Mössbauer Study of Soluble Prussian Blue, Insoluble Prussian Blue, and Turnbull's Blue

Ito, A.; Suenaga, M.; Ono, Kashichi

doi:10.1063/1.1669656

Cited by 162 publications

(76 citation statements)

References 7 publications

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“…The blue precipitate, once recovered, isolated, and dried, gave an IR spectrum coincident with that of a sample of Prussian Blue obtained by mixing ferrocyanide and ferric ions, and also with that of a sample of Turnbull Blue obtained by mixing ferricyanide and ferrous ions; it is well known that both species are the same, ferric ferrocyanide, since ferricyanide oxidizes ~e ' + to ~e~+ , being itself reduced to ferrocyanide (45)(46)(47)(48). There exist, in fact, two different types of Prussian Blue: (a) soluble Prussian Blue, Fe1'1M+Fe11(CN)6, which is formed when the alkaline ion M+ is in excess, and (b) insoluble Prussian Blue, Fe4[Fe(CN)6]3, when the alkaline and ferric ions are present in similar amounts (49, 50); the IR spectra of both species are identical.…”

Section: Generalmentioning

confidence: 99%

“…Two contributions were found in the literature on the reduction of ferricyanide by cyanide (21,22). In basic medium, cyanide reduces femcyanide to ferrocyanide in 48 11; this reduction is pH dependent. Below pH 9 the reaction rate decreases greatly and becomes negligible after three weeks at pH 1-2; at this acidity level cyanide is present mainly as HCN, which confirms our observations.…”

Section: 13mentioning

confidence: 99%

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Acid–base behaviour of the ferricyanide ion in perchloric acid media. Spectrophotometric and kinetic study

Domingo¹,

Garcı́a²,

Leal³

1990

Can. J. Chem.

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A wide study was carried out of the acid-base behaviour of ferricyanide ions in aqueous perchloric acid media in the range 0.1-1 1.5 M. 'This study shows that protonation and decomposition of the ferricyanide ions occur simultaneously. The three successive protonation equilibria were found in the acidity ranges 0.1-4.0, 3.5-8.5, and 7.0-11.5 M HC104, respectively. A kinetic study was also made of the decomposition reaction at 60°C. The kinetic data are explained by considering a reaction mechanism involving homolytic and heterolytic dissociation steps. The homolytic and heterolytic rate constants corresponding to each of the four protonated species were determined, along with the acid-base protonation constants, pK1 = -6.25 + 0.10; pK2 = -3.23 * 0.03; and pK3 = -0.60 2 0.02. Mots clis : comportement acide-base, espkces protonks, dtcomposition, dissociation homolytique, dissociation hCtCrolytique.[Traduit par la revue] Introduction In a previous paper, the acid-base behaviour of the ferrocyanide ion in perchloric acid media was studied by potentiometry and spectrophotometry ( 1). In this paper, the corresponding acid-base investigation of the ferricyanide ion is undertaken; this study, however, involves also kinetic measurements, since femcyanide ions decompose at high acid concentrations.The potentiometric titration of a sample of 0.01 N K3Fe(CN)6 with aqueous HCl shows no evidence of protonation; the curve coincides with that obtained in the titration of a blank solution containing pure water, this fact indicating that the three ionization constants of ferricyanic acid, H3Fe(CN)6, are higher than 0.1 (2,3). On the other hand, the titration curves of a sample of 0.01 M H3Fe(CN)6 with NaOH, obtained by potentiometric and conductimetric techniques, are identical to those achieved titrating 0.03 M HC1. Thus the three constants must be quite high (4). None of the three pK values was found in the literature; however, to be able to explain the effect of acidity on the rate constant, several contributions on the oxidation of organic substrates by femcyanide in acid media (5-1 1) suggest that the first protonation occurs in the range 0.1-3.8 M HC104.

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Section: Generalmentioning

confidence: 99%

Section: 13mentioning

confidence: 99%

Acid–base behaviour of the ferricyanide ion in perchloric acid media. Spectrophotometric and kinetic study

Domingo¹,

Garcı́a²,

Leal³

1990

Can. J. Chem.

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“…As the temperature decreases from 295 to 85 K, both isomer shifts, as expected, become more positive as a result of the second-order Doppler shift. 34 The relative areas of the iron(II) and iron(III) absorptions are temperature independent and, if the recoil-free fractions of iron(II) and iron(III) are assumed equal, a reasonable assumption at 85 K, 35 Because the relative areas were found to be independent of temperature in the pure soluble Prussian blue, the M€ ossbauer spectra of the mixtures of Prussian blue with white lead, (PbCO 3 ) 2 Pb(OH) 2 , and zinc oxide, ZnO, were only measured at 295 K; the resulting spectra are shown in Fig. 8b and 8c, respectively.…”

Section: 28mentioning

confidence: 99%

“…The chamber is equipped with a xenon lamp and a window glass filter that removed UV radiation below 320 nm was used to simulate outdoor ageing, as recommended in ISO 105-B04. A ventilation system was used to cool the ageing chamber to a constant temperature of about 35 C. The luminance at the surface of the sample was approximately 120 000 lux. During the ageing process half of the painted canvas surface area was covered with aluminium to serve as reference after ageing.…”

Section: Accelerated Ageingmentioning

confidence: 99%

Fading of modern Prussian blue pigments in linseed oil medium

Samain

Silversmit

Sanyova

et al. 2011

J. Anal. At. Spectrom.

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The fading of modern laboratory-synthesized and commercial Prussian blue, iron(III) hexacyanoferrate (II), based pigments in a linseed oil medium during exposure to light has been investigated. The Prussian blue pigments were painted with linseed oil, as a pure pigment and mixed with white lead, (PbCO 3 ) 2 Pb (OH) 2 , zinc white, ZnO, or titanium white, TiO 2 , pigment. The samples were subjected to accelerated ageing for 800 h and the light fastness of the Prussian blue pigment was evaluated by reference to blue wool standards. Pure Prussian blue is extremely light fast whilst it strongly fades when mixed with a white pigment, especially with lead white or zinc oxide. The painted samples were studied by UV-visible, iron K-edge X-ray absorption, iron-57 transmission M€ ossbauer, and attenuated total reflectance infrared spectroscopy. X-ray absorption results reveal a decrease in the iron coordination number in aged samples in the presence of white pigment. The M€ ossbauer spectra of the pure Prussian blue and the unaged and aged mixtures of Prussian blue and lead white or zinc oxide at 1 : 100 and 1 : 10 dilution ratios, respectively, indicate the presence of iron(II) and iron(III) in a ratio close to one as expected for the bulk stoichiometric KFe

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“…5 (top)). 20 We observed the following influence of light illumination on the magnetic properties of the film. The cis state of the film, prepared by the UV light illumination of the trans film at room temperature, was cooled down to 2 K in a SQUID magnetometer.…”

Section: Photo-controllable Magnetic Vesicles Containingmentioning

confidence: 84%

Photo-Control of Magnetization by Photochromic Compounds

Einaga¹

2006

Bulletin of the Chemical Society of Japan

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The development of new magnetic materials in which magnetic properties are combined with optical properties has been extensively studied. So far, several photo-responsive molecular solids have been reported. However, the strategies that are necessary to achieve photoinduced switching in a solid state are yet to be clarified. Here, I have focused on composite materials as a novel strategy for realizing such photo-functional magnetic systems. These include the incorporation of organic photochromes into magnetic systems, e.g., photo-controllable magnetic vesicles and LB films containing Prussian blue or iron oxide nanoparticles and azobenzene.Optically-switchable magnetic materials are becoming increasingly important in the field of high density information storage media, because the photon mode allows us to access a variety of different types of materials with high speed and superior resolution. [1][2][3] In particular, the design of molecular compounds that exhibit photoinduced magnetization behavior has attracted great attention. 4,5 In fact, several molecular photomagnetic materials were developed. They include, for example, cyanide-bridged complexes such as Prussian blue analogues, [6][7][8] and crystalline metal-assembled complexes.9 Although reversible photo-control of magnetic properties or electronic states including spin states were realized in these compounds, most of the interesting phenomena were observed only at low temperature. Furthermore, the number of the optically switchable molecular solids reported has been quite small. This is because the strategies that are necessary to achieve photoinduced switching in a solid state are yet to be clarified.On the other hand, the use of organized organic assemblies to direct the formation of mesoscopic inorganic structures under mild conditions is of topical interest. [10][11][12][13][14][15][16] In particular, attempts to intercalate inorganic materials into functional organic molecules offer many possibilities for developing novel functional materials whose physicochemical properties are superior to those of conventional materials. Likewise, the design and synthesis of functional materials with nanometer dimensions (mesoscopic materials) are also subjects of intense current research. Although several studies have been devoted to the synthesis of nanometer-sized compound semiconductors, relatively little work exists for magnetic materials of similar dimensions.Here, I will describe several examples of the photo-switching magnetic systems designed by a novel strategy, i.e., preparing composite magnetic materials containing photochromic compounds. Up to now, researchers have found that the photoswitching at room temperature was also possible by designing photochromic compound-modified magnetic nanoparticles. This article shows that this strategy is useful for the development of the photo-functional magnetic materials.

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Mössbauer Study of Soluble Prussian Blue, Insoluble Prussian Blue, and Turnbull's Blue

Cited by 162 publications

References 7 publications

Acid–base behaviour of the ferricyanide ion in perchloric acid media. Spectrophotometric and kinetic study

Acid–base behaviour of the ferricyanide ion in perchloric acid media. Spectrophotometric and kinetic study

Fading of modern Prussian blue pigments in linseed oil medium

Photo-Control of Magnetization by Photochromic Compounds

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