CONICET | Buscador de Institutos y Recursos Humanos

Second- and third-order multivariate calibration is reviewed, based on the growing literature in this field, the variety of instrumental data which are being produced by modern instruments, and the proliferation of algorithms capable of dealing with higher-order data. The emphasis of the review is primarily on the relevance of the subject to analytical chemistry. A terminology section intends to clarify some confusing features related to the definition of sample constituents which surround the second-order calibration scenario. Instrumental data and available algorithms are then classified and compared. Insight is provided into the relative advantages and disadvantages of the existing algorithms, in terms of achievement of the second-order advantage (the ability to cope with varying amounts of potential interferents in test samples), presence of linear dependency in the data, handling of trilinearity deviations, use of incomplete calibration data, extension to higher-order information, handling of missing values, provision of physico-chemical information, etc. Finally, a number of applications is presented, selected from recent second- and third-order experimental works based on data obtained through excitation-emission fluorescence spectroscopy, spectral-kinetic and spectral-pH measurements, and hyphenated techniques.