Solution freezing-point depression

Tfp) the freezing point of a solution is always lower than the freezing point of the pure solvent. The freezing point depression is roughly proportional to the molality of solute particles in the solution. Freezing point depression is an example of a colligative property of a solution. 

A solutions freezing point depression, ATf, is the difference in temperature between its freezing point and the freezing point of its pure solvent. Molal freezing point depression constants (Kf) for several solvents are shown in Table 14.6. For nonelectrolytes, the value of the freezing point depression is directly proportional to the solutions molality. 

Osmotic pressure is a colligative property. A colligative property solely depends on the concentration of the dissolved molecules or ions and is independent of the nature of the solute. Freezing point depression is also a colligative property and can be indirectly used to determine osmotic pressure. In practice, it is much more difficult to determine the osmotic pressure of a solution than to measure its freezing point depression. The freezing point of a solution can be measured and the osmotic pressure can be calculated from it. 

Freezing-Point Depression Solid/Liquid Equiiibrium Freezing-Point Depression Addition of a Solute Freezing-Point Depression Solid/Solution Equilibrium... 

This is an expression of Raoult s law which we have used previously. Freezing point depression. A solute which does not form solid solutions with the solvent and is therefore excluded from the solid phase lowers the freezing point of the solvent. It is the chemical potential of the solvent which is lowered by the solute, so the pure solvent reaches the same (lower) value at a lower temperature. At equilibrium... 

Fig. 1. Freeze point depression as a function of solute concentration (1,2). Calcium chloride sucrose (-------), and urea (------) become...

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. 

In carrying out a molar mass determination by freezing point depression, we must choose a solvent in which the solute is readily soluble. Usually, several such solvents are available. Of these, we tend to pick one that has the largest kf. This makes ATf large and thus reduces the percent error in the freezing point measurement From this point of view, cyclohexane or other organic solvents are better choices than water, because their kf values are larger. 

It is found empirically and can be justified thermodynamically that the freezing-point depression for an ideal solution is proportional to the molality of the solute. For a nonelectrolyte solution. 

Here, i, the van t Hoff i factor, is determined experimentally. In a very dilute solution (less than about 10 3 mol-I. ), when all ions are independent, i = 2 for MX salts such as NaCl, i = 3 for MX2 salts such as CaCl2, and so on. For dilute nonelectrolyte solutions, i =l. The i factor is so unreliable, however that it is best to confine quantitative calculations of freezing-point depression to nonelectrolyte solutions. Even these solutions must be dilute enough to be approximately ideal. 

The presence of a solute lowers the freezing point of a solvent if the solute is nonvolatile, the boiling point is also raised. The freezing-point depression can be used to calculate the molar mass of the solute. If the solute is an electrolyte, the extent of its dissociation, protonation, or deprotonation must also be taken into account. 

Step 1 Convert the observed freezing-point depression into solute molality by writing F.q. 5b in the form... 

Colligative properties can be sources of insight into not only the properties of solutions, but also the properties of the solute. For example, acetic acid, CH.COOH, behaves differently in two different solvents, (a) The freezing point of a 5.00% by mass aqueous acetic acid solution is — l.72°C. What is the molar mass of the solute Explain any discrepancy between the experimental and the expected molar mass, (b) The freezing-point depression associated with a 5.00% by mass solution of acetic acid in benzene is 2.32°C. Whar is the experimental molar mass of the solute in benzene What can you conclude about the nature of acetic acid in benzene ... 

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... 

Using the information content, H, to describe the structure at any temperature, it is possible to estimate the new temperature of water when a solute has been added. An increase in this temperature corresponds to the freezing point depression because the water must experience a greater decrease in temperature in order to arrive at the point of solidification. 

Example 4.6. Modeling the freezing point depression due to a solute... 

A = Kj- Cflj A 7b = Ki) Cflj We use molality in these equations because they describe temperature changes. The constant Zf is called the freezing point depression constant, and is called the boiling point elevation constant. These constants are different for different solvents but do not depend on the identity of the solutes. For water, Zf is 1.858 °C kg/mol and is 0.512 °C kg/mol. 

Like freezing point depression and boiling point elevation, osmotic pressure is proportional to the concentration of solute molecules. Experiments show that osmotic pressure is proportional to both concentration (expressed as... 

In the freezing point depression method, one measures the temperature lowering AT/ required to render the activity of the solvent in the solution equal to that of the pure crystalline solvent (referred to the pure liquid as the standard state see above). Then... 

The solvent s activity can be determined by measuring the saturation vapor pressure above the solution. Such measurements are rather tedious and their accuracy at concentrations below 0.1 to 0.5M is not high enough to produce reliable data therefore, this method is used only for concentrated solutions. The activity can also be determined from the freezing-point depression or boiling-point elevation of the solution. These temperature changes must be ascertained with an accuracy of about 0.0001 K, which is quite feasible. This method is used primarily for solutions with concentrations not higher than 1M. 

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