Chemistry: The Central Science, 14e

Chemistry: The Central Science, 14e

Chemistry: The Central Science Fourteenth Edition Chapter 19 Chemical Thermodynamics Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved First Law of Thermodynamics You will recall from Chapter 5 that energy cannot be created or destroyed. Therefore, the total energy of the universe is a constant. Energy can, however, be converted from one form to another or transferred from a system to the surroundings or vice versa.

Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Enthalpy/Entropy Enthalpy is the heat absorbed by a system during a constant-pressure process. Entropy is a measure of the randomness in a system. Both play a role in determining whether a process is spontaneous. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Spontaneous Processes Spontaneous processes proceed without any outside assistance. Processes that are spontaneous in one

direction are nonspontaneous in the reverse direction. Dont confuse spontaneous with fast. There are fast and slow reactions that are spontaneous. Dont confuse nonspontaneous with impossible. Energy can be used to make some reactions spontaneous that otherwise would not be. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Experimental Factors Affect Spontaneous Processes Temperature and pressure can affect spontaneity. An example of how temperature affects spontaneity is ice melting or freezing.

Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Reversible and Irreversible Processes (1 of 2) Reversible process: The system changes so that the system and surroundings can be returned to the original state by exactly reversing the process. This maximizes work done by a system on the surroundings. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Reversible and Irreversible Processes (2 of 2) Irreversible processes cannot be undone by exactly reversing the change to the system or cannot have the process exactly followed in reverse. Also, any

spontaneous process is irreversible! Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Entropy Entropy can be thought of as a measure of the randomness of a system. It is a state function: S S final Sinitial It can be found by heat transfer from surroundings at a given temperature: q rev S constant T T Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Second Law of Thermodynamics The entropy of the universe increases in any spontaneous processes. This results in the following relationships: Reversible Process : Suniv Ssys Ssurr 0 Irreversible Process : Suniv Ssys Ssurr 0 Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Entropy on the Molecular Scale (1 of 2) Entropy on the molecular level (Boltzmann) Gas molecule expansion: Two molecules start on one side above. What is the likelihood they end up there? 1 2

2 If one mole is used? 1 2 6.0210 23 ! Zero ! Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Entropy on the Molecular Scale (2 of 2) Gases spontaneously expand to fill the volume given. Most probable arrangement: approximately equal molecules in each side. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Statistical Thermodynamics Thermodynamics looks at bulk properties of substances (the big picture). We have seen what happens on the molecular scale. How do they relate? We use statistics (probability) to relate them. The field is called statistical thermodynamics.

Microstate: A single possible arrangement of position and kinetic energy of molecules Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Boltzmanns Use of Microstates Because there are so many possible microstates, we cant look at every picture. W represents the number of microstates. Entropy is a measure of how many microstates are associated with a particular macroscopic state. The connection between the number of microstates and the entropy of the system is: S k ln W Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Entropy Change Since entropy is a state function, the final value minus the initial value will give the overall change. In this case, an increase in the number of microstates results in a positive entropy change (more disorder). S k ln W final k ln Winitial W final k ln Winitial Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Effect of Volume and Temperature Change

on the System If we increase volume, there are more positions possible for the molecules. This results in more microstates, so increased entropy. If we increase temperature, the average kinetic energy increases. This results in a greater distribution of molecular speeds. Therefore, there are more possible kinetic energy values, resulting in more microstates, increasing entropy. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Molecular Motions Molecules exhibit several types of motion. Translational: Movement of the entire molecule from one place to another

Vibrational: Periodic motion of atoms within a molecule Rotational: Rotation of the molecule about an axis Note: More atoms means more microstates (more possible molecular motions). Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Entropy on the Molecular Scale The number of microstates and, therefore, the entropy tend to increase with increases in temperature. volume. the number of independently moving molecules. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Entropy and Physical States (1 of 2) Entropy increases with the freedom of motion of molecules. S(g) > S(l) > S(s) Entropy of a system increases for processes where: gases form from either solids or liquids. liquids or solutions form from solids. the number of gas molecules increases during a chemical reaction. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Entropy and Physical States (2 of 2) Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Third Law of Thermodynamics The entropy of a pure crystalline substance at absolute zero is 0. Consider all atoms or molecules in the perfect lattice at 0 K; there will only be one microstate. S k ln w k ln 1 0 Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Standard Entropies (1 of 3) The reference for entropy is 0 K, so the values for elements are not 0 J/mol K at 298 K. Standard molar enthalpy for gases are generally

greater than liquids and solids. (Be careful of size!) Standard entropies increase with molar mass. Standard entropies increase with number of atoms in a formula. (Remember: More microstates!) Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Standard Entropies (2 of 3) Table 19.1 Standard Molar Entropies of Selected Substances at 298 K S naught in joules per mole Kelvin Substance H2 g S J mol K

130.6 H 2gas. N2 g 191.5 N 2, gas O2 g H 2O g NH3 g 205.0

O 2, gas H 2 O, gas 188.8 N H 3, gas 192.5 CH3OH g C 6H6 g H 2O l CH3OH l C H 3 O H, gas

C 6 H 6, gas H 2 O, liquid C H 3 O H, liquid 237.6 269.2 69.9 126.8 Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Standard Entropies (3 of 3) [Table 19.1 continued]

S naught in joules per mole Kelvin Substance C 6H6 l Li s Na s K s C 6 H 6, liquid L I, solid 29.1 N ay, solid

51.4 64.7 K, solid Fe s 27.23 F e, solid. FeCl3 s NaCl s S J mol K 172.8

F e C l 3, solid N ay C l, solid 142.3 72.3 Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Entropy Changes Entropy changes for a reaction can be calculated in a manner analogous to that by which H is calculated: S n S products mS reactants where n and m are the coefficients in the balanced chemical equation.

Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Entropy Changes in Surroundings Heat that flows into or out of the system changes the entropy of the surroundings. For an isothermal process q surr q sys S surr T T At constant pressure, q sys is simply H for the system. S surr

H sys T at constant P Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Entropy Change in the Universe The universe is composed of the system and the surroundings. Therefore, Suniverse Ssystem Ssurroundings For spontaneous processes Suniverse 0 Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Total Entropy and Spontaneity Suniverse Ssystem Ssurroundings Substitute for the entropy of the surroundings: Suniverse Ssystem H system T Multiply by T: T Suniverse T Ssystem H system Rearrange: T Suniverse H system T Ssystem Call T Suniverse the Gibbs Free Energy G :

G H T S Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Gibbs Free Energy 1) If G is negative, the forward reaction is spontaneous. 2) If G is 0, the system is at equilibrium. 3) If G is positive, the reaction is nonspontaneous, but spontaneous in the reverse direction. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Standard Free Energy Changes (1 of 2) Analogous to standard enthalpies of formation are standard free energies of formation, Gf : G = n Gf products mGf reactants where n and m are the stoichiometric coefficients. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Standard Free Energy Changes (2 of 2) Table 19.2 Conventions Used in Establishing Standard Free Energies State of Matter Standard State Solid

Pure solid Liquid Pure liquid Gas 1 atm pressure Solution 1 M concentration Element

G 0 for element in standard state f Delta G naught of f = 0 Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Free Energy Changes (1 of 2) Table 19.3 How Signs of H and S Affect Reaction Spontaneity Delta H H

delta S negative T delta S delta G = delta H minus T delta S S T S G H T S Reaction Characteristics Example Spontaneous at all + 2 O3 g 3 O2 g temperatures 2 O 3, gas, yields 3 O 2, gas.

+ + + Nonspontancous at all temperatures

+ + or Spontaneous at low T; nonspontaneous at high T + + + or Spontaneous at high T;

nonspontaneous at low T 3 O 2, gas, yields 2 O 3, gas 3 O2 g 2 O3 g H 2 O, liquid, yields H 2 O, solid H 2 O l H 2O s H 2 O, solid, yields H 2 O, liquid. H 2O s H 2 O l Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Free Energy Changes (2 of 2) How does G change with temperature?

G H T S Since reactions are spontaneous if G < 0, the sign of enthalpy and entropy and the magnitude of the temperature matters to spontaneity. Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Free Energy and Equilibrium (1 of 2) Under any conditions, standard or nonstandard, the free energy change can be found this way: G G+RT ln Q (Under standard conditions, concentrations are 1 M, so Q = 1 and ln Q = 0; the last term drops out.) Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Free Energy and Equilibrium (2 of 2) At equilibrium, Q = K, and G = 0. The equation becomes 0 G+RT ln K Rearranging, this becomes G =- RT ln K or K e G RT Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

Coupling Reactions (1 of 2) Many natural processes would NOT occur alone! Nature couples them to offer the favorable energy conditions to cause something to occur, which is nonspontaneous alone. ATP ADP Pi Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Coupling Reactions (2 of 2) Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved Copyright Copyright 2018, 2015, 2012 Pearson Education, Inc. All Rights Reserved

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