Structure of aqueous solutions of group IIIA metals perchlorates by near infrared spectroscopy

David’yan, A. G.; Kudrev, A. G.; Myund, L. A.; Khripun, M. K.

doi:10.1134/s107036321303002x

Cited by 8 publications

(9 citation statements)

References 7 publications

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“…These fairly well known provisions are fully confirmed for indium perchlorate, which is proved by various research methods [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. The absence of coordination interaction of acid ions in the "In 3 + -ClO 4 − -H 2 O" system is indicated by the spectra of Raman scattering [5][6][7][8][9][10][11].…”

Section: Ionic State Of Indium In Perchlorate Solutionsmentioning

confidence: 74%

“…It is noted that hydrolysis occurs in indium (III) perchlorate solutions, and due to the high enthalpy of hydration of In3 +, exclusively solvate-separated ion pairs are formed. In other words, the formation of complexes of the composition In 3+ (Н 2 О) n (ClO 4 ) − occurs, where n = 1-2 with a decrease in the symmetry of the ClO 4 − ion: Тd → C 3v → C 2v with an increase in the concentration of indium in solutions acidified with perchloric acid [14,15].…”

Section: Study Of Ion Hydration By the Methods Of Electrical Conductivmentioning

confidence: 99%

“…The absence of coordination interaction of acid ions in the "In 3 + -ClO 4 − -H 2 O" system is indicated by the spectra of Raman scattering [5][6][7][8][9][10][11]. IR spectra [12] including near infrared [13][14][15] and spectroscopy of disturbed total internal reflection [13,16], NMR signals [17,18]. However, partial formation of ion pairs between them is allowed [8,18].…”

Section: Ionic State Of Indium In Perchlorate Solutionsmentioning

confidence: 99%

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Features of the Ionic State of Indium in Perchlorate Solutions and the Physicochemical Properties of Indium Perchlorate

Konstantinovich¹,

Anatolievich²

2021

Post-Transition Metals

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The possibility of the formation of India perchlorate and mixed ligand complexes has been studied. It is assumed that during the extraction of indium in aqueous solutions of hydrochloric acid at various concentrations and constant ionic strength maintained by the addition of perchloric acid, indium is present in the organic phase in the form of ionic aggregates HClO4 · HInCl4. To study the hydration of Ions, the method of electrical conductivity was carried out in the “In(ClO4)3 - HClO4 - H2O” system. The structure of aqueous solutions of India perchlorates was determined by IR spectroscopy. The structures of trivalent perchlorate India have been established.

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Section: Ionic State Of Indium In Perchlorate Solutionsmentioning

confidence: 74%

Section: Study Of Ion Hydration By the Methods Of Electrical Conductivmentioning

confidence: 99%

Section: Ionic State Of Indium In Perchlorate Solutionsmentioning

confidence: 99%

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Features of the Ionic State of Indium in Perchlorate Solutions and the Physicochemical Properties of Indium Perchlorate

Konstantinovich¹,

Anatolievich²

2021

Post-Transition Metals

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“…As an almost required method, it appears in the assessments of concentration‐dependent spectra of various aqueous solutions, as well as in those of two or more component liquid mixtures, too . PCA is primarily utilized for the determination of systematic principal components (PCs) including deterministic information and for the generation of the input matrix of discriminant analysis, respectively. Mostly due to ambiguity of PCA results and lack of knowledge of the relationships between systematic PCs and the latent factors, the only PCA itself has not been applied to mapping the concentration‐dependent factor effects.…”

Section: Introductionmentioning

confidence: 99%

Detectability of concentration‐dependent factors by application of PCA. An indicator curve for the determination of important principal components and a post‐correction for transformation of principal components to factors

Németh

Rákosa

2018

Journal of Chemometrics

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A semi empirical model of light absorption for binary liquid mixtures, which includes linear, parabolic, and periodic terms of concentration-dependent factors, has been developed and applied for investigating the revealability of the factors. Concentration-dependent near infrared spectra of ethanol-water mixtures and a two-component model were decomposed by principal component analysis. Generated from the principal component analysis results and called the mean coefficient of determination, an indicator is introduced for separating the important or systematic principal components with deterministic information (factor PCs) from stochastic principal components originating from spectral noise (error PCs). Moreover, a post-correction method is proposed to pull the concentration-dependent factor effects out of the systematic principal components. The first PC of ethanol-water NIR mixture spectra defines the contributions of clusters of both water and ethanol molecules in the solution to resultant absorbance signals. The second PC includes partial absorptions from ethanol-water dimers and ethanol-water-ethanol trimers. The third PC is assumed to reflect concentration-dependent restructuring of mixture structure. KEYWORDS empirical absorption model, ethanol-water mixture, indicator MCD, PCA post-correction, V-plot | INTRODUCTIONPerhaps, the principal component analysis (PCA) is the most often applied multivariate data analysis method. As an almost required method, it appears in the assessments of concentration-dependent spectra of various aqueous solutions, as well as in those of two or more component liquid mixtures, too. 1-12 PCA is primarily utilized for the determination of systematic principal components (PCs) including deterministic information [13][14][15][16] and for the generation of the input matrix of discriminant analysis, 17-19 respectively. Mostly due to ambiguity of PCA results and lack of knowledge of the relationships between systematic PCs and the latent factors, the only PCA itself has not been applied to mapping the concentration-dependent factor effects. Based on the general transformation between decompositions of common factor analysis and PCA, 20 the idea was raised how the PCs of PCA could be traced back to the factor effects. The PCs involve the factor effects of examined phenomenon. In the cases of concentration-dependent spectra of aqueous solution, particularly some alcohol-water mixtures, we have tried to reveal the potential factors out of the PCA decompositions.

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“…The perchlorate anion is convenient because of its weak complexing, electron-donor and proton-acceptor properties. 3 NaClO 4 and LiClO 4 aqueous solutions have been studied using several methods: viscometry, 4 cryoscopy, 5 proton relaxation, 6 Raman spectroscopy in the frequency range of totally symmetric stretch vibration, n Cl-O of the ClO 4 ion, 7 Fouriertransform infrared attenuated total reflection spectroscopy in the frequency range of the fundamental harmonic of stretch vibrations of water in perchlorate solutions up to the salt concentration 3 M 8 and absorption spectroscopy in the near infrared (NIR) region of 2 M sodium perchlorate water solution . 9 The special features of the physical and chemical properties of concentrated solutions are attributed to ion-ion interactions, in particular, the formation of solvent-separated and contact ion pairs.…”

Section: Introductionmentioning

confidence: 99%

Detection of Hydrate Forms of Lithium and Sodium Perchlorates in Aqueous Solutions Using near Infrared Spectroscopy

Davidian

Kudrev

Myund

et al. 2014

Journal of Near Infrared Spectroscopy

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A new approach to the study of concentrated electrolyte water solutions is proposed. NIR spectra of aqueous solutions of LiClO 4 and NaClO 4 were studied. The pure spectra and concentration profiles of spectral forms in the solutions were found by deconvolution of an experimentally measured data matrix. The chemometric analysis and the generalised phenomenological model of the structure of aqueous electrolyte solutions were used to establish that the variation in spectra of LiClO 4 solutions with concentration is due to antibatic changes in the fractions of water that is unbonded with ions and of water in the structure of the cybotactic group of lithium perchlorate trihydrate. Corresponding changes in NaClO 4 solutions are also associated with interconversion of sodium perchlorate forms of di-and monohydrates. Hydrate forms of lithium and sodium perchlorates in aqueous solutions are described, and a cybotactic group in a saturated solution is found to be equivalent to a solid-phase structure fragment. A strategy for selecting the nature of a background electrolyte is recommended. IntroductionAqueous solutions of alkali metal salts are of interest from the viewpoint of their use as background electrolytes. A number of studied parameters of chemical processes (the constants of complex formation, hydrolysis etc.) depend on the nature and concentration of the background electrolyte. 1 From a chemical viewpoint, the cations of sodium and lithium differ in the nature of their interaction with water, e.g. the free energies of Li + and Na + ion hydration are 114.6 and 89.7 kcal mol -1 , respectively. 2 The energy of the ion-dipole interaction of singly charged ions with water exceeds that of water-structure destruction by a quantity necessary for ion hydration. Therefore, lithium and sodium ions cannot cause strong polarisation of coordinated water molecules in the solution or change the spectral characteristics of such molecules to any considerable degree. 2 This makes the interpretation of spectral data more involved.The perchlorate anion is convenient because of its weak complexing, electron-donor and proton-acceptor properties. 3 NaClO 4 and LiClO 4 aqueous solutions have been studied using several methods: viscometry, 4 cryoscopy, 5 proton relaxation, 6 Raman spectroscopy in the frequency range of totally symmetric stretch vibration, n Cl-O of the ClO 4 -ion, 7 Fouriertransform infrared attenuated total reflection spectroscopy in the frequency range of the fundamental harmonic of stretch vibrations of water in perchlorate solutions up to the salt concentration 3 M 8 and absorption spectroscopy in the near infrared (NIR) region of 2 M sodium perchlorate water solution . 9 The special features of the physical and chemical properties of concentrated solutions are attributed to ion-ion interactions, in particular, the formation of solvent-separated and contact ion pairs. 7The aim of this paper is to detail a study of hydrate forms of lithium and soldium perchlorates in aqueous solutions using NIR spectroscopy. The prese...

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Structure of aqueous solutions of group IIIA metals perchlorates by near infrared spectroscopy

Cited by 8 publications

References 7 publications

Features of the Ionic State of Indium in Perchlorate Solutions and the Physicochemical Properties of Indium Perchlorate

Features of the Ionic State of Indium in Perchlorate Solutions and the Physicochemical Properties of Indium Perchlorate

Detectability of concentration‐dependent factors by application of PCA. An indicator curve for the determination of important principal components and a post‐correction for transformation of principal components to factors

Detection of Hydrate Forms of Lithium and Sodium Perchlorates in Aqueous Solutions Using near Infrared Spectroscopy

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