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Reine Angew. Math. 398, 187-218 (1989; Zbl 0664.10008)]. The pfaffian of an Azumaya algebra A with involution of rank 16 is a quadratic form of rank 6, defined on the set of alternating elements, with value in a discriminant module pf(A). We show that two such algebras are isomorphic (as algebras) if and only if their pfaffians are similar. This generalizes a result of Jacobson on tensor products of quaternion algebras over fields of characteristic different from 2. Another application is the following generalization of a theorem of Albert. Let R be a commutative ring in which 2 is invertible. If A is an Azumaya algebra of rank 16 over R with an involution of orthogonal type and if the discriminant module pf(A) of A is trivial, then A is isomorphic, as an algebra with involution, to a tensor product of quaternion algebras. As a consequence, we get a necessary and sufficient condition for an involution of a rank 16 Azumaya algebra to admit an invariant quaternion subalgebra. We recall that there are examples of \\textit{S. A. Amitsur}, \\textit{L. H. Rowen} and \\textit{J. P. Tignol} of involutions on central simple algebras of rank 16 which do not have any invariant quaternion algebras [Isr. J. Math. 33, 133-148 (1979; Zbl 0422.16010)]. In the last section we use the same techniques to compute the group of special similitudes of rank 6 quadratic spaces over commutative rings. This puts in a general set-up the classical computations of \\textit{J. Dieudonn\u00e9} [Acta Math. 87, 175-242 (1952; Zbl 0049.025)] for forms of dimension 6 over fields of characteristic not equal to 2. 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