Association/Hydrogen Bonding of Acetone in Polar and Non-polar Solvents: NMR and NIR Spectroscopic Investigations with Chemometrics Yulia B. Monakhova • Mikhail V. Pozharov • Tamara V. Zakharova • Evgeniya K. Khvorostova • Aleksej V. Markin • Dirk W. Lachenmeier • Thomas Kuballa • Svetlana P. Mushtakova Received: 28 October 2013 / Accepted: 12 July 2014 / Published online: 30 October 2014 Ó Springer Science+Business Media New York 2014 Abstract This paper reports 1 H NMR and NIR spectroscopic analysis of hydrogen bonding in acetone mixtures with water, CHCl 3 , CCl 4 , and CDCl 3 with varying acetone concentrations (0–100 vol%). Spectroscopic data were chemometrically analyzed using independent component analysis to resolve the spectra of complexes existing in the solutions and to obtain their concentration profiles. Ab initio calculations provided addi- tional information (hydrogen-bond energy and bond distance) about the investigated complexes. We have found that in addition to independent solvent associates, acetone– water mixtures contain three intermolecular complexes with acetone–water ratios of 1:1, 1:2 and 1:3. In less polar solvents with hydrogen or deuterium atoms (CDCl 3 , CHCl 3 ), acetone does not generate self-associates and forms an intermolecular complex (1:1). In contrast, in aprotic non-polar carbon tetrachloride (CCl 4 ) solutions, where no hydrogen- bonding is possible, self-association (as mentioned above for water–acetone mixtures) of two acetone molecules is preferred. The combination of spectroscopic techniques ( 1 H NMR, NIR) with chemometric modeling and ab initio calculations leads to a better understanding of concentration dependent changes in the structure of acetone solutions. The approach discussed can be used for investigation of hydrogen-bonded interactions in other mixed solvents. Keywords Acetone-containing mixtures  NIR  1 H NMR  Chemometrics  Independent component analysis  Ab initio calculations Y. B. Monakhova  M. V. Pozharov  T. V. Zakharova  E. K. Khvorostova  A. V. Markin  S. P. Mushtakova Institute of Chemistry, Saratov State University, Astrakhanskaya Street 83, 410012 Saratov, Russia Y. B. Monakhova Bruker Biospin GmbH, Silberstreifen, 76287 Rheinstetten, Germany Y. B. Monakhova (&)  D. W. Lachenmeier  T. Kuballa Chemisches und Veterina ¨runtersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, 76187 Karlsruhe, Germany e-mail: yul-monakhova@mail.ru 123 J Solution Chem (2014) 43:1963–1980 DOI 10.1007/s10953-014-0249-1