Solution process entropy change

As known, SEC separates molecules and particles according to their hydro-dynamic volume in solution. In an ideal case, the SEC separation is based solely on entropy changes and is not accompanied with any enthalpic processes. In real systems, however, enthalpic interactions among components of the chromatographic system often play a nonnegligible role and affect the corresponding retention volumes (Vr) of samples. This is clearly evident from the elution behavior of small molecules, which depends rather strongly on their chemical nature and on the properties of eluent used. This is the case even for... 

Potassium nitrate dissolves readily in water, and its enthalpy of solution is +34.9 kj-niol. (a) Does the enthalpy of solution favor the dissolving process (b) Is the entropy change of the system likely to be positive or negative when the salt dissolves (c) Is the entropy change of the system primarily a result of changes in positional disorder or thermal disorder ... 

When ammonium nitrate, NH jNOj, dissolves in water, it absorbs heat. Consequently, its standard enthalpy of solution must be positive. This means that the entropy change caused by ammonium nitrate going from solid to solution must increase for the process to proceed spontaneously. This is exactly what one would expect based on the concept of entropy as a measure of randomness or disorder. 

Solid ammonium nitrate is an orderly, crystalline substance, a state considerably less random than a solution of ions in water. In this case, the positive entropy change outweighs the enthalpy change. That is TAS > AH. The Gibbs free energy change is negative, so the process will proceed spontaneously. 

The solubility of solids in liquids is an important process for the analyst, who frequently uses dissolution as a primary step in an analysis or uses precipitation as a separation procedure. The dissolution of a solid in a liquid is favoured by the entropy change as explained by the principle of maximum disorder discussed earlier. However it is necessary to supply energy in order to break up the lattice and for ionic solids this may be several hundred kilojoules per mole. Even so many of these compounds are soluble in water. After break up of the lattice the solute species are dispersed within the solvent, requiring further energy and producing some weakening of the solvent-solvent interactions. 

The crystallization process involves a system (which we are interested in) and the surroundings. In terms of the component entropies in this example, we say AS,iSyiSlcm, is the entropy of the solute crystallizing and that A.S liSlllTOimdmgiS I represents the entropy change of the solvent molecules released. 

Table III gives values of the changes in Gibbs energy, enthalpy, entropy, and heat capacity of the solution process as calculated from the equations of Table I. Figure 1 shows the recommended noble gas mole fraction solubilities at unit gas partial pressure (atm) as a function of temperature. The temperature of minimum solubility is marked.

In order for mixing and solution to occur, it is essential that the change in free energy, AG, which is the driving force in the solution process, decrease to below zero. A/f and AG are equal to the change in enthalpy and change in entropy, and for constant temperature the relationship is the classical Gibbs equation ... 

The entropy of a solution is increased by the mixing of solvents, and it is decreased by interactions among the solvent molecules or interactions of solutes with the solvent. The mixing of two miscible liquids is a thermodynamically favorable process because it increases the number of positions available to the molecules. The entropy change on going from the unmixed liquids to the mixed state can be calculated from the expression... 

Is it possible for a spontaneous process to absorb heat Use the Enthalpy of Solution activity (eChapter 17.2) to find a solution process that confirms your answer. What entropy change must accompany this process ... 

The addition of a diluent to a crystalline polymer depresses its melting point, as is shown schematically in Figure 2.43. The upper sketch again shows the standard reference case. In the lower sketch, solvent molecules are available to mix with the polymer chains once they separate from the crystalline lattice. The final state is now a polymer solution, instead of a molten polymer. This additional disordering greatly increases the entropy change for the process and therefore decreases the melting point, frequently to the extent of 40-50 °C. 

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