Determination of the activity of a molecular solute in saturated solution

• Prediction of the solubility of a solid molecular compound in a solvent, as well as, estimation of the solution activity coefficient from experimental solubility data both require estimation of the activity of the solute in the saturated solution. The activity of the solute in the saturated Solution is often defined using the pure melt at the same temperature as the thermodynamic reference. In chemical engineering literature also the activity of the solid is usually defined on the same reference state. However, far below the melting temperature, the properties of this reference state cannot be determined experimentally, and different simplifications and approximations are normally adopted. In the present work, a novel method is presented to determine the activity of the solute in the saturated solution (=ideal solubility) and the heat capacity difference between the pure supercooled melt and solid. The approach is based on rigorous thermodynamics, using standard experimental thermodynamic data at the melting temperature of the pure compound and solubility measurements in different solvents at various temperatures. The method is illustrated using data for ortho-, meta, and para-hydroxybenzoic acid, salicylamide and paracetamol. The results show that complete neglect of the heat capacity terms may lead to estimations of the activity that are incorrect by a factor of 12. Other commonly used simplifications may lead to estimations that are only one-third of the correct value.

Ämnesord

TEKNIK OCH TEKNOLOGIER  -- Kemiteknik (hsv//swe)

ENGINEERING AND TECHNOLOGY  -- Chemical Engineering (hsv//eng)

Nyckelord

Solid-state activity

Activity of the solute

Ideal solubility

Heat of

fusion

Heat capacity

Supercooled liquid heat capacity

molar heat-capacities

hydroxybenzoic acid

melting properties

organic-compounds

solubility

thermodynamics

paracetamol

point

Chemical engineering

Kemiteknik

Publikations- och innehållstyp

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