Tetraalkylammonium Halides Research Articles

Study of the Charge Transfer Spectra of the Complexes of S-trinitrobenzene and Tetraalkylammonium Halides

Abstract The n,π complexes of s-trinitrobenzene (TNB) and the tetraalkylammonium halides have been studied from the analytical point of view in nonaqueous solvents. Mixtures of tetraalkylammonium chlorides and TNB give little evidence of charge transfer spectra in the visible region, but both the corresponding bromides and iodides form colored complexes with TNB. Proton donors are poor solvents, but acetonitrile, methylene chloride, and chloroform are useful for analytical work. Using excess TNB, plots of absorbance at 410, 415 or 425 mu versus concentration of the bromides are linear and can be used for analysis.

EFFECTS OF TETRAALKYLAMMONIUM HALIDES ON THE AQUEOUS SOLUBILITIES OF DISPERSE DYES

The solubililities of disperse dyes such as azobenzene and p-hydroxyazobenzene in water and aqueous tetraalkylammonium halide (R4NX) solutions were determined at 5°C intervals from 5°C to 40°C. The tetraalkylammonium halides used in this work are tetramethylammonium bromide (Me4NBr), tetraethylammonium chloride (Et4NCl), tetraethylammonium bromide (Et4NBr), tetraethylammonium iodide (Et4NI), and tetra-n-butylammonium bromide (n-Bu4NBr). All experiments were carried ou_??_ below the critical micell concentration of R4NX.From the results the thermodynamic parameters for the process (A) which consists of the transfer of one mole of the solute from a water environment to an aqueous R4NX solution have been calculated from the equations (1), (2) and (3).Process (A): disperse dye in water (mole fraction N0)→ disperse dye in aqueous R4NX solution (mole fraction N)In any case the solubilities of disperse dyes in aqueous R4NX solutions increase regularly with the R4NX concentration for any particular R4NX. It is to be noted that the effects of R4NX on the solubilities are in the follwing order, Me4NBr<Et4NCl<Et4NBr<Et4NI<n-Bu4NBr. This fact indicates that an increase in the solubitity by addition of R4NX is largely dependent on the alkyl chain length of the added R4NX and suggests that the hydrophobic portion of R4NX plays an important role in enhancement of the solubilities of disperse dyes in water. This salting-in maybe explained in terms of an interaction between the dye and the tetraalkylammonium ion, which is induced by the increase in the structure of water near large nonpolar parts of the dye and the organic ion.The resulting ΔSu•trans• are positive for any particular R4NX and ΔHtrans• are positive except for-p-hydroxyazobenzene in aqueous Me4NBr and Et4NI solutions, so it is clear that the favorable transfer of the disperse dye from a water environment to an aqueous R4NX solution comes from the contribution of entropy term. This result strongly suggests that the increase in the solubilities of disperse dyes is the result of the binding of the nonpolar portions of the tetraalkylammoniumm ion to the disperse dye molecule and that this binding comes from the hydrophobic interaction between the hydrocarbon portions of the R4NX and the nonpolar portions of the disperse dye.

Heat capacity changes and standard partial molal heat capacities of aqueous solutions of some tetra-alkyl ammonium halides at 30°C and the effect on water structure

ΔC°p values of tetra-alkylammonium halide salts Me4NBr, Me4NI, Et4NBr, Et4NI, Pr4 NBr, Pr4NI and Bu4NBr in aqueous solutions at 30°C have been determined by measuring integral heats of solution at 25 and 35°C ΔC°p values which vary from –16.5 to 179 cal deg.–1 mole–1 are in the increasing order of Me4NI < Me4NBr < Et4NBr ≃ Et4NI < Pr4NBr ≃ Pr4NI < Bu4NBr. Results are discussed in terms of the influence of tetra-alkylammonium halide salts on the water structure. Me4NBr and Me4NI break water structure, while all other tetra-alkylammonium bromide and iodide salts enhance or promote water structure. The influence of R4N+ salts in promoting water structure increases greatly with increase in the size of the alkyl group R. The influence of anions (bromide and iodide) does not appear to be significant in modifying the structure of water. Results from this work support the concept of “cation-cation interactions” in explaining the nature of interaction of tetra-alkylammonium halide salts with water.

Five-co-ordinate copper(II) complexes of the quadridentate Schiff-base ligand NN′-bis-(2-pyridylmethylene)ethane-1,2-diamine, and some related ligands

Three classes of complexes of copper(II) with the quadridentate Schiff-base ligand (bpe) derived from pyridine-2-carbaldehyde and ethane-1,2-diamine are described: (a) Cu2 bpe X4(where X = Cl, Br, and NCS); (b) Cu bpe X′X″(where X′= X″= ClO4 and Br, and X′= l, X″= ClO4); and (c)[Cu2 bpe3](ClO4)4. Complexes of the first type appear to be polymeric, possibly based on a five-co-ordinate copper(II) stereochemistry. Evidence is given for the existence of the five-co-ordinate cations [Cu bpe X]+(where X = Br, I) in the solid compounds of type (b), and in solution in nitromethane (X = Cl, Br, l). Details are given of a reaction in which the compound Cu bpe (ClO4)2 reacts with alcohol solutions of a tetra-alkylammonium halide or thiocyanate to form five-co-ordinate compounds of the type [Cu(bpe,ROH)X]ClO4(where R = Me, Et; and X = Cl, Br, l, NCS). One molecule of alcohol adds across only one of the Schiff-base CN groups. The rationalisation of this reaction by consideration of the steric requirements of the ligand is supported by a recent X-ray structural determination of one of the crystalline compounds. Compounds of the homologous Schiff-base ligand (bpt) derived from pyridine-2-carbaldehyde and propane-1,3-diamine, Cu bpt (ClO4)2 and [Cu bpt I] ClO4 are also described.

Volume changes on mixing solutions of potassium halides and symmetrical tetraalkylammonium halides. Evidence for cation-cation interaction. A correction and further comments

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTVolume changes on mixing solutions of potassium halides and symmetrical tetraalkylammonium halides. Evidence for cation-cation interaction. A correction and further commentsWen-Yang Wen, Kenichi Nara, and R. H. WoodCite this: J. Phys. Chem. 1968, 72, 8, 3048–3049Publication Date (Print):August 1, 1968Publication History Published online1 May 2002Published inissue 1 August 1968https://doi.org/10.1021/j100854a072RIGHTS & PERMISSIONSArticle Views22Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (266 KB) Get e-Alerts

The electrical conductivity of aqueous tetraalkylammonium halide solutions under hydrostatic pressure

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe electrical conductivity of aqueous tetraalkylammonium halide solutions under hydrostatic pressureR. A. Horne and R. P. YoungCite this: J. Phys. Chem. 1968, 72, 5, 1763–1767Publication Date (Print):May 1, 1968Publication History Published online1 May 2002Published inissue 1 May 1968https://doi.org/10.1021/j100851a065RIGHTS & PERMISSIONSArticle Views58Altmetric-Citations14LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (522 KB) Get e-Alerts

Ultrasonic Vibration Potentials in Tetraalkylammonium Halide Solutions

Abstract : Ultrasonic vibration potentials were measured in tetraalkylammonium halides at 220 kHz. The experimental and theoretically predicted values are in good agreement at low concentrations. The concentration dependence can be explained in terms of cation-cation pairs and ion triplets provided the volumes of these aggregates are much less than the sum of the volumes of the separate ions. The partial molal volumes of the tetralkylammonium cations determined from vibration potential measurements are proportional to the cube of their radii as predicted by Hepler's equation with the proportionality constant close to that expected for spherical solute molecules which are large compared to the solvent molecules. (Author)

Volume changes on mixing solutions of potassium halides and symmetrical tetraalkylammonium halides. Evidence of cation-cation interaction

Volume changes on mixing solutions of potassium halides and symmetrical tetraalkylammonium halides. Evidence of cation-cation interaction

The Conductance Behavior of the Symmetrical Tetraalkylammonium Halides in Aqueous Solution at 25 and 10°1

The Conductance Behavior of the Symmetrical Tetraalkylammonium Halides in Aqueous Solution at 25 and 10°¹

The liquid hydrogen chloride solvent system. Part VIII. Reactions of halide ions with halogens

The reactions of some halogens, interhalogens, and related compounds with the tetra-alkylammonium halides in liquid hydrogen chloride have been investigated. In general, polyhalide ions were formed. The reactions were followed conductometrically.

Liquid hydrogen sulphide as an ionising solvent. Part I. Base analogues and their neutralisation with hydrogen halides

Tetra-alkylammonium hydrogen sulphides, R4NSH, have been prepared. The salts co-ordinate hydrogen sulphide loosely at low temperatures; the hydrogen-bond energy is about 5 kcal. mole–1. Solutions of the salts in liquid hydrogen sulphide are strongly conducting, compared with solutions of amines and phosphines. A hydrogen dichloride salt was formed in the neutralisation of tetra-n-propylammonium hydrogen sulphide in liquid hydrogen sulphide. Similar reaction of hydrogen halides with tetra-alkylammonium halides in liquid hydrogen sulphide gave salts containing the anions, HCl2–, HBr2–, Hl2–, HBrCl–, and HCll–.

The Conductance of the Symmetrical Tetraalkylammonium Halides and Picrates in Methanol at 25 and 10°1

The Conductance of the Symmetrical Tetraalkylammonium Halides and Picrates in Methanol at 25 and 10°¹

THE PREPARATION AND CONFIGURATIONS OF TRI-O-ACETYL-α-D-GLUCOPYRANOSE 1,2-(ORTHOESTERS)

Reaction of tri-O-acetyl-2- O-acyl (acetyl, benzoyl, pivalyl, and methoxycarbonyl)-α-D-glucopyranosyl halides with a variety of alcohols in sym-collidine containing a tetraalkylammonium halide gave the 1,2-orthoesters in near quantitative yields. In each case one of the two diastereoisomeric orthoesters was obtained in high yield and was shown by application of n.m.r. spectroscopy to be that isomer which has the alkoxy group on the dioxolan ring trans to the pyranose ring (exo-configuration). Participation of a methoxycarbonyloxy group allowed the preparation of a 1,2-(dimethyl orthocarbonate). 1,2-(Phenyl orthoacetates) were prepared.

Voltammetry of tetra-alkyl ammonium salts at platinum in sulphur dioxide solution: Oxidation of the halides

The polarographic or voltammetric behaviour of a selected group of tetra-alkyl ammonium halides and related compounds in liquid sulphur dioxide was investigated, using a stationary disk platinum indicating micro-electrode and a silver/silver-bromide reference electrode with compensation for the IR drop of the solution. The electrochemical oxidation-reduction patterns are characteristic of the natures of the cation and anion composing the compound.Generally, good reproducible polarograms are obtained. The anodic patterns indicate that the oxidation of each halogen ion can occur in multiple stages, although the bromides generally show only a single anodic wave. The order of ease of electrolytic oxidation in sulphur dioxide is iodide (easiest), bromide and chloride.Sulphur dioxide solutions of the tetra-alkyl ammonium salts show a characteristic cathodic discharge potential in the range of −0·3 to −0·6 V vs Ag/AgBr. If the sulphur dioxide is insufficiently purified, two cathodic waves appear, which are apparently due to a non-condensable gas other than oxygen, sulphur trioxide or water.

Osmotic and Activity Coefficients for the Symmetrical Tetraalkyl Ammonium Halides in Aqueous Solution at 25°1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTOsmotic and Activity Coefficients for the Symmetrical Tetraalkyl Ammonium Halides in Aqueous Solution at 25°1S. Lindenbaum and G. E. BoydCite this: J. Phys. Chem. 1964, 68, 4, 911–917Publication Date (Print):April 1, 1964Publication History Published online1 May 2002Published inissue 1 April 1964https://doi.org/10.1021/j100786a038RIGHTS & PERMISSIONSArticle Views573Altmetric-Citations208LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (564 KB) Get e-Alerts

Polarography of zirconium and hafnium in acetonitrile

Data on the polarographic behaviour of zirconium and hafnium tetrachlorides in acetonitrile, in electrolytes of tetra alkylammonium perchlorate and halide are presented. The stepwise reduction of these metal ions to M (III), M (II), and M (O) is proposed and supported by the polarographic data.

Electron Spin Resonance Spectra of Unsaturated Radicals in Irradiated Tetra-alkyl Ammonium Halides

SEVERAL workers have reported on the electron spin resonance spectra of allyl radicals in various glassy matrices1–3. The observed spectra are poorly resolved because of large anisotropic interactions3. Recently I have observed well-resolved electron spin resonance spectra of ‘allyl-type’ radicals in irradiated polycrystalline tetra-alkyl ammonium halides at room temperature. The spectra were recorded on a Varian electron spin resonance spectrometer with 100 kc/s field modulation. The experimental details are similar to those published previously4.

Carbanions. II. Cleavage of Tetraalkylammonium Halides by Sodium in Dioxane1,2

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbanions. II. Cleavage of Tetraalkylammonium Halides by Sodium in Dioxane1,2Erling Grovenstein Jr., Elwood P. Blanchard Jr., David A. Gordon, and Robert W. StevensonCite this: J. Am. Chem. Soc. 1959, 81, 18, 4842–4850Publication Date (Print):September 1, 1959Publication History Published online1 May 2002Published inissue 1 September 1959https://doi.org/10.1021/ja01527a023RIGHTS & PERMISSIONSArticle Views317Altmetric-Citations18LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

Carbanions. III. Cleavage of Tetraalkylammonium Halides by Sodium in Liquid Ammonia1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbanions. III. Cleavage of Tetraalkylammonium Halides by Sodium in Liquid Ammonia1Erling Grovenstein Jr. and Robert W. StevensonCite this: J. Am. Chem. Soc. 1959, 81, 18, 4850–4857Publication Date (Print):September 1, 1959Publication History Published online1 May 2002Published inissue 1 September 1959https://doi.org/10.1021/ja01527a024RIGHTS & PERMISSIONSArticle Views110Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

891. The reaction of tetra-alkylammonium halides with potassium in liquid ammonia

891. The reaction of tetra-alkylammonium halides with potassium in liquid ammonia