AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 1 of 15 AP Chemistry Review Session UCLA April 23, 2016 Michael A. Morgan Richard Erdman Larry Walker mmorgan@lausd.net xchemteach@yahoo.com walker@lvusd.org Francisco Bravo Medical Magnet High School Venice High School (Emeritus) Calabasas High School Thermodynamics and Electrochemistry What is Thermodynamics? Our Guiding Question: Spontaneity The quality or state of being spontaneous (Webster's Ninth New Collegiate Dictionary) A spontaneous process is one that will proceed on its own without further input from the rest of the universe, one that is thermodynamically stable. Spontaneity has nothing to do with time. What are the three factors that will determine spontaneity? Consider three identical beakers containing identical amount of water and ice. The only difference is the temperature of each beaker What happens spontaneously in each of the three beakers?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 2 of 15 Entropy An ordered state is not generally going to occur spontaneously. You must do work! Piggy Bank analogy. Disorder favors spontaneity. So we developed a way to measure disorder. Absolute Entropy What is our reference point? What about a negative number? For the three states of matter: Entropy is a State Function! The Second Law of Thermodynamics What happens when you try to clean up your room?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 3 of 15 General Statement Clausius Statement It is impossible to have a natural process whose sole outcome is the transfer of heat from a colder body to a hotter body. Free Energy Josiah Willard Gibbs When is a reaction spontaneous? Free Energy is a state function. The Gibbs Equation Conditions other then normal. Can an equilibrium constant predict spontaneity? Return of conditions other then normal. What about phase changes?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 4 of 15 Exothermic Reactions are often spontaneous, but not necessarily. Endothermic Reactions are often non-spontaneous, but not necessarily. What favors a chemical reaction being spontaneous? Do you need to do any work to heat up a Tea Kettle? Do you need to do any work to let a Tea Kettle cool off? Do you have to do work to clean your room? Do you have to do work to let your room get messy? Who is going to do the work? The single most important table in all of chemistry. Enthalpy Entropy Free Energy Best Conditions for Spontaneity
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 5 of 15 Predicting Thermodynamic Change With out doing any calculations make the following predictions: Use your everyday knowledge to help reason your way through these. The following phase change at 298 Kelvin: H 2 O(l) H 2 O(g) What are the signs of: ΔG ΔS ΔH Now consider the reverse reaction at 298 Kelvin: H 2 O(g) H 2 O(l) What are the signs of: ΔG ΔS ΔH The following phase change at 298 Kelvin: H 2 O(s) H 2 O(l) What are the signs of: ΔG ΔS ΔH Now what if we changed the temperature: The following phase change at 271 Kelvin: H 2 O(s) H 2 O(l) What are the signs of: ΔG ΔS ΔH
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 6 of 15 Electrochemical Cells Any device in which a redox reaction occurs is an Electrochemical Cell What is the difference between an Electrolytic Cell and a Galvanic (Voltaic) Cell? The Daniell Cell Left side Right side Half Reaction Change Electrode Charge on electrode Ion Flow from Salt Bridge What is the purpose of the salt bridge? Standard Reduction Potentials Who is SHE? (The Standard Hydrogen Electrode)
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 7 of 15 Copper and Zinc Cells Calculate the cell potential for electrochemical cells based on the following reactions: 1) Ag + (aq) + Cu(s) Cu 2+ (aq) + Ag(s) 2) Zn 2+ (aq) + Ni(s) Zn(s) + Ni 2+ (aq) 3) F 2 (aq) + Br (aq) F (aq) + Br 2 (aq) 4) Zn(s) + 2H + (aq) Zn 2+ (aq) + H 2 (g) 5)Cu(s) + 2H + (aq) Cu 2+ (aq) + H 2 (g)
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 8 of 15 Summing it all up Keq ΔG E Spontaneous Reaction Non Spontaneous Reaction Electrolysis Michael Faraday Faraday = F = 96, 485 coulombs/mole electrons Let's learn some units from Physics Name Unit of? Basis Derived From Electrolysis problems are much the same as stoichiometry problems. Watch the units! 1) What mass of copper can be produced by the electrolysis of a copper(ii) sulfate solution for 1.00 hours at a current of 10.0 amps?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 9 of 15 2) Calculate the amount of current necessary to deposit 2.00 g of platinum from a solution of PtCl 6 2 in 2.0 hours? 3) The same quantity of charge that deposited 0.583 g of silver was passed through a solution of a gold salt and 0.355 g of gold was formed. What is the oxidation state on gold in this solution? 4) A solution containing a 3+ ion is electrolyzed by a 5.0 A current for 10.0 minutes. If 1.99 g of the metal is plated out what is the molar mass of the metal? 5) It took 156.2 seconds for a 3.00 A current to plate out 0.233 g of a metal from a solution of M 2+. What is the metal?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 10 of 15 EMF and Free Energy What determines if a reaction happens? How can we relate EMF and Free Energy? Who is this Nernst guy anyway? Equilibrium Constants Units can be a problem Calculate ΔG o and the Equilibrium constant for the following reactions: Ag + (aq) + Cu(s) Cu 2+ (aq) + Ag(s) Zn 2+ (aq) + Ni(s) Zn(s) + Ni 2+ (aq)
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 11 of 15 Consider the following reaction at 25 C: Fe (s) + Cd 2+ (aq) Fe 2+ (aq) + Cd (s) a) What is the standard EMF for the reaction? b) What is the value of ΔG for this reaction? c) What is the equilibrium constant expression for the reaction? d) What is the value of the equilibrium constant for this reaction at 25 C? e) What is the EMF when the concentration of iron (II) is 0.010 M and cadmium (II) is 1.0 M? f) What is the EMF when the concentration of iron (II) is 1.0 M and cadmium (II) is 0.010 M? g) What is the value of ΔG for this reaction when the concentration of iron (II) is 1.0 M and cadmium (II) is 0.010 M?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 12 of 15 Electrolysis of Water What happens when you run electricity through water? There are three reactions that we are concerned with here: 2H 2 O(l) O 2 (g) + 4H + (aq) + 4e E = 1.23V 2H 2 O(l) + 2e H 2 (g) + 2OH (aq) E = 0.83V H 2 (g) 2H + (aq) + 2e E = 0.00 V To make this work we must add some electrolyte (usually H 2 SO 4 ). Why? What does SHE have to say about this? The EMF for this is negative is that cool? Think about the driving forces. What if it were a solution of NaCl instead of water? What species are really present?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 13 of 15 What are the four possible reactions? Anode (oxidation) Cathode (reduction) Which two actually happen? Why? Overvoltage Imagine you had a mixture of three ions: Ag + (aq) Cu 2+ (aq) Zn 2+ (aq) Ag + (aq) + e Ag Cu 2+ (aq) + 2e Cu Zn 2+ (aq) + 2e Zn E = 0.80 V E = 0.34 V E = 0.76 V If you run a current through a solution containing all three ions which one would plate out first?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 14 of 15 This is from the 1994 exam 2 H 2 S(g) + SO 2 (g) <==> 3 S(s) + 2 H 2 O(g) At 298 K, the standard enthalpy change, H for the reaction represented above is 145 kilojoules. (a) Predict the sign of the standard entropy change, S, for the reaction. Explain the basis for your prediction. (b) At 298 K, the forward reaction (i.e., toward the right) is spontaneous. What change, if any, would occur in the value of G for this reaction as the temperature is increased? Explain your reasoning using thermodynamic principles. (c) What change, if any, would occur in the value of the equilibrium constant, K eq, for the situation described in (b)? Explain your reasoning. (d) The absolute temperature at which the forward reaction becomes nonspontaneous can be predicted. Write the equation that is used to make the prediction. Why does this equation predict only an approximate value for the temperature?
AP Chemistry Readiness Thermodynamics and Electrochemistry Review Page 15 of 15 This is from the 1998 exam 8. Answer the following questions regarding the electrochemical cell shown. (a) Write the balanced net-ionic equation for the spontaneous reaction that occurs as the cell operates, and determine the cell voltage. (b) In which direction do anions flow in the salt bridge as the cell operates? Justify your answer. (c) If 10.0 ml of 3.0-molar AgNO 3 solution is added to the half-cell on the right, what will happen to the cell voltage? Explain. (d) If 1.0 gram of solid NaCl is added to each half-cell, what will happen to the cell voltage? Explain. (e) If 20.0 ml of distilled water is added to both half-cells, the cell voltage decreases. Explain.