Manual The Solution

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The enthalpy change that accompanies a process is important because processes that release substantial amounts of energy tend to occur spontaneously. A second property of any system, its entropy, is also important in helping us determine whether a given process occurs spontaneously. A perfect crystal at 0 K, whose atoms are regularly arranged in a perfect lattice and are motionless, has an entropy of zero.

In contrast, gases have large positive entropies because their molecules are highly disordered and in constant motion at high speeds. The formation of a solution disperses molecules, atoms, or ions of one kind throughout a second substance, which generally increases the disorder and results in an increase in the entropy of the system. Thus entropic factors almost always favor formation of a solution.

In contrast, a change in enthalpy may or may not favor solution formation. The London dispersion forces that hold cyclohexane and n-hexane together in pure liquids, for example, are similar in nature and strength. Mixing equal amounts of the two liquids, however, produces a solution in which the n-hexane and cyclohexane molecules are uniformly distributed over approximately twice the initial volume. In other cases, such as mixing oil with water, salt with gasoline, or sugar with hexane, the enthalpy of solution is large and positive, and the increase in entropy resulting from solution formation is not enough to overcome it.

Thus in these cases a solution does not form. The column on the far right uses the relative magnitudes of the enthalpic contributions to predict whether a solution will form from each of the four. Keep in mind that in each case entropy favors solution formation. In two of the cases the enthalpy of solution is expected to be relatively small and can be either positive or negative.

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Thus the entropic contribution dominates, and we expect a solution to form readily. In the other two cases the enthalpy of solution is expected to be large and positive. The entropic contribution, though favorable, is usually too small to overcome the unfavorable enthalpy term. Hence we expect that a solution will not form readily. In contrast to liquid solutions, the intermolecular interactions in gases are weak they are considered to be nonexistent in ideal gases.

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Consequently, all gases dissolve readily in one another in all proportions to form solutions. In contrast, naphthalene is a nonpolar compound, with only London dispersion forces holding the molecules together in the solid state. Hence we do not expect naphthalene to be very soluble in water, if at all. Benzoic acid has a polar carboxylic acid group and a nonpolar aromatic ring.

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The strength of the interaction of benzoic acid with water should also be intermediate between those of LiCl and naphthalene. The most soluble is cyclohexane; the least soluble is ammonium chloride. Solutions are homogeneous mixtures of two or more substances whose components are uniformly distributed on a microscopic scale. The component present in the greatest amount is the solvent, and the components present in lesser amounts are the solute s.


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Substances that are miscible, such as gases, form a single phase in all proportions when mixed. Substances that form separate phases are immiscible. Solvation is the process in which solute particles are surrounded by solvent molecules. When the solvent is water, the process is called hydration.