Showing papers on "Ionic liquid published in 1973"
TL;DR: In this article, the reversible addition of molecular oxygen to the tetrasodium salt of cobalt phthalocyanine-4,4?,4?4??-tetrasulphonic acid in aqueous solution was confirmed.
Abstract: The reversible addition of molecular oxygen to the tetrasodium salt of cobalt phthalocyanine-4,4?,4?,4??-tetrasulphonic acid in aqueous solution has been confirmed. Visible absorption spectra of the monomeric and dimeric species and of the oxygen adduct have been determined. A monomer-dimer system prevails at neutral pH, low ionic strength, and low dye concentrations. The oxygen adduct and the dimeric form of the dye predominate in alkaline solution.
67 citations
TL;DR: In this article, the mercuric arenesulphonate dihydrates Hg(03SR)2,2H20 (R = m-HC6X4S03-), derivatives, sulphonic acids, polyhalogenobenzenes RH, and sulphur trioxide (or sulphuric acid) in all cases.
Abstract: Thermal decomposition of the mercuric arenesulphonate dihydrates Hg(03SR)2,- 2H20 (R = C6X5, p-HC6X4, or m-HC6C14; X = C1 or F) at c. 130-240" gave the corresponding diarylmercurials, the polyhalogenobenzenes RH, and sulphur trioxide (or sulphuric acid) in all cases, together with RS03H (R = C6F5 or p-HC6F4), and p-(p-HC6F4S03Hg),C6F4. By contrast, decomposition of Hg(03SR)2,2H20 (R = m-HC6F4 or o-HC6X4) gave the corresponding (-HgC6X4S03-), derivatives, sulphonic acids, polyhalogenobenzenes, and sulphur trioxide in all cases, together with m-HC6F4HgO3S-m-HC6F4 and o-(o-HC~C~~SOJH~),C~C~~. The compounds RHg03SR (R = C6C15, isolated as the monopyridinate, or p-HC6C14) were obtained from decomposition of the appropriate mercuric sulphonates at c. 165'. Identities of (-HgC6X4S03-), derivatives were established mainly by cleavage with triiodide ions in N,N-dimethylformamide giving the salts M(IC6X,S03) (M = Na or S-benzylthiouron- ium), and of (HC6X4S03Hg)2C6X4 derivatives by similar degradation giving 12C6X4 and M(HC6X4S03) (M = Na or Ph4As). Similar degradation of C6C15Hg03SC6C15,py, p-HC6Cl,Hg03S-p-HC6C14, and the known mercurials C6C15HgCl, (p-HC6C14),Hg, and (0-HC6C14),Hg gave the corresponding iodopolychlorobenzenes. The mercurated derivative (-o-H~C,F~SO~-)~ gave (-0-HgCsF4-)3 on thermal decomposition, and crystallization from water yielded ( - o - H ~ C ~ F ~ S ~ ~ - ) , , ~ ~ H ~ ~ , which was converted into (Ph4As)(o-C1HgC6F4S03) by tetraphenylarsonium chloride. The mercuric sulphonates were prepared from mercuric acetate and the appro- priate sulphonic acids in acetic acid (X = C1) or water (X = F). Sulphonic acids, obtained by sulphonation reactions, were characterized as the dihydrates and in some cases sodium salts (polychloro derivatives) or as barium and tetraphenylarsonium salts (tetrafluoro derivatives).
21 citations
TL;DR: Spectrophotometric absorbance measurements on sodium metavanadate solutions in the region 240-300 nm were made at 10°, 25°, and 40°C on: (1) a series of solutions 2.46 x 10-5M in vanadium and covering the pH range 7-9; and (2) an equilibrium solution at constant pH and covering a concentration range from 4x10-5 to 1.2×10-2M as discussed by the authors.
Abstract: Spectrophotometric absorbance measurements on sodium metavanadate solutions in the region 240-300 nm were made at 10°, 25°, and 40°C on: (1) a series of solutions 2.46 x 10-5M in vanadium and covering the pH range 7-9; and (2) a series of solutions at constant pH and covering the concentration range from 4x10-5 to 1.2x10-2M. All solutions contained 3.0M NaClO4 and 0.10M Tris buffer. From these data were computed the extinction coefficients of HVO42-, H2VO4-, and (VO3-), as well as the pKa of H2VO4- (7.62±0.07). Metavanadate is probably a mixture of V3O93- and V4O124- under the conditions of the experiment. Upper limits on the formation constants at 25° are K3 = 10.8±0.5x106 12 mol-2 and K4 = 73±7x 10913 mol-3. The temperature dependence of the data gives for the enthalpy of polymerization, ΔH° = -21±2 kJ mol-1 H2VO4-.
13 citations
01 Jan 1973
TL;DR: The mechanism of ionic transport was one of the earliest problems to interest the physical chemist as mentioned in this paper, which resulted not only from the intrinsic importance of the problem but also from a number of important developments before the turn of the last century.
Abstract: The mechanism of ionic transport was one of the earliest problems to interest the physical chemist. This early interest resulted not only from the intrinsic importance of the problem but also from a number of important developments before the turn of the last century. The Arrhenius theory(26) established the dissociated nature of electrolytic solutions and precise methods for the measurement of both conductances(456) and transference numbers(378) were developed quite early. The introduction of transference data was the most significant contribution since they permitted an unambiguous split into ionic conductances to be made and thereby allowed comparisons between anions and cations and between all ions at different temperatures and pressures. Until very recently ionic mobilities were the only ionic property that could be obtained independent of any arbitrary split.†
9 citations
TL;DR: Triphenylphosphine and triphenylarsine derivatives of W(CO)4(NO)X (X = Cl, Br, I) have been prepared.
Abstract: Triphenylphosphine and triphenylarsine derivatives of W(CO)4(NO)X (X = Cl, Br, I) have been prepared. These compounds have the form mer- W(CO)3(NO)LX, cis-W(CO)2(NO)L2X, and trans-W(CO)2(NO)(PPh3)2X. A trans complex with triphenylarsine could not be prepared. Further substitution with either ligand was not achieved. In addition, the tri(ortho-, meta-, and para-)tolylphosphine and arsine complexes of W(CO)4(NO)I have been isolated. Their nuclear magnetic resonance spectra indicate interaction between neighbouring ligands in some cases, and suggest that possible rotation about the metal-phosphorus and arsenic bonds may occur in these compounds.
9 citations
TL;DR: In this paper, a facile route for the preparation of 1,2-diaryl-4-arylmethylene-2-imidazolin-5-ones was established by the direct interaction of primary aromatic amines with 2-(m-tolyl)-4-yrm-methylene 2-oxazolin 5-ones in acetic acid containing catalytic amounts of sodium acetate.
Abstract: A facile route for the preparation of 1,2-diaryl-4-arylmethylene-2-imidazolin-5-ones was established by the direct interaction of primary aromatic amines with 2-(m-tolyl)-4-arylmethylene-2-oxazolin-5-ones in acetic acid containing catalytic amounts of sodium acetate. The same imidazolones were also obtained by cyclization of the aryl- carboxamides of α-arylcarboxamido-β-arylacrylic acids under the same reaction conditions. A possible reaction mechanism was discussed.
8 citations
TL;DR: In this article, the authors measured the temperature range 5-50° for aqueous solutions of sodium 4?-dimethylaminoazobenzene-4-sulphonate (methyl orange) and sodium 4?-dimethyl ammonium-2- sulphonate(ortho-methyl orange), and calculated the standard enthalpy, entropy and heat capacity changes for these compounds.
Abstract: Thermodynamic acidity constants have been measured over the temperature range 5-50° for aqueous solutions of sodium 4?-dimethylaminoazobenzene- 4-sulphonate (methyl orange) and sodium 4?-dimethylaminoazobenzene-2- sulphonate (ortho-methyl orange). From these data values of the standard enthalpy, entropy, and heat capacity changes have been calculated for these compounds. These results are discussed in conjunction with previous spectrophotometric and other data with reference to the nature of the equilibrium systems involved in these protonation reactions. It is concluded that existing evidence does not allow an unequivocal assignment of the sites of protonation of these and related molecules.
8 citations
TL;DR: In this article, the macrocyclic substance robustol trimethyl ether (2) has been synthesized by an unambiguous method and a new synthesis of 1,14-bis-(3,5,dimethoxyphenyl)tetradecane has been developed.
Abstract: The macrocyclic substance robustol trimethyl ether (2) has been synthesized by an unambiguous method. During a study of the reactions of model compounds a new synthesis of 1,14-bis-(3?,5?-dimethoxyphenyl)tetradecane (4) has been developed.
7 citations
TL;DR: The structure determination of 4-amino-5-aminomethyl-2-methylpyrimidine with formamidine salts yields not the expected dihydropyrimidopyrimidine, but rather its ring-opened hydrate as mentioned in this paper.
Abstract: Treatment of 4-amino-5-aminomethyl-2-methylpyrimidine with formamidine salts yields not the expected dihydropyrimidopyrimidine, but rather its ring-opened hydrate, 4-amino-5-formamidomethyl-2-methylpyrimidine. Other workers had previously prepared the latter compound by other methods, but had assigned a wrong structure. The present structure determination is based mainly on i.r., N.M.R., and mass spectrometric analysis, as well as examination of the corresponding acetamido series. Mass spectra include a noteworthy fragmentation process, expulsion of neutral, even-electron NH.
4 citations
TL;DR: The n.m. spectra of anisole and 20 methyl-, t-butyl-, adamant-1-yl-, and chloro-substituted anisoles were obtained in dilute solutions in CCl4, CHCl3, and C6H6 as mentioned in this paper.
Abstract: The n.m.r. spectra of anisole and 20 methyl-, t-butyl-, adamant-1-yl-, and chloro-substituted anisoles were obtained in dilute solutions in CCl4, CHCl3, and C6H6. In the non-aromatic solvents the methoxyl proton resonance shifts upfield with di-o-alkyl substitution, relative to anisole or o-alkyl substitution. However, this upfield shift is not observed in the case of di-o-chloro substitution. In benzene the methoxyl resonance exhibits the aromatic-solvent induced shift, and this shift is larger with ortho than with di-ortho substitution. Relative to anisole, alkyl substitution at the para or meta position shifts the methoxyl resonance slightly upfieid in the non-aromatic solvents, but slightly downfield in benzene. However, chloro substitution at the ortho or the para position shifts this resonance upfield in benzene. In the mono-o-substituted derivatives, the methoxyl resonance shows a doublet structure, consistent with spin-spin coupling with the o-proton (J c. 0.20 Hz).
4 citations
TL;DR: The cyclic sulphites from cis-endo-bornane-2,3-diol and cis-exo-expander-2.3-Diol have been identified and their pyrolysis products identified as discussed by the authors.
Abstract: The cyclic sulphites (6), (7), and (8) from cis-endo-bornane-2,3-diol and cis-exo-bornane-2,3-diol have been prepared and their pyrolysis products identified.
TL;DR: In this paper, the e.m.f. of the galvanic cell was measured as a function of the concentration of silver chloride in the solution of MgCl2-NaCl-KCl.
Abstract: The activities of silver chloride in molten MgCl2-KCl (32.5 : 67.5 mole %) and in molten MgCl2-NaCl-KCl (50 : 30 : 20 mole %) as solvent at 475°C have been determined by measuring the e.m.f. of the galvanic cell: Ag | AgCl (in melt) || melt | Cl2 (graphite) as a function of silver chloride concentration in the solution. The extent of deviations from ideal behaviour in these solvents has been compared with those observed in other mixed chloride solvents and the results are interpreted on the basis of the interactions of the various solvent cations.
TL;DR: In this paper, the synthesis of N-(2-bromoethyl)-N-(1,2-diphenylethyl)ammonium bromide and its aluminium chloride catalysed decomposition to 1-benzyl-1, 2, 3, 4 tetrahydro-isoquinoline is described.
Abstract: The synthesis of N-(2-bromoethyl)-N-(1,2-diphenylethyl)ammonium bromide and its aluminium chloride catalysed decomposition to 1-benzyl-1,2,3,4- tetrahydro-isoquinoline is described.
TL;DR: In this article, the existence of parallel routes for carbon disulphide formation was detected by using a mechanistic argument to remove the redundancy in the system where carbon disulo-phide was concerned.
Abstract: The kinetically effective stoichiometry of reactions resulting from contacting carbon and sulphur dioxide at elevated temperatures involves the five overall reactions: 2C + 2SO2 → 2CO2 + S2 C+ S2 + CO2 → 2COS C+ 2COS → CS2 + 2CO C+ COz -, 2C0 C+S, -+ CS, The rates of the two reactions forming carbon disulphide are shown to have similar temperature dependence in the range 800-950°C, while the carbon-carbon dioxide reaction is shown to be more temperature sensitive than the carbon-carbonyl sulphide reaction in the same temperature range. The existence of parallel routes for carbon disulphide formation was detected by using a mechanistic argument to remove the redundancy in the system where carbon disulphide was concerned.
Book•
01 Jan 1973
TL;DR: In this article, the authors present some useful conversion factors for Electrochemistry and some interesting properties of the double layer of the electrical double layer, as well as more basic Electrode Kinetics.
Abstract: 1. General Questions about Electrochemistry.- 2. Ion-Solvent Interactions.- 3. Ion-Ion Interactions.- 4. Ion Transport in Solutions.- 5. Protons in Solution.- 6. Ionic Liquids.- 7. The Electrical Double Layer.- 8. Basic Electrode Kinetics.- 9. More Basic Electrode Kinetics.- 10. Some Electrodic Reactions of Interest.- 11. Some Aspects of Electrochemical Technology.- 12. Miscellaneous Problems.- Appendices.- 1. Values of Some Important Physical Constants.- 2. Some Useful Conversion Factors.
TL;DR: In this article, the reactions of various oxo compounds of manganese were examined in several melts and peroxide- and/or superoxide-melt solutions, and the green MnO42- ion was favored in KNO2 melts and also in nitrate melts in which K+ predominates over Na+.
Abstract: The reactions of various oxo compounds of manganese were examined in several melts and peroxide- and/or superoxide-melt solutions. Whilst MnO43- appears to be the most stable species in NaNO2 and Na2O2-NaNO2 solutions, the green MnO42- ion is favoured in KNO2 melts and also in nitrate melts in which K+ predominates over Na+.
TL;DR: In this article, the structural formulae of α- and β-carvone tetrabromides and the α-and β-Carvone pentabromide are deduced.
Abstract: The structural formulae of the α- and β-carvone tetrabromides and the α- and β-carvone pentabromides are deduced. The reaction of sodium iodide upon these compounds has been investigated. Two new crystalline carvone tetrachlorides have been synthesized and their structural relationship with carvone tetrabromide determined.