Electrolytes Electrolyte solutions, colligative

In contrast to nonelectrolyte solutions, in the case of electrolyte solutions the col-ligative properties depart appreciably from the values following from the equations above, even in highly dilute electrolyte solutions that otherwise by all means can be regarded as ideal (anomalous colligative properties). 

The second period, from 1890 to around 1920, was characterized by the idea of ionic dissociation and the equilibrium between neutral and ionic species. This model was used by Arrhenius to account for the concentration dependence of electrical conductivity and certain other properties of aqueous electrolytes. It was reinforced by the research of Van t Hoff on the colligative properties of solutions. However, the inability of ionic dissociation to explain quantitatively the properties of electrolyte solutions was soon recognized. 

According to modem theory, many strong electrolytes are completely dissociated in dilute solutions. The freezing-point lowering, however, does not indicate complete dissociation. For NaCl, the depression is not quite twice the amount calculated on the basis of the number of moles of NaCl added. In the solution, the ions attract one another to some extent therefore they do not behave as completely independent particles, as they would if they were nonelectrolytes. From the colligative properties, therefore, we can compute only the "apparent degree of dissociation" of a strong electrolyte in solution. 

Unlike weak electrolytes, solutions of strong ones have a far higher specific conductance the rise of the latter with rising concentration is also much more rapid. There is another difference the anomalies ascertained in the colligative properties of strong electrolytes cannot be ascribed to partial dissociation of molecules to ions as in the case of weak electrolytes. 

D) The van t Hoff factor is in the calculations for colligative properties of solutions. Because the number of solute particles in solution affects these factors, an adjustment must be made for electrolytic solutes. This is due to the fact that electrolytes, when dissolved, yield as many particles as the number of ions in the... 

Strong Electrolytes. Solutes of this type, such as HCl, are completely dissociated in ordinary dilute solutions. However, their colligative properties when interpreted in terms of ideal solutions appear to indicate that the dissociation is a little less than complete. This fact led Arrhenius to postulate that the dissociation of strong electrolytes is indeed incomplete. Subsequently this deviation in colligative behavior has been demonstrated to be an expected consequence of interionic attractions. 

The colligative properties of electrolyte solutions are described by including the van t Hoff factor in the appropriate equation. For example, for changes in freezing and boiling points the modified equation is... 

COLLIGATIVE PROPERTIES OF ELECTROLYTES AS COMPARED WITH NON-ELECTROLYTE SOLUTES... 

On application of the van t Hoff equation to the dmg molecules in solution, consideration must be made of any ionisation of the molecules, since osmotic pressure, being a colligative property, will be dependent on the total number of particles in solution (including the free counterions). To allow for what was at the time considered to be anomalous behaviour of electrolyte solutions, van t Hoff introduced a correction factor, i. The value of this factor approaches a number equal to that of the number of ions, v, into which each molecule dissociates as the solution is progressively diluted. The ratio ijv is termed the practical osmotic coefficient, [Pg.69]

Nonelectrolytes in aqueous solution Many molecular compounds dissolve in solvents but do not ionize. Such solutions do not conduct an electric current, and the solutes are called nonelectrolytes. Sucrose is an example of a nonelectrolyte. A Im sucrose solution contains only one mole of sucrose particles. Figure 15-16 compares the conductivity of a solution containing an electrolyte solute with one containing a nonelectrolyte solute. Which compound would have the greater effect on colligative properties, sodium chloride or sucrose ... 

An electrolyte in solution dissociates into two (in the case of NaCl) or three (in the case of CaCh) particles, and therefore the colligative effects of such solutions are multiplied by the number of dissociated ions formed per molecule. However, because of incomplete electrolyte dissociation and associations between the solute and solvent molecules, many solutions do not behave in the ideal case, and a 1-molal solution may give an osmotic pressure lower than theoretically expected. The osmotic activity coefficient is a factor used to correct for the deviation from the "ideal behavior of the system ... 

COLLIGATIVE PROPERTIES OF ELECTROLYTE SOLUTIONS Review Questions... 

Why is the discussion of the colligative properties of electrolyte solutions more involved than that of nonelectrolyte solutions ... 

Electrolyte solutions are solutions which can conduct electricity. Colligative properties such as the lowering of the vapour pressure, depression of the freezing point, elevation of the boiling point and osmotic pressure all depend on the number of individual particles present in solution. They thus give information about the number of particles actually present in solution. For some solutes it is found that the number of particles actually present in solution is greater than would be expected from the formula of the compound. 

To calculate the colligative properties of strong electrolyte solutions, we incorporate the van t Hoff factor into the equation ... 

Colligative properties are related to the number of dissolved solute particles, not their chemical nature. Compared with the pure solvent, a solution of a nonvolatile nonelectrolyte has a lower vapor pressure (Raoult s law), an elevated boiling point, a depressed freezing point, and an osmotic pressure. Colligative properties can be used to determine the solute molar mass. When solute and solvent are volatile, the vapor pressure of each is lowered by the presence of the other. The vapor pressure of the more volatile component is always higher. Electrolyte solutions exhibit nonideal behavior because ionic interactions reduce the effective concentration of the ions. 

Describe electrolyte behavior and the four colligative properties, explain the difference between phase diagrams for a solution and a pure solvent, explain vapor-pressure lowering for nonvolatile and volatile nonelectrolytes, and discuss the van t Hoff factor for colligative properties of electrolyte solutions ( 13.5) (SPs 13.6-13.9) (EPs 13.59-13.83)... 

Distinguish between a strong electrolyte, a weak electrolyte, and a nonelectrolyte. How can colligative properties be used to distinguish between them What is the van t Hoff factor Why is the observed freezing-point depression for electrolyte solutions sometimes less than the calculated value Is the discrepancy greater for concentrated or dilute solutions ... 

---