TY - JOUR
T1 - Determination of the Distribution of Cupric Chloro-Complexes in Hydrochloric Acid Solutions at 298 K
AU - Uchikoshi, Masahito
N1 - Publisher Copyright:
© 2017, Springer Science+Business Media New York.
PY - 2017/3/1
Y1 - 2017/3/1
N2 - The distribution of metal-chloro complexes in hydrochloric acid solutions is a fundamental aspect of anion exchange reactions that allows ultrahigh purification during hydrometallurgical processes. However, these exchange reactions are not yet understood in detail. To clarify and improve anion exchange separation so as to obtain a more sophisticated purification process, it is necessary to accurately determine the distribution of metal-chloro complexes. In the present work, cupric-chloro complexes were investigated because copper is one of the most important base metals in modern society. The absorption spectra of solutions of these complexes were acquired at 298 K and analyzed by multivariate curve resolution–alternating least squares method (MCR–ALS), a factor analysis technique widely used in chemometrics. The resulting cupric-chloro complex distributions were fitted with a thermodynamic model using appropriate activity coefficients extended to the concentrated solutions. These calculations employed a modified Debye–Hückel model because the distributions acquired through the model-free MCR–ALS analysis were less meaningful, both physically and chemically. It was concluded that five [CuIICln]2−n species, where n = 0–4, are present in the hydrochloric acid solutions. In addition, cumulative formation constants and pure molar attenuation coefficients were obtained.
AB - The distribution of metal-chloro complexes in hydrochloric acid solutions is a fundamental aspect of anion exchange reactions that allows ultrahigh purification during hydrometallurgical processes. However, these exchange reactions are not yet understood in detail. To clarify and improve anion exchange separation so as to obtain a more sophisticated purification process, it is necessary to accurately determine the distribution of metal-chloro complexes. In the present work, cupric-chloro complexes were investigated because copper is one of the most important base metals in modern society. The absorption spectra of solutions of these complexes were acquired at 298 K and analyzed by multivariate curve resolution–alternating least squares method (MCR–ALS), a factor analysis technique widely used in chemometrics. The resulting cupric-chloro complex distributions were fitted with a thermodynamic model using appropriate activity coefficients extended to the concentrated solutions. These calculations employed a modified Debye–Hückel model because the distributions acquired through the model-free MCR–ALS analysis were less meaningful, both physically and chemically. It was concluded that five [CuIICln]2−n species, where n = 0–4, are present in the hydrochloric acid solutions. In addition, cumulative formation constants and pure molar attenuation coefficients were obtained.
KW - Cumulative formation constant
KW - Cupric chloro-complexes
KW - Factor analysis
KW - Hydrochloric acid solution
KW - Molar attenuation coefficient
KW - Multivariate curve resolution–alternating least squares
KW - Principal component analysis
KW - UV–Visible spectroscopy
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U2 - 10.1007/s10953-017-0597-8
DO - 10.1007/s10953-017-0597-8
M3 - Article
AN - SCOPUS:85015669610
SN - 0095-9782
VL - 46
SP - 704
EP - 719
JO - Journal of Solution Chemistry
JF - Journal of Solution Chemistry
IS - 3
ER -