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Connection between Ecell, ∆G, and K

The connection between cell potential, Gibbs free energy and constant equilibrium are directly related in the following multi-part equation:

∆G: Gibbs Free Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 E° cell: Standard Cell Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Difference between Ecell and Eºcell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 K: The Equilibrium Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 The Relationship Between The Three . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Summary Table. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Example Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Using ∆G=-RTlnK . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Using ∆G=-nFE°cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Using E° cell=(RT/nF) lnK. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Answer Key . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

∆G: Gibbs Free Energy
∆G is the change of Gibbs (free) energy for a system and ∆G° is the Gibbs energy change for a system under standard conditions (1 atm, 298K). On an energy diagram, ∆G can be represented as:

Where ∆G is the difference in the energy between reactants and products. In addition ∆G is unaffected by external factors that change the kinetics of the reaction. For example if Ea (activation energy) were to decrease in the

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Deviations from 25ºC requires the use of the original equation. E° cell: Standard Cell Potential E° cell is the electromotive force (also called cell voltage or cell potential) between two half-cells. The two are closely related in the sense that the standard cell potential is used to calculate for the cell potential in many cases. the morEe likely the reaction will proceed. The greater the E° cell of a reaction the greater the driving force of electrons through the system.2M)||Ag+(0. Eº is E at standard conditions Example Applying the Nernst Equation for Determining Ecell What is the value of Ecell for the voltaic cell below: Pt(s)|Fe2+(0. the higher the cell is on the table. E° cell is measured in volts (V). Ecell = Ereduction + Eoxidation or Ecell = Ecathode + Eanode The potential of an oxidation reduction (loss of electron) is the negative of the potential for a reduction potential (gain of electron). Difference between Ecell and Eºcell Eº cell is the standard state cell potential. Most tables only record the standard reduction half-reactions. the Ecell is the non-standard state cell potential.1M)|Ag(s) Ecell = ? Analysis: Copyright © The Regents of the University of California. The overall voltage of the cell = the half-cell potential of the reduction reaction + the half-cell potential of the oxidation reaction.presence of a catalyst or the kinetic energy of molecules increases due to a rise in temperature.1M). the higher potential it has as an oxidizing agent. which means that it is not determined under a concentration of 1 Molar and pressure of 1 atm. simply reverse the sing of the standard reduction potential. Davis 2 . most tables only record the standard reduction potential. Similar to the standard state cell potential. so in order to find the standard oxidation potential.Fe3+(0. instead of the natural logarithm (base e) Both equations applies when the temperature is 25ºC. the ∆G value would remain the same. *Note: The more positive reduction potential of reduction reactions are more spontaneous. Other simplified forms of the equation that we typically see: or in terms of log base 10. The standard states include a concentration of 1 Molar (mole per liter) and an atmospheric pressure of 1. When viewing a cell reduction potential table. Essentially. which means that the value was determined under standard states. Eºcell. We will revisit spontaneity later in the module. In other words. To simplify.

800V-0.029V Now to determine Ecell for the reaction Fe2+(0.Eo anode = EoAg/Ag . K.0592V*log [0.1]*[1.EoFe3+/Fe2+ = 0.To use the Nersnt equation. Once we have determined the form of the Nernst equation.1M) + Ag+(1. we need to establish Eocell and the reaction to which the cell diagram corresponds so that the form of the reaction quotient (Q) can be revealed.029V -(0.771V = 0.011V K: The Equilibrium Constant K is the equilibrium constant of a reaction and is given by the reaction quotient: The Relationship Between The Three The relationship between ∆G. Solve: Eocell = Eo cathode . Davis 3 .Fe3+(0.2]/[0. Copyright © The Regents of the University of California.0M) ------.0] =0.029V . we can insert the concentration of the species.0.20M) + Ag(s) Use the Nernst equation E_{cell}= 0. and E° cell can be represented by the following diagram.0592V/1)log [Fe3+]/[Fe2+][Ag] =0.

? Cu(s) Cathode.? Cu(s) 3.(-0.where • • • • R = 8. Reduction (since 2+ Cu (aq) decreases oxidation state from +2 to 0) 2.from balanced redox reaction F = Faraday's constant = 96.340 .340 Copyright © The Regents of the University of California.E°anode = 0.314 J mol C-1 T = Temp in K n = moles of e.103 V -0.763 +0. Determine the E° cell values using the standard reduction potential table Zn(s) ? Zn2+(aq) + 2eCu2+(aq) + 2e.763) = 1. Davis 4 . Oxidation (since Zn(s) increase oxidation state from 0 to +2) Cu2+(aq) + 2e. Use E° cell = E°cathode .485 C/mol E°cell can be calculated using the following formula: E°cell = E° (cathode) – E° (anode) = E°(Reduction) – E°(Oxidation) Example Question Find the E° cell for the following coupled half-reactions Solution 1. Determine the cathode and anode in the reaction Zn(s) ? Zn2+(aq) + 2eAnode.

314 x 298 x ln(2. Cr2+(aq) 2.81x10-16) = -8. Solution: Use the following formula: ∆G=-RTlnK = 8. Davis 5 . then the reaction is NOT spontaneous and therefore the reverse reaction is occuring and the electrons are flowing in the opposite direction.87x105 = 8. 3.81x10-16 for a following reaction Cu2+(aq) + Ag(s) ? Cu(s) + 2Ag+. Summary Table Eo cell >0 <0 =0 Delta G + =0 Q & K Relationship Q<K Q>K Q=K Reaction Direction Forward Backward No Reaction Spontaneity (as written) Spontaneous Non-spontaneous N/A Example Problems Example Using ∆G=-RTlnK Question: Given K = 2. Find E° cell for 2Br-(aq) + I2(s) ? Br2(s) + 2I-(aq) Find E° for Sn(s) ? Sn2+(aq) + 2eFind E° cell for Zn(s) | Zn2+(aq) || Cr3+(aq) . (See answer key for solutions) *If the E° values of the reaction is negative. find ∆G.871 kJ Copyright © The Regents of the University of California. * These values are tabulated in the standard reduction potential table.Problems 1.

676V +1. the RT is a constant then the following equation can be used: E°cell= (0. we can conclude the number of moles of e .741 V Step 5: Once E° cell has be calculated and the number of moles of electrons have been determined. we can use ∆G = -nFE°cell = (-6 mol e-)(96458 C/mol e-)(2.741 V) = -1586kJ Example Using E° cell=(RT/nF) lnK This equation can be used to calculate E° cell given K or K given E° cell. H. If T=298K.+ 3Br2(l) ? 6Br-(aq) Step 3: From the balanced half reactions.025693V/n) ln K Copyright © The Regents of the University of California.065V Step 4: Determine E°cell = E°cathode .for use later in the calculation of ∆G. 1M) Find ∆G of the reaction Solution: Step 1: Separate the reaction into its two half reactions 2Al(s) ? 2Al3+(aq) 3Br2(l) ? 6Br-(aq. 1M) + 6Br-(aq. 1M) Step 2: Balance the half equations using O.(-1. Davis 6 . Determine the E° values using the standard reduction potentials. and charge using e2Al(s) ? 2Al3+(aq) +6e6e.E°anode.065 . 2Al2(s) ? Al3+(aq) +6e3Br2(l) + 6e. using the E° cell table.676) = 2.Example Using ∆G=-nFE°cell Question: Consider the following equation: 2Al(s) +3Br2(l) ? 2Al3+(aq. = 1.? 6Br-(aq) -1.

E° cell = E°cathode.34 = (0.(-2. Label which one is reduction and which one is oxidation.025693) K = 3.x 96458C x 4.15 = -800.19 x 10-12 Example Given the following reaction determine ∆G.? K(s) Step 2: Reduction Oxidation +1.92) = 4.92V Write net balanced reaction in acidic solution.60kJ Copyright © The Regents of the University of California. E° cell = -0. and determine the E° cell.34V. MnO2(s) + 4H+(aq) + 2e ? -Mn2+(aq) + 2H2O(l) K+(aq) + e. Davis 7 . Find the corresponding E° values for the half reactions. Solution: Step 1: Split into two half reaction Cu(s) ? Cu2+(aq) 2H+(aq)? H2(g) Step 2: Balance the half reactions with charges to determine n Cu(s) ? Cu2+(aq) + 2e2H+(aq) +2e.15 Mn2+(aq) + 2K+(aq) + 2H2O(l) ? MnO2(s) + 4H+(aq) + K(s) E° cell = 4.15V Step 3: Find ∆G for the reaction. Use Delta G = -nFE°cell = -2 mol e. find the equilibrium constant (K) for the reaction.34V -0.23 .E°anode = +1. and Eo cell for the following reaction at standard conditions? Is this reaction spontaneous? Mn2+(aq) + K(s) ? MnO2(s) + K(aq) Solution Step 1: Separate and balance the half reactions.Question: Given the E° cell for the reaction Cu(s) + 2H+(aq) ? Cu2+(aq) +H2(g) is -0.? H2(g) Therefore n=2 Step 3: From the example above.34 x 2/0.025693/2) lnK K = e(-0. K.23V -2.

Englewood Cliffs.68 kJ 5.4 x 10^25 6.195V References 1.? 2I-(aq) (See answer key for solutions) Answer Key 1. Inc. Gho. +0. Gesser. +0. Eugene Jr. John R. Brady. Shamsher Singh This page viewed 61747 times The ChemWiki has 6630 Modules.137V 3.? 2F-(aq) Li+(aq) + e. +0. Prentice-Hall. H. Find the equilibrium constant (K) for the following reaction: (Hint: Find E°Cell first!) Zn(s) + 2H+(aq) ? Zn2+(aq) + H2(g) 6.V.? Li(s) 5. Find ∆G for the following combined half reactions: F2(g) + 2e.New Jersey.339V 4. Brown.? Cu(s) I2(s) + 2e. 07632 1991 4. James E. “ Descriptive Principles of Chemistry”. 6. Find E°Cell for the given reaction at standard conditions: Cu+(aq) + e.Therefore. Bursten.. Contributors • Deborah S. Hyman D. LeMay. Theodore L. Theodore L.530V 2. 2007. Problems 4. Jeffry. Herring. +1139. Davis 8 . Bruce E. Inc. and Petrucci. Englewood Cliffs. H. John Wiley & Sons Inc 1993 2. Eugene Jr. N. 07632 1985 3.. Holum. Upper Saddle River. “Chemistry: The Study of Matter and Its Changes”. Harwood. The ChemWiki was viewed a total of 14338011 times Copyright © The Regents of the University of California. Mosby Company 1974 5. LeMay.J. General Chemistry: Principles and Modern Applications. +0.. Ninth Edition. “Chemistry: The Central Science” Fifth Edition. N. C. Ralph. Brown. “Chemistry: The Central Science” Third Edition. Geoffrey.. Pearson Prentice Hall. William. since Eocell is positive and ∆G is negative. Madura. this reaction is spontaneous.J. Prentice-Hall.