Colligative properties concentration

The properties of a solution differ considerably from those of the pure solvent Those solution properties that depend primarily on the concentration of solute particles rather than their nature are called colligative properties. Such properties include vapor pressure lowering, osmotic pressure, boiling point elevation, and freezing point depression. This section considers the relations between colligative properties and solute concentration, with nonelectrolytes that exist in solution as molecules. 

The relationships among colligative properties and solute concentration are best regarded as limiting laws. They are approached more closely as the solution becomes more dilute. In practice, the relationships discussed in this section are valid, for nonelectrolytes, to within a few percent at concentrations as high as 1 Af. At higher concentrations, solute-solute interactions lead to larger deviations. 

Vapor pressure lowering is a true colligative property that is, it is independent of the nature of the solute but directly proportional to its concentration. For example, the vapor pressure of water above a 0.10 M solution of either glucose or sucrose at 0°C is the same, about 0.008 mm Hg less than that of pure water. In 0.30 M solution, the vapor pressure lowering is almost exactly three times as great, 0.025 mm Hg. 

Boiling point elevation and freezing point lowering, like vapor pressure lowerings are colligative properties. They are directly proportional to solute concentration, generally expressed as molality, m. The relevant equations are... 

Molar masses can also be determined using other colligative properties. Osmotic pressure measurements are often used, particularly for solutes of high molar mass, where the concentration is likely to be quite low. The advantage of using osmotic pressure is that the effect is relatively large. Consider, for example, a 0.0010 M aqueous solution, for which... 

As noted earlier, colligative properties of solutions are directly proportional to the concentration of solute particles. On this basis, it is reasonable to suppose that, at a given concentration, an electrolyte should have a greater effect on these properties than does a nonelectrolyte. When one mole of a nonelectrolyte such as glucose dissolves in water, one mole of solute molecules is obtained. On the other hand, one mole of the electrolyte NaCl yields two moles of ions (1 mol of Na+, 1 mol of Cl-). With CaCl three moles of ions are produced per mole of solute (1 mol of Ca2+, 2 mol of Cl-). 

This behavior is generally typical of electrolytes. Their colligative properties deviate considerably from ideal values, even at concentrations below 1 m. There are at least a couple of reasons for this effect... 

Two measures of concentration that are useful for the study of colligative properties, because they indicate the relative numbers of solute and solvent molecules, are mole fraction and molality. We first met the mole fraction, x, in Section 4.8, where we saw that it is the ratio of the number of moles of a species to the total number of moles of all the species present in a mixture. The molality of a solute is the amount of solute species (in moles) in a solution divided by the mass of the solvent (in kilograms) ... 

The lowering of freezing point and the generation of osmotic pressure both depend on the total concentration of solute particles. Therefore, by using the colligative property to determine the amount of solute present, and knowing its mass, we can infer its molar mass. 

In physical chemistry, we apply the term colligative to those properties that depend upon number of molecules present. The principal colligative properties are boiling point elevation, freezing point depression, vapour pressure lowering, and osmotic pressure. All such methods require extrapolation of experimental data back to infinite dilution. This arises due to the fact that the physical properties of any solute at a reasonable concentration in a solvent are... 

Table 6.2 Colligative properties of a solution of polymer of molar mass 20 000 at a concentration o/O.Ol g (from F. W. Billmeyer, Textbook of Polymer Science , John Wiley Sons, New York, 1962)...

Of great importance for the development of solution theory were the studies of col-ligative solution properties, detected in the 1870s and 1880s by F. M. Raoult, J. H. van t Hoff, and others. These are properties that depend not on the chemical nature of solutes but on their concentration. Three such colligative properties exist ... 

When the variation of any colligative property of a surfactant in aqueous solution is examined, two types of behavior are apparent. At low concentrations, properties approximate those to be expected from ideal behavior. However, at a concentration value that is characteristic for a given surfactant system (critical micelle concentration, CMC), an abrupt deviation from such behavior is observed. At concentrations above the CMC, molecular aggregates called micelles are formed. By increasing the concentration of the surfactant, depending on the chemical and physical nature of the molecule, structural changes to a more... 

Table 2 Approximate change of colligative properties for solutions of polymers with M — 20 kg/mol at 1 wt% concentration according to Ref. [10]...

The dissolution of a solute into a solvent perturbs the colligative properties of the solvent, affecting the freezing point, boiling point, vapor pressure, and osmotic pressure. The dissolution of solutes into a volatile solvent system will affect the vapor pressure of that solvent, and an ideal solution is one for which the degree of vapor pressure change is proportional to the concentration of solute. It was established by Raoult in 1888 that the effect on vapor pressure would be proportional to the mole fraction of solute, and independent of temperature. This behavior is illustrated in Fig. 10A, where individual vapor pressure curves are... 

Sources of Error 1. Experimental error in measurement 2. Measuring tools not reliable or not sensitive enough 3. Activity of ions as proposed by Debye and Huckel which states an effective concentration called activity which takes into account interionic attractions resulting in a decrease in the magnitude of colligative properties, especially for concentrated solutions. 

The changes in a colligative property of a polymer solution with concentration can be expressed by a virial expansional given below ... 

Osmotic pressure is a colligative property and is dependent on the number of particles of solute(s) in a solution. The total number of particles of a solute in a solution is the sum of the undissociated molecules and the number of ions into which the molecule dissociates. The number of ions, in turn, depends on the degree of ionization. Thus, a chemical that is highly ionized contributes a greater number of particles to the solution than the same amount of a poorly ionized chemical. When a chemical is a nonelectrolyte such as sucrose or urea, the concentration of the solution depends only on the number of molecules present. The values of the osmotic pressure and other colligative properties are approximately the same for equal concentrations of different nonelectrolyte solutions. 

The major goal of this chapter is to help you master the concepts associated with solutions—concentration units, solubility, and especially colligative properties. We will also examine the properties of colloids. If you are still unsure about calculations and the mole concept, review Chapters 1,3, and 4. And again, the only way to master these concepts is to Practice, Practice, Practice. 

One important aspect of solutions is their concentration, the amount of solute dissolved in the solvent. In the chapter on solutions and colligative properties we will cover several concentration units, but for the purpose of stoichiometry, the only concentration unit we will use at this time is molarity. Molarity (M) is defined as the moles of solute per liter of solution ... 

Experimental procedures for solutions fall into two broad categories. One group involves concentration units, and the other involves colligative properties. In both cases, keeping... 

A—Freezing-point depression is a colligative property, which depends on the number of particles present. The solution with the greatest concentration of particles will have the greatest depression. The concentration of particles in E (a non electrolyte) is 0.10 m. All other answers are strong electrolytes, and the concentration of particles in these may be calculated by multiplying the concentration by the van t Hoff factor. 

Using measurements of different half-cell combinations, a set of standard reduction potentials may be constructed. This set will be similar to a table of standard reduction potentials. The solutions used in the half-cells must be of known concentration. These solutions are produced by weighing reagents and diluting to volume. The measurements will require a balance and a volumetric flask. It is also possible to produce known concentrations by diluting solutions. This method requires a pipette and a volumetric flask. Review the Solutions and Colligative Properties chapter for solution techniques. 

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. 

Beyond basic concentration measurements come colligative properties, such as freezing point depression and boiling point elevation. 

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