2016-07-07

Chapter 17
Spontaneous Change: How Far?

• Understanding and applying the second law of
thermodynamics.
• Understanding the relationship between ∆rG° and
K and the dependence of equilibrium constants on
temperature.

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2016-07-07

Lecture Outline
Spontaneous Direction of Change and Equilibrium
Entropy and Second Law of Thermodynamics
Standard Molar Entropy of Substances, S°
Entropy Changes and Spontaneity
Gibbs Free Energy and Spontaneity
∆rG° and E°cell for Voltaic Cell Reactions
Dependence of Equilibrium Constants on Temperature
Dependence of Equilibrium Vapour Pressures on
Temperature

Spontaneous Direction of Change and
Equilibrium
• Spontaneous refers to the direction of reaction that would take a reaction
mixture closer to a state of chemical equilibrium.
• To predict whether a process is spontaneous, we can use a thermodynamic
property called entropy (S).
• The concept of entropy is built on the idea that spontaneous change results in
dispersal of energy.
• Entropy (S) is a measure of the lack of order resulting from dispersal of energy
and matter.
q qrev = the heat absorbed in
ΔS  rev the reversible change
T ΔS (J/K)
• The Second Law of Thermodynamics: Any spontaneous process is
accompanied by an increase in the entropy of the universe.
• The reference point for entropy is provided by The Third Law of
Thermodynamics: There is no disorder in a perfect crystal at 0 K, or S = 0.
• All substances have positive entropy values at temperatures above 0 K.

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2016-07-07

Sample Problem 1
When ammonia changes from liquid to vapor at
its normal boiling point (239.7K), the heat
absorbed is 29.1 kJ/mol. Calculate the entropy
change of vaporization of ammonia at normal
boiling point.

Solution
When ammonia changes from liquid to vapor at its
normal boiling point (239.7K), the heat absorbed is
29.1 kJ/mol. Calculate the entropy change of
vaporization of ammonia at normal boiling point.

ΔS = q / T = 29.1 × 103 J / 239.7 K = 121 J K−1

i.e., the entropy of 1 mol of ammonia vapour is 121
J K−1 greater than the entropy of 1 mol of the liquid.

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2016-07-07

Entropy
Entropy increases with the number of
energetically equivalent ways to arrange the
components of a system
The Boltzmann Equation for entropy states:

S = k log W

where k is the Boltzmann constant, and W
represents the number of different ways that the
energy can be distributed over the available
energy levels.

k = Boltzmann Constant = 1.38 x 10−23 J/K
W is the number of energetically equivalent ways
a system can exist 7

Entropy and the Second Law of
Thermodynamics
• The standard molar entropy (S°) of a substance
is the entropy of 1 mol of a substance in its
standard state at a specific temperature.
• When comparing the same or similar substances,
the molar entropies of gases are much larger
than those for liquids, and the molar entropies
of liquids are larger than those for solids.

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S° • Substances composed of large molecules have higher molar entropy than substances with smaller molecules.8 9 Standard Molar Entropy of Substances. 2016-07-07 Relative Standard Entropies: States • The gas state has a larger entropy than the liquid state at a particular temperature • The liquid state has a larger entropy than the solid state at a particular temperature S°. • Substances whose molecules have complex structures have more entropy than those with simpler molecules. S° (J K1 mol1) 10 5 . Substance (J/mol∙K) H2O (l) 70.0 H2O (g) 188.

greater entropy. Ozone has more ways of distributing its energy which corresponds to greater disorder—i. (c) 3 mol of O2(g) has more entropy than 2 mol of O3(g). There is more energetically equivalent ways that system can exist in 3 mol of O2 6 . There is the same number of O atoms—i. Oxygen molecules have only one stretching vibrational mode and two rotational modes (rotation about the bond does not constitute rotation of the molecule). Ozone has more internal degrees of freedom. 2 mol of the larger molecules is a more ordered/constrained arrangement of those 6 mol of O atoms than is 3 mol of O2 molecules. There are 1. as well as three distinct rotational modes.e.5 times as many O atoms in 1 mol of O3(g) than there are in 1 mol of O2(g) so there are many more possibilities for different arrangements of the atoms. Ozone molecules have more modes of vibration (two stretching vibrations and a bending mode).e. 2016-07-07 Sample Problem 2 For each of the pair listed... The gas molecules are free to explore the entire container—liquid molecules have less volume available and reduced mobility within the bulk. (b) 1 mol of SnCl4(g) has more entropy than 1 mol of SnCl4(ℓ). (a) 1 mol of O3(g) or 1 mol of O2(g) 1 mol of O3(g) or 1 mol of O2(g) (b) 1 mol of SnCl4(g) or 1 mol of SnCl4(ℓ) 1 mol of SnCl4(g) or 1 mol of SnCl4(ℓ) (c) 3 mol of O2(g) or 2 mol of O3(g) 3 mol of O2(g) or 2 mol of O3(g) Solution (a) 1 mol of O3(g) has higher entropy than 1 mol of O2(g). Gases have much more entropy per mole than the corresponding liquid. 6 mol. predict which substance has the higher entropy and explain your reasoning.

More complex molecules have more entropy than less complex molecules. 2016-07-07 Active Learning: Think-Pair-Share Activity #1 Which substance has the higher entropy in each of the following pairs? 1a. 2. 1 mol of N2(g) at 10 bar pressure 2a. 1 mol of N2(g) at 1 bar or 1b. Lower pressure means higher volume and consequently less constrained distribution of molecules. 1 mol of N2(g) at 1 bar pressure has more entropy than 1 mol of N2(g) at 10 bar pressure (both at 298 K). They have more internal motions which mean more ways of distributing energy. C2H4(g) has more entropy than N2(g). 7 . 1 mol of N2(g) Solution 1. 1 mol of C2H4(g) or 2b.

Standard Entropy Change of Reaction (∆rS°): ∆rS° = ∑ni S°(products)  ∑ni S°(reactants) 15 Sample Problem 3 Calculate the ΔSο at 298 K for the following process. 2016-07-07 Entropy and the Second Law of Thermodynamics The standard molar entropy (S°) of a substanceis the entropy of 1 mol of a substance in its standard state at a specific temperature. N2 (g) + 3H2 (g)   2 NH3 (g) 8 .

Active Learning: Think-Pair-Share Activity #2 Calculate the standard entropy change for the formation of 1 mol of gaseous ethane (C2H6) 2C(graphite) + 3H 2 (g)   C2 H 6 (g) 9 . 2016-07-07 Solution N2 (g) + 3H2 (g)   2 NH3 (g) ∆rS° = ∑ni S°(products)  ∑ni S°(reactants) We predict a decrease in entropy as the reaction converts a total of 4 mol of gas to 2 mol of gas. which is consistent with the calculation.

6 J K 1 mol 1 + 3 130. g)] = 229.g)  [2  S o (C.2 J K 1 mol1  [2  5.7 J K 1 mol 1 ] =  174. 2016-07-07 Solution 2C(graphite) + 3H2 (g)   C2 H6 (g) Δ r S ° = 1  S o (C2 H 6 .graphite) + 3  S o (H 2 .1 J K 1 mol1 Lecture # 2 on Chapter 17 Spontaneous Change: How Far? 10 .

S° Entropy Changes and Spontaneity Gibbs Free Energy and Spontaneity ∆rG° and E°cell for Voltaic Cell Reactions Dependence of Equilibrium Constants on Temperature Dependence of Equilibrium Vapour Pressures on Temperature Entropy Changes and Spontaneity • A spontaneous process is one that results in an increase of entropy in the universe. 2016-07-07 Lecture Outline  Spontaneous Direction of Change and Equilibrium  Entropy and Second Law of Thermodynamics  Standard Molar Entropy of Substances. ∆Suniv = ∆Ssys + ∆Ssurr • The standard entropy change at any specified temperature can be expressed as: ∆S°univ = ∆S°sys + ∆S°surr • The entropy change in the surroundings is proportional to the amount of heat gained or lost qsurroundings = −qsystem 22 11 .

2016-07-07 Sample Problem 4 Consider the reaction represented as Si(s) + 2Cl2 (g)   SiCl4 (g) In a reaction vessel in which all the reactants and products are in their standard states at 298 K.12 J K 1 mol 1  2224 J K 1 mol 1 =  2090 J K 1 mol 1 Since the change in entropy for the universe upon reaction in the direction indicated by the equation is positive.75 × 103 J mol1 ΔS osurr =  =  = +2224 J K 1 mol1 T 298K ΔS o univ = ΔS o sys  ΔS o surr =  134.8) ΔH osys 662. is this reaction direction indicated by the chemical equation spontaneous? Answer this question by calculating ∆Sοsys. the reaction is spontaneous. ∆S οsurr and ∆S ο univ Conceptual Plan: • Calculate ∆Ssys using the formula: ∆rS° = ∑ni S°(products)  ∑ni S°(reactants) • Calculate ∆Ssurr • ∆S°univ = ∆S°sys + ∆S°surr Solution Si(s) + 2Cl2 (g)   SiCl4 (g) (prior knowledge from section 7. 12 .

2 kJ mol1 .T (+) low T (-) = (+) . Δ r S o =  375.T (+) at high and low T (+) = (+) . is the maximum amount of work energy that can be released to the surroundings by a system DGsys = DHsys−TDSsys (-) = (-) .2J K 1 mol1 b) At low temperature N 2 (g) + 2 O2 (g)   2 NO2 (g) Δ r H =  66.5kJ mol 1 . 2016-07-07 Gibbs Free Energy and Spontaneity The Gibbs Free Energy. Δr S o =  121. G.T (-) low T (+) = (-) .T (-) high T (+) = (+) .6J K 1 mol 1 o 13 .T (+) high T 25 Active Learning: Think-Pair-Share Activity #3 Indicate if the reaction is spontaneous or non- spontaneous based on the information provided a) At low temperature Fe2O3 (s) + 2 Al(s)   2 Fe(s) + Al2 O3 (s) Δ r H o =  851.T (-) at high and low T (-) = (-) .

(-) = (-) . but NOT spontaneous at high temperature. Δr S o =  121. • ∆rG changes as the amounts of reactants and products change during chemical reaction.5kJ mol 1 .T (-) low T N 2 (g) + 2 O2 (g)   2 NO2 (g) Δ r H o =  66. this equation cannot be used to calculate ∆rG since the molar free energies of substances are not known. 2016-07-07 Solution Fe2O3 (s) + 2 Al(s)   2 Fe(s) + Al2 O3 (s) Δ r H o =  851. 28 14 .T (-) at high and low T Gibbs Free Energy • The Free Energy Change of Reaction (∆rG) at any stage in the reaction can be defined as the following: ∆rG = ∑ni G (products)  ∑ni G (reactants) • However.6J K 1 mol 1 This reaction is NOT spontaneous at any temperature (+) = (+) .2J K 1 mol1 This reaction is spontaneous at low temperature. Δ r S o =  375.2 kJ mol1 .

the reaction is at equilibrium. Copyright © 2015 by Nelson Education Limited 30 15 . – If ∆rG > 0. the reaction is not spontaneous (but reaction in the opposite direction is). – If ∆rG = 0. the reaction is spontaneous as written. 2016-07-07 Gibbs Free Energy ∆rG and Spontaneity of Reaction • The second law states that a reaction is spontaneous if ΔSuniv > 0. A more convenient definition of reaction spontaneity is as follows: ΔrG ΔSuniv   T – If ∆rG < 0. 29 Gibbs Free Energy Change of free energy of a reaction mixture during reaction.

∆rG = ∆rH ̶ T∆rS • In the particular case of a reaction mixture. 2016-07-07 Gibbs Free Energy • At any instant during a chemical reaction held at constant temperature and pressure. the free energy change of reaction is the Standard Free Energy Change of Reaction (∆rG°) ∆rG° = ∆rH° ̶ T∆rS° 31 Sample Problem 5 Calculate the ΔrGο for the following reaction by calculating the ΔrSο and ΔrHο N 2  g  + 3 H 2  g    2 NH3  g  16 . in which all reactants and products are in their standard states.

80 kJ mol1  298 K  (  198.g)] =  2  (45.g) + 3  Δ f H o (H 2 .77 J K 1 mol1  [191.8kJ mol1 Enthalpy Driven Reaction Active Learning: Think-Pair-Share Activity #4 Is the following reaction enthalpy driven or entropy driven? 17 .g)  [Δ f H o (N 2 .56 J K 1 mol 1  3 130.g)  [1  S o (N 2 .1 J K 1 mol1 Δ r H ° = 2  Δ f H o (NH 3 .1 J K 1mol1 ) / 1000 J /kJ =  32. 2016-07-07 Solution N 2  g  + 3 H 2  g    2 NH3  g  Δ r S ° = 2  S o (NH 3 .80 kJ mol1 Δ r G° = Δ r H o  TΔ r S o =  91.7J K 1 mol 1 ] =  198.90 kJ mol1 ) =  91.g) + 3  S o (H 2 .g)] = 2  192.

Δr S o =  316. the standard molar free energy change of formation of an element in its standard state is zero.5 J K−1 mol−1) / (1000 J / kJ) = −112. 2016-07-07 Solution C6 H 6 ( ) + 3H 2 (g)   C6 H12 ( ) Δ r H o =  206. Gibbs Free Energy • The Standard Molar Free Energy Change of Formation (∆fG°) of a compound is the standard free energy change when 1 mol of the compound is formed from its component elements in their standard states.5J K1 mol 1 ΔrGº = ΔrHº − T ΔrSº = −206.4 kJ mol−1 This reaction is spontaneous at 25C in a reaction mixture with all reagent species in their standard states. • By definition. It is enthalpy driven—the negative enthalpy change more than compensates for the negative entropy change at 25C.7 kJ mol1 .7 kJ mol−1 − (298 K) × (−316. • See Appendix D for a list of ∆fG° values. 36 18 .

the free energy change is the maximum energy that becomes available to do useful work. 2016-07-07 Gibbs Free Energy • The standard free energy change of a reaction can be calculated from ∆fG° of reactants and products using the following equation: ∆rG° = ∑ni ∆fG° (products) ̶ ∑ni ∆fG° (reactants) • In any process. Mathematically. • K > 1. ∆rG = wmax 37 Gibbs Free Energy Direction of spontaneous reaction in a standard- state reaction mixture where ∆rG° < 0. the reaction is product-favoured Copyright © 2015 by Nelson 38 Education Limited 19 .

Is this reaction spontaneous? 3H 2 (g) + CO(g)   CH4 (g) + H2 O(g) ∆rG° = ∑ni ∆fG° (products) ̶ ∑ni ∆fG° (reactants) 20 . 2016-07-07 Gibbs Free Energy Direction of spontaneous reaction in a standard- state reaction mixture where ∆rG° > 0. the reaction is reactant-favoured Copyright © 2015 by Nelson 39 Education Limited Sample Problem 5 Calculate the ∆rG° for the following reaction at 298 K. • K < 1.

2 kJ mol1 This reaction is spontaneous in the forward direction (at 25C. the temperature at which the system is at equilibrium can be calculated. 2016-07-07 Solution 3H 2 (g) + CO(g)   CH4 (g) + H2 O(g) ∆rG° = ∑ni ∆fG° (products) ̶ ∑ni ∆fG° (reactants) Δ r G o = 1  Δ f G o (CH 4 . 42 21 . Using this equation.g) + 1  Δf G o (CO. and if all of the reagents are simultaneously at 1 bar pressure) Gibbs Free Energy • ∆rH° and ∆rS° can be assumed temperature independent over moderate changes of temperature.59 kJ mol1 )  [3 0 kJ mol1  137. the mixture is at equilibrium.g)] =  50.168kJ mol1 ] =  142. • When ∆rG° = ∆rH°  T ∆rS°.8 kJ mol1 + (228. ∆rG° = 0.g) + 1  Δf G o (H2 O.g)  [3  Δf G o (H2 .

2016-07-07 Sample Problem 6 Use the thermodynamic data of Appendix D to approximate the temperature at which HgO in a vessel decomposes sufficiently to be in equilibrium with 1 bar pressure of O2(g) 2 HgO(s)   2 Hg( ) + O2 (g) Solution 2 HgO(s)   2 Hg( ) + O2 (g) Δ r S ° = 2  S o (Hg.s) = 0 + 0  2  (90.g)  2  Δ f H o (HgO.66 kJ mol1 Δ r G° = Δ r H o  TΔ r S o = 0 when Δr H o 181.29 J K 1 mol1 = 216.83kJ mol1 ) = +181.0 K Δr S o 216.53 J K 1 mol1 Δ r H ° = 2  Δ f H o (Hg.l)  1  S o (O 2 .53 J K 1 mol1 22 .66  1000 J mol 1 T= = = 839.s) = 2  76.g)  2  S o (HgO.07 J K 1 mol1  2  70.l)  1  Δ f H o (O 2 .02 J K 1 mol1  205.

Ni(CO)4 is represented as follows: Ni(CO)4 ( )   Ni(s) + 4CO(g) Δr G o at 25oC = 40kJ mol 1 Solution Ni(CO)4 ( )   Ni(s) + 4CO(g) Δr G o at 25oC = 40kJ mol 1 23 . 2016-07-07 Active Learning Activity: Think-Pair- Share Activity #5 The decomposition of liquid nickel carbonyl.

∆rG° and K at the same temperature are mathematically. The magnitude of the difference between the free energies of reaction is as follows: ∆rG = ∆rG° + RT ln Q Where R is the universal gas constant. very seldom do reaction mixtures have all species in their standard states. and T is the temperature in K. ∆rG = ∆rG° 47 The Relationship Between ∆rG° and K • For a specified reaction. 48 24 . • If Q = 1. 2016-07-07 Gibbs Free Energy Free Energy Change of Reaction in Non-standard Reaction Mixtures • In practice. • It provides a direct route to determine ∆rG° from experimentally determined equilibrium constants. 0 = ∆rG° + RT ln K ∆rG° = ̶ RT ln K • This equation allows calculation of an equilibrium constant at the same temperature as thermochemical data in tables or obtained from an experiment.

314 J K 1 mol 1  298 K =  48.168 kJ mol 1 )  [0  (  394.44 K = e 48.18 × 1022 25 .s) + 1  Δ f G o (CO 2 .44 = 9.359 kJ mol 1 )] =  120.g)  [1  Δ f G o (C. Calculate the ∆rG° and K for the following reaction C  s  + CO2  g    2 CO  g  Solution C  s  + CO2  g    2 CO  g  Δ r G o = 2  Δf G o (CO. 2016-07-07 Sample Problem 7 Using the data given in Appendix D.023 kJ mol 1 ΔrG o 120.023 × 103 J mol 1 ln K =  = RT 8.g)] = 2  ( 137.

2016-07-07 Active Learning Activity: Think-Pair- Share Activity #6 The equilibrium constant (K) is 0.871 kJ mol1 26 .14) = 4871 J mol1 = 4.314J K 1 mol 1  298 K ln(0.14 for the following reaction. Calculate the ∆rG° N2O4 2NO2 (g) (g) Solution ΔrG o =  RT ln K =  8.

S°  Entropy Changes and Spontaneity  Gibbs Free Energy and Spontaneity ∆rG° and E°cell for Voltaic Cell Reactions Dependence of Equilibrium Constants on Temperature Dependence of Equilibrium Vapour Pressures on Temperature 27 . 2016-07-07 Lecture # 3 on Chapter 17 Spontaneous Change: How Far? Lecture Outline  Spontaneous Direction of Change and Equilibrium  Entropy and Second Law of Thermodynamics  Standard Molar Entropy of Substances.

K > 1. E°cell and K for the following reaction 2 Fe3+  aq  + 2 I  aq    2 Fe2+  aq  + I2  s 28 . E°cell > 0. 2016-07-07 ∆rG° and E°cell for Voltaic Cell Reactions Related “Driving Forces” of Reaction: ∆rG°. and ∆rG° < 0. 55 Sample Problem 8 Calculate ∆rG°. K and E°cell For a spontaneous reaction in a standard-state mixture (Q = 1).

55 104 CVmol1 =  45. 2016-07-07 Solution 2 Fe3+  aq  + 2 I  aq    2 Fe2+  aq  + I2  s n = 2 here Ecell = E[Fe3+|Fe2+] − E[I2|I−] = 0.236 V ΔrGo =  nFEocell =  (2)(96 450 Cmol1 )(0.236V) =  4.5kJ mol1  4.535 V = 0.771 V − 0.55  104 J mol 1  K  exp( D rG / RT )  exp  1 1   8.46  107 Active Learning Activity: Think-Pair- Share Activity # 7 Calculate the Ecellο.314 J K mol  298 K   9. ΔrGο and K at 25 Οc for the following reaction Zn 2+  aq  + Ni  s    Zn  s  + Ni2+  aq  29 .

72 = 5.51 V) = 98379 CV mol−1 = 98. ∆rG° and K vary as temperature changes. 2016-07-07 Solution Zn 2+  aq  + Ni  s    Zn  s  + Ni2+  aq  Eº = Eº[Zn2+(aq)| Zn(s)] − Eº[Ni2+(aq)| Ni(s)] = −0.51 V ΔrGº = −nF Eº = −2 × 96450 C mol−1 × (−0.4 kJ mol−1 ΔrG o 98.314 J K 1 mol1  298 K =  39.25 V) = −0.4 × 103 J mol 1 ln K =  = RT 8. • The dependence of the equilibrium constant on temperature is given by the following relationship ∆rG° = ̶ RT ln K = ∆rH° ̶ T∆rS° Δ rHo Δ r S o lnK    RT R 60 30 .72 K = e 39. so we need to relate these values.62 × 1018 Dependence of Equilibrium Constants on Temperature • For any reaction.763 V − (−0.

2016-07-07 Dependence of Equilibrium Constants on Temperature N2(g) + 3 H2(g) ⇌ 2 NH3(g) Δ rHo Δ r S o lnK    RT R Copyright © 2015 by Nelson 61 Education Limited Dependence of K on Change of Temperature • For an exothermic reaction (∆rHo negative). an increase of T brings about a smaller value of ln K. Δ rHo Δ r S o lnK    RT R Copyright © 2015 by Nelson 62 Education Limited 31 . increase of T increases K. • For an endothermic reaction. and of K.

2016-07-07 Dependence of Equilibrium Constants on Temperature • The van’t Hoff equation can be used to estimate K at one temperature from an experimentally measured value at another temperature ΔrHo  1 1  lnK 1  lnK 2      R  T1 T2  63 Sample Problem 9 ΔrHo  1 1  lnK 1  lnK 2      R  T1 T2  Conceptual Plan: • Calculate the K1 • Calculate ΔrHº 32 .

2016-07-07 Solution ΔrHo  1 1  lnK1  lnK 2      R  T1 T2  Solution 33 .

2016-07-07 Solution Dependence of Equilibrium Vapour Pressures on Temperature • The dependence of equilibrium vapour pressures of liquids and solids on temperature is a particular case of dependence of equilibrium constants on temperature and corresponding mathematical relationships apply. 68 34 .

is more dense than the air above it. This cold layer acts as a reaction vessel. • Secondary pollutants are substances formed by the chemical reactions of primary pollutants. and after absorbing energy from the sun. 2016-07-07 Photochemical Smog and the Dependence of K on T • Primary pollutants are substances that have been directly admitted to the atmosphere. 69 Photochemical Smog and the Dependence of K on T • If a layer of cold air. pollutants react with each other. it remains trapped near ground level. perhaps polluted. Copyright © 2015 by Nelson 70 Education Limited 35 .

71 Video: The Science Behind the Smog 36 . 2016-07-07 Photochemical Smog and the Dependence of K on T • Conditions that are most suited to formation of photochemical smog: – High concentrations of nitrogen oxides and VOCs. – Thermal inversion. – Relatively still conditions so that the pollutants are not swept away and diluted by winds. – Long periods of relatively intense sunlight.

2016-07-07 Cumulative Knowledge Testing on Chapters 16 & 17 Cumulative Knowledge Testing Q#1 From the thermodynamic data provided. (a) calculate the (ΔGrο) at 298 K. (b) K at 298 K and (C) K at 1500 οC 37 .

38 × 1025 Solution c) K at 1500 C ΔrG o 141.g)  2×Δf G o (SO3 .82 kJ mol1 (b) K at 298 K ΔrG o 141.g) = 2×( 300.82 × 103 J mol 1 ln K =  = RT 8.24 = 1.314 J K 1 mol 1  1773 K =  9.64 × 105 38 .g) + 1  Δf G o (O2 .13kJ mol1 )  0 kJ mol1  2×( 371.04 kJ mol1 ) = 141.314 J K 1 mol 1  298 K =  57.62 = 6.24 K = e 57. 2016-07-07 Solution (a) DrG at 298 K Δ r G o = 2×Δf G o (SO2 .62 K = e 9.82 × 103 J mol 1 ln K =  = RT 8.

e) If the concentration Cd+2(aq) ions is reduced to 0. (b) Ecell = E[Ni2+(aq)|Ni(s)] − E[Cd2+(aq)|Cd(s)] = −0. keeping the the [Ni+2] 1 M. 2016-07-07 Cumulative Knowledge Testing Q#2 Consider the half reactions given below to answer the following questions E[Ni2+(aq)|Ni(s)] = −0. the Ni(s) electrode is the cathode.25 V E[Cd2+(aq)|Cd(s)] = −0. which way the NO-3ions move? d) Calculate the equilibrium constant for the cell reaction at 298 K.15 V (c) The NO3−(aq) ions (anions) move toward the anode compartment. 39 .25 V − (−0.403 V a) Which half reaction is taking place at the cathode? b) What is the Ecellο ? c) If a salt bridge containing NaNO3 connects the two half cells.403 V) = +0.010 M. what is the Ecell Solution (a) Since Ni2+(aq)|Ni(s) has the higher reduction potential.

0257 V  0.0257 V = 11. 2016-07-07 Solution (d) DG° = −RTlnK = −nFE°cell 2 2 ln K = × E o cell = ×(+ 0.7 and K = 1.0  40 .15 V) 0.15 V  × ln   = + 0.0257 V 0.0257 V  [Cd2 ]  Ecell = E o cell  × ln Q = + 0.0257V Ecell  E o cell  ln Q  E o cell  ln Q at 25o C nF n 0.010  = + 0.15 V  × ln  2  n 2  [Ni ]  0.2 105 Solution (e) RT 0.21V 2  1.0257 V 0.