Solubility as a function of temperature

When a solid is brought into contact with a liquid in which it can dissolve, a certain amount of it passes into solution; the process continues until the concentration of the solute in the solution reaches a definite value independent of the solid present. A condition of equilibrium is thus established between the solid and the solution; the solution is saturated. The term solubility refers to a measure, on some arbitrarily selected scale, of the concentration of the solute in the saturated solution. Here the concentration scale in mol.dm3 will be used, and the solubility then becomes equal to the concentration c2 (mol.dm3) of the solute (component 2) in the saturated solution. The amount of the substance dissolved depends not only on the substance and the solvent, but also on the temperature. Saturation implies equilibrium, and at equilibrium the chemical potential of the pure solid solute and the chemical potential of the solute in solution are equal. This equilibrium condition leads for aqueous solutions to the relation

L2 ln c 2 . = T p 2 RT 2

(1)

Here L2 is the differential heat of solution at saturation (J mol1) at the given temperature and pressure, defined as the difference between the partial molar enthalpy of the solute in the saturated solution and the enthalpy of this component in the solid state at given temperature, concentration of the saturated solution in mol dm3 (solubility) c2 R gas constant (8,314 J mol1 K1) 2 number of ions arising by the dissociation of one molecule of the solute in water Integration of Eq.(1) under the assumption that L2 is independent of temperature gives the relation L2 1 ln c 2 = (2) R + const. , 2 T which is valid for ideal solutions as well as for diluted real solutions (in the case of sparingly soluble salts). The heat of solution may be then determined from the slope of the plot ln c2 versus 1/T.

Determination of the temperature dependence of the sodium oxalate solubility in a sample of solvent Apparatus For the solubility determinations a test tube fitted with a stirrer, placed in a constanttemperature bath, is used. The stirrer is made from a glass rod bent into a ring. Samples of the solution are withdrawn with a pipette, fitted with a filter to prevent the entrance of small crystals along with the sample (for draining the filter is removed). The filter is a small glass tube bent to the J-shape. The shorter arm we fill with the cotton-wool, the longer one we connect to the tip of the pipette via a piece of rubber tubing. Experiments Preparations. As the first thing we pour about 1 dm3 from stock ca 0.04M-KMnO4 solution (it is prepared in advance by the service in laboratory). To determine its precise concentration we use the oxalic acid as a standard. We calculate the amount of the oxalic acid, which is
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needed to react with about 25 cm3 of ca 0.04M-KMnO4 solution (1 cm3 of this solution is equivalent to 12.607 mg of (COOH)2.2H2O), weigh it to the titration flask, dissolve it in ca 50 cm3of distilled water and add 20 cm3 of diluted H2SO4 (1:4)*. Then we add 2-3 drops of KMnO4 solution from the burette, which was filled up to the zero mark. We heat the solution to 60-70 C and titrate by the KMnO4 solution to the first pink color (excess of KMnO4serves as an indicator). We calculate the concentration of the KMnO4 solution in mol dm3. *In your laboratory cupboard you will find a stock flask with concentrated sulfuric acid (96 wt.%, density 1.84 kg dm3). Use it to preparation of 300 cm3 of diluted sulfuric acid (1:4) into a beaker. Be careful! Dont pour water into the concentrated sulfuric acid! Always vice versa! Measurement. We weigh approximately 5 g of sodium oxalate into the wide test-tube and add the examined solvent (the level should be about 2 cm under the rim of the test-tube). We insert the stirrer, cover the test-tube with a rubber stopper (it has a hole for the stirrer) and place it into the constant-temperature bath adjusted to the lowest prescribed temperature. We stir the contents of the test-tube vigorously for 20 minutes (the stirrer is moved up and down by hand). Before taking a sample to the analysis we leave the system in piece (at constant temperature) for some time to subside the solid. A 5-ml sample is then removed with a pipette provided with a filter (see above). After draining the contents of the pipette (the filter is removed for draining) into a titration flask we add 20 cm3 of diluted H2SO4, 2-3 drops of KMnO4 solution, rinse the walls of the flask with distilled water (about 50 cm3), heat it and titrate with KMnO4 solution as we did previously when determining the concentration of KMnO4 solution. We repeat the determination after 10 minutes of stirring. If both results aree within the limits of experimental errors (to about 3 %), we adjust the bath to the higher temperature (by 5C) and at this temperature we repeat the whole procedure. If the results do not agree (the second value is usually a little higher) the solution may not be entirely saturated. In that case we stir the system for further 10 minutes and than repeat the solubility determination. This third determination is usually sufficient; if not, we must repeat the measurement till we do not get two subsequent results differing in the limits of experimental errors. Calculations. Calculate the solubility in moles of sodium oxalate per 1 dm3 of solution at each temperature. The results plot in rectangular coordinates, the temperature being plotted as abscise, and solubility as ordinates. It is recommended to plot each new experimental value into this graph imediately, so that you can see if a smooth curve is obtained. Calculate the heat of solution: Draw a plot of ln c2 versus 1/T . Under the assumption that the heat of solution is independent of temperature you obtain a straight line, which is described by Eq. (2). Determine the slope of this line and using Eq. (2) calculate L2. Calculate the mean deviation of calculated and experimental solubility values. Using the equation of the straight line ln c2 = f(1/T), derived in the above paragraph, calculate the values (c2)calc and deviations in per cents: = 100 [(c2)calc (c2)exp]/(c2)exp.