Molar mass calculated from a colligative property assumes a dilute solution with no association or dissociation of solute. In concentrated solutions, or when the solute associates (combines into dimers/trimers) or dissociates (splits into ions), the calculated molar mass differs from the true value -- called the abnormal molar mass.
Association reduces the true particle count, so the calculated molar mass comes out higher than actual. Example: acetic acid dimerises in benzene (2CH3COOH→(CH3COOH)2), giving a measured molar mass (~120 g/mol) roughly double the true value (60 g/mol).
Dissociation increases the true particle count, so the calculated molar mass comes out lower than actual. Example: NaCl dissociates completely, NaCl(s)→Na+(aq)+Cl−(aq) -- 1 mole of NaCl gives 2 moles of particles, roughly doubling the measured colligative property.
Van't Hoff factor (i) quantifies this: i=observed (abnormal) molar massnormal molar mass=calculated colligative propertyobserved colligative property. Degree of dissociation (into n species): αdissociation=n−1i−1. Degree of association (of n molecules): αassociation=n−1(1−i)n. …