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Sampling is a statistical procedure that involves the selection of a finite number of individuals to represent and infer some knowledge about a population of concern. Sampling techniques are used in a wide range of science and engineering applications; they are of basic importance in computational statistics, in the implementation of probabilistic algorithms, and in related problems of statistical computing that have a stochastic ingredient (eg, financial modeling, artificial intelligence, computational chemistry, risk and uncertainty analysis, and design of experiments). This article is devoted to the role of sampling in process systems engineering.