Chemometrics of NIR spectra of aqueous salt solutions M(ClO4)n, where Mn+: Li+, Na+, Mg2+, Ca2+, Sr2+, Ba2+, Zn2+, Cd2+, Al3+, Ga3+, In3+, Sc3+, Y3+, La3+ were used to establish the effect of the cation nature on the structure of aqueous electrolytes solutions. Principal component analysis showed that near infrared (NIR) spectra of the systems under study are grouped into clusters. It was found that the values of the eutectic concentrations of aqueous salt solutions and the polarising powers of cations correlate. The combined use of NIR spectroscopy, chemometrics of the spectral data and a generalised phenomenological model of the structure of aqueous electrolytes solutions is a new approach to studying of the structure of concentrated solutions.
SubramanianS. and FisherH.F., “Near-infrared spectral studies on effects of perchlorate and tetrafluoroborate ions on water structure”, J. Chem. Phys.76, 84 (1972) doi: http://dx.doi.org/10.1021/j100645a015
2.
BergstromP.A.LindgrenJ.ReadM. and SandstromM., “Infrared spectroscopic evidence for 2nd-sphere hydration in aqueous-solutions of AL-3+, CR-3+, and RH-3+”, J. Phys. Chem.95, 7650 (1991). doi: http://dx.doi.org/10.1021/j100173a018
3.
ChenY.ZhangY.H. and ZhaoL.J., “ATR-FTIR spectroscopic studies on aqueous LiClO4, NaClO4, and Mg(ClO4) (2) solutions”, Phys. Chem. Chem. Phys.6, 537 (2004). doi: http://dx.doi.org/10.1039/b311768e
4.
JamesD.W. and CutlerP.G., “Ion–ion solvent interactions in solution. 10. Group-2 perchlorates in water”, Aust. J. Chem.39, 137 (1986). doi: http://dx.doi.org/10.1071/CH9860137
5.
GowenA.A.AmigoJ.M. and TsenkovaR., “Characterisation of hydrogen bond perturbations in aqueous systems using aquaphotomics and multivariate curve resolution-alternating least squares”, Anal. Chim. Acta759, 8 (2013). doi: http://dx.doi.org/10.1016/j.aca.2012.10.007
6.
MaxJ.J.de BloisS.VeileuxA. and ChapadosC., “IR Spectroscopy of aqueous alkali halides. Factor analysis”, Can. J. Chem.79, 13 (2001). doi: http://dx.doi.org/10.1139/cjc-79-1-13
7.
MaxJ.J. and ChapadosC., “Infrared spectra of cesium chloride aqueous solutions”, J. Chem. Phys.113, 6803 (2000). doi: http://dx.doi.org/10.1063/1.1290133
8.
MaxJ.J. and ChapadosC., “IR spectroscopy of aqueous alkali halide solutions: Pure salt-solvated water spectra and hydration numbers”, J. Chem. Phys.115, 2664 (2001). doi: http://dx.doi.org/10.1063/1.1337047
9.
SchmidtW., Optical Spectroscopy in Chemistry and Life Sciences. An Introduction.John Wiley & Sons, Weinheim, Germany (2005).
10.
DavidianA.G.KudrevA.G.MyundL.A. and KhripunM.K., “Structure of aqueous solutions of group III metals perchlorates by near infrared spectroscopy”, Russ. J. General Chem.83, 415 (2013). doi: http://dx.doi.org/10.1134/S107036321303002X
11.
CharlotG., Les Methodes de la Chimie Analytique Analyse Quantitative Minerale, 4th edn.Masson et Cie, Paris, France (1961).
12.
SamuelsonO., Ion Exchange Separations in Analytical Chemistry, Almqvist and Wiksell, John Wiley & Sons, New York, USA (1963).
13.
BrinkG. and FalkM., “Infrared spectrum of deuterium-water in aqueous solutions of perchlorates and tetra-fluoroborates”, Can. J. Chem.48, 3019 (1970). doi: http://dx.doi.org/10.1139/v70-509
14.
McCabeW.C. and FisherH.F., “Near-infrared spectroscopic method for investigating the hydration of a solute in aqueous solution”, J. Phys. Chem.74, 2990 (1970). doi: http://dx.doi.org/10.1021/j100709a026
15.
McCabeW.C.SubramanianS. and FisherH.F., “Near-infrared spectroscopic investigation of the effect of temperature on the structure of water”, J. Phys. Chem.74, 4360 (1970). doi: http://dx.doi.org/10.1021/j100719a011
16.
KristianssonO., “Hydration of ions in aqueous solution studied by infrared spectroscopy”, Acta Univ. Upsaliensis.1 (1989).
17.
MalinowskiE.R., Factor Analysis in Chemistry.Wiley, New York, USA (1991).
18.
EsbensenK., Multivariate Data Analysis in Practice.CAMO Software, Trondheim, Norway (2010).
19.
SmithG.L., “Principal component analysis: An introduction”, Anal. Proc.28, 150 (1991).
20.
MassartD.L.VandeginsteB.G.BuydensL.M.C.De JongS.LewiP.J. and Smeyers-VerbekeJ., Handbook of Chemometrics and Qualimetrics Part A.Elsevier, Netherlands (1997).
21.
JaumotJ.GargalloR.De JuanA. and TaulerR., “A graphical user-friendly interface for MCR-ALS: A new tool for multivariate curve resolution in MATLAB”, Chemometr. Intell. Lab. Syst.76, 101 (2005). doi: http://dx.doi.org/10.1016/j.chemolab.2004.12.007
MikendaW., “IR study of cation effects on the oxygen-deuterium stretching frequencies of isotopically dilute HDO in aqueous salt solutions”, MonatshChem.117, 977 (1986). doi: http://dx.doi.org/10.1007/BF00811267
24.
BrookerM.H. and BredigM.A., “Significance of both polarizability and polarizing power of cations in nitrate vibrational spectra”, J. Chem. Phys.58, 5319 (1973). doi: http://dx.doi.org/10.1063/1.1679146
25.
DavidianA.G., “Hydrated forms of lithium and sodium perchlorate in aqueous solutions by IR spectroscopy”, in International Student Conference: “Science and Progress”, St Petersburg, Russia, p. 23 (2011).
26.
PestovaO.N.MyundL.A.KhripunM.K. and PrigaroA.V., “Polytermal study of the systems M(ClO4)2-H2O (M+2 = Mg+2, Ca+2, Sr+2, Ba+2)”, Rus. J. Applied Chem.78, 409 (2005). doi: http://dx.doi.org/10.1007/s11167-005-0306-z
27.
PestovaO.N.MyundL.A. and KhripunM.K., “Polytermal study of the aqueous solutions of zinc, cadmium, and mercury perchlorates”, Vestn. St Petersburg. Gos. Univ.4, N. 4, 65 (2005) (in Russian).
28.
PestovaO.N.DavidianA.G.MyundL.A. and KhripunM.K., “Solubility of aluminum, gallium, and indium perchlorates in water”, Russ. J. Gen. Chem.81, 1583 (2011). doi: http://dx.doi.org/10.1134/S1070363211080020
29.
DavidianA.G., “Strukturnyie perehody v vodnykh rastvorakh solei metallov III gruppy Periodicheskoi sistemy D.I. Mendeleeva”, in V Vserossiiskaya konferenciya: “Khimiya v sovremennom mire”, St Petersburg, Gos. University, St Petersburg, Russia, pp. 174–175 (2011) (in Russian).
30.
DavidianA.G.PestovaO.N.StarovaG.L.GurzhiiV.V.MyundL.A. and KhripunM.K., “X-ray diffraction study of isomorphous crystal nonahydrates of aluminum, gallium, and scandium perchlorates”, Russ. J. General Chem.82, 621 (2012). doi: http://dx.doi.org/10.1134/S1070363212040019
31.
StewartG.H., “Evidence for the cybotactic group view of the interior of a liquid”Ind. J. Phys.7(5), 603 (1932).
32.
LatyshevaV.A. and HefferlinR., “Periodic Systems of molecules as elements of Shchukarev's ‘Supermatrix’, i.e. the chemical element Periodic System”, J. Chem. Inf. Comput. Sci.44, 1202 (2004). doi: http://dx.doi.org/10.1021/ci034279p
