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Heat treatment (HT) is a well-known means to reduce the equilibrium wood moisture content (EMC) at a specified relative humidity (RH). EMC is profoundly decreased by the loss of accessible hydroxyl groups (OH acc ) in the wood matrix by thermochemical reactions. However, the obtained EMC reduction after HT can be partly reversible, depending on the ability of the wood matrix polymers to fully mechanically relax during HT. We discuss the results of our earlier experimental study on the OH acc  content and the associated EMC decrease at 93% RH by a relaxation inhibiting dry-HT vs. a relaxation enabling wet-HT. New experimental results, showing that OH acc  does not significantly change during reversible EMC changes, are added to the discussion. This study quantitatively supports a molecular explanation of the reversible EMC, in which wood moisture is principally bound at sorption sites, composed of two functional groups, constituting a hydrogen-donor/acceptor pair, involving at least one OH acc  group. The irreversible part of EMC reduction is assigned to the thermochemical removal of OH acc  from the wood matrix. The reversible part is attributed to a process of wood polymer conformal rearrangements, bringing an isolated OH acc  group in proximity of another free hydrogen-bonding functional group, creating a site for water sorption.

A molecular model for reversible and irreversible hygroscopicity changes by thermal wood modification