Showing papers on "Bromide published in 1969"
TL;DR: The kinetics of the association reaction reveal the presence of a fast binding process followed by several slow unimolecular steps, from which it is concluded that several forms of the complex are present at equilibrium.
116 citations
TL;DR: In this paper, the electrochemistry of solutions of lithium bromide and bromine in acetonitrile has been investigated in the temperature range from 0 to 30°C, using a platinum rotating disk working electrode from 200 to 2000 rpm.
71 citations
TL;DR: In this paper, the same authors showed that Ni(IV) flow spin d6) is surrounded by 6 S atoms in octahedral symmetry, and they obtained diamagnetic and diamagnetic diamagnetic oxide complexes of composition [Ni(bu2dtc)3]X.
Abstract: Oxidation of N,N-di-n-butyldithiocarbamato (bu2dtc) complexes of Cu(I), Ni(II), Zn(II), Cd(II) and Hg(II) is reported. Oxidation of Ni(bu2dtc)2 with Cl2, Br2, or of NiX2 (X = Cl, Br, NO3) with N,N,N′,N′-tetra-n-butylthiuram disulfide (bu4tds) gives complexes of composition [Ni(bu2dtc)3]X. These compounds are diamagnetic and dissolve in nitrobenzene as 1:1 electrolytes, their UV spectra resemble that of the iso-electronic Co(bu2dtc)3. The experimental data are in accord with the assumption that in these compounds Ni(IV) flow spin d6) is surrounded by 6 S atoms in octahedral symmetry. The analogous selenium compound tris (N, N-di-n-butyldiselenocarbamato) nickel(IV) bromide, having the same properties as the thio compounds, can also be prepared. Oxidation of Cu(bu2dtc) with Cl2 or Br2 yields paramagnetic products with the composition CuX3(bu2dtc), in which Cu also has the formal oxidation number + 4, but the structure of these compounds is still obscure. Oxidation of Zn(bu2dtc)2 and the corresponding Cd and Hg compounds yields products, the analysis of which suggests the composition MX2(bu2dtc)2 (M = Zn, Cd or Hg, X = Br or I), but infrared studies indicate that the dithiocarbamato ligands of the starting substances are oxidized to bu4tds, which in the reaction products is coordinated to the metal in its normal oxidation state + 2.
69 citations
TL;DR: In this article, the authors studied the electrochemical reduction of halonitrobenzenes in three solvents: dimethylformamide (DMF), acetonitrile (AN), and dimethyl sulfoxide (DMSO).
66 citations
TL;DR: In this paper, the preparation of the addition compounds of phthalimide, succinimide and isatin with antimony(V) chloride, tin(IV) chloride and bromide is reported.
55 citations
TL;DR: The results suggest passive binding of sulfate, but could reflect active cell uptake in these tissues, and the distribution of body chloride and the measurement of extracellular space are discussed.
Abstract: Radiosulfate, (35)SO(4), and radiobromide, (82)Br, were administered simultaneously to rats and dogs. In rats, the apparent volume of distribution of (82)Br averaged 30% of body weight and was constant between 0.5 and 35 hr after injection. The apparent volume of distribution of (35)SO(4), corrected for urinary loss, increased by 6% body weight/hr: the extrapolated volume at zero time was 88% of bromide space. Analysis of individual tissues and carcasses for (82)Br and inorganic (35)SO(4) showed that equilibration of both isotopes in several organs and in the whole carcass was rapidly achieved within 1 to 2 hr: no further increase in measured spaces occurred in 24 hr. The carcass inorganic sulfate space was 92%+/-2% of the bromide space in intact rats, and showed no increase with time. However, a progressively greater fraction of the injected (35)SO(4) was not recovered, owing to metabolic alteration. In eviscerated rats, the inorganic sulfate space was a smaller and much more constant fraction (79.8% +/-0.4%) of the bromide space, showing that at least 20% of body bromide (and hence chloride) is nonextracellular. The viscera chiefly responsible for the higher ratio of spaces in the intact animal were the liver, small bowel, and kidney. In the last two organs, excess inorganic (35)SO(4) (beyond the bromide space) was attributable to trapped transcellular fluid in which sulfate had been concentrated more than chloride (or bromide). Excess sulfate in liver and cartilage could not be explained in this manner: the results suggest passive binding of sulfate, but could reflect active cell uptake in these tissues. No excess sulfate was found in skin or tail. The implications of these observations with respect to the distribution of body chloride and the measurement of extracellular space are discussed. The extracellular volume of the rat is estimated to be 24% of body weight.
47 citations
TL;DR: In this article, simultaneous analyses in TGA, DTA and DTG on the several aquopentaamminechromium(III) complexes were attempted, and the activation energies, E\eweq, in the corresponding processes of the nitrate, chloride, bromide, iodide, sulfate and sulfite were obtained by the DTG curve analysis as 18, 28, 38, 36 and 33 kcal/mol.
Abstract: By using a Derivatograph, the simultaneous analyses in TGA, DTA and DTG on the several aquopentaamminechromium(III) complexes were attempted. The enthalpy changes, ΔH, in the deaquation-anation processes of aquopentaamminechromium(III) nitrate, chloride, bromide, iodide, sulfate and sulfite were calculated as 11.9, 6.1, 9.0, 10.8, 13.8 and 12.8 kcal/mol, respectively, the activation energies, E\eweq, in the corresponding processes of the nitrate, chloride, bromide, sulfate and sulfite were obtained by the DTG curve analysis as 18, 28, 38, 36 and 33 kcal/mol, and those in the nitrate, chloride, bromide, iodide, sulfate and sulfite were obtained by the DTA curve analysis as 14, 25, 36, 19, 39 and 32 kcal/mol, respectively.
45 citations
TL;DR: In this paper, a membrane potential technique has been used to determine the degree of dissociation of eight different surfactant micelles, and the measurements have been extended over a 50° temperature range and values of 2.0 and 1.9 kcal mole 1 respectively have been obtained for the energy of desorption of counterions from the micelle surfaces.
Abstract: A membrane potential technique has been used to determine the degree of dissociation of eight different surfactant micelles. For two compounds, n-dodecyltrimethylammonium bromide and n-dodecylpyridinium bromide, the measurements have been extended over a 50° temperature range and values of 2.0 and 1.9 kcal mole–1 respectively have been obtained for the energy of desorption of counterions from the micelle surfaces. Estimates of the heat of micellization as a function of temperature are also reported for these two compounds.
39 citations
TL;DR: The structure of (−)D-[Co(tn)3]Br3·H2O (tn: H2N-CH2-Ch2-CH 2-CH1-NH2) has been solved by the heavy atom method and refined to R=0.11 by least-squares analysis based on 1845 threedimensional data.
Abstract: The structure of (−)D-[Co(tn)3]Br3·H2O (tn: H2N–CH2-CH2-CH2-NH2) has been solved by the heavy atom method and refined to R=0.11 by least-squares analysis based on 1845 threedimensional data. The substance crystallizes in the monoclinic space group P21 with unit cell dimensions: a=16.274, b=9.863, c=9.489 A, β=126.4° and Z=2. The complex ion in the structure has approximately a three-fold axis of rotation. The three six-membered Co-tn rings are nearly identical and take chair form. The chelate ring is rather flattened out, owing to the strong H-H repulsion. The absolute configuration of (−)D-[Co(tn)3]3+ has been found to be the same as that of (+)D-[Co(en)3]3+.
39 citations
TL;DR: In this article, a reasonably stable bromonium bromide (II) is formed when a solution of adamantylideneadamantane (I) in carbon tetrachloride is treated with bromine in carbon threetextraction.
Abstract: A reasonably stable bromonium bromide (II) is formed when a solution of adamantylideneadamantane (I) in carbon tetrachloride is treated with bromine in carbon tetrachloride.
39 citations
TL;DR: In this article, the mechanism of the reaction of triarylsulfonium bromide with phenyllithium in ether was investigated and it was shown that the reaction proceeds through two mechanistic routes, i.e., one involving the nucleophilic attack of phenyl anion on the sulfur atom (about 70%) and the other the "benzyne" route (about 20%).
Abstract: Tritolylsulfonium bromide was subjected to alkaline decomposition in order to clarify the mechanism of the reaction of triarylsulfonium bromide with phenyllithium in ether. Diaryl sulfides, diaryls, and other aryl derivatives were obtained and the combined yield was nearly quantitative. On the basis of the ratio of the products formed in the reaction, the alkaline decomposition is considered to proceed through two mechanistic routes, i. e., one involving the nucleophilic attack of phenyl anion on the sulfur atom (about 70%) and the other the “benzyne” route (about 20%).
TL;DR: In this article, allylic organoalkali metal compounds have been observed to exhibit reversible changes in nmr spectra (e.g., AA'BB'C → AB_4 for allyllithium) over the temperature range from -100 to + 110o.
Abstract: Allylic organoalkali metal compounds have been observed to exhibit reversible changes in nmr spectra (e.g., AA'BB'C → AB_4 for allyllithium) over the temperature range from -100 to + 110o. In contrast, allymagnesium bromide is reported to display a simple AB_4 spectrum at -80o and diallylmagnesiurn to behave similarly from -60 to +37o in tetrahydrofuran.
01 Aug 1969
TL;DR: In this paper, the synthesis of surface-active pyridinium halides containing a nonionic polar group in the 4-position of the pyrinium ring is described.
Abstract: The synthesis of some new surface-active pyridinium halides containing a nonionic polar group in the 4-position of the pyridinium ring is described. Conductivity measurements have been made to determine the c.m.c. of the amphipathic electrolytes from 5° to 60° C at 5° intervals. Changing the anion from bromide to chloride causes an increase in the temperature at which the minimum c.m.c. occurs. The effect of the nonionic polar group on the c.m.c. is discussed. For each salt a series of polynomials has been fitted to the c.m.c.-temperature data with the use of a Stantec Zebra Computer. These polynomials have been used to give the conventional thermodynamic parameters of micelle formation.
TL;DR: In this paper, a new type of halide-selective membrane electrode was described, which can be prepared by thorough mixing of a silver halide precipitate with a thermoplastic polymer followed by heat treatment under pressure.
TL;DR: In this paper, the alkylation of benzene with (+)-propylene oxide (I) in the presence of Lewis acid gave (+)-2-phenyl-1-propanol (II), and a mixture of (−)-1-halo-2-pro panol (III or V) and (+)- 2-hexane-1 propanol(IV or VI) as the by-products.
TL;DR: In this paper, photolysis of mixtures of t-butyl peroxide, triethylsilane, and an organic bromide RBr, in the cavity of an e.s.r. spectrometer affords a convenient specific source of the radical R·.
Abstract: Photolysis of mixtures of t-butyl peroxide, triethylsilane, and an organic bromide RBr, in the cavity of an e.s.r. spectrometer affords a convenient specific source of the radical R·.
TL;DR: In this paper, the authors developed a nozzle burner, schlieren cone angle method of burning velocity determination, involving measurement of unburnt gas velocity under flame conditions, to permit precise measurements of the burning velocity of inhibited flames.
TL;DR: In this article, a sensitive and selective molecular-emission method for the determination of chloride, bromide and iodide is described, involving measurement of the intense InCl, InBr and InI band-emissions signals.
Abstract: A sensitive and selective molecular-emission method for the determination of chloride, bromide and iodide is described, involving measurement of the intense InCl, InBr and InI band-emission signals. A cool nitrogen-hydrogen diffusion flame is used and measurements are made at 360, 376 and 410 nm, respectively. Chloride can be determined in the presence of a large excess of bromide and iodide, bromide in the presence of a large excess of chloride and iodide, and iodide in the presence of a large excess of chloride. The use of other flame types and the gallium halide system are also described.
TL;DR: In this paper, it was shown that gold can be displaced from one methyl group only, to be replaced by mercury in an SE2 process, which is the rate of formation of a carbanion by heterolysis.
Abstract: Reactions in which gold, bound to methyl, ethyl, and 1-cyano-1-ethoxycarbonylpentyl groups in their triphenylphosphinegold(I) derivatives, is displaced therefrom by entering mercury from mercuric or alkylmercuric halides, acetates, or nitrates have been examined kinetically in dioxan, acetone, dimethylformamide, and dimethyl sulphoxide solvents. Most of the mercury-for-gold substitutions are second-order processes, and, where this is so, the effect on rate of changes of the anion in the mercurial, and also the kinetic effect of added salts, make clear that the bimolecular electrophilic mechanism of substitution, SE2, is under observation. However, the reactions in which hold from the cyano(ethoxycarbonyl)pentylgold complex is replaced by mercury in solvents containing dimethyl sulphoxide are kinetically of first order in the gold complex, and zeroth order in the mercurial. They illustrate the unimolecular electrophilic mechanism, SE1. In this mechanism all mercurials react at the same rate, which is the rate of formation of a carbanion by heterolysis of the carbon–gold bond. The reaction between mercuric bromide and one gold(III) complex, viz. trimethyl(triphenylphosphine)gold(III), has been examined. In dioxan and acetone as solvents, the gold is displaced from one methyl group only, to be replaced by mercury in an SE2 process.
TL;DR: Using the principles of the quasi-equilibrium theory, substituent effects, deuterium labeling and comparison of compound behavior, the authors provided strong evidence for aryl participation in the expalsion of Br· from the molecular ion of β-phenylethyl bromide and eleven of its ringsubstitued derivatives.
Abstract: Using the principles of the quasi-equilibrium theory, substituent effects, deuterium labeling and comparison of compound behavior, we provide strong evidence for aryl participation in the expalsion of Br· from the molecular ion of β-phenylethyl bromide and eleven of its ringsubstitued derivatives. This reaction shows a kinetic behavior which is typical of rearrangements, its activation energy is lower than that of similar reactions where participation is partially or completely precluded and substitute effects are not only consistent with a particular process, but are also consistent with those predicted from solution chemistry.
TL;DR: Comparison of metallo-enzymes with metal-free proteins gives evidence for bromide ion binding independent of metallic sites, and some measurements on 85 Rb, 79 Br and 35 C1 resonances are included for comparison.
TL;DR: In this paper, the results showed that these acid halides exist in the vapor and liquid states as a mixture of two isomers, only one of which remains in the solid state.
Abstract: Infrared and Raman spectra are reported for the acid fluoride, chloride, and bromide derivatives of chloroacetic acid. Data from vapor, liquid, and solid spectra are given. The results show that these acid halides exist in the vapor and liquid states as a mixture of two isomers, only one of which remains in the solid state. The more stable isomer was found to have the trans conformation. Calculations of the normal vibrations using a Urey–Bradley potential function serve to indicate that the other isomer has a staggered conformation with an azimuthal angle close to 180°. The measured enthalpy differences (H°trans − H°staggered) between the isomers in the vapor state were − 0.76 ± 0.2 kcal/mole, − 0.97 ± 0.2 kcal/mole, and − 1.86 ± 0.27 kcal/mole for the acid fluoride, chloride, and bromide, respectively.
TL;DR: In this article, a series of salts of the dication, NN′-dimethyl-4,4′-bipyridyl, with anions of the type MX4n−, where M can be a unibi-, or ter-valent cation and X is chloride, bromide, or iodide, has been prepared.
Abstract: A series of salts of the dication, NN′-dimethyl-4,4′-bipyridyl, with anions of the type MX4n–, where M can be a unibi-, or ter-valent cation and X is chloride, bromide, or iodide, has been prepared. Their formulae have been obtained chemically and in certain cases by complete structure analyses. The absorption spectra of the solids have been measured and an intermolecular charge-transfer band, from anion to cation, has been assigned. E.p.r. spectra of the FeCl42– and of the Cu2Cl42– compound shows that these solids contain some of the reduced radical cation and some oxidised anion. The electrical conductivity of this type of compound is high. The relevance of the observations to the effect of the cation (paraquat) on electron-transfer in photosynthesis and oxidative phosphorylation is discussed.
TL;DR: In this article, the light absorption spectra of americium(III) in concentrated aqueous lithium bromide, iodide and nitrate, magnesium iodide, potassium carbonate and nitric acid have been obtained, together with those of extracts into triisooctylammonium nitrate solutions in xylene.
TL;DR: In this article, the thermodynamic properties of electrochemical cells consisting of Li with lithium chloride or bromide and thallium amalgam with thalli amalgam in propylene carbonate were investigated.
Abstract: Thermodynamics of electrochemical cells consisting of Li with lithium chloride or bromide and thallium amalgam with thallium chloride or bromide in propylene carbonate