Chemistry 6A F2007. Dr. J.A. Mack. Freezing Point Depression: 11/16/07. t f = nk f M

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Chemistry 6A F2007 Dr. J.A. Mack 11/16/07 11/14/07 Dr. Mack. CSUS 1 Freezing Point Depression: Similarly: The Freezing point of a solution is always lower than the freezing point of the pure solvent of the solution. t f (solvent) < t f (solution) The difference in freezing point between pure solvent and solution depends on the concentration of solute particles, and is calculated using the following equation: t f = t f (solution) t f (solvent) the molarity of the solution n = total number of particles in solution K f = fp constant (depends on the substance) n = 1 for molecular compounds n = 2 for NaCl (Na + and Cl ) 11/14/07 Dr. Mack. CSUS 2 Calculate the freezing point of a solution made up by adding and completely dissolving 4.52g sodium phosphate to 100.0 ml of water. o C Kf = 1.86 M step 1: Calculate the molarity of the solution step 2: Recognize that n = 4 Na 3 PO 4 (aq) 3Na + (aq) + PO step 3: enter the values into the equaton 3 4 (aq) n = 3 + 1= 4 Calculate the freezing point of a solution made up by adding and completely dissolving 4.52g sodium phosphate to 100.0 ml of water. n = 4 K f o C = 1.86 M o CL t f =4 1.86 mol 4.52g Na 1molNa 3PO 3 4 1 3PO 4 10 ml 163.94g 100.0mL 1L t f = 2.05 o C t f = 0.00 o C+ t f = 0.00 o C 2.05 o C= 2.05 o C 11/14/07 Dr. Mack. CSUS 3 11/14/07 Dr. Mack. CSUS 4

OSMOTIC PRESSURE OF SOLUTIONS When solutions having different concentrations of solute are separated by a semi-permeable membrane, the solvent tends to flow across the membrane from a less concentrated solution towards a more concentrated solution in a process called osmosis. Solution opposite the water: The height of the more concentrated solution to rises! water on each side, same height: h By spreading salt on the roadway, the freezing point of water is lowered, thus preventing ice formation or causing already solid ice to melt! 11/14/07 Dr. Mack. CSUS 5 The solvent molecules (water) want to dilute the solution by moving across the membrane. 11/14/07 Dr. Mack. CSUS 6 Recall that pressure is related to the height of a column of liquid: Analogously, the height increase due to osmosis is like a pressure: π = osmotic pressure (torr) A 1.00 liter aqueous solution containing 1.00 g of bovine insulin g Need to find molar mass: mol grams are given in the problem you need moles! mols/l T = Kelvins L torr R = 62.4 mol K 11/14/07 Dr. Mack. CSUS 7 Look at the definition of osmotic pressure: Where do you see moles? correct, Molarity! mols L 11/14/07 Dr. Mack. CSUS 8

A 1.00 liter aqueous solution containing 1.00 g of bovine insulin So you need to solve for molarity. Then, molarity and volume will give moles! rearranging: (n = 1 as the protein does not ionize) π nrt M Vol = moles grams and moles yield molar mass 11/14/07 Dr. Mack. CSUS 9 A 1.00 liter aqueous solution containing 1.00 g of bovine insulin 1 4 1.7 10 mols 1L 62.4 L torr mol K 3.1 torr π nrt (25.0 +273.15)K 1.00 L = 1.7 10 4 mols 1.00g = 1.7 10 4 M = 4 6.0 10 1.7 10 mol 3 g/mol 11/14/07 Dr. Mack. CSUS 10 Chapter 8: LEARNING OBJECTIVES Please read section 7.8 and 7.9 (colloids and dialysis) This material will not be covered in class, however there may be HW questions. After completing this chapter, you should be able to: 1. Use energy and entropy considerations to predict the spontaneity of a process or reaction. 2. Calculate reaction rates from experimental results. 3. Use the basic assumptions of reaction mechanisms to explain reaction characteristics. 4. Represent and interpret the energy relationships for reactions by using energy diagrams. 5. Explain how factors such as concentration, temperature, and catalysts influence reaction rates. 6. Perform calculations based on equilibrium expressions for reactions. 7. Explain the concept of equilibrium and use Le Châtelier's principle to predict the influences of concentrations of reactants, concentrations of products, catalysts, and reaction temperature on the position of equilibrium. 11/14/07 Dr. Mack. CSUS 11 11/14/07 Dr. Mack. CSUS 12

Why are certain processes or reactions spontaneous? Why are others not? Heat spontaneously flows from a hot object to a cold object heat after some time, both blocks are at the same temp Any process that occurs spontaneously must be related to energy: Recall out discussion of energy Reactions that give off heat are Exothermic Reactions that absorb heat are Endothermic up hill E (Products) E (Reactants) Potassium will spontaneously react with water! (click here) Aluminum however does not react with water. 11/14/07 Dr. Mack. CSUS 13 Energy E RXN > 0 E RXN < 0 E (Reactants) Endothermic E (Products) Exothermic down hill 11/14/07 Dr. Mack. CSUS 14 From this, you might think that all exothermic reactions (down hill) are spontaneous This is not true! The reaction of hydrogen and oxygen is quite exothermic: 1 H 2(g) + O 2(g) H2O(g) H = 241.7kJ / mol 2 However, when hydrogen is released into the atmosphere, it does not spontaneously react. We know that KNO 3 (s) dissolves in water. When this happens, the solution gets cold. (endothermic) + K & NO 3 11/14/07 Dr. Mack. CSUS 15 This means that there must be some other force that plays a part in determining whether or not a process is spontaneous. Energy does play a part, but in addition, an increase randomness or Entropy can help or hinder a process to be spontaneous. Entropy measures the disorder of a system. The more disordered the system, the higher the entropy. low entropy order high entropy disorder 11/14/07 Dr. Mack. CSUS 16

1 H 2(g) + O 2(g) H2O(g) H = 241.7kJ / mol 2 1.5 mol (more disorder) 1 mol (less disorder) Water does not spontaneously form from the reaction of H 2 and O 2 because there are fewer moles of product than reactants. Potassium nitrate spontaneously dissolves even though the process is endothermic (up hill). FACTORS THAT INFLUENCE SPONTANEITY A process will always be spontaneous if it is exothermic and the entropy of the system increases. A process that is endothermic will be spontaneous only if an increase in entropy of the system overwhelms the up hill energy climb. A process that causes an entropy decrease in the system will be spontaneous only if the exothermisity overwhelms the loss of entropy. KNO (s) K (aq) + NO (aq) 1 mol (less disorder) HO(l) 2 + 3 3 2 mol (more disorder) With some entropy increases, the increase prevents the system form returning to its original state 11/14/07 Dr. Mack. CSUS 17 11/14/07 Dr. Mack. CSUS 18