Thermodynamics Research Center / ThermoML | Thermochimica Acta

ABSTRACT

Ultrasonic velocity and density values have been measured for ternary systems (amino acid/di-peptide + salt +water): l-leucine/lasparagine/ glycylglycine each in 1.5M aqueous solutions of NaCl or NaNO3 or KNO3 used as solvents for several concentrations of amino acids/di-peptide at different temperatures in the range of 298.15 323.15 K. The ultrasonic velocity values have been found to increase with increase in amino acids/di-peptide concentration and temperature in all the systems. The increase in ultrasonic velocity with increase in concentration has been discussed in terms of electrostatic interactions occurring between terminal groups of zwitterions (NH4 + and COO-) and Na+, K+, Cl-, NO3- ions. The interactions of water dipoles with cations/anions and with zwitterions have also been taken into consideration. It has been observed that the ion-zwitterion and ion-dipole attractive forces are stronger than those of ion-hydrophobic repulsive forces. These interactions comprehensively introduce the cohesion into solutions under investigation. The cohesive forces are further enhanced on successive increases in solute concentration. Using ultrasonic velocity and density data, the parameters such as isentropic compressibility (.s), change (?.s) and relative change (?.s/.0) in isentropic compressibility, specific acoustic impedance (Z) and relative association (RA) have been computed. The isentropic compressibility values decrease with increase in the concentration of solutes as well as with temperature. The decrease in .s values with increase in concentration of l-leucine, l-asparagine and glycylglycine in 1.5M aqueous solutions of NaCl, NaNO3 and KNO3 have been explained in terms of an increase in the number of incompressible molecules/zwitterions in solutions and the formation of compact zwitterions water dipole and zwitterions-ions structures in solutions. The decrease in .s values with increase in temperature has been attributed to the corresponding decrease of .relax. (relaxational part of compressibility), which is dominant over the corresponding increase in .8 (instantaneous part of compressibility). The trends of variations of ?.s, ?.s/.0, Z and RA with change of concentration and temperature have also been interpreted in terms of various intermolecular/interionic interactions existing in the systems.