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Liquid−liquid equilibrium (LLE) phase diagrams have been determined, by means of the critical opalescence method with a laser scattering technique, for the mixtures 4-phenylbutan-2- one + CH3(CH2)nCH3 (n = 10,12,14) and for benzyl ethanoate + CH3(CH2)nCH3 (n = 12,14). The systems are characterized by having an upper critical solution temperature (UCST), which increases with n. The corresponding LLE curves show a rather horizontal top and become skewed toward higher mole fractions of the polar compound when n is increased. Calorimetric and LLE measurements show that, for mixtures with molecules with a given functional group, interactions between aromatic molecules are stronger than those between homomorphic linear molecules (aromaticity effect). This has been ascribed to proximity effects arising from the presence of the polar group and the aromatic ring within the same molecule. Proximity effects become weaker in the sequence 1-phenylpropan-2-one >4-phenylbutan-2-one >1-phenylethanone and are more important in benzyl ethanoate than in ethyl benzoate molecules. Values of the critical compositions and temperatures calculated with the DISQUAC group contribution model are in good agreement with the experimental results. Accordingly, the shape of the LLE curves is also correctly described by DISQUAC., Junta de Castilla y León, under Project BU034U16