrial waste management. For this purpose, all generated industrial waste during the production process was determined using a checklist. Four main industrial wastes were identified as follows: spent industrial soil, spent catalyst, spent molecular sieves and spent N-formyl morpholine (NFM) solvent. The amount of heavy metals and organic compounds in these wastes were further measured in order to identify the nature and toxicity of such a dangerous compound. Then industrial wastes were classified based on lab analysis results as well as using different international lists of hazardous waste identification such as EPA, UNEP and Basel Convention. Finally, the best method of waste disposal is selected based on environmental, economic and technical aspects. 

Keywords: aromatic compounds, industrial soil, molecular sieve, normal formyl morpholine solvent

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Authors: M. A. Moussa, M. H. Abdel Rehim, G.M. Turky

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Polyaniline composites with carbon nitride, to overcome compatibility restriction with graphene, were prepared with the solution method. FTIR and Uv-vis spectra were used for structural conformation. While XRD and XPS confirmed the structures in addition to estimation of nitrogen atom surroundings, the pore sizes and the active surface area were determined from BET adsorption isotherm. The electrical and dielectric parameters were measured and calculated with BDS .

Keywords: carbon nitride, dynamic relaxation, electrical conductivity, polyaniline

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Authors: Julian Mehler, Marcus Fischer, Martin Hartmann, Peter S. Schulz

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During the last two decades, the synthesis of metal-organic frameworks (MOFs) has gained ever increasing attention. Based on their pore size and shape as well as host-guest interactions, they are of interest for numerous fields related to porous materials, like catalysis and gas separation. Usually, MOF-synthesis takes place in an organic solvent between room temperature and approximately 220 °C, with mixtures of polyfunctional organic linker molecules and metal precursors as substrates. Reaction temperatures above the boiling point of the solvent, i.e. solvothermal reactions, are run in autoclaves or sealed glass vessels under autogenous pressures. A relatively new approach for the synthesis of MOFs is the so-called ionothermal synthesis route. It applies an ionic liquid as a solvent, which can serve as a structure-directing template and/or a charge-compensating agent in the final coordination polymer structure. Furthermore, this method often allows for less harsh reaction conditions than the solvothermal route. Here a variation of the ionothermal approach is reported, where the ionic liquid also serves as an organic linker source. By using 1-ethyl-3-methylimidazolium terephthalates ([EMIM][Hbdc] and [EMIM]₂[bdc]), the one-step synthesis of MIL-53(Al)/Boehemite composites with interesting features is possible. The resulting material is already formed at moderate temperatures (90-130 °C) and is stabilized in the usually unfavored ht-phase. Additionally, in contrast to already published procedures for MIL-53(Al) synthesis, no further activation at high temperatures is mandatory. A full characterization of this novel composite material is provided, including XRD, SS-NMR, El-Al., SEM as well as sorption measurements and its interesting features are compared to MIL-53(Al) samples produced by the classical solvothermal route. Furthermore, the syntheses of the applied ionic liquids and salts is discussed. The influence of the degree of ionicity of the linker source [EMIM]x[H(2-x)bdc] on the crystal structure and the achievable synthesis temperature are investigated and give insight into the role of the IL during synthesis. Aside from the synthesis of MIL-53 from EMIM terephthalates, the use of the phosphonium cation in this approach is discussed as well. Additionally, the employment of ILs in the preparation of other MOFs is presented briefly. This includes the ZIF-4 framework from the respective imidazolate ILs and chiral camphorate based frameworks from their imidazolium precursors.

Keywords: ionic liquids, ionothermal synthesis, material synthesis, MIL-53, MOFs

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Authors: Norman Farb, Anirudh Kumar, Abdul Subhan, Pallavi Gupta, Jahnavi Mundluru, Abdul Subhan, Shankar Pathmakanthan

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Long term meditation practice is increasingly recognized for its health benefits. Among a diversity of contemplative traditions, Heartfulness meditation represents a quickly growing set of practices that is largely unstudied. Heartfulness is unique in that it is a meditation practice that focuses on the Heart. It helps individuals to connect to themselves and find inner peace while meditating. In order to deepen ones’ meditation on the heart, the element of Yogic Energy (‘pranahuti’) is used as an aid during meditation. The purpose of this study was to determine whether consistent EEG effects of Heartfulness meditation be observed in sixty experienced Heartfulness meditators, each of whom attended 6 testing sessions. In each session, participants performed three conditions: a set of cognitive tasks, Heartfulness guided relaxation, and Heartfulness Meditation. To measure EEG, the MUSE EEG head band (product of Interaxon Inc) was used. Participants during the cognitive portion were required to answer questions that tested their logical thinking (Cognitive Reflective Test) and creative thinking skills. (Random Associative Test) The order of condition was randomly counter balanced across six sessions. It was hypothesized that Heartfulness meditation would bring increased alpha (8-12Hz) brain activity during meditation and better cognitive task scores in sessions where the tasks followed meditation. Results show that cognitive task scores were higher after meditation in both CRT and RAT, suggesting stronger right brain and left brain activation. Heartfulness meditation produces a significant decrease in brain activity (as indexed by higher levels of alpha) during the early stages of meditation. As the meditation progressed deep meditative state (as indexed by higher levels of delta) were observed until the end of the condition. This lead to the conclusion that Heartfulness Meditation produces a state that is clearly distinguishable from effortful problem solving.

Keywords: heartfulness meditation, neuroplasticity, brain activity, relaxation response

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Authors: Mohd Adil, Rosina Khan, Danishuddin, Asad U. Khan

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The aim of this study was to evaluate the influence of the crude and active solvent fraction of Trachyspermum ammi on S. mutans cariogenicity, effect on expression of genes involved in biofilm formation and caries development in rats. GC–MS was carried out to identify the major components present in the crude and the active fraction of T. ammi. The crude extract and the solvent fraction exhibiting least MIC were selected for further experiments. Scanning electron microscopy was carried out to observe the effect of the extracts on S. mutans biofilm. Comparative gene expression analysis was carried out for nine selected genes. 2-Isopropyl-5-methyl-phenol was found as major compound in crude and the active fraction. Binding site of this compound within the proteins involved in biofilm formation was mapped with the help of docking studies. Real-time RT-PCR analyses revealed significant suppression of the genes involved in biofilm formation. All the test groups showed reduction in caries (smooth surface as well as sulcal surface caries) in rats. Moreover, it also provides new insight to understand the mechanism influencing biofilm formation in S. mutans. Furthermore, the data suggest the putative cariostatic properties of T. Ammi and hence can be used as an alternative medicine to prevent caries infection.

Keywords: bio-film, Streptococcus mutans, dental caries, bio-informatic

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Authors: Ndidi F. Amulu, Godian O. Mbah, Maxwel I. Onyiah, Callistus N. Ude

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Analysis of the properties of coconut (Cocos nucifera) and its oil was evaluated in this work using standard analytical techniques. The analyses carried out include proximate composition of the fruit, extraction of oil from the fruit using different process parameters and physicochemical analysis of the extracted oil. The results showed the percentage (%) moisture, crude lipid, crude protein, ash, and carbohydrate content of the coconut as 7.59, 55.15, 5.65, 7.35, and 19.51 respectively. The oil from the coconut fruit was odourless and yellowish liquid at room temperature (30oC). The treatment combinations used (leaching time, leaching temperature and solute: solvent ratio) showed significant differences (P˂0.05) in the yield of oil from coconut flour. The oil yield ranged between 36.25%-49.83%. Lipid indices of the coconut oil indicated the acid value (AV) as 10.05 Na0H/g of oil, free fatty acid (FFA) as 5.03%, saponification values (SV) as 183.26 mgKOH-1 g of oil, iodine value (IV) as 81.00 I2/g of oil, peroxide value (PV) as 5.00 ml/ g of oil and viscosity (V) as 0.002. A standard statistical package minitab version 16.0 program was used in the regression analysis and analysis of variance (ANOVA). The statistical software mentioned above was also used to generate various plots such as single effect plot, interactions effect plot and contour plot. The response or yield of oil from the coconut flour was used to develop a mathematical model that correlates the yield to the process variables studied. The maximum conditions obtained that gave the highest yield of coconut oil were leaching time of 2 hrs, leaching temperature of 50 oC and solute/solvent ratio of 0.05 g/ml.

Keywords: coconut, oil-extraction, optimization, physicochemical, proximate

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Authors: Dharamashi Rabari, Anand Patel

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n-Butanol can be regarded as a potential biofuel. Being resistive to corrosion and having high calorific value, butanol is a very attractive energy source as opposed to ethanol. By fermentation process called ABE (acetone, butanol, ethanol), bio-butanol can be produced. ABE carried out mostly by bacteria Clostridium acetobutylicum. The major drawback of the process is the butanol concentration higher than 10 g/L, delays the growth of microbes resulting in a low yield. It indicates the simultaneous separation of butanol from the fermentation broth. Two hydrophobic Ionic Liquids (ILs) 1-butyl-1-methylpiperidinium bis (trifluoromethylsulfonyl)imide [bmPIP][Tf₂N] and 1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl)imide [hmim][Tf₂N] were chosen. The binary interaction parameters for both ternary systems i.e. [bmPIP][Tf₂N] + water + n-butanol and [hmim][Tf₂N] + water +n-butanol were taken from the literature that was generated by NRTL model. Particle swarm optimization (PSO) with the isothermal sum rate (ISR) method was used to optimize the cost of liquid-liquid extractor. For [hmim][Tf₂N] + water +n-butanol system, PSO shows 84% success rate with the number of stages equal to eight and solvent flow rate equal to 461 kmol/hr. The number of stages was three with 269.95 kmol/hr solvent flow rate for [bmPIP][Tf₂N] + water + n-butanol system. Moreover, both ILs were very efficient as the loss of ILs in raffinate phase was negligible.

Keywords: particle swarm optimization, isothermal sum rate method, success rate, extraction

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Authors: Saeed Chehri, Sirvan Moradi, Amin Rostami

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Cooperative catalyst systems have been developed as highly promising sustainable alternatives to traditional catalysts. In these catalysts, two or more catalytic centers cooperate to reduce the energy of chemical transformations. In nature, such systems are abundantly seen in metalloenzymes that use metal and an organic cofactor. We have designed a reusable cooperative catalyst oxidation system consisting of palladium nanoparticles and polyoxometalate. This biomimetic cooperative catalytic system was synthesized by the stepwise immobilization of palladium nanoparticlesandpolyoxometalateinto the same cavity of siliceous mesocellularfoams (Pd-POM@MCF)and wascharacterizedby SEM, EDX, FT-IR, TGAand ICP techniques. POM-Pd@MCF/HQexhibits high activity toward aerobic oxidation of alcohols to the corresponding carbonyl compoundsin water solvent at room temperature. The major novelties and advantages of this oxidation method are as follows: (i) this is the first report of the co-immobilization of polyoxometalateand palladium for use as a robust and highlyefficient heterogeneouscooperative oxidative nanocatalyst system for aerobic oxidation of alcohols, (ii) oxidation of alcoholswere performed using an ideal oxidant with good to high yields in a green solvent at ambient temperature and (iii) the immobilization of the oxygen-activating catalyst(polyoxometalate) and oxidizing catalyst (Pd) onto MCF provide practical cooperative catalyst the system that can be reused several times without a significant loss of activity (vi) the methodsconform to several of the guiding principles of green chemistry.

Keywords: palladium nanoparticles, polyoxometalate, reusable cooperative catalytic system, biomimetic oxidation reaction

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Authors: Birute Bugelyte, Ingrida Jurkute, Vida Vickackaite

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The most complicated step of the determination of volatile compounds in complex matrices is the separation of analytes from the matrix. Traditional analyte separation methods (liquid extraction, Soxhlet extraction) require a lot of time and labour; moreover, there is a risk to lose the volatile analytes. In recent years, headspace gas chromatography has been used to determine volatile compounds. To date, traditional extraction solvents have been used in headspace gas chromatography. As a rule, such solvents are rather volatile; therefore, a large amount of solvent vapour enters into the headspace together with the analyte. Because of that, the determination sensitivity of the analyte is reduced, a huge solvent peak in the chromatogram can overlap with the peaks of the analyts. The sensitivity is also limited by the fact that the sample can’t be heated at a higher temperature than the solvent boiling point. In 2018 it was suggested to replace traditional headspace gas chromatographic solvents with non-volatile, eco-friendly, biodegradable, inexpensive, and easy to prepare deep eutectic solvents (DESs). Generally, deep eutectic solvents have low vapour pressure, a relatively wide liquid range, much lower melting point than that of any of their individual components. Those features make DESs very attractive as matrix media for application in headspace gas chromatography. Also, DESs are polar compounds, so they can be applied for microwave assisted extraction. The aim of this work was to investigate the possibility of applying deep eutectic solvents for microwave assisted extraction and headspace gas chromatographic determination of hexanal in fat-rich food. Hexanal is considered one of the most suitable indicators of lipid oxidation degree as it is the main secondary oxidation product of linoleic acid, which is one of the principal fatty acids of many edible oils. Eight hydrophilic and hydrophobic deep eutectic solvents have been synthesized, and the influence of the temperature and microwaves on their headspace gas chromatographic behaviour has been investigated. Using the most suitable DES, microwave assisted extraction conditions and headspace gas chromatographic conditions have been optimized for the determination of hexanal in potato chips. Under optimized conditions, the quality parameters of the prepared technique have been determined. The suggested technique was applied for the determination of hexanal in potato chips and other fat-rich food.

Keywords: deep eutectic solvents, headspace gas chromatography, hexanal, microwave assisted extraction

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Authors: Iman Adnan Annon, Kadhim F. Alsultan

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This study investigate the internal corrosion of low carbon steel pipelines in the crude oil, as well as prepare and use natural and locally available plant as a natural corrosion inhibiter, the nature extraction achieved by two types of solvents in order to show the solvent effect on inhibition process, the first being distilled water and the second is diethyl ether. FT-IR spectra and using a chemical reagents achieved to detection the presence of many active groups and the presence of tannins, phenols, and alkaloids in the natural extraction. Some experiments were achieved to estimate the performance of a new inhibitor, one of these tests include corrosion measurement by simple immersion in crude oil within and without inhibitors which added in different amounts 30,40,50and 60 ppm at tow temperature 300 and 323k, where the best inhibition efficiencies which get when added the inhibitors in a critical amounts or closest to it, since for the aqueous extract (EB-A) the inhibition efficiency reached (94.4) and (86.71)% at 300 and 323k respectively, and for diethyl ether extract (EB-D) reached (82.87) and (84.6)% at 300 and 323k respectively. Optical microscopy examination have been conducted to evaluate the corrosion nature where it show a clear difference in the topography of the immersed samples surface after add the inhibitors at two temperatures. The results show that the new corrosion inhibitor is not only equivalent to a chemical inhibitor but has greatly improvement properties such as: high efficiency, low cost, non-toxic, easily to produce, and nonpolluting as compared with chemical inhibitor.

Keywords: corrosion in pipeline, inhibitors, crude oil, carbon steel, types of solvent

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Authors: Muhammad Arshad, Ghulam Hussain Bhatti, Abdul Qayyum

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Zinc-doped silica oxide nanoparticles having size 7.93nm were synthesized by the deposition precipitation method by using different solvents (acetonitrile, n-hexane, isoamylalchol). Biological potential such as antibacterial activities against Bacillussubtilusand Escherichia coli, and antifungal activities against Candida parapsilosis and Aspergilusniger were also investigated by Disc diffusion method. Different characterizations techniques including Fournier Transmission Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Thermo-gravimeteric Analysis (TGA), Atomic forced microscopy (AFM), and Dynamic Light Scattering (DLS) were used. FT-IR characterization confirmed the presence of metal oxide bond (SiO2) while XRD showed the hexagonal structure. SEM and TEM characterization showed the morphology of nanoparticles. AFM study showed good particle size distribution as depicted by a histogram. DLS study showed the gradual decease in the size of nanoparticles from 24.86nm to 13.24 nm. Highest antibacterial activities revealed by acetonitrile solvents (6%and 4.5%) followed by isoamylalchol (3% and 2.4%) while n-hexane solvent showed the lowest activity (2%and 1%) respectively. Higher antifungal activities exhibited by n-hexane (0.34 % and 0.43%) followed by isoamylalchol (0.27% and 0.19%) solvent while acetonitrile (0.21% and 0.17%) showed least activity respectively. Statistical analysis by using one-way ANOVA also indicated the significant results of both biological activities.

Keywords: nanoparticles, precipitation methods, antibacterial, antifungal, characterizations

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Authors: Abdulrazaq Yahaya, Omobola Okoh, Anthony Okoh

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Polychlorinated biphenyls (PCBs) are generated from short emission or leakage from capacitors and electrical transformers, industrial chemicals wastewater discharge and careless disposal of wastes. They are toxic, semi-volatile compounds which can persist in the environment, hence classified as persistent organic pollutants. Their presence in the environmental matrices has become a global concern. In this study, we assessed the concentrations and distribution patterns of 19 polychlorinated biphenyls congeners (PCB 1, 5, 18, 31, 44, 52, 66, 87, 101, 110, 138, 141, 151, 153, 170, 180, 183, 187, and 206) at six sampling points in water along the course of Buffalo River, Eastern Cape, South Africa. Solvent extraction followed by sulphuric acid, potassium permanganate and silica gel cleanup were used in this study. The analysis was done with gas chromatography electron capture detector (GC-ECD). The results of the analysis of all the 19 PCBs congeners ranged from not detectable to 0.52 ppb and 2.5 ppb during summer and autumn periods respectively. These values are generally higher than the World Health Organization (WHO) maximum permissible limit. Their presence in the waterbody suggests an increase in anthropogenic activities over the seasons. In view of their volatility, the compounds are transportable over long distances by air currents away from their point of origin putting the health of the communities at risk, thus suggesting the need for strict regulations on the use as well as save disposal of this group of compounds in the communities.

Keywords: organic pollutants, polychlorinated biphenyls, pollution, solvent extraction

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Authors: Marjan Javanmard

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The rheological properties of dairy products critically depend on the underlying organisation of proteins at multiple length scales. When heated and acidified, milk proteins form particle gel that is viscoelastic, solvent rich, ‘soft’ material. In this work recent developments on the rheology of soft particles suspensions were used to interpret and potentially define the properties of dairy gel structures. It is discovered that at volume fractions below random close packing (RCP), the Maron-Pierce-Quemada (MPQ) model accurately predicts the viscosity of the dairy gel suspensions without fitting parameters; the MPQ model has been shown previously to provide reasonable predictions of the viscosity of hard sphere suspensions from the volume fraction, solvent viscosity and RCP. This surprising finding demonstrates that up to RCP, the dairy gel system behaves as a hard sphere suspension and that the structural aggregates behave as discrete particulates akin to what is observed for microgel suspensions. At effective phase volumes well above RCP, the system is a soft solid. In this region, it is discovered that the storage modulus of the sheared AMG scales with the storage modulus of the set gel. The storage modulus in this regime is reasonably well described as a function of effective phase volume by the Evans and Lips model. Findings of this work has potential to aid in rational design and control of dairy food structure-properties.

Keywords: dairy suspensions, rheology-structure, Maron-Pierce-Quemada Model, Evans and Lips Model

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Authors: Mohamed Rehan, Gamil E. Ibrahim, Mohamed S. Abdel-Aziz, Shaimaa R. Ibrahim, Tawfik A. Khattab

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The utilization of natural products in finishing textiles toward multifunctional applications without side effects is an extremely motivating goal. Hibiscus sabdariffa usually has been used for many traditional medicine applications. To develop an additional use for Hibiscus sabdariffa, an extraction of bioactive compounds from Hibiscus sabdariffa followed by finishing on cellulosic fibers was designed to cleaner production of the value-added textiles fibers with multifunctional applications. The objective of this study is to explore, identify, and evaluate the bioactive compound extracted from Hibiscus sabdariffa by different solvent via ultrasonic technique as a potential eco-friendly agent for multifunctional cellulosic fabrics via two approaches. In the first approach, Hibiscus sabdariffa extract was used as a source of sustainable eco-friendly for simultaneous coloration and multi-finishing of cotton fabrics via in situ incorporations of nanoparticles (silver and metal oxide). In the second approach, the micro-capsulation of Hibiscus sabdariffa extracts was followed by coating onto cotton gauze to introduce multifunctional healthcare applications. The effect of the solvent type was accelerated by ultrasonic on the phytochemical, antioxidant, and volatile compounds of Hibiscus sabdariffa. The surface morphology and elemental content of the treated fabrics were explored using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDX). The multifunctional properties of treated fabrics, including coloration, sensor properties and protective properties against pathogenic microorganisms and UV radiation as well as wound healing property were evaluated. The results showed that the water, as well as ethanol/water, was selected as a solvent for the extraction of natural compounds from Hibiscus Sabdariffa with high in extract yield, total phenolic contents, flavonoid contents, and antioxidant activity. These natural compounds were utilized to enhance cellulosic fibers functionalization by imparting faint/dark red color, antimicrobial against different organisms, and antioxidants as well as UV protection properties. The encapsulation of Hibiscus Sabdariffa extracts, as well as wound healing, is under consideration and evaluation. As a result, the current study presents a sustainable and eco-friendly approach to design cellulosic fabrics for multifunctional medical and healthcare applications.

Keywords: cellulosic fibers, Hibiscus sabdariffa extract, multifunctional application, nanoparticles

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Authors: Anupalli Roja Rani, Saraswathi Jaggali

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Rose-scented geranium (Pelargonium graveolens L’Hér.) is an erect, much-branched shrub. It is indigenous to various parts of southern Africa, and it is often called Geranium. Pelargonium species are widely used by traditional healers in the areas of Southern Africa by Sotho, Xhosa, Khoi-San and Zulus for its curative and palliative effects in the treatment of diarrhea, dysentery, fever, respiratory tract infections, liver complaints, wounds, gastroenteritis, haemorrhage, kidney and bladder disorders. We have used Plant materials for extracting active compounds from analytical grades of solvents methanol, ethyl acetate, chloroform and water by a soxhlet apparatus. The phytochemical screening reveals that extracts of Pelargonium graveolens contains alkaloids, glycosides, steroids, tannins, saponins and phenols in ethyl acetate solvent. The antioxidant activity was determined using 1, 1-diphenyl-2-picrylhydrazyl (DPPH) bleaching method and the total phenolic content in the extracts was determined by the Folin–Ciocalteu method. Due to the presence of different phytochemical compounds in Pelargonium the anti-microbial activity against different micro-organisms like E.coli, Streptococcus, Klebsiella and Bacillus. Fractionation of plant extract was performed by column chromatography and was confirmed with HPLC analysis, NMR and FTIR spectroscopy for the compound identification in different organic solvent extracts.

Keywords: Pelargonium graveolens L’Hér, DPPH, micro-organisms, HPLC analysis, NMR, FTIR spectroscopy

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Authors: Shrawan Baghel, Helen Cathcart, Biall J. O'Reilly

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Amorphous drug formulations have great potential to enhance solubility and thus bioavailability of BCS class II drugs. However, the higher free energy and molecular mobility of the amorphous form lowers the activation energy barrier for crystallization and thermodynamically drives it towards the crystalline state which makes them unstable. Accurate determination of the crystallization tendency/kinetics is the key to the successful design and development of such systems. In this study, dipyridamole (DPM) and cinnarizine (CNZ) has been selected as model compounds. Thermodynamic fragility (m_T) is measured from the heat capacity change at the glass transition temperature (Tg) whereas dynamic fragility (m_D) is evaluated using methods based on extrapolation of configurational entropy to zero 〖(m〗_(D_CE )), and heating rate dependence of Tg 〖(m〗_(D_Tg)). The mean relaxation time of amorphous drugs was calculated from Vogel-Tammann-Fulcher (VTF) equation. Furthermore, the correlation between fragility and glass forming ability (GFA) of model drugs has been established and the relevance of these parameters to crystallization of amorphous drugs is also assessed. Moreover, the crystallization kinetics of model drugs under isothermal conditions has been studied using Johnson-Mehl-Avrami (JMA) approach to determine the Avrami constant ‘n’ which provides an insight into the mechanism of crystallization. To further probe into the crystallization mechanism, the non-isothermal crystallization kinetics of model systems was also analysed by statistically fitting the crystallization data to 15 different kinetic models and the relevance of model-free kinetic approach has been established. In addition, the crystallization mechanism for DPM and CNZ at each extent of transformation has been predicted. The calculated fragility, glass forming ability (GFA) and crystallization kinetics is found to be in good correlation with the stability prediction of amorphous solid dispersions. Thus, this research work involves a multidisciplinary approach to establish fragility, GFA and crystallization kinetics as stability predictors for amorphous drug formulations.

Keywords: amorphous, fragility, glass forming ability, molecular mobility, mean relaxation time, crystallization kinetics, stability

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Authors: Ghulam Murshid

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Carbon dioxide is one of the major greenhouse gas (GHG) contributors. It is an obligation of the industry to reduce the amount of carbon dioxide emission to the acceptable limits. Tremendous research and studies are reported in the past and still the quest to find the suitable and economical solution of this problem needed to be explored in order to develop the most plausible absorber for carbon dioxide removal. Amino acids are reported by the researchers as a potential solvent for absorption of carbon dioxide to replace alkanolamines due to its ability to resist oxidative degradation, low volatility due to its ionic structure and higher surface tension. In addition, the introduction of promoter-like piperazine to amino acid helps to further enhance the solubility. In this work, the effect of piperazine on thermophysical properties and solubility of β-Alanine aqueous solutions were studied for various concentrations. The measured physicochemical properties data was correlated as a function of temperature using least-squares method and the correlation parameters are reported together with it respective standard deviations. The effect of activator piperazine on the CO2 loading performance of selected amino acid under high-pressure conditions (1bar to 10bar) at temperature range of (30 to 60)oC was also studied. Solubility of CO2 decreases with increasing temperature and increases with increasing pressure. Quadratic representation of solubility using Response Surface Methodology (RSM) shows that the most important parameter to optimize solubility is system pressure. The addition of promoter increases the solubility effect of the solvent.

Keywords: amino acids, co2, global warming, solubility

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Authors: Ndidi F. Amulu, Patrick E. Amulu, Gordian O. Mbah, Callistus N. Ude

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Comparative analysis of the properties of melon seed, coconut fruit and their oil yield were evaluated in this work using standard analytical technique AOAC. The results of the analysis carried out revealed that the moisture contents of the samples studied are 11.15% (melon) and 7.59% (coconut). The crude lipid content are 46.10% (melon) and 55.15% (coconut).The treatment combinations used (leaching time, leaching temperature and solute: solvent ratio) showed significant difference (p < 0.05) in yield between the samples, with melon oil seed flour having a higher percentage range of oil yield (41.30 – 52.90%) and coconut (36.25 – 49.83%). The physical characterization of the extracted oil was also carried out. The values gotten for refractive index are 1.487 (melon seed oil) and 1.361 (coconut oil) and viscosities are 0.008 (melon seed oil) and 0.002 (coconut oil). The chemical analysis of the extracted oils shows acid value of 1.00mg NaOH/g oil (melon oil), 10.050mg NaOH/g oil (coconut oil) and saponification value of 187.00mg/KOH (melon oil) and 183.26mg/KOH (coconut oil). The iodine value of the melon oil gave 75.00mg I2/g and 81.00mg I2/g for coconut oil. A standard statistical package Minitab version 16.0 was used in the regression analysis and analysis of variance (ANOVA). The statistical software mentioned above was also used to optimize the leaching process. Both samples gave high oil yield at the same optimal conditions. The optimal conditions to obtain highest oil yield ≥ 52% (melon seed) and ≥ 48% (coconut seed) are solute - solvent ratio of 40g/ml, leaching time of 2hours and leaching temperature of 50oC. The two samples studied have potential of yielding oil with melon seed giving the higher yield.

Keywords: Coconut, Melon, Optimization, Processing

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Authors: Geeta Gahlawat, Sanjeev Kumar Soni

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An imprudent use of environmentally hazardous petrochemical-based plastics and limited availability of fossil fuels have provoked research interests towards production of biodegradable plastics - polyhydroxyalkanoate (PHAs). However, the industrial application of PHAs based products is primarily restricted by their high cost of recovery and extraction protocols. Moreover, solvents used for the extraction and purification are toxic and volatile which causes adverse environmental hazards. Development of efficient downstream recovery strategies along with utilization of non-toxic solvents will accelerate their commercialization. In this study, various extraction strategies were designed for sustainable and cost-effective recovery of PHAs from Cupriavidus necator using non-toxic environment friendly solvents viz. 1,2-propylene carbonate, ethyl acetate, isoamyl alcohol, butyl acetate. The effect of incubation time i.e. 10, 30 and 50 min and temperature i.e. 60, 80, 100, 120°C was tested to identify the most suitable solvent. PHAs extraction using a recyclable solvent, 1,2 propylene carbonate, showed the highest recovery yield (90%) and purity (93%) at 120°C and 30 min incubation. Ethyl acetate showed the better capacity to recover PHAs from cells than butyl acetate. Extraction with ethyl acetate exhibited high recovery yield and purity of 96% and 92%, respectively at 100°C. Effect of non-toxic surfactant such as linear alkylbenzene sulfonic acid (LAS) was also studied at 40, 60 and 80°C, and detergent pH range of 3.0, 5.0, 7.0 and 9.0 for the extraction of PHAs from the cells. LAS gave highest yield of 86% and purity of 88% at temperature 80°C and 5.0 pH.

Keywords: polyhydroxyalkanoates, Cupriavidus necator, extraction, recovery yield

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Authors: Emad A. Ahmed

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Computer software to calculate electron mobility with respect to different scattering mechanism has been developed. This software is adopted completely Graphical User Interface (GUI) technique and its interface has been designed by Microsoft Visual Basic 6.0. As a case study the electron mobility of n-GaN was performed using this software. The behaviour of the mobility for n-GaN due to elastic scattering processes and its relation to temperature and doping concentration were discussed. The results agree with other available theoretical and experimental data.

Keywords: electron mobility, relaxation time, GaN, scattering, computer software, computation physics

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Authors: Orose Rugchati, Khumthong Mahawongwiriya

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Dendrobium hybrid cv. Ear-Sakul has become one of the important commercial commodities in Thailand agricultural industry worldwide, either as potted plants or as cut flowers due to the attractive color produced in flower petals. Anthocyanins are the main flower pigments and responsible for the natural attractive display of petal colors. These pigments play an important role in functionality, such as to attract animal pollinators, classification, and grading of these orchids. Dendrobium hybrid cv. Ear-Sakul has been collected from local area farm in different stage flowers (F1, F2-F5, and F6). Anthocyanins pigment were extracted from the fresh flower by solvent extraction (MeOH–TFA 99.5:0.5v/v at 4ºC) and purification with ethyl acetate. The main anthocyanins components are cyanidin, pelargonidin, and delphinidin. Pure anthocyanin contents were analysis by UV-Visible spectroscopy technique at λ max 535, 520 and 546 nm respectively. The anthocyanins contents were converted in term of monomeric anthocyanins pigment (mg/L). The anthocyanins contents of all sample were compared with standard pigments cyanidin, pelargonidin and delphinidin. From this experiment is a simple extraction and analysis anthocyanins content in different stage of flowers results shown that monomeric anthocyanins pigment contents of different stage flowers (F1, F2-F5 and F6 ): cyanidin – 3 – glucoside (mg/l) are 0.85+0.08, 24.22+0.12 and 62.12+0.6; Pelargonidin 3,5-di- glucoside(mg/l) 10.37+0.12, 31.06+0.8 and 81.58+ 0.5; Delphinidin (mg/l) 6.34+0.17, 18.98+0.56 and 49.87+0.7; and the appearance of extraction pure anthocyanins in L(a, b): 2.71(1.38, -0.48), 1.06(0.39,-0.66) and 2.64(2.71,-3.61) respectively. Dendrobium Hybrid cv. Ear-Sakul could be used as a source of anthocyanins by simple solvent extraction and stage of flowers as a guideline for the prediction amount of main anthocyanins components are cyanidin, pelargonidin, and delphinidin could be application and development in quantities, and qualities with the advantage for food pharmaceutical and cosmetic industries.

Keywords: analysis, anthocyanins contents, different stage flowers, Dendrobium Hybrid cv. Ear-Sakul

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Authors: Felipe Azocar Simonet, Luis Acosta Espejo

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In this article, we will try to find an efficient boundary approximation for the bi-objective location problem with coherent coverage for two levels of hierarchy (CCLP). We present the mathematical formulation of the model used. Supported efficient solutions and unsupported efficient solutions are obtained by solving the bi-objective combinatorial problem through the weights method using a Lagrangean heuristic. Subsequently, the results are validated through the DEA analysis with the GEM index (Global efficiency measurement).

Keywords: coherent covering location problem, efficient frontier, lagragian relaxation, data envelopment analysis

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Authors: Tarnveer Kaur

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Amino acids, as fundamental structural units of peptides and proteins, have an important role in biological systems by affecting solubility, denaturation, and activity of biomolecules. A study of these effects on thermophysical properties of model compounds in the presence of electrolytes solutions provides information about solute-solvent and solute-solute interactions on biomolecules. Ionic liquids (ILs) as organic electrolytes and green solvents are composed of an organic cation and an inorganic anion, which are liquid at ambient conditions. In the past decade, extensive investigations showed that the use of ILs as reaction media for processes involving biologically relevant compounds is promising in view of their successful application in kinetic resolution, biocatalysis, biosynthesis, separation, and purification processes. The scope of this information is valuable to explore the interactions of amino acids in ILs. To reach this purpose, apparent molar volumes of glycine/L-alanine in aqueous solutions of 1-butyl-3-methylimidazolium bromide/chloride were determined from precise density measurements at temperatures T = (288.15-318.15) K and at atmospheric pressure. Positive values for all the studied amino acids indicate the dominance of hydrophilic-ionic interactions between amino acids and Ionic liquids. The effect of temperature on volumetric properties of glycine/L-alanine in solutions has been determined from the partial molar expansibility and second-order partial molar expansibility. Further, volumetric interaction parameters and hydration number have been calculated, which have been interpreted in terms of possible solute-solvent interactions.

Keywords: ILs, amino acids, volumetric properties, hydration numbers

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Authors: Mohamad Saab, Florent Real, Francois Virot, Laurent Cantrel, Valerie Vallet

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All spent nuclear fuel reprocessing plants use the PUREX process (Plutonium Uranium Refining by Extraction), which is a liquid-liquid extraction method. The organic extracting solvent is a mixture of tri-n-butyl phosphate (TBP) and hydrocarbon solvent such as hydrogenated tetra-propylene (TPH). By chemical complexation, uranium and plutonium (from spent fuel dissolved in nitric acid solution), are separated from fission products and minor actinides. During a normal extraction operation, uranium is extracted in the organic phase as the UO₂(NO₃)₂(TBP)₂ complex. The TBP solvent can form an explosive mixture called red oil when it comes in contact with nitric acid. The formation of this unstable organic phase originates from the reaction between TBP and its degradation products on the one hand, and nitric acid, its derivatives and heavy metal nitrate complexes on the other hand. The decomposition of the red oil can lead to violent explosive thermal runaway. These hazards are at the origin of several accidents such as the two in the United States in 1953 and 1975 (Savannah River) and, more recently, the one in Russia in 1993 (Tomsk). This raises the question of the exothermicity of reactions that involve TBP and all other degradation products, and calls for a better knowledge of the underlying chemical phenomena. A simulation tool (Alambic) is currently being developed at IRSN that integrates thermal and kinetic functions related to the deterioration of uranyl nitrates in organic and aqueous phases, but not of the n-butyl phosphate. To include them in the modeling scheme, there is an urgent need to obtain the thermodynamic and kinetic functions governing the deterioration processes in liquid phase. However, little is known about the thermodynamic properties, like standard enthalpies of formation, of the n-butyl phosphate molecules and of the UO₂(NO₃)₂(TBP)₂ UO₂(NO₃)₂(HDBP)(TBP) and UO₂(NO₃)₂(HDBP)₂ complexes. In this work, we propose to estimate the thermodynamic properties with Quantum Methods (QM). Thus, in the first part of our project, we focused on the mono, di, and tri-butyl complexes. Quantum chemical calculations have been performed to study several reactions leading to the formation of mono-(H₂MBP), di-(HDBP), and TBP in gas and liquid phases. In the gas phase, the optimal structures of all species were optimized using the B3LYP density functional. Triple-ζ def2-TZVP basis sets were used for all atoms. All geometries were optimized in the gas-phase, and the corresponding harmonic frequencies were used without scaling to compute the vibrational partition functions at 298.15 K and 0.1 Mpa. Accurate single point energies were calculated using the efficient localized LCCSD(T) method to the complete basis set limit. Whenever species in the liquid phase are considered, solvent effects are included with the COSMO-RS continuum model. The standard enthalpies of formation of TBP, HDBP, and H2MBP are finally predicted with an uncertainty of about 15 kJ mol⁻¹. In the second part of this project, we have investigated the fundamental properties of three organic species that mostly contribute to the thermal runaway: UO₂(NO₃)₂(TBP)₂, UO₂(NO₃)₂(HDBP)(TBP), and UO₂(NO₃)₂(HDBP)₂ using the same quantum chemical methods that were used for TBP and its derivatives in both the gas and the liquid phase. We will discuss the structures and thermodynamic properties of all these species.

Keywords: PUREX process, red oils, quantum chemical methods, hydrolysis

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