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The topological algebra \\(\\tilde {\\mathcal M}\\) of \\(\\tau\\)-measurable operators affiliated with \\({\\mathcal M}\\) is introduced in the sense of \\textit{E. Nelson} [J. Funct. Anal. 15, 103-116 (1974; Zbl 0292.46030)] and \\textit{Terp} [Copenhagen Univ. Notes (1981)] together with several spectral relations on \\(\\tilde {\\mathcal M}\\) in terms of generalized s-numbers [see \\textit{T. Fack} and \\textit{H. Kosaki}, Pac. J. Math. 123, 269-300 (1986; Zbl 0617.46063)]. Then the condition of unitary mixing is characterized in terms of spectral relations such as majorization or submajorization between positive elements of \\(\\tilde {\\mathcal M}\\). The main result is that, for positive x and y in \\(L^ 1({\\mathcal M},\\tau)\\), x is in the \\(\\| \\|_ 1\\)-closed convex hull of the unitary orbit of y if and only if ex is majorized by ey for every central projection 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