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### Thermodynamic data by indirect measurement

The enthalpy of solution, solubility and temperature are related by equation 2.303 log C= - Δ H / RT + b or between limits.

Where C 2 is the concentration of the saturated solution at T 2 and C 1 is the concentration at T 1 . ΔH is the enthalpy of solution of one mole of the salt in a very large amount of nearly saturated solution. If the solubilities are measured at several temperatures and graphed as log C Vs 1/T, the slope of the line is - Δ H / 2.303 R. Note that C 2 and C 1 can be in any consistent units. Thus Δ H can be obtained without calorimetric measurements. Since a saturated solution is at equilibrium with the undissolved solid, and equilibrium constant can be calculated, in this case the solubility product constant, Ksp. Equilibrium constants are related to free energies by the equation,

### AG° = - RT In Ksp

Since Δ G° = ΔH° - T Δ S°, Δ S° can be calculated once Δ G° and ΔH° are known. In this experiment you will determine enthalpy free energy and enthalpy of solution of a salt by measurements of its solubility over a range of temperatures.

### EXPERIMENTAL PROCEDURE

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Assemble an eight inch. Test tube, a two hole stopper, a 110° thermometer and a glass stirrer with a loop at the bottom as shown in the sketch. Be sure that the stirrer slides easily in the hole in the stopper and that it clears the thermometer bulb. When putting the thermometer in the stopper, first lubricate it with a drop of glycerin or soapy water. After it is properly positioned, rinse off the glycerin or soap and dry the thermometer and the stopper. Put a 400ml beaker 3/4 full of water on an asbestos screen and start heating it. While it is heating, weight the empty test tube to the nearest 0.00 lg on the analytical balance. (Without the stopper thermometer and stirrer) Next add 5g of KNO 3 or KBr and weigh again. Add exactly 3ml of distilled water to the KNO 3 or 6ml if using KBr. (Use a graduated pipette or burette). Put in the thermometer, stirrer and stopper and clamp the assembly in the beaker of hot water. Heat the solution with steady stirring until the entire solid is dissolved. If it has not dissolved completely when water in the beaker is boiling, add exactly 1ml of distilled water and continue stirring (Keep a record of the amount of water added) to avoid evaporation losses. Do not heat longer than necessary. When the salt has dissolved completely clamp the test tube out if the water above the beaker so that it can cool slowly. Stir steadily as the solution cools and record the temperature at which the first crystals appear. In order to check this result warm again with stirring until all the crystals have dissolved and cool with stirring until the first crystals reappear. If the second result agree with the first add exactly 1ml of water to KNO 3 solution or l/2ml to KBr and warm until the crystals disappear, then cool until the new saturation temperature is reached, After the second saturation temperature has been re-checked, continue to determine the new solution temperatures in this way until the solution is at room temperature. If you are using KBr additions of 0.5ml should be made. With KNO 3 the additions can be 2ml near the room temperature, large additions may be needed to give a reasonable separation of temperature.

### Calculation

1. Graph your results as logarithm of solubility in gr. Moles per liter of water Vs 1/T on a rectilinear paper 2. Choose two points on the smooth line through the experimental points on your graphed calculate the slope of the line. From this slope calculate the enthalpy of the solution 3. From the solubility at 25°C or 30°C, calculate Ksp and AG° for the reaction 4.Calculate the entropy of solution. What do your data indicate thermodynamically about the solubility of the salt you used?

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