Abstract

Excess molar volumes (VE ) and average thermal expansivities (α) of the systems, water (W) + n-butylamine (NBA), W + sec-butylamine (SBA), and W + tert-butylamine (TBA), have been calculated from the density data at temperatures ranging from 298.15–323.15 K. The VE and α values have been plotted as functions of mole fraction of amines. The systems show large negative excess volumes, magnitude of which varies in the order, W + TBA > W + SBA > W + NBA. The curves are found to be symmetrical along the composition axis, with minima occurring at 0.5 mole fraction of butylamines. The negative excess volumes have been interpreted primarily by two effects: (i) strong chemical interaction leading to the formation of 1:1 complexes through H-bonding and (ii) hydrophobic hydration causing significant contraction of volume.

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