Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 34 , Issue 7
Showing 1-35 articles out of 35 articles from the selected issue
  • Yasuaki Okumura, Hiroshi Kakisawa, Mitsuko Kato, Yoshimasa Hirata
    1961 Volume 34 Issue 7 Pages 895-897
    Published: 1961
    Released: April 12, 2006
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  • Takashi Amiya
    1961 Volume 34 Issue 7 Pages 898-899
    Published: 1961
    Released: April 12, 2006
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    Luciculine (II) was isomerized to a ketone base, isoluciculine (III), and this fact shows the presence of an allyl alcohol system in the structure of compound II. The previous report concerning bromoanhydrolucidusculine hydrobromide (IV) was in part revised.
  • Yuzo Kakiuti, Jiro Ogura
    1961 Volume 34 Issue 7 Pages 899-905
    Published: 1961
    Released: April 12, 2006
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  • Masanosuke Takagi
    1961 Volume 34 Issue 7 Pages 905-910
    Published: 1961
    Released: April 12, 2006
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    Polarographic and spectrophotometric behavior of trimethylpyruvic acid has been investigated.
    The limiting current of trimethylpyruvic acid shows a minimum value in pH about 0.5. The absorption spectra show the absorption maximum at about 310 mμ in aqueous solutions, indicating the decrease of the optical density in strongly acid pH. These facts have been accounted for by the hydration of carbonyl group of undissociated acid.
    pKa for apparent dissociation constant of trimethylpyruvic acid has been spectrophoto-metrically obtained to be 1.52 at 25°C.
    Hydration constant of the undissociated acid (Kh=[AHaq]/[AH]) has been kinetically obtained to be 0.46 at 25°C. The rate constant of dehydration of hydrated trimethylpyruvate in buffer solution of pH about 5 was 2.8×10−2 sec−1 at 25°C. From the temperature dependence of the hydration constant, the heat of hydration of unhydrated acid has been found to be −8.2kcal.
    A quantitative interpretation of the pH-dependence of the limiting current has been attempted by deriving the equation, involving the hydration and dissociation factors. The agreement of the theoretical curve with the experimental is good, except for the pH range below 0.5, where acid catalyzed dehydration of hydrated acid should be taken into consideration.
    Rate constants of the dissociation and recombination of trimethylpyruvic acid have been found to be kd=6.0×105 sec−1 and kr=1.4×107 1. mol−1 sec−1, respectively.
  • Yasuo Deguchi
    1961 Volume 34 Issue 7 Pages 910-915
    Published: 1961
    Released: April 12, 2006
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    Electron paramagnetic resonance experiments of diphenyl nitric oxide single crystals were performed. Variation of exchange narrowed line were measured by changing the magnitude of magnetic dilution in crystals. Angular variations of g-value and of hyperfine spectra were investigated. The value of the exchange integral in pure crystal and the spin density on 14N atom in the molecule were determined.
  • Seishi Machida, Sadanori Nishikori
    1961 Volume 34 Issue 7 Pages 916-919
    Published: 1961
    Released: April 12, 2006
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    The hemicellulose of Ganpi bast fibers (Wickstroemia sikokiana Franch. et Sav.) gave upon hydrolysis a mixture of an aldobiouronic acid, 4-O-methyl-D-glucuronic acid and D-xylose together with small amounts of D-galacturonic acid, D-mannose, D-galactose, L-arabinose and L-rhamnose.
    The acidic components were separated, and by means of chromatography on a column of cellulose, 4-O-methyl-D-glucuronic acid, D-galacturonic acid and 2-O-(4-O-methyl-D-glucopyranosyluronic acid)-D-xylopyranose were isolated and characterized.
    A structure was proposed for the hemicellulose which has a straight chain of about 160 1,4-linked-β-D-xylopyranose residues with, on the average, every sixth residue carrying a terminal 4-O-methyl-α-D-glucopyranosyluronic acid residue linked through position 2.
    The D-galacturonic acid is believed to originate in pectic substance and not a component of the hemicellulose.
    A part of the expense for this work was defrayed by the Grant-in-Aid for Scientific Research from the Ministry of Education. This is gratefully acknowledged.
  • Koichi Okamoto
    1961 Volume 34 Issue 7 Pages 920-924
    Published: 1961
    Released: April 12, 2006
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    The polarographically new sulfur compound, potassium thiobenzoate, was investigated, using A.C. and D.C. polarographs. Comparatively complicated three oxidation waves were observed in both polarograms.
    According to the various investigations about the properties of these waves, it was found that the whole reaction was the oxidation of PTB to its disulfide, benzoyl disulfide. The 1st wave was mainly due to this oxidation reaction and the two others were mainly due to the adsorption and the desorption of PTB at the surface of D.M.E.
    The reversible oxidation-reduction system consisting of PTB and benzoyl disulfide would not be expected owing to the adsorption and desorption processes that interfered with the normal oxidation of PTB to benzoyl disulfide, if the studies were done with a dropping mercury electrode.
  • Jun’ichi Hayami
    1961 Volume 34 Issue 7 Pages 924-926
    Published: 1961
    Released: April 12, 2006
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  • Jun’ichi Hayami
    1961 Volume 34 Issue 7 Pages 927-932
    Published: 1961
    Released: April 12, 2006
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  • Kenichi Fukui, Hiroshi Kato, Chikayoshi Nagata, Teijiro Yonezawa
    1961 Volume 34 Issue 7 Pages 933-939
    Published: 1961
    Released: April 12, 2006
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  • Shunsuke Murahashi, Shun’ichi Nozakura, K\={o}ichi Hatada
    1961 Volume 34 Issue 7 Pages 939-944
    Published: 1961
    Released: April 12, 2006
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  • Sadaharu Toyoda
    1961 Volume 34 Issue 7 Pages 944-951
    Published: 1961
    Released: April 12, 2006
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  • Fujio Ichikawa, Shinobu Uruno, Hisashi Imai
    1961 Volume 34 Issue 7 Pages 952-955
    Published: 1961
    Released: April 12, 2006
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    Distribution coefficient of some metallic elements between nitric acid and anion exchange resin were measured. From the results described above, the fundamental data on the separation of each element in nitric acid were obtained.
  • Goro Wada
    1961 Volume 34 Issue 7 Pages 955-962
    Published: 1961
    Released: April 12, 2006
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    Various characteristic properties of liquid water can be explained fairly well by a simple structural model proposing that water consists of an equilibrating mixture between two states: the icy state which possesses ice structure and appears and disappears locally and temporarily, and the packed state in which water molecules are closely packed without hydrogen bondings. Only assuming that the fraction of the icy state at 100°C is 0.2, the fractions and the equilibrium constants at various temperatures are calculated, and therefrom the heat and the entropy of fusion of ice, the specific heat and the heat of vaporization of liquid water are derived, which are all in good agreement with the observed values. The radial distribution function of water obtained by X-rays reveals the packed state to have a structure similar to the closest packing, and the surface tension of water tells that the surface of water is more abundant in the icy state than the bulk water is, positively adsorbed as if it were a kind of surfactants. The heat of ionization and the activation energy of electric conduction are qualitatively described by the rotation mechanism of water molecules in the icy state. A reasonable explanation concerning the existence of the temperature of the maximum density and the effects of different substances upon it are also offered.
  • Sigeo Kida
    1961 Volume 34 Issue 7 Pages 962-968
    Published: 1961
    Released: April 12, 2006
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    The stability of a mixed complex, [MAiBj], was discussed and compared with the complexes, [MAn] and [MBn], (where A, B and M represent ligands and central ion, respectively, and i+j=n).
    It was verified by calculation that the electrostatic effect exerts an influence so as to promote the formation of a mixed complex. The effect of σ-covalency of the coordination bond can be considered analogously to the electrostatic one, and is expected to have a similar influence upon mixed-complex formation. The above discussion is supported by experimental data, showing that the mixed complex is formed, in general, more often than can be expected statistically.
    However, there are some exceptions to the above-mentioned rule, for instance, in the cases of cyano platinum(II) complexes or dipyridyl complexes. They are attributed to π-bonding between the ligands and the central ion. Discussion has been made concerning the reason why π-bonds depress the formation of mixed complexes.
  • Kozo Fujita
    1961 Volume 34 Issue 7 Pages 968-971
    Published: 1961
    Released: April 12, 2006
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    On oxidation with tert-butyl chromate, d-p-menthene-3 gave d-carvenone as a main product and dl-p-menthen-3-one-5 as a by-product.
    In this oxidation, it is found that, when an endocyclic double bond is in the position between C(3) and C(4) in monocyclic terpenes of p-menthane type, two active methylenes adjacent to the endocyclic double bond are selectively oxidized to carbonyls as in the case of the terpenes containing an endocyclic double bond in the position between C(1) and C(2), and that, between the two active methylenes, the one remote from the isopropyl group attached to C(4) is preferentially attacked rather than the other which is close to the same group.
  • Shigeru Yamashita
    1961 Volume 34 Issue 7 Pages 972-976
    Published: 1961
    Released: April 12, 2006
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    The rate of isomerization of cis- and trans-stilbene in n-hexane solution has been studied spectrophotometrically over the temperature range 10∼30°C in the presence of iodine under irradiation of light. The conversion rate of cis-stilbene has been found to be proportional to the square root of light intensity, to the concentration of cis-stilbene and to the square root of the iodine concentration in both wavelength ranges 360∼430 and 530∼600 mμ. The activation energies and quantum yields of conversion are however different in these ranges of wavelength. These results, combined with absorption curves of various components present in solution, show that the primary process in the range 530∼600 mμ is I2+hv→2I and that in the range 360∼430 mμ it is probably CI2+hv→CI2* followed by CI2*+C→2CI, where CI2 represents a molecular complex formed between iodine and cis-stilbene. Secondary reactions, suggested from the kinetics, are C+I\leftrightarrowsCI and CI→TI→T+I with one or more elimination steps for unstable species, T representing trans-stilbene. Rate of isomerization of trans-stilbene in the presence of iodine under irradiation of light in the range of wavelength 310∼400 mμ has been found to be identical with the rate observed in the absence of iodine under the same condition, excepting the absence of iodine. An explanation for this finding has been given.
  • Nobukazu Okazaki, Eiko Takemura
    1961 Volume 34 Issue 7 Pages 977-982
    Published: 1961
    Released: April 12, 2006
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    The deuterium exchange reaction in the course of the hydration of anhydrous oxalic acid with heavy water vapor and subsequent dehydration of the product has been studied.
    Two exchange mechanism have been suggested to be operative; the hydrate formation mechanism and the surface exchange mechanism. A distinction may be made between the two by the dependence of exchange reaction on the molar ratio of the reactants.
    Anhydrous oxalic acid prepared by dehydration at 100°C takes part in the exchange reaction through hydrate formation; while, with the anhydrous acid prepared by dehydration in vacuo at ordinary temperatures, the surface exchange mechanism comes into play.
    For the specimens of anhydrous acid prepared in vacuo, the molar ratio of oxalic acid in the surface to that of the bulk is estimated to be 0.6∼0.7 from the results of the deuterium exchange reaction. Dehydration of oxalic acid dihydrate in the vacuum of electron microscope yields amorphous anhydrous acid.
    The recrystallization of amorphous anhydrous oxalic acid was studied by the use of deuterium exchange reaction as a measure of surface area. It has been shown that adsorbed water exerts catalytic effect on the recrystallization. The process is associated with small or zero activation energy. Anhydrous oxalic acid recrystallized in the presence of water has been identified with α-form.
    Deuterium exchange reaction between unhydrated oxalic acid and hydrate water occurs in anhydrous oxalic acid partially hydrated with heavy water vapor. The rate of this exchange is practically independent of temperature. The reaction probably consists in the deuteration of the molecules in the interior of the anhydrate lattice.
    Treatment of amorphous anhydrous acid with a small amount of water vapor causes a peculiar change in the rate of subsequent rehydration. There is a considerable retarding effect on the rehydration rate for a particular range of the amount of water vapor.
  • Nobukazu Okazaki, Akiko Okumura, Keiko Nakagawa
    1961 Volume 34 Issue 7 Pages 983-985
    Published: 1961
    Released: April 12, 2006
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    The deuterium and oxygen-18 exchange reaction of amorphous and crystalline copper sulfate monohydrate with water in the course of the hydration of the monohydrate with heavy water vapor and the subsequent dehydration of the product has been studied.
    The exchange reaction of crystalline monohydrate is associated with the formation of hydrate. Amorphous monohydrate shows an increased degree of exchange over crystalline monohydrate. This increased exchangeability of amorphous monohydrate is due to the exchange reaction between surface molecules and adsorbed water. The similarity of the results of deuterium exchange reaction between oxalic acid and copper sulfate confirms the suggestion of the previous report that anhydrous oxalic acid prepared by dehydration in vacuo at low temperatures is amorphous and the degree of deuterium exchange reaction is related to the surface area of the dehydration product.
    The results of the oxygen-18 exchange reaction of copper sulfate monohydrate with water vapor are almost identical in essentials with those of the deuterium exchange reaction. The fifth water molecule of copper sulfate is interchangeable with the other four in the process of dehydration of pentahydrate and the hydration of monohydrate.
  • Nobukazu Okazaki, Akiko Okumura
    1961 Volume 34 Issue 7 Pages 985-989
    Published: 1961
    Released: April 12, 2006
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    In order to examine the generality of the results obtained with oxalic acid, the following questions were studied with sodium dihydrogen phosphate and in part with racemic acid: (1) the relation between the deuterium exchange reaction and the surface area of the anhydrate, and the amorphous character of the anhydrate prepared by dehydration in vacuo at low temperatures, (2) recrystallization of the amorphous anhydrate under the catalytic action of adsorbed water, and (3) deuterium exchange reaction in anhydrate-hydrate mixture.
    The results obtained with sodium dihydrogen phosphate and racemic acid are similar to those obtained with oxalic acid. It appears that formation of amorphous anhydrate in the dehydration of crystal hydrate in vacuo at low temperatures and its recrystallization under the catalytic action of adsorbed water are phenomena of general occurrence.
    The deuterium exchange reaction of crystalline anhydrate may be used to determine the composition of the hydrate formed on hydrating an anhydrate under a given condition.
  • Nobukazu Okazaki, Akiko Okumura
    1961 Volume 34 Issue 7 Pages 989-995
    Published: 1961
    Released: April 12, 2006
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    The rearrangement of N-deuterated aromatic amine hydrochloride into its ring-deuterated analogues has been studied in the solid and the liquid phases with o- and m-toluidines, and studied kinetically with anilinium chloride and bromide at 173∼194°C and at 210∼225°C, respectively.
    The ease of the rearrangement of the hydrochlorides in the solid phase is in the order,
    o-toluidine hydrochloride
    >aniline hydrochloride
    >p-toluidine hydrochloride
    which is the reverse of the order of the basic dissociation constants of the amines at 25°C. m-Toluidine hydrochloride is more reactive than o-toluidine hydrochloride.
    The numbers of nuclear hydrogen atoms which take part in the rearrangement are, 2 in the solid phase and >3 in the liquid phase rearrangement of o-toluidine hydrochloride, and for m-toluidine hydrochloride 3 and 4 in the solid and the liquid phases respectively. This result, taken in conjunction with the earlier ones with aniline and p-toluidine hydrochlorides, confirms the view that in the solid phase rearrangement the ortho and the para positions are exclusively deuterated, and in the liquid phase deuteration of the meta positions takes place.
    The rearrangement of the anilinium salts is characterized by high activation energy (ca. 45kcal.) and large positive entropy of activation (ca. 15cal./deg.).
    These results are reasonably interpreted by the intramolecular electrophilic mechanism.
    A small difference of the activation energies between the rearrangement of the two anilinium salts (ca. 2 kcal.) may be explained in terms of the different polarizing effects of the halide ions on initial state and possibly also on the activated complex.
  • Shingo Matsumura
    1961 Volume 34 Issue 7 Pages 995-999
    Published: 1961
    Released: April 12, 2006
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  • Fumio Toda, Masazumi Nakagawa
    1961 Volume 34 Issue 7 Pages 1000-1001
    Published: 1961
    Released: April 12, 2006
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  • Manabu Sen\={o}, Takeo Yamabe
    1961 Volume 34 Issue 7 Pages 1002-1006
    Published: 1961
    Released: April 12, 2006
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    Some observations are presented on the aggregation behavior of the ion-exchange resin particles. On mixing the hydrogen-form cation-exchange resin particles with the hydro-xyl-form anion-exchange resin particles, remarkable aggregation takes place. It seems that this aggregation is due to the electrostatic attraction force exerted between resin particles. This is supported by the results that the aggregation is destroyed by addition of salts and that the agglomerates are not formed in non-polar medium in the complete absence of water. Moreover, it was demonstrated that the variation of the size ratio of particles influences markedly the aggregation behavior. A simple explanation is given for such a coagulation phenomena.
  • Noboru Sonoda, Shigeru Tsutsumi
    1961 Volume 34 Issue 7 Pages 1006-1010
    Published: 1961
    Released: April 12, 2006
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    1) Selenium dioxide catalyzed oxidation of desoxybenzoin with hydrogen peroxide in tertiary butyl alcohol gave diphenyl acetic acid which was produced by the rearrangement of phenyl group to the methylene carbon atom.
    2) Baeyer-Villiger reaction was also occurred competitively in this reaction system, and benzyl benzoate was isolated as ester from the neutral products. Such an observation shows that the active oxidizing species may be some kind of peroxyacid. This fact is consistent with our previous assumption that peroxy-selenious acid is the most probable catalytic form.
    3) It is assumed in the reaction path of the formation of the rearranged carboxylic acid that the initial state of the attack of the peroxyselenious acid to the ketone may be analogous to that of selenious acid. From this point of view, a possible reaction path was proposed.
  • Hideo Okabayashi
    1961 Volume 34 Issue 7 Pages 1010-1015
    Published: 1961
    Released: April 12, 2006
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    A formula for the Kerr constant in liquid state has been derived, in which the form of the local field is assumed to be the same as that derived previously. The formnla is able to explain experimental data to some extent, although there are some exceptions.
  • Tokiko Uchida, Hideo Akamatu
    1961 Volume 34 Issue 7 Pages 1015-1020
    Published: 1961
    Released: April 12, 2006
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    Concerning the solid complex of perylene-iodine system, it has been clarified that two sorts of molecular addition compounds are formed. One has the composition of Perylene· 1.5 I2 (or 2 Perylene· 3 I2) and the other is Perylene· 3 I2. Both complexes are semiconductive with low resistivity; the resistivity at the room temperature is 9∼10 ohm.cm. and the energy gap is 0.06 eV. Concerning those values, both complexes possess almost the same values. Not only the elecrical properties and the magnetic properties, but also, both complexes possess similar crystal structures. To explain those facts, the structural units for those complexes have been proposed. These consist of the conjugation between perylene molecules and iodine molecules with the charge tranfer type of interaction.
  • Manabu Sen\={o}, Takeo Yamabe
    1961 Volume 34 Issue 7 Pages 1021-1026
    Published: 1961
    Released: April 12, 2006
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    The ion-exchange behavior of the acidic and the basic amino acids was described and discussed. The maximum uptake of amino acids takes place in the pH range close to the iso-electric points and the pH effect is more remarkable and more characteristic, in comparison with the case of neutral amino acids. Theoretical treatment on ion-exchange equilibria, which takes account of the dissociation equilibria of amino acids, explains well the experimental results and the selectivity coefficients were estimated herefrom.
  • Shunji Kato, Shigekazu Minagawa, Masao Koizumi
    1961 Volume 34 Issue 7 Pages 1026-1031
    Published: 1961
    Released: April 12, 2006
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    1. The deaerated solution of acridine 1×10−4M in ethanol, when irradiated by 365 mμ produces acridane with a quantum yield of about 0.13. This reductive reaction can proceed even in the air-saturated solution with the rate about one third of that of the deaerated solution. For both cases the rate is simply proportional to the absorption of light.
    2. When the concentration of dissolved oxygen is more than about twice that of acridine concentration, the rate of the reaction is approximately equal to that of the air-saturated solution independent of the oxygen concentration, and at the same time oxygen is consumed at the rate about twice as great as that of the reduction of acridine. Hence, when the existent oxygen is exhausted, the rate gains the value of the deaerated solution.
    3. All the above results are almost entirely independent of temperature.
    4. A possible scheme was proposed in which a certain type of intermediate is formed between semireduced acridine and oxygen and, from this intermediate acridine is partially recovered accompanied with the consumption of oxygen and, in competition with this, acridane is poduced, both by a bimolecular process.
  • Yuji Mori
    1961 Volume 34 Issue 7 Pages 1031-1035
    Published: 1961
    Released: April 12, 2006
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    The electronic structure of benzyl radical was shown by the approximation of the composite system in which all of the interactions are ignored except only the interaction by exchange between π-electrons of the benzene ring and the methylene group (CH2). The results are qualitively in agreement with the experimental observations and the results of the other calculations. The discrepancy between the results of the present paper and the other calculations are discussed.
    The lowest excited states of some conjugated free radicals are also discussed.
  • Yuji Mori
    1961 Volume 34 Issue 7 Pages 1035-1039
    Published: 1961
    Released: April 12, 2006
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    The method of composite system was applied to the calculation of the electronic spectra of benzyl radical. The results are very similar to those in the previous paper and there is no important difference between these two results though the procedures of calculation are different.
    The effect of electron transfer on the transition moments of lower bands of some radicals was discussed.
  • Nobuyuki Tanaka, Hiroshi Ogino
    1961 Volume 34 Issue 7 Pages 1040-1045
    Published: 1961
    Released: April 12, 2006
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    A method for the determination of the formation constants of less stable metal complexes has been developed. The method is based on the polarographic measurement of the sum of the equilibrium concentrations of hydrated metal ions and the complexes coordinating with acetate and/or co-existing ions in the presence of an appropriate auxiliary complex-forming substance. Essential advantages of the method are those of the method that was previously reported and applied to the formation constants of acetatonickel(II) complex.
    The procedure developed is applied to the study of the nickel (II) complexes present in the acetate buffer solution containing nitrilo-triacetate as an auxiliary complex-forming substance and sulfate as co-existing ions. The results obtained reveal that, under the experimental condition, the monoacetatonickel(II) ions NiOAc+ and the monosulfatonickel(II) NiSO4 are present in the solution but not the acetatosulfatoniccolate(II) Ni(OAc)(SO4). The formation constants of monosulfato complex, KNiSO4, at ionic strength 0.2 are calculated to be 14.3±0.4 at 15°C, 11.6±0.9 at 25°C and 14.6±0.7 at 35°C.
  • Masamichi Kobayashi
    1961 Volume 34 Issue 7 Pages 1045-1046
    Published: 1961
    Released: April 12, 2006
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  • Yoshizo Tsuda
    1961 Volume 34 Issue 7 Pages 1046-1048
    Published: 1961
    Released: April 12, 2006
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  • Susumu Hirase, Choji Araki
    1961 Volume 34 Issue 7 Pages 1048
    Published: 1961
    Released: April 12, 2006
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