Relevant bibliographies by topics / Solvolysis. Solution (Chemistry) Solvents

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  1. Journal articles
  2. Dissertations / Theses
  3. Books
  4. Book chapters
  5. Conference papers

Academic literature on the topic 'Solvolysis. Solution (Chemistry) Solvents'

Author: Grafiati
Published: 4 June 2021
Last updated: 13 February 2022

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Journal articles on the topic "Solvolysis. Solution (Chemistry) Solvents"

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Pieper, Thomas, Wolfgang Peti, and Bernhard K. Keppler. "Solvolysis of the Tumor-Inhibiting Ru(III)-Complex trans-Tetrachlorobis(Indazole)Ruthenate(III)." Metal-Based Drugs 7, no. 4 (January 1, 2000): 225–32. http://dx.doi.org/10.1155/mbd.2000.225.

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The ruthenium(III) complex Hlnd trans-[RuCl4,(ind)2], with two trans-standing indazole (ind) ligands bound to ruthenium via nitrogen, shows remarkable activity in different tumor models in vitro and in vivo. The solvolysis of the complex trans-[RuCl4,(ind)2]- has been investigated by means of spectroscopic techniques (UV/vis, NMR)in different solvents. We investigated the indazolium as well as the sodium salt, the latter showing improved solubility in water. In aqueous acetonitrile and ethanol the solvolysis results in one main solvento complex. The hydrolysis of the complex is more complicated and depends on the pH of the solution as well as on the buffer system.
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Thiare, Diène Diègane, Abdourakhmane Khonté, Diegane Sarr, Cheikh Diop, Mame Diabou Gaye-Seye, Atanasse Coly, François Delattre, Alphonse Tine, and Jean-Jacques Aaron. "Solvolysis kinetic study and direct spectrofluorimetric analysis of the fungicide benomyl in natural waters." Macedonian Journal of Chemistry and Chemical Engineering 33, no. 2 (November 7, 2014): 237. http://dx.doi.org/10.20450/mjcce.2014.513.

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<p>A direct spectrofluorimetric method for the quantitative analysis of benomyl in natural waters is described. Benomyl is an instable, fluorescent fungicide that mainly decomposes into carbendazim and n-butyl-isocyanate in organic and aqueous solutions. The kinetics of benomyl solvolysis reactions were investigated in organic solvents (methanol and acetonitrile) and in aqueous solvent systems, including β–cyclodextrin (β-CD), sodium dodecyl sulfate (SDS), dodecyltrimethylammonium chloride (DTAC), cetyltrimethylammonium chloride (CTAC), cetyltrimethylammonium hydroxide (CTAOH), Brij-700, Triton X-100 and water, at different pH and/or NaOH concentrations. The benomyl fluorescence signal was found to be quasi-completely stable in 10<sup>-2</sup> M NaOH aqueous solution, various alkaline (10<sup>-2</sup> M NaOH) organized media, β-CD neutral solution and Triton X-100 aqueous solutions of different pH. Based on these results, a direct spectrofluorimetric analytical method was developed for the determination of benomyl in 10<sup>-2</sup> M NaOH aqueous solution and Triton X-100 solutions (pH7 and 10<sup>-2</sup> M NaOH), with wide linear dynamic range (LDR) values of two to three orders of magnitude, very low limit of detection (LOD) and limit of quantification (LOQ) values of, respectively, 0.002-0.5 ng/mL and 0.007-2.0 ng/mL, and small relative standard deviation (RSD) values of 0.2-1.7 %, according to the medium. This direct spectrofluorimetric method was applied to the evaluation of benomyl residues in natural waters, with satisfactory recovery values (87-94%).</p>
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Hojo, Masashi. "Elucidation of specific ion association in nonaqueous solution environments." Pure and Applied Chemistry 80, no. 7 (January 1, 2008): 1539–60. http://dx.doi.org/10.1351/pac200880071539.

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The paper reviews ion aggregation in ionic solution in solvents of low and high permittivity. Although higher ion aggregates from 1:1 type electrolytes in low-pemittivity media (εr &lt; 10) are widely accepted, only a few chemists have recognized the higher ion aggregation in the higher-permittivity media. However, we have clarified that the chemical interaction, such as coordination, can operate between simple anions and cations in nonaqueous solvents (20 &lt; εr &lt; 65) of low solvation ability. Acids (HA) and their conjugate base anions (A-) may react with each other to form homoconjugated species, such as A-(HA)2, in acetonitrile or benzonitrile (i.e., solvents possessing poor hydrogen-bonding donor and acceptor abilities). An analytical method of conductivity data for 1:1 electrolytes has been developed and successfully applied to very complicated systems, in which the ion pair (1:1), triple ions (2:1 and 1:2), and the quadrupole (2:2 association) are involved in a solution at the same time. After observing the direct reaction of some anions (e.g., Cl-) and cations (e.g., Li+) toward a certain species, we interpreted comprehensively the salt effects in chemical equilibria, based on distinct chemical interactions and not merely a vague term, "medium effect". The mechanism of salt effects on solvolysis reactions of the SN1 type in organic-aqueous mixed solvents has been elucidated. We discussed that a reaction manner similar to that in nonaqueous solution can take place even in some "aqueous" solution if the huge network of hydrogen-bonding of bulk water (the number of water, nw &gt; ~108) is destroyed due to any spatial barriers (such as ions, molecules, surface) or elevated temperature.
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Dionísio, Madalena S., Joaquim J. Moura Ramos, and Raquel M. Gonçalves. "The enthalpy and entropy of cavity formation in liquids and Corresponding States Principle." Canadian Journal of Chemistry 68, no. 11 (November 1, 1990): 1937–49. http://dx.doi.org/10.1139/v90-299.

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A new method to calculate the enthalpy and entropy of cavity formation in liquids is proposed. The reference cavity formation process is identified with the vaporization of liquid in the absence of order and Corresponding States Principle is used to eliminate the order contribution to vaporization enthalpy. The proposed method agrees very well with Claverie's modification of the Pierotti's method but strongly disagrees with the Sinanoglu's method, particularly in the context of entropy of cavity formation.The new method is checked by applying it to the description of solution process in alkane binary mixtures at infinite dilution and is used to study the solvent effect on the solvolysis of t-butyl chloride and bromide. Keywords: cavity formation, enthalpy and entropy of cavity formation, Corresponding States Principle, alkanes, intermolecular interactions, acentric factor, solvent effect.
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Brown, Robert Stan. "Bio-inspired approaches to accelerating metal ion-promoted reactions: enzyme-like rates for metal ion mediated phosphoryl and acyl transfer processes." Pure and Applied Chemistry 87, no. 6 (June 1, 2015): 601–14. http://dx.doi.org/10.1515/pac-2014-1008.

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Abstract Intense efforts by many research groups for more than 50 years have been directed at biomimetic approaches to understand how enzymes achieve their remarkable rate accelerations. Nevertheless, it was noted in 2003 that, despite numerous efforts to design models for catalyzing the cleavage of such species as phosphate diesters, “none of the several models so far described approaches the enormous catalytic efficiency of natural enzymes”. The same could be said for biomimetics of other enzymes promoting acyl or phosphoryl transfer reactions, particularly those mediated by metal ions such as Zn(II). Clearly other important factors were being overlooked or awaiting discovery. In this manuscript we describe two important effects that we have implemented to accelerate metal ion catayzed phosphoryl and acyl transfer reactions. The first of these relates to a medium effect where the polarity of the solution, as measured by dielectric constant, is reduced from that of water (ε = 78) to values of 31.5 and 24.3 when the solvent is changed to methanol or ethanol. Among organic solvents these light alcohols are closest to water in terms of structure and properties as well as retaining important H-bonding properties. The second important effect involves a known but difficult to demonstrate mode of catalysis where the leaving group (LG) in a solvolysis reaction is accelerated as it becomes progressively poorer. In the cases described herein, the LG’s propensity to depart from a substrate during the course of reaction is accelerated by coordination to a metal ion in a process known as leaving group assistance, or LGA. These two effects can each impart accelerations of 109–1017 for certain metal ion catalyzed reactions relative to the corresponding solvent, or base induced reactions.
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Bolton, Judy L., and Robert A. McClelland. "Azide ion trapping and lifetime in aqueous solution of a primary carbenium ion stabilized by a 2-imidazoyl ring." Canadian Journal of Chemistry 67, no. 7 (July 1, 1989): 1139–43. http://dx.doi.org/10.1139/v89-171.

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2-Chloromethyl-1-methylimidazole undergoes a pH-dependent aqueous hydrolysis with the neutral substrate being the reactive species, and the imidazole-protonated form (pKa = 5.7) unreactive. Addition of sodium chloride retards the hydrolysis, evidence that there is a free carbenium ion intermediate (the common ion effect). The rate constant ratio Kcl/Kw for the reactions of this cation with the added chloride and with the solvent is 7.4 M−1. Further evidence for a free cation is the observation of the 2-azidomethyl product when the hydrolysis is carried out with sodium azide present, but with no change in the rate constant. The Kaz/Kw ratio as determined by product analysis is 1.1 × 102 M−1 With the assumption that kaz represents a diffusion-controlled reaction and has a value of 7 × 109 M−1 s−1, the rate constant kw for the reaction of the cation with solvent is 6 × 107 s−1. A comparison with azide–water selectivity ratios reported for other cations shows that the imidazole-stabilized primary cation of this study is relatively long-lived. A possible explanation for this is given, in terms of the extensive resonance delocalization of the positive charge in this cation. Keywords: solvolysis, carbenium ion, heterocycle.
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Park, Kyoung Ho, Mi Hye Seong, Jin Burm Kyong, and Dennis N. Kevill. "Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions." International Journal of Molecular Sciences 22, no. 14 (July 9, 2021): 7394. http://dx.doi.org/10.3390/ijms22147394.

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A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (kexp) for the solvolysis of 1 were separated into k1-Ad+Cl− and k1-AdSCO+Cl− through a product study and applied to the Grunwald–Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.
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D’Souza, Malcolm J., Jeremy Wirick, Osama Mahmoud, Dennis N. Kevill, and Jin Burm Kyong. "The Influence of a Terminal Chlorine Substituent on the Kinetics and the Mechanism of the Solvolyses of n-Alkyl Chloroformates in Hydroxylic Solvents." International Journal of Molecular Sciences 21, no. 12 (June 19, 2020): 4387. http://dx.doi.org/10.3390/ijms21124387.

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A previous study of the effect of a 2-chloro substituent on the rates and the mechanisms of the solvolysis of ethyl chloroformate is extended to the effect of a 3-chloro substituent on the previously studied solvolysis of propyl chloroformate and to the effect of a 4-chloro substituent on the here reported rates of solvolysis of butyl chloroformate. In each comparison, the influence of the chloro substituent is shown to be nicely consistent with the proposal, largely based on the application of the extended Grunwald–Winstein equation, of an addition-elimination mechanism for solvolysis in the solvents of only modest solvent ionizing power, which changes over to an ionization mechanism for solvents of relatively high ionizing power and low nucleophilicity, such as aqueous fluoroalcohols with an appreciable fluoroalcohol content.
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D’Souza, Malcolm J., Zoon Ha Ryu, Byoung-Chun Park, and Dennis N. Kevill. "Correlation of the rates of solvolysis of acetyl chloride and α-substituted derivatives." Canadian Journal of Chemistry 86, no. 5 (May 1, 2008): 359–67. http://dx.doi.org/10.1139/v08-028.

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Additional specific rates of solvolysis have been determined for acetyl chloride and diphenylacetyl chloride. These are combined with literature values to carry out correlation analyses, using the extended Grunwald–Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Parallel analysis are carried out using literature values for the specific rates of solvolysis of trimethylacetyl chloride, chloroacetyl chloride, phenylacetyl chloride, and α-methoxy-α-trifluoromethylphenylacetyl chloride (MTPAC). Chloroacetyl chloride and MTPAC react by an addition-elimination pathway, with the addition step rate-determining, over the full range of solvents. Acetyl chloride reacts over the full range of solvents by an ionization pathway, with considerable nucleophilic solvation. The other three substrates can solvolyze with the domination of either mechanism, depending on the properties of the solvent. Reports concerning the use of product selectivity values, kinetic solvent isotope effects, and computational studies as additional probes of the mechanism of solvolysis are discussed.Key words: Grunwald-Winstein equation, acyl chlorides, mechanism of solvolysis, solvent nucleophilicity.
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Kevill, Dennis N., and Malcolm J. D’Souza. "Article." Canadian Journal of Chemistry 77, no. 5-6 (June 1, 1999): 1118–22. http://dx.doi.org/10.1139/v99-083.

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The specific rates of solvolysis of phenyl chlorothionoformate (PhOCSCl) are remarkably similar to those previously reported for phenyl chlorothioformate (PhSCOCl). When analyzed using the extended Grunwald-Winstein equation over the usual range of solvent types, these solvolyses show essentially identical divisions into the solvents favoring the addition-elimination channel and those favoring the ionization channel. The introduction of one sulfur caused a partial shift away from the addition-elimination pathway, which was dominant over the full range of solvents for phenyl chloroformate (PhOCOCl). Consistent with these results, introduction of the second sulfur within phenyl chlorodithioformate (PhSCSCl) leads to a completion of this shift, such that an extended Grunwald-Winstein treatment of the specific rates of solvolysis now shows the ionization pathway to be dominant over the full range of solvents.Key words: Grunwald-Winstein equation, solvent nucleophilicity, solvolysis, phenyl chlorothionoformate, phenyl chlorodithioformate.
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Dissertations / Theses on the topic "Solvolysis. Solution (Chemistry) Solvents"

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Hait, Mitchell Jay. "Measurement and prediction of infinite dilution properties in nonionic solutions." Diss., Georgia Institute of Technology, 1992. http://hdl.handle.net/1853/11212.

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Guo, Zhonghua. "Room Temperature Tunable Energy Transfer Systems in Different Solvents." Fogler Library, University of Maine, 2009. http://www.library.umaine.edu/theses/pdf/GuoZ2009.pdf.

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Conner, John K. "Kinetic and product analytical studies of the solvolysis of 2-adamantyl azoxytosylate and related compounds in a range of solvents." Thesis, University of Stirling, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.257438.

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Young, Christi Lynn Patton. "Solute separabilities in solvent gas-rich liquid-liquid-vapor systems topographical and molecular consideration /." Access abstract and link to full text, 1993. http://0-wwwlib.umi.com.library.utulsa.edu/dissertations/fullcit/9313535.

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Cheng, Chin-Hwa 1957. "Solubility of diuron in complex solvent systems." Thesis, The University of Arizona, 1989. http://hdl.handle.net/10150/277194.

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The solubility of diuron was determined in binary and ternary cosolvent-water systems. The binary systems were composed of a completely miscible organic solvent (CMOS) and water while the ternary systems incorporate partially miscible organic solvents (PMOS) into the binary systems. Due to the low aqueous solubilities of trichloroethylene and toluene, the PMOS's do not behave as cosolvents and they do not play an important role in altering solubility.
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Deng, Tʻai-ho. "Thermodynamic Properties of Nonelectrolyte Solutes in Ternary Solvent Mixtures." Thesis, University of North Texas, 1999. https://digital.library.unt.edu/ark:/67531/metadc279275/.

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The purpose of this dissertation is to investigate the thermodynamic properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing that behavior in the solvent mixtures. Thirty-four ternary solvent systems were studied containing either alcohol (1-propanol, 2-propanol, 1-butanol, and 2-butanol), alkane (cyclohexane, heptane, and 2,2,4-trimethylpentane) or alkoxyalcohol (2-ethoxyethanol and 2-butoxyethanol) cosolvents. Approximately 2500 experimental measurements were performed. Expressions were derived from the Combined Nearly Ideal Multiple Solvent (NIMS)/Redlich-Kister, the Combined Nearly Ideal Multiple Solvent (NIMS)/Bertrand, Acree and Burchfield (BAB) and the Modified Wilson models for predicting solute solubility in ternary solvent (or even higher multicomponent) mixtures based upon the model constants calculated from solubility data in sub-binary solvents. Average percent deviation between predicted and observed values were less than 2%, documenting that these models provide a fairly accurate description of the thermodynamic properties of nonelectrolyte solutions. Moreover, the models can be used for solubility prediction in solvent mixtures in order to find the optimum solvent composition for solubilization or desolubilization of a solute. From a computational standpoint, the Combined Nearly Ideal Multiple Solvent/Redlich-Kister equation is preferred because the needed model constants can be calculated with a simple linear regressional analysis. Model constants for the Modified Wilson equation had to be calculated using a reiterative trial-and-error method. The C++ program for the Modified Wilson equation applied to ternary and heptanary solvent mixtures is attached.
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Kleyi, Phumelele Eldridge. "Solvent-free synthesis of bisferrocenylimines and their coordination to rhodium (I)." Thesis, Nelson Mandela Metropolitan University, 2009. http://hdl.handle.net/10948/1053.

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Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.
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Lui, Chung-wai. "A study of the understanding of key concepts and processes in unit 5 "solvents and solution" of the Hong Kong integrated science syllabus by the science majors of a college of education." Click to view the E-thesis via HKUTO, 1988. http://sunzi.lib.hku.hk/HKUTO/record/B38627012.

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Pribyla, Karen J. "Thermochemical Study of Crystalline Solutes Dissolved in Ternary Hydrogen-Bonding Solvent Mixtures." Thesis, University of North Texas, 2001. https://digital.library.unt.edu/ark:/67531/metadc2783/.

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The purpose of this dissertation is to investigate the thermochemical properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing behavior in the solvent mixtures. Forty-five ternary solvent systems were studied containing an ether (Methyl tert-butyl ether, Dibutyl ether, or 1,4-Dioxane), an alcohol (1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, or 2-Methyl-1-propanol), and an alkane (Cyclohexane, Heptane, or 2,2,4-Trimethylpentane) cosolvents. The Combined NIBS (Nearly Ideal Binary Solvent)/Redlich-Kister equation was used to assess the experimental data. The average percent deviation between predicted and observed values was less than ± 2 per cent error, documenting that this model provides a fairly accurate description of the observed solubility behavior. In addition, Mobile Order theory, the Kretschmer-Wiebe model, and the Mecke-Kempter model were extended to ternary solvent mixtures containing an alcohol (or an alkoxyalcohol) and alkane cosolvents. Expressions derived from Mobile Order theory predicted the experimental mole fraction solubility of anthracene in ternary alcohol + alkane + alkane mixtures to within ± 5.8%, in ternary alcohol + alcohol + alkane mixtures to within ± 4.0%, and in ternary alcohol + alcohol + alcohol mixtures to within ± 3.6%. In comparison, expressions derived from the Kretschmer-Wiebe model and the Mecke-Kempter model predicted the anthracene solubility in ternary alcohol + alkane + alkane mixtures to within ± 8.2% and ± 8.8%, respectively. The Kretschmer-Wiebe model and the Mecke-Kempter model could not be extended easily to systems containing two or more alcohol cosolvents.
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De, Fina Karina M. "Thermodynamics of Mobile Order Theory: Solubility and Partition Aspects." Thesis, University of North Texas, 2004. https://digital.library.unt.edu/ark:/67531/metadc4626/.

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The purpose of this thesis is to analyze the thermochemical properties of solutes in nonelectrolyte pure solvents and to develop mathematical expressions with the ability to describe and predict solution behavior using mobile order theory. Solubilities of pesticides (monuron, diuron, and hexachlorobenzene), polycyclic aromatic hydrocarbons (biphenyl, acenaphthene, and phenanthrene), and the organometallic ferrocene were studied in a wide array of solvents. Mobile order theory predictive equations were derived and percent average absolute deviations between experimental and calculated mole fraction solubilities for each solute were as follows: monuron in 21 non-alcoholic solvents (48.4%), diuron in 28 non-alcoholic solvents (60.1%), hexachlorobenzene (210%), biphenyl (13.0%), acenaphthene (37.8%), phenanthrene (41.3%), and ferrocene (107.8%). Solute descriptors using the Abraham solvation model were also calculated for monuron and diuron. Coefficients in the general solvation equation were known for all the solvents and solute descriptors calculated using multilinear regression techniques.
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Books on the topic "Solvolysis. Solution (Chemistry) Solvents"

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Torraca, Giorgio. Solubility and solvents for conservation problems. 4th ed. Rome: ICCROM, 1990.

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Reichardt, Christian. Solvents and solvent effects in organic chemistry. 3rd ed. Weinheim: Wiley-VCH, 2003.

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Solvent mixtures: Properties and selective solvation. New York: Marcel Dekker, 2002.

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Răileanu, Metodiu. Rolul solvenților în chimie. București: Editura Academiei Republicii Socialiste România, 1988.

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Solvents and solvent effects in organic chemistry. 3rd ed. Weinheim: Wiley-VCH, 2003.

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Reichardt, C. Solvents and solvent effects in organic chemistry. 2nd ed. Weinheim, Federal Republic of Germany: VCH, 1988.

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Reichardt, C. Solvents and solvent effects in organic chemistry. 3rd ed. Weinheim: Wiley-VCH, 2003.

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Ėksperimentalʹnye metody khimii rastvorov: Densimetrii︠a︡, viskozimetrii︠a︡, konduktometrii︠a︡ i drugie metody. Moskva: "Nauka", 1997.

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The properties of solvents. Chichester: Wiley, 1998.

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Popovych, Orest. Nonaqueous Solution Chemistry. Krieger Publishing Company, 1990.

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Book chapters on the topic "Solvolysis. Solution (Chemistry) Solvents"

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Jolivet, Jean-Pierre. "Water and Metal Cations in Solution." In Metal Oxide Nanostructures Chemistry. Oxford University Press, 2019. http://dx.doi.org/10.1093/oso/9780190928117.003.0005.

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Water has an exceptional ability to dissolve minerals. It is safe and chemically stable, and it remains liquid over a wide temperature range. Thus, it is the best solvent and reaction medium for both laboratory and industrial purposes. Water is able to dissolve ionic and ionocovalent solids because of the high polarity of the molecule (dipole moment μ = 1.84 Debye) as well as the high dielectric constant of the liquid (ε = 78.5 at 25°C). This high polarity allows water to exhibit a strong solvating power: that is, the ability to fix onto ions as a result of electrical dipolar interactions. Water is also an ionizing liquid able to polarize an ionocovalent molecule. For example, the solvolysis phenomenon increases the polarization of the HCl molecule in aqueous solution. Finally, owing to the high dielectric constant of the liquid, water is a dissociating solvent that can decrease the electrostatic forces between solvated cations and anions, allowing their dispersion as H+solvated and Cl−solvated through the liquid. (The attractive force F between charges q and q′ separated by the distance r is given by Coulomb’s law, F = qq′/εr2.) These characteristics are rarely found together in common liquids. The dipole moment of the ethanol molecule (μ = 1.69 Debye) is close to that of water, but the dielectric constant of ethanol is much lower (ε = 24.3). Ethanol is a good solvating liquid, but a poor dissociating one; consequently, it is considered a bad solvent of ionic compounds. Dissolution in water of an ionic solid such as sodium chloride is limited to dipolar interactions with Na+ and Cl− ions and their dispersion in the liquid as solvated ions, regardless of the pH of the solution. Cations with higher charge, especially cations of transition metals, retain a fixed number of water molecules, thereby forming a true coordination complex [M(OH2)N]z+ with a well-defined geometry. In addition to the dipolar interactions, water molecules behave as true ligands because they are Lewis bases exerting an electron σ-donor effect on the empty orbitals of the cation.
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"CHARACTERIZATION OF NON-AQUEOUS SOLVENTS." In Lecture Notes on Solution Chemistry, 129–44. WORLD SCIENTIFIC, 1995. http://dx.doi.org/10.1142/9789812830975_0013.

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"SOLVATION IN NON-AQUEOUS SOLVENTS." In Lecture Notes on Solution Chemistry, 145–56. WORLD SCIENTIFIC, 1995. http://dx.doi.org/10.1142/9789812830975_0014.

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Watanabe, Iwao. "EXAFS of bromide ion in solvents and at air/solution interface." In Studies in Physical and Theoretical Chemistry, 245–52. Elsevier, 1995. http://dx.doi.org/10.1016/s0167-6881(06)80783-4.

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Sumi, Hitoshi. "Theory on rates of solution reactions influenced by slow fluctuations in viscous solvents, and its experimental confirmation." In Studies in Physical and Theoretical Chemistry, 65–73. Elsevier, 1995. http://dx.doi.org/10.1016/s0167-6881(06)80762-7.

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Leitner, Walter. "Fluorous Phases and Compressed Carbon Dioxide as Alternative Solvents for Chemical Synthesis: A Comparison." In Green Chemistry Using Liquid and Supercritical Carbon Dioxide. Oxford University Press, 2004. http://dx.doi.org/10.1093/oso/9780195154832.003.0009.

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The principal goal of basic research in chemical synthesis is the development of efficient tools for functional group transformations and for the assembly of building blocks during the construction of molecules with increasing complexity. Traditionally, new approaches in this area have focused on the quest for new reaction pathways, reagents, or catalysts. Comparably less effort has been devoted to utilize the reaction medium as a strategic parameter, although the use of solvents is often crucial in synthetically useful transformations. The first choice for a solvent during the development of a synthetic procedure is usually an organic liquid, which is selected on the basis of its protic or aprotic nature, its polarity, and the temperature range in which the reaction is expected to proceed. Once the desired transformation is achieved, yield and selectivity are further optimized in the given medium by variation of temperature, concentration, and related process parameters. At the end of the reaction, the solvent must be removed quantitatively from the product using conventional workup techniques like aqueous extraction, distillation, or chromatography. If the synthetic procedure becomes part of a large-scale application, the solvent can sometimes be recycled, but at least parts of it will ultimately end up in the waste stream of the process. Increasing efforts to develop chemical processes with minimized ecological impact and to reduce the emission of potentially hazardous or toxic organic chemicals have stimulated a rapidly growing interest to provide alternatives to this classical approach of synthesis in solution. At the same time, researchers have started to realize that the design and utilization of multifunctional reaction media can add a new dimension to the development of synthetic chemistry. In particular, efficient protocols for phase separations and recovery of reagents and catalysts are urgently required to provide innovative flow schemes for environmentally benign processes or for high-throughput screening procedures. Fluorous liquid phases and supercritical carbon dioxide (sc CO2) have received particular attention among the various reaction media that are discussed as alternatives to classical organic solvents. The aim of this chapter is to compare these two media directly and to critically evaluate their potential for synthetic organic chemistry.
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Knicker, Heike, and Rüdiger Fründ. "Characterization of Nitrogen in Plant Composts and Native Humic Material by Natural-Abundance 15N CPMAS and Solution NMR Spectra." In Nuclear Magnetic Resonance Spectroscopy in Environment Chemistry. Oxford University Press, 1997. http://dx.doi.org/10.1093/oso/9780195097511.003.0022.

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Soil organic matter (SOM) provides one of the major deposits for carbon and nitrogen on the surface of the Earth. It is continuously produced, mainly from dead plant material, by composting and humification processes. During these processes microorganisms thoroughly convert the starting material, which consists mostly of insoluble lignocelluloses. The end products of these processes in average middle-European soils, that contain typically 1 to 5% w/w of organic material, are clay–SOM complexes which are insoluble in all the usual organic and inorganic solvents. The standard aqueous sodium hydroxide extraction procedure dissolves at most 40% of the total organic carbon in all the soils tested by our group. The insoluble majority, the humin fraction, remains as poorly defined aluminosilicate- SOM complexes. During the decomposition and conversion processes the carbon to nitrogen ratio–decreases. Compared to the starting material, SOM is enriched in nitrogen. Under natural conditions, i.e., without the artificial addition of nitrogen in the form of manure or fertilizer, SOM provides the major part of the nitrogen available for plant growth. The chemical characterization of this ubiquitous but ill-defined material has only been partly successful until now. For characterization of the organic carbon in complete soils and extracts, nuclear magnetic resonance (NMR) methods appear to be most promising, especially since the application of high-resolution solid-state methods has become almost a laboratory routine. The combination of proton–carbon cross polarization with high-speed magic angle rotation (the CPMAS technique) permits the study of complete native soils, and thus provides detailed information about the gross chemical structure of the total SOM, without introducing any of the chemical modifications that could result from aggressive chemical extraction procedures. It has been shown by 13C CPMAS and high-resolution (HR) solution 13C NMR studies of a series of typical European soils, in which the concentration of paramagnetic metal ions was fairly low and which contained humic material with an aromatic carbon content ≤20%, that the carbon could be quantitatively assigned. The measurement of the 13C CPMAS spectra of complete native soils with a carbon content in the region of 1 % w/w is rather instrument-time consuming, and appeared to be at the limit of sensitivity.
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Cammish, Linda E., and Steven A. Kates. "Instrumentation for automated solid phase peptide synthesis." In Fmoc Solid Phase Peptide Synthesis. Oxford University Press, 1999. http://dx.doi.org/10.1093/oso/9780199637256.003.0017.

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The concept of solid phase peptide synthesis introduced by Merrifield in 1963 involves elongating a peptide chain on a polymeric support via a two-step repetitive process: removal of the Nα-protecting group and coupling of the next incoming amino acid. A second feature of the solid phase technique is that reagents are added in large excesses which can be removed by simple filtration and washing. Since these operations occur in a single reaction vessel, the entire process is amenable to automation. Essential requirements for a fully automatic synthesizer include a set of solvent and reagent reservoirs, as well as a suitable reaction vessel to contain the solid support and enable mixing with solvents and reagents. Additionally, a system is required for selection of specific solvents and reagents with accurate measurement for delivery to and removal from the reaction vessel, and a programmer to facilitate these automatic operations is necessary. The current commercially available instruments offer a variety of features in terms of their scale (15 mg to 5 kg of resin), chemical compatibility with 9-fluorenylmethyloxycarbonyl/tert-butyl (Fmoc/tBu) and tert-butyloxycarbonyl/ benzyl (Boc/Bzl)-based methods, software (reaction monitoring and feedback control), and flexibility (additional washing and multiple activation strategies). In addition, certain instruments are better suited for the synthesis of more complex peptides such as cyclic, phosphorylated, and glycosylated sequences while others possess the ability to assemble a large number of peptide sequences. The selection of an instrument is dependent on the requirements and demands of an individual laboratory. This chapter will describe the features of the currently available systems. As the field of solid phase synthesis evolved, manufacturers designed systems based on the synergy between chemistry and engineering. A key component to an instrument is the handling of amino acids and their subsequent activation to couple to a polymeric support. The goal of an automated system is to duplicate conditions that provide stability to reactive species that might decompose. Standard protocols for automated synthesis incorporate carbodiimide, phosphonium, and aminium/uronium reagents, preformed active esters, and acid fluorides. For further details on coupling methods, see Chapter 3. A second issue related to coupling chemistry is the time required to dissolve an amino acid and store this solution.
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Fawcett, W. Ronald. "Electrolyte Solutions." In Liquids, Solutions, and Interfaces. Oxford University Press, 2004. http://dx.doi.org/10.1093/oso/9780195094329.003.0007.

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Electrolyte solutions are important in all branches of chemistry, but especially in analytical chemistry, and biochemistry. These systems by their nature are always non-ideal, and represented an early challenge to theoreticians interested in describing their thermodynamic properties. The solute components are ions, cations, and anions, which carry opposite charges and thus interact very differently with one another. The existence of electrolyte solutions depends on the polar properties of the solvent through which the individual ions are stabilized. When one recognizes the molecular nature of the solvent, one must also consider the interactions between solvent dipoles and the ion. This results in changes in solvent structure in the immediate vicinity of the ions. It follows that a complete description of an electrolyte solution at the molecular level requires the consideration of ion–dipole, ion–ion, and dipole–dipole interactions. In addition to these simple electrostatic interactions, one must also consider the role of hydrogen bonding in protic solvents like water. In very dilute electrolyte solutions, the most important consideration is ion– dipole interactions. One expects these interactions to be different for cations and anions. This follows from the fact that the solvent molecule is not a simple dipole in the electrostatic sense but instead it has a chemical structure which is different at each end of the molecular dipole. Each ion interacts locally with four to six solvent molecules in its immediate surroundings. In the case of water, the concentration of water molecules in the pure liquid is 55.5 M; it follows that the number of water molecules experiencing direct interaction with ions in dilute solutions represents a small fraction of the total number. As the electrolyte concentration increases, ion–ion interactions become more important in determining the thermodynamic properties of the solution. The electrostatic field of an ion is long ranged, decreasing with the reciprocal of the distance from the charge center of the ion. As a result a given ion has an ionic atmosphere in which the concentration of oppositely charged ions in its vicinity is slightly greater on the average than that of ions of the same charge.
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"• MISER; • SEAWINDS; • Pathfinder. and many others. Since the assemblies produced in this laboratory always fall in the high performance, high reliability category, cleaning is mandatory, not op-tional . With the demise of the ozone-depleting solvents that were the mainstay of the electronics industry for twenty years, it was necessary to turn to alternative chemistries an d cleaning systems to ensure cleanliness and high reliability of the surface mount assemblies (SMAs). The initial cleaning system chosen for the SMT Laboratory was a two-stage batch semi-aqueous (SA) cleaning system. Although this system worked satisfac-torily for a number of years, the decision was reached recently to replace it. Part of the reason was the increasing complexity of the SMT PWAs. Equipment to en-sure that the cleaning solution would successfully penetrate under the small standoff s and tight spacings found under the newer components now being in-creasing employed was considered mandatory. Another factor in the decision was that the initial equipment manufacturer sold off this portion of the business and no longer supported the equipment. It proved increasingly more difficult to maintain it in good working condition. In addition, isopropyl alcohol (IPA), used in the original equipment, came under increasing scrutiny by the South Coast Air Qual-ity Management District (SCAQMD). Because IP A is a volatile organic com-pound (VOC), its emission into the atmosphere is tightly controlled. The decision was made to investigate a new cleaning system and a chemistry that would sup-port JPL's need for clean PWAs to meet the newer challenges. 3. PERTINENT PROCESS INFORMATION The following JPL process information is pertinent to the discussion: • Rosin-based fluxes and pastes are used to produce all electronic hardware. Using the terminology of Mil-F-14256, the classification of these products is rosin mildly activated (RMA). • The solder paste is applied using a semi-automated screen printer ensuring that the paste is deposited in a uniform and consistent manner. Only stainless steel stencils are used in conjunction with a stainless steel squeegee. All boards are visually inspected for proper paste deposition after the stencil operation. • A laser-based solder paste height and width measurement system is used with a resolution of 0.0001 inch (2.5 jxm). This system provides real time informa-tion on the uniformity of solder paste deposition. All boards are subjected to this measurement prior to the reflow operation. • A batch reflow operation is used to create the solder joints of the SMT PWAs. The SMT PWAs are thermally profiled using aM.O.L.E.® - a thermocouple." In Surface Contamination and Cleaning, 235–41. CRC Press, 2003. http://dx.doi.org/10.1201/9789047403289-34.

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Conference papers on the topic "Solvolysis. Solution (Chemistry) Solvents"

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Kunchala, Praveen, Hyejin Moon, Yasith Nanayakkara, and Daniel W. Armstrong. "EWOD Based Liquid-Liquid Extraction and Separation." In ASME 2009 Summer Bioengineering Conference. American Society of Mechanical Engineers, 2009. http://dx.doi.org/10.1115/sbc2009-206690.

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Liquid-liquid extraction techniques are one of the major tools in chemical engineering, analytical chemistry, and biology, especially in a system where two immiscible liquids have an interface solutes exchange between the two liquid phases along the interface up to a point where the concentration ratios in the two liquids reach their equilibrium values [1]. Solutes including nucleic acids and proteins of interests can be extracted from one liquid phase to the other immiscible liquid phase as a preparation step for many analytical processes. There are several advantages in miniaturizing the liquid-liquid extraction methods to on-chip level extraction. Usual advantages of miniaturization are the reduction in the sample size and portability. In addition, transport phenomena is faster in Micro-systems than in ordinary size systems, and therefore, one may expect that liquid-liquid extraction takes less time to achieve in miniaturized devices. It is due to shorter diffusion time in micro scale as well as high surface to volume ratio of Microsystems. Electrowetting on dielectric (EWOD) digital microfluidics is an efficient platform to process droplet based analytical processes [2]. Nanoliter (nL) or smaller volume of aqueous liquid droplets can be generated and transported on a chip by EWOD process. In addition to the high surface to volume ratio, high chemical potential can be expected in droplet based extraction when the droplets are in motion. In this paper, we propose to use room temperature ionic liquid (RTIL) as a second liquid phase for extraction, which forms immiscible interface with aqueous solutions. Properties of RTIL can be tailored by choice of cation, anion and substituents. RTIL has been investigated as replacements for the organic solvents and various “task-specific” ionic liquid are being developed which exhibit many attractive properties such as very low vapor pressure, high thermal stability [3]. We recently published EWOD properties of various RTILs toward microfluidic applications [4]. To demonstrate liquid-liquid micro extraction on chip, we fabricated and tested EWOD digital microfluidic devices. Fig. 1 shows (a) top and (b) cross sectional views of EWOD device. Two model extraction systems were tested. One is organic dye extracted from RTIL (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonylimide or BMIMNTf2) to water and the other is iodine (I2) extracted from water to BMIMNTf2. The later model experiment is demonstrated in Fig. 2. Droplets of aqueous solution and BMIMNTf2 solution were generated on chip reservoir then transported for extraction and separated by EWOD actuation. When an aqueous solution and BMIMNTf2 solution join together, they created an interface, since water and BMIMNTf2 are immiscible. Extraction of I2 was done along the interface. After successful extraction, two immiscible liquid phases were separated by EWOD actuation and formed two separate droplets. From the result shown in Fig 2 (g), it is expected that extraction performance at the interface of moving droplet would be enhanced compared to the stationary droplet, because a moving interface prevent the chemical equilibrium, thus more chemical extraction potential can be provided with a moving interface than at a stationary interface. This demonstration is the first step toward total analysis system. The presented result opens the way to on-chip micro extraction, which will be readily integrated with other sample preparation microfluidic components and detection components. Currently, micro extraction systems for larger molecules such as nucleic acids, proteins and biological cells are being developed for further analytical applications.
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