Analysis of water in liquid and solid samples by headspace gas chromatography

Summary The water content of solid samples, which are insoluble in organic solvents, is determined by equilibrium headspace gas chromatography after suspending the samples in a water-miscible dry solvent such as ethylene glycol monomethylether. The accuracy of this suspension approach was tested with sodium tartrate-2-hydrate, a calibration standard for the Karl-Fischer titration, and good agreement was found. Partical applications are given for water analysis in an ionic detergent, in paper, and in solid food samples such as instant soup or drink powder and roasted coffee. The preferred calibration procedure was the standard addition technique, but internal or external standard calibration is also possible, particularly in the case of insoluble samples since the water only is extracted into the solvent. The resulting aqueous solution in the organic solvent represents an ideal matrix for all calibration techniques. The suspended particles from the solid sample were found not to cause additional matrix effects.Paper presented partly at the International Symposium Die Bestimmung des Wassers organized by the Fachgruppe Analytische Chemie der GDCH, Hannover, 4–6 November, 1987.Part I: Fresenius Z Anal Chem 336:291–296     

Solvent effects on chemical processes. 4. Complex formation between naphthalene and theophylline in binary aqueous-organic solvents

The standard free energy change for complex formation is written as a sum of effects arising from solvent-solvent interactions (the general medium effect), solvent-solute interactions (the solvation effect), and solute-solute interactions (the intersolute effect). The general medium effect is given by gA(–_o), where g is a curvature correction factor to the solvent surface tension , A is the change in surface area as the two solvent cavities containing the substrate (naphthalene) and ligand (theophylline) collapse into a single cavity containing the complex, and _o is the value of surface tcnsion at which there is no net solvophobic interaction; is defined to be the value appropriate to the equilibrium mean solvation shell composition. The solvation effect is modeled by equilibrium stoichiometric formation of solvated species. All data are related to the fully aqueous system to give _MG^o, the solvent effect on the free energy change, as an explicit function of solvent composition. Solvent effects on bimolecular association are related to solvent effects on the solubilities of the substrate, ligand, and complex. Approximation methods for interpreting such systems are described and are applied to the naphthalene-theophylline complex. It is shown that complex destabilization in mixed aqueous-organic solvents (relative to the fully aqueous system) may receive contributions from both the general medium and the solvation effects, and that these contributions can be quantitatively estimated.     

Information theory of miniaturization advantages of column liquid chromatography for quantitative analysis

Summary The influences of decreasing column diameter and length on two analytical goals, the precision and solvent efficiency, in reversed-phase liquid-chromatography are studied. Low solvent consumption is one of analytical advantages of miniaturized columns and is shown to be quantitatively evaluated by the precision and solvent efficiency which are defined to be the total Shannon mutual information obtained from an assay and the information obtained in a unit solvent volume, respectively. Analysis of paraben food additives on a microbore column is taken as an example. In trace analysis, the relative standard deviation (RSD) of measurements theoretically derived from the precision is shown to approach to the observed ones.     

Radiochemical solvent extraction of molybdenum/VI/ using99Mo tracer

A radiochemical solvent extraction method has been developed for the micro determination of Mo/VI/ using⁹⁹Mo tracer. It involves removal of^99mTc by ethyl methyl ketone /EMK/ and extraction of Mo with tri-n-butyl phosphate /TBP/ from 5M HCl. Different parameters affecting the extraction such as pH dependence, nature of solvent and interferences due to other radionuclides have been studied. The method can be used up to 2 g of Mo.     

Study of Solvent Composition Effects on the Protonation Equilibria of Various Anilines by Multiple Linear Regression and Factor Analysis Applied to the Correlation Between Protonation Constants and Solvatochromic Parameters in Ethanol–Water Mixed Solvents

The stoichiometric protonation constants (log) of aniline derivatives were determined potentiometrically over a wide range of solvent composition (0–0.74 mole fraction of ethanol). To explain the variation of the log values obtained over the whole composition range studied, the quasi-lattice quasi-chemical theory of preferential solvation was applied. The results were discussed in terms of macroscopic properties of the mixed solvent and different microscopic parameters, such as the Kamlet–Taft solvatochromic parameters to identify the solvent characteristics affecting the log values. Kamlet and Taft's general equation was reduced to two terms by using both multiple-linear regression analysis and combined factor analysis and target factor analysis in these mixtures: the independent term and the hydrogen-bond donating ability (HBD), which is a solvatochromic parameter. Hammett's reaction constant for the protonation of anilines has been obtained for all the solvent mixtures and correlates well with (HBD) of the solvent.     

Viscosities of 1,2-Ethanediol-2-Methoxyethanol solvent mixtures at various temperatures

Viscosities were measured for binary solvent mixtures of 1,2-ethanediol-2-methoxyethanol at 19 temperatures ranging from –10 to 80°C. Several different equations, such as those of Arrhenius, Waterton, and Williams et al., have been applied in order to establish the best regression fit for as a function of temperature. For this binary solvent system, the viscometric properties are continuous but not a linear function of the mixture composition. The deviations of the excess viscosities from ideality were found to be useful in detecting the formation of solvent-cosolvent complex species and to evaluate their stoichiometrical composition.     

The determination of241Pu by liquid scintillation spectrometry using the Packard 2250CA

The results of this study indicate that in terms of efficiency, the Packard 2250Ca liquid scintillation spectrometer is sensitive to the scintillation cocktail employed for²⁴¹Pu analysis, particularly when the burst counting circuit is enabled. Cocktails exhibiting low t-SIE values should be avoided since quenching has a critical influence on such a low energy ^– emitter. This effect would be independent of burst circuitry use. Cocktails which include naphthalene type derivatives such as the alkylnaphthalene solvent employed in Optiphase HiSafe 3 and Ultima Gold should be avoided since the broad pulse shapes produced are incompatible with the burst counting circuit which distinguishes background events from true ^– events by means of pulse shape/duration analysis. Efficiency is also sensitive to the concentration of bis-MSB employed in conjunction with the primary fluor. Enhancements in efficiency are observed with appropriate concentrations. These results are in line with previous work with¹⁴C and are postulated as being a consequence of sharpening prompt pulse widths or suppression of afterpulsing. It is recommended that Instafluor should be used to maximize response, or a cocktail such as butyl-PBD/bis-MSB in pseudocumene at rates of 6 and 1.5 mg ml^–1, respectively, where a lower vapor pressure solvent is particularly required.     

Solution properties of polystyrene–polybutadiene block copolymers

Dilute solution viscosity and osmotic pressure measurements were performed on polystyrene (PS), polybutadiene (PB), polystyrene–polybutadiene (SB) diblock and polystyrene–polybutadiene (SBS) triblock copolymers. Anionic polymerization was used in such a way that the molecular weight of the PS block was kept constant (ca. 10 000), while the molecular weight of the PB block varied from 18000 to 450000. The measurements were carried out at a fixed temperature of 34.20°C in three solvents, namely toluene, a good solvent for PS as well as for PB, dioxane, which is a good solvent for PS and almost a theta solvent for PB, and cyclohexane, which is nearly a theta solvent for PS and a good solvent for PB. The compositions of SB and SBS, as derived from kinetic data agree with ultraviolet measurements in CHCl₃ solutions. The viscosity and osmotic pressure results indicate that the properties of SB and SBS are similar. Their intrinsic viscosities and second virial coefficients can be calculated from their chemical compositions, molecular weight, properties of parent polymers, and values of the interaction parameter \documentclass{article}\pagestyle{empty}\begin{document}$\bar \beta _{{\rm SB}}$\end{document} between styrene and butadiene units, for molecular weights not exceeding approximately 10⁵. The magnitude of \documentclass{article}\pagestyle{empty}\begin{document}$\bar \beta _{{\rm SB}} $\end{document} varies with the solvent. The results suggest that the domains of the PS and PB blocks overlap to a great extent.     

Kinetics of oxidation of bis(ethylenediamine)mercaptoacetatocobalt (III) ion by periodate in water-t-butanol and water-methanol mixtures at different perchloric acid concentrations

Summary The kinetics of oxidation of the bis(ethylenediamine)mercaptoacetatocobalt (III) ion by periodate were investigated as a function of perchloric acid concentration, ionic strength and temperature. Furthermore, the effect of a nonaqueous component of the solvent on the rate constant and activation parameters H and S in the water-t-butanol and water-methanol mixtures was estimated. The solvent effect is discussed from the viewpoint of the change in solvation of initial and transition states on going from water to a mixed solvent.     

Vapochromism of a Pyrrolizinato-nickel(II) Complex Incorporated in Polyvinylbutyral. An Optochemical Detecting System for Alcohols in Air

The bis(1,2,6,7-tetracyano-3,5-dihydro-3,5-diiminopyrrolizinido)nickel(II ) complex (NiL2, L = C11H2N7-) has been incorporated as dispersed monomer in polyvinylbutyral (PVB) at a fairly high concentration (0.021 M). NiL2/PVB spin coated thin films (thickness, 2 m) on glass and silicon and evaporated free standing thicker films (thickness, 50 m) have been studied by means of absorption or reflectivity visible as well as infrared spectroscopy. The light-blue NiL2/PVB film fades slightly on heating (for 7 min at 90 °C) and remains as such after cooling to room temperature. The optical spectrum of the thermally activated NiL2/PVB system, in contact with organic solvent vapors at room temperature, changes with time evolving towards the initial spectrum before the thermal treatment. The system is therefore amenable for sensing organic solvents in air. Several ordinary solvents have been tested. After 12 min exposure to air saturated with vapor a steady-state absorbance signal at the most sensitive wavelength (661 nm) is reached for any tested solvent. The system is most sensitive to alcohols. Response cycles are reported for methanol as solvent.     

Solvent generated liquid-liquid chromatography with nonaqueous ternary systems

Summary It is demonstrated that highly stable and reproducible LLC-columns can be prepared by generating the stationary phase dynamically by the mobile phase. It is shown that such a solvent generated liquid-liquid chromatography can be realized if two conditions are fulfilled: one phase of a liquid-liquid system must be used as mobile phase and the solid support must be better wetted by the other phase of the system. This general principle of solvent generated LLC was investigated for nonaqueous ternary liquid-liquid systems. The liquid-liquid retention mechanism was verified by correlation of chromatographic and partition data. It is shown that significant changes in the retention characteristics occur when going from the liquid-solid to the liquid-liquid retention mode for systems having the same qualitative composition.Presented at the 14th International Symposium on Chromatography London, September, 13–17, 1982.     

Reactivity and selectivity of homolytic substitution reactions on the peroxyacid group

Peracids in solution may undergo homolytic decomposition leading mostly to mixtures of acid and alcohols, these Latters being formed from either the peracid or the solvent

The peracid behaves as source of radicals and also as substrate thus presenting two radicophile centers

- with a nucleophilic radical (R' from peracid or S' from solvent) the site of attack is the 0-0 bond of the peracid yielding an alcohol (NuOH). The rate of this reaction increases with increasing nucleophilicity of the radical ; this reactivity is interpreted in terms of frontier orbital perturbation theory, taking into account both the orbital energy level difference and the orbital overlap.- when the radical is electrophilic, it abstracts rather the hydrogen of the peroxidic group Leading to decomposition of the peracid into acid.Hydrogen abstraction from the solvent may be also observed in appropriate cases : this process can be used for free radical hydroxylation of hydrocarbons.The relative importance of these three chain reactions in competition : 0-0 bound attack, hydrogen abstraction from the peracid and solvent transfer reaction were studied as a function of structure of the radicals, solvent properties and temperature.     

Substoichiometric isotope dilution analysis of arsenic in biological and environmental standard reference materials by solvent extraction using toluene-3,4-dithiol in benzene

A radiochemical solvent extraction procedure has been developed for the determination of As(III) using⁷⁶As tracer. It is based on the complexation of As(III) with toluene-3,4-dithiol (TDT) at pH 2 and subsequent extraction in benzene. The effect of various parameters such as pH, time of equilibration, nature of solvent, quantitative character and interferences have been studied. The method has been further developed into substoichiometric isotope dilution analysis for the determination of As at < 1 g level and employed for the analysis of several environmental and biological standard Reference Materials from NIST (USA), IAEA (Vienna) and NIES (Japan).     

Octahedral and tetrahedral configuration changes of nickel(II) chloro complexes from spectrophotometric studies in aprotic solvents

Four NiII chloro complexes were identified spectrophotometrically in aprotic media such as DMSO, DMF and propylene carbonate for the first time. An original multiwavelength numerical treatment, based on a Marquardt method, results in the determination of the individual electronic spectra of the mononuclear chloro complexes and of their stability constants, the values of which indicate the presence of rather weak complexes in DMSO and DMF, much stronger in the less solvating propylene carbonate solvent. The overall stability constants calculated for the NiII chloro complexes are: 1=52, 2=140, 3=160, 4=210 in DMSO, 1=60, 2=110, 3=900, 4=15000 in DMF, 1=1.6×109, 2=6.4×1015, 3=2.7×1021, 4= 5.1×1026 in PC.The solvent effect is discussed in terms of the quantitative results obtained from this spectrophotometric study and reveals that the stability of the complexes is an inverse function of the donor properties of the solvent. This result illustrates the general behavior of complex formation in dipolar aprotic solvents, i.e. the substitution of one solvent molecule in the inner coordination sphere by the ligand is easier if the solvation strength of the solvent is lower. The solvent effect is also described in terms of the variation of shifts of the calculated absorption maxima for the individual electronic spectra of the chloro complexes. This result is used to identify clearly at which step of coordination the octahedral configuration of the nickel ion changes to the tetrahedral configuration, by comparison with the well-known structural properties of these complexes in the solid state.     

NMR study of the stoichiometry,stability and exchange kinetics of complexation reaction between Pb2+ ion and 18-crown-6 in binary acetonitrile-water mixtures

Proton NMR was used to study the complexation reaction between lead ion and 18-crown-6 in a number of binary acetonitrile-water mixtures. Formation constant for the resulting 11 complexes in different solvent mixtures was determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and amount of water in the mixed solvent. The dissociative kinetics of the complex was studied by proton line-shape analysis. The Arrhenius plots showed a distinct isokinetic temperature at about 25°C at which the decomplexation rate is more or less independent of the solvent composition. the complexation rate and the activation parameters E _a , H and S, for the exchange have been determined and found to be strongly solvent dependent. There is actually a linear relationship between the mole fraction of acetonitrile in the mixed solvent and logarithm of the stability constant as well as activation parameters.     

Structure and dynamics of pyrimidine-based macrocycles in solution

The conformational structure of macrocycles obtained from two thiopyrimidine and uracil nucleic acids linked by polymethylene spacers is determined by the length of the spacers, intramolecular NH bonding, pH and solvent. In CDCl₃, NH-OC hydrogen bonding can impact the overall stabilization of the folded conformation, however spatial preorganization to such hydrogen bonding is a prerequisite. Protonation leads to disruption of intramolecular hydrogen bonds, destabilization of the folded conformation and to strong counterion assisted self-aggregation of macrocyles which can be destroyed in polar solvents.     

Thermodynamic parameters for the reaction of 1,8-diazabicyclo [5.4.0] undec-7-ene with 4-nitrophenylnitromethane in several aprotic solvents

Equilibrium constants K for reaction of the C-acid, 4-nitro/phenylnitromethane with 1,8-diazabicyclo [5.4.0] undec-7-ene have been determined in aprotic solvents over a range of temperature. Corresponding measurements have been made for the deuterated acid 4-NPNM-d₂. Thermodynamic parameters K, H^o and S^o, for proton and for deuteron transfers are not very differet in a given solvent, but show a considerable solvent dependence. There is an increase in magnitude of K with increase in solvent dielectric constant, a finding which is consistent with formation of an ion-pair. The range of extent of exothermicity of the reaction is quite small, –40 to-65 kJ-mol^–1, and the values of S^o (large, negative) indicate, in general, increasing solvent restriction by the product with increasing solvent polarity. A modest bathochromic solvatochromism of the product is observed as the dielectric constant increases.     

Solvent extraction of silver/I/ with 2,4-dihydroxy-acetophenone thiosemicarbazone

The solvent extraction of silver/I/ is carried out in acetic acid-sodium acetate buffer solution at pH 5.0 by 2,4-dihydroxyacetophenone thiosemicarbazone /DATS/. Ethyl acetate has been used as a solvent and is found that single extraction is sufficient to remove silver/I/ completely from the aqueous phase. Silver/I/ forms 11 complex /metalreagent/ with DATS. The effect of diverse ions on the extraction of silver/I/ has been investigated.     

Solvent effect on intensities off-ftransitions in lanthanide(III) complexes

A general theory of the solvent effect on the intensities of f-f; transitions of lanthanide complexes based on static and dynamic coupling between metal ion and ligands and solvent molecules is presented. New expressions are found correlating the intensity parameters with physical characteristics of the solvent. It is shown that the solvent effect influences only in the parameter ₂.     

The Compressibilities of Liquid Phase Host-Guest Systems

The compressibilities of seven liquidphase, macrocyclic host-guest systems were determinedat approximately 25 °C and 3.4 × 10⁷ Pa.Each two-component system consisted of a cyclodextrin,a calixarene, or a crown ether as host and anappropriate solvent as guest. In each case studied,the host-guest system was found to be lesscompressible than the pure solvent, with thedifferences ranging from 2 to 18% of the magnitudesof the pure solvent compressibilities. These findingshave enabled us to better understand how strong,ambient pressure, intermolecular host–guestinteractions influence the compressibility ofsolutions. Both inclusion and solvationcontribute.