CHEMISTRY 2000 Topic #3: Thermochemistry and Electrochemistry – What Makes Reactions Go? Spring 2008 Dr. Susan Lait.

Slides:



Advertisements
Similar presentations
Solubility Equilibria
Advertisements

Chapter 17 Additional Acid/ Base Equilibria Buffers Common Ion Effects
Chapter 16 Precipitation Equilibria
AQUEOUS EQUILIBRIA AP Chapter 17.
AP Chemistry Unit 11 – Additional Equilibrium Topics Lesson 1 – The Common Ion Effect Book Section: 17.1.
Acid-Base Titrations. Acid-Base Equilibria Chapter 16.
Chapter 17 Additional Aspects of Aqueous Equilibria
Thermodynamics “the branch of science that deals with energy levels and the transfer of energy between systems and between different states of matter”
Precipitation Equilibrium
The K sp of chromium (III) iodate in water is 5.0 x Estimate the molar solubility of the compound. Cr(IO 3 ) 3 (s)  Cr 3+ (aq) + 3 IO 3 - (aq)
Copyright McGraw-Hill Chapter 17 Acid-Base Equilibria and Solubility Equilibria Insert picture from First page of chapter.
Chemistry Thermodynamics Lecture 13 : Non Ideal Solutions and Activity Lecture 14 : Chemical Equilibria Lecture 15 : Kinetic Coefficients & the.
Precipitation Reactions. Double Replacement Reactions The ions of two compounds exchange places in an aqueous solution to form two new compounds. AX +
Ch. 16: Ionic Equilibria Buffer Solution An acid/base equilibrium system that is capable of maintaining a relatively constant pH even if a small amount.
Chapter 18: Solubility and Complex-Ion Equilibria Chemistry 1062: Principles of Chemistry II Andy Aspaas, Instructor.
Chapter 16: Applications of Aqueous Equilibria Renee Y. Becker Valencia Community College 1.
Aqueous Equilibria Chapter 15 Applications of Aqueous Equilibria.
1 Applications of Aqueous Equilibria Chapter 15 AP Chemistry Seneca Valley SHS.
Equilibrium SCH4U organic photochromic molecules respond to the UV light.
CHEMISTRY 2000 Topic #3: Thermochemistry and Electrochemistry – What Makes Reactions Go? Spring 2008 Dr. Susan Lait.
1 The Laws of Thermodynamics in Review 1.The internal energy* of an isolated system is constant. There are only two ways to change internal energy – heat.
CHEMISTRY 2000 Topic #3: Thermochemistry and Electrochemistry – What Makes Reactions Go? Spring 2008 Dr. Susan Lait.
Chapter 17 buffers- resist changes in pH by neutralizing added acid or base -acid will neutralize added OH - (base) and base will neutralize added H +
Solubility and Complex-ion Equilibria. 2 Solubility Equilibria Many natural processes depend on the precipitation or dissolving of a slightly soluble.
11111 Chemistry 132 NT The most difficult thing to understand is the income tax. Albert Einstein.
Solubility and Complex-ion Equilibria. Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 18–2 Solubility Equilibria.
Aqueous Equilibria © 2009, Prentice-Hall, Inc. Chapter 17 Additional Aspects of Aqueous Equilibria Chemistry, The Central Science, 11th edition Theodore.
Chapter 17 Additional Aspects of Aqueous Equilibria Subhash Goel South GA State College Douglas, GA © 2012 Pearson Education, Inc.
Chapter 14 Equilibria in Acid-Base Solutions. Buffers: Solutions of a weak conjugate acid-base pair. They are particularly resistant to pH changes, even.
Aqueous Equilibria Chapter 15 Additional Aspects of Aqueous Equilibria © 2009, Prentice-Hall, Inc.
Chapter 17 Additional Aspects of Aqueous Equilibria
AP Chapter 17 Additional Aspects of Equilibrium Acid Base and Solubility Equilibria HW:7, 15, 29, 39,
CHEMISTRY 2000 Topic #3: Thermochemistry and Electrochemistry – What Makes Reactions Go? Spring 2012 Dr. Susan Lait.
Chem. 1B – 9/22 Lecture. Announcements I Exam 1 –On Oct. 1 (week from next Thurs.) –Some example exams posted (my last Exam 2 for this class is closest.
Aqueous Equilibria Chapter 17 Additional Aspects of Aqueous Equilibria.
Aqueous Equilibria Chapter 16 Solubility Equilibria.
Terms Solute Substance that has been dissolved in a liquid Solvent the solution (liquid or gas) part of the solute concentration Dissolves the solute Solubility.
Ksp: The Solubility Product Constant
Introduction and Example 1—Molar Solubility of an AB type Compound. Molar Solubility from K sp.
Le Chatelier’s Principle
Saturated solution – no more solute will dissolve solubility product constant – equilibrium constant for ionic compounds that are only slightly soluble.
Much important chemistry, including almost all of the chemistry of the natural world, occur in aqueous solution. We have studied one very significant.
Solubility & SOLUBILITY PRODUCT CONSTANTS. Solubility Rules All Group 1 (alkali metals) and NH 4 + compounds are water soluble. All nitrate, acetate,
Solubility Equilibria 16.6 AgCl (s) Ag + (aq) + Cl - (aq) K sp = [Ag + ][Cl - ]K sp is the solubility product constant MgF 2 (s) Mg 2+ (aq) + 2F - (aq)
Chemistry 1011 Slot 51 Chemistry 1011 TOPIC Thermochemistry TEXT REFERENCE Masterton and Hurley Chapter 8.
1 Solubility Equilibria Dissolution M m X x (s)  m M n+ (aq) + x X y- (aq) Precipitation m M n+ (aq) + x X y- (aq)  M m X x (s) For a dissolution process,
Mixing in water Solutions dominated by water (1 L=55.51 moles H 2 O) a A =k H X A where K H is Henry’s Law coefficient – where is this valid? Low concentration.
Solubility Equilibria Solubility Product Constant, K sp Precipitation Complex Ions.
CHAPTER 15 REACTIONS AND EQUILIBRIA INVOLVING ACIDS, BASES, AND SALTS.
Chapter 17 Additional Aspects of Aqueous Equilibria John D. Bookstaver St. Charles Community College Cottleville, MO Lecture Presentation © 2012 Pearson.
Chapter 16: Aqueous Ionic Equilibria CHE 124: General Chemistry II Dr. Jerome Williams, Ph.D. Saint Leo University.
Chapter 17 Additional Aspects of Aqueous Equilibria
Ksp – Solubility Product Constant
Chapter 18 Chemical Equilibrium =yes&pid=806# =yes&pid=806#
CHAPTER 14 Chemical Equilibrium. 14.1: Equilibrium Constant, K eq  Objective: (1) To write the equilibrium constant expression for a chemical reaction.
Ionic Equilibrium When a slightly soluble or insoluble salt is mixed with water, a saturated solution quickly results and a dynamic equilibrium.
Chemical Equilibrium l The Nature of Chemical Equilibrium l Shifting Equilibrium l Equilibria of Acids, Bases, and Salts l Solubility Equilibrium.
Pages , Sections 18.1, 18.2, and 18.4 (excluding , Section 18.3)
SOLUBILITY – The maximum amount of solute that will dissolve in a specific amount of solvent EQUILIBRIA WITH SALTS SATURATED – A solution where the solid.
Chapter 16 Solubility Equilibria. Saturated solutions of “insoluble” salts are another type of chemical equilibria. Ionic compounds that are termed “insoluble”
© 2015 Pearson Education, Inc. Chapter 17 Additional Aspects of Aqueous Equilibria James F. Kirby Quinnipiac University Hamden, CT Lecture Presentation.
Equilibrium Expressions. Equilibrium When the rate of the forward and reverse reactions are equal. The equilibrium constant K eq is a value that shows.
Ionic Equilibria III: The Solubility Product Principle
Chemistry: The Central Science
Presentation transcript:

CHEMISTRY 2000 Topic #3: Thermochemistry and Electrochemistry – What Makes Reactions Go? Spring 2008 Dr. Susan Lait

2 Free Energy Change and Equilibrium We saw that the free energy change for a reaction under any conditions (  r G) can be calculated from the free energy change of the same reaction under standard conditions (  r Gº): where Q is the reaction quotient: We also know that: The forward reaction is spontaneous if ____________ The reverse reaction is spontaneous if ____________. What if  r G = 0?

3 Free Energy Change and Equilibrium When  r G = 0, we can say that: Which rearranges to give: But what is Q at equilibrium? So, we can say that:

4 Free Energy Change and Equilibrium If we know the equilibium constant for a reaction, we can calculate its standard molar free energy change: If we know the standard molar free energy change for a reaction, we can therefore calculate its equilibrium constant: Note that these equations refer to  r Gº (for standard conditions) NOT to  r G (which is ZERO at equilibrium!)

5 Q vs. K So, what’s the difference? Consider a very generic equilibrium reaction: When does Q = K? When is Q < K? When is Q > K? and

6 Free Energy Change and Equilibrium Now, consider a real reaction, the dimerization of NO 2 : Calculate the equilibrium constant for this reaction at 25 ºC.

7 Free Energy Change and Equilibrium Is the dimerization of NO 2 spontaneous at 25 ºC if the partial pressure of NO 2 is 0.4 bar and the partial pressure of N 2 O 4 is 1.8 bar?

8 Free Energy Change and Equilibrium: Acids The acid ionization constant, K a, is the equilibrium constant for the reaction in which an acid ionizes. As an equilibrium constant (and therefore based on activities), K a has no units. e.g. In CHEM 1000, we used pK a as a measure of strength of an acid. An acid with a low pK a was _______________ than an acid with a high pK a. The pK a value for an acid comes from its acid ionization constant: So, we can also say that an acid will be _________________ than another acid whose K a value is smaller. (Even a “big” K a value is pretty small. K a values range from about to )

9 Free Energy Change and Equilibrium: Acids Calculate the standard molar free energy of formation for HF (aq).

10 Free Energy Change and Equilibrium:Solubility The solubility product, K sp, is the equilibrium constant for the reaction in which an ionic compound dissolves in water. Like all other equilibrium constants, K sp has no units. e.g. Calculate the solubility of lead(II) iodide in water at 25 ºC. Solubility is reported in #moles of solid soluble in 1L water.

11 Free Energy Change and Equilibrium:Solubility

12 Free Energy Change and Equilibrium:Solubility The problem with simple K sp calculations is that they almost never give good numbers. Why not? Most of the time, there are multiple equilibria that must be considered, but the K sp expression only accounts for one. When PbI 2 is dissolved in water, two complex ions also form: In the case of PbI 2, the “simple” K sp calculation gives almost the same answer as a proper calculation factoring in both complex ions because the K f values for both complex ions are relatively small (compared to some K f values in the range). In many systems, however, the complex ion formation is significant enough that it must be accounted for or the K sp calculation will give very poor values.

13 Free Energy Change and Equilibrium:Solubility Complex ions are not the only factor complicating solubility calculations. What equilibria would you have to consider if you wanted to calculate the solubility of sodium carbonate in water? How would you increase the solubility of sodium carbonate in water?