Freezing Point Depression (A Colligative Property)

FREEZING POINT DEPRESSION (A Colligative Property) The physical properties of vapor pressure, boiling point, melting point, and
osmotic pressure for a pure solvent will show a change upon the addition of a solute. This is largely due to the introduction of molecular interactions between solute and solvent that disrupts the pure solvent interactions. Freezing points of pure solvents are observed to decrease upon the introduction of any form of solute impurity. This is the principle behind the use of road salt on a snowy day or the use of antifreeze inside an automobile radiator. The depression of a freezing point is directly proportional to the amount of solute impurity introduced into a pure solvent. In fact, it can be expressed through a simple formula: Tf = Kf m i (1)
Kf is the freezing point depression constant which differs depending upon the pure solvent being used. The molality, m, is a temperature independent expression of the composition of the solution. The value, i, is the number of ions produced by dissociation. For a covalent solute, i will always be 1. For ionic materials, i represents the number of moles of ions that are present when the material dissolves into solution. For example, when dissolving NaCl, the number of ions will be (at most) 2, one mole Na+ and one mole Cl while, when dissolving CaCl2, that value would be 3, one mole Ca2+ and two moles Cl. In practice the value of i is less than 1.00 indicating incomplete dissociation. PROCEDURE A temperature probe will be interfaced with the LoggerPro 3 application pre-installed on each computer to collect temperature data. This probe will be used to collect and plot data, which will determine the freezing point of the solutions used in each experiment. Part I. Determining The Freezing Point of Pure Cyclohexane Solvent A set of test tubes (one small and one large) will be placed next to each computer. These must be returned at the end of class. Carefully dispense 12.0 mL of cyclohexane (Caution: Flammable!) into the small test tube and place the small test tube into the large test tube. Calculate the sample mass from the density, which is 0.779 g/mL. In a 250 mL beaker, prepare an ice bath. Place the temperature probe and a magnetic stir bar into the cyclohexane solution, and place the test tube set inside the ice bath that has been set atop a magnetic stirrer (clamp the test tube set to a ring stand to secure the apparatus). Begin stirring the solution. On the computer, click the Collect button to begin collecting data. Keep an eye on the solution and also watch your temperature data to determine when freezing has occurred. You should see the cyclohexane turn into a solid, and temperature data should hold constant. Once this occurs, stop data collection, and save the data file. Remove the cyclohexane from the ice bath, allow the sample to thaw, and repeat data collection for a second time. Once completed, remove the cyclohexane from the ice bath and retain it for experimentation in Part II. Part II. Observing Colligative Properties and Calculating Molecular Weight Weigh approximately 0.14 grams of biphenyl (record your mass, nearest 0.001 g) and transfer the solid into the cyclohexane used in Part I. Gently agitate the test tube to make sure that all the solid has dissolved. If necessary, you may place the solution inside a warm water bath to help it to dissolve. Do not use a hot plate, as
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cyclohexane boils at a very low temperature. Once the solute has dissolved, set up the apparatus as in Part I and begin stirring. Press Collect on the computer interface and begin collecting data. Continue data collection until you observe a constant temperature, and the cyclohexane appears as a solid. Stop data collection and save the data file. Remove the cyclohexane solution from the ice bath, allow the sample to thaw, and repeat data collection for a second time. Once completed, do not dispose of the cyclohexane down the sink. Pour your waste into an appropriately labeled container inside the fume hood. DATA volume of cyclohexane (mL) mass of cyclohexane (kg) mass of biphenyl (g) data file names CALCULATIONS AND RESULTS The Kf value for cyclohexane is 20.2 C kg mol-1 (or, C/m). Biphenyl (C12H10) is covalent in nature, making its i value equal to 1. The solvent mass, calculated initially in Part I, can be converted to kilograms for appropriate molality expression. The freezing points for all four runs are obtained as follows. Open the data file and examine the thermogram for the temperature break at the freezing point. If this is well defined, that value may be taken to be the freezing point. Otherwise, fit the liquid part to a straight line (regression), and also fit the solid part to a second straight line. The intersection of the two lines gives the freezing temperature. In fitting the data, choose relatively linear portions of the thermogram plot just before and just after the apparent freezing point. Using average values of Tf from the two runs of each system, calculate Tf as Tf = Tf, impure cyclohexane Tf, pure cyclohexane From these values, calculate the solution molality: m = Tf / (Kf i) and then calculate the formula weight of biphenyl: Formula weight = (masssolute, g) / (m masssolvent, kg) Compare your results with the known formula weight for biphenyl. DISCUSSION QUESTIONS AND PROBLEMS 1. How would the freezing point be affected if you were to spill some solute on the bench prior to adding it to the cyclohexane? How would the molecular mass be affected? 2. The Kf value for water is 1.862 C kg mol-1. What would be the new freezing point of a sample of 12.10 grams of NaCl dissolved in 200.0 grams of water? (4) (3) (2)

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FREEZING POINT DEPRESSION (A Colligative Property) The physical properties of vapor pressure, boiling point, melting point, and

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