Electrochemistry Electrochemistry brings together two topics you have already learned: Redox Reactions Thermodynamics To learn about

ut how to use chemical reactions to do work. Electrochemical cells: Batteries: Storing energy using electrochemical cells Corrosion: Unwanted electrochemical cells Electrolysis and electroplating calculations
Petrucci 5.4

Review of redox reactions What you (should) know about redox reactions from Chem 2A: Redox reaction involves transfer of electrons Reduction oxidation Oxidation is loss of electrons Reduction is gain of electrons Oxidizing agent: gains electrons, therefore is reduced itself (causes oxidation) Reducing agent: losses electrons, so is oxidized (causes reduction) An oxidation and reduction must always occur together Redox reaction may all seem very different, but on a molecular level they all involve the transfer of electrons and hence a change in oxidation states Remember OILRIG

Oxidation Is Loss Reduction Is Gain (of electrons)

Examples of redox reactions Some redox reactions have an obvious transfer of electrons Zn (s) + 2 Ag+ (aq) Zn2+ (aq) + 2 Ag (s)

Zn (s) looses two electrons (is oxidized ) Each Ag+ ion gains an electron (is reduced ) Other times it is less obvious because it happens along with breaking and making of chemical bonds CH4 + 2O2 Oxidation: CH4 + 2H2 O
+

CO2 + 2H2 O C looses 8 electrons

CO2 + 8e + 8H+ 4H2 O

Reduction: 8H + 8e + 2O2
Petrucci 11 + 18

Each O gains 2 electrons

Thermodynamics Two driving forces for chemical reactions, Energy (U ) and Entropy (S) Minimize energy Maximize entropy Gibbs free energy Combine energy and entropy change G = H T S A reaction is spontaneous if G < 0 and at equilibrium if G = 0 Gand Spontaneity aA + bB cC + dD Gr = G + RT lnQ r G = r p G (products) f r G (products) f G = cG (C) + dG (D) aG (A) + bG (B) r f f f f G < 0 Reaction is spontaneous in forward direction at current concentrations G > 0 Reaction is spontaneous in backward direction at current concentrations 2

The reaction quotient, Q {C}c {D}d Q= {A}a {B}b {A }, {B }, {C }, {D } are the activities of A, B, C, and D, respectively In solution: [A]/c Gases: {A} =

{A} = PA /P

Solids: {A} = 1 1 for near ideal solutions and gases. P is the pressure in the reference state (1 bar). Likewise c = 1 M. Thermodynamics Work Chemical reactions can do work The energy released during a reaction is released as either heat and/or work U = q + w The size of q and w depends on how the reaction is carried out The maximum amount of work that can be done by a chemical reaction (at constant pressure) equals G Energy transfer during a redox reaction To harness the intrinsic chemical energy stored in these oxidizing and reducing agents, we must separate them to force the electrons to ow though an external circuit and do some work. Zn(s) + Cu
2+

(aq) Zn
Gf =

2+

(aq) + Cu(s)

p Gf (products)

r Gf (reactants)

= (147.1 kJ/mol + 0 kJ/mol) (65.49 kJ/mol + 0 kJ/mol) = 212.59kJ/mol

Gr = Gr + RT ln Q Zn 2+ Q= Cu 2+

All energy is in this conguration released as heat

Petrucci 19.1

Galvanic cell: Spontaneous redox reaction generate electricity Spontaneous G < 0. Produces electricity (Batteries, etc.) 3

 Electrolytic cell: Non-spontaneous redox reaction is driven by electric current NON-spontaneous G > 0 DRIVEN by electricity. (Charging of batteries, electroplating, etc) Electrochemistry Overview Chem2A knowledge: Redox reactions How to identify redox reactions Oxidation state How to balance redox reactions (acidic and basic environment) Utilizing redox reactions: Electrochemical cells Galvanic cells (spontaneous reaction generates electricity) Electrolytic cell (driving non-spontaneous redox reactions with electricity) Chem2B knowledge: Thermodynamics and chemical equilibrium Gibbs free energy work Spontaneous and non-spontaneous reactions Equilibrium constant Concentration dependence of G The connection between Ecell , G, and K Nernst equations USE
Petrucci 3.4

Oxidation States Binary ionic compounds Metal + non-metal Electronegativity difference between metal and non-metal so large that we assume that the electron is 100% located at the non-metal

 Molecular compounds The electrons are shared between atoms

Oxidation states Book keeping method, that is not necessarily the same as the actual electric charge on an atom. It is only a formalism, but a very useful one! Imagine each atom in a molecule, formula unit, or polyatomic ion in ionic form: The O.S. is the imaginative "charge" on each "ion" Not necessarily the same as the actual electric charge on an atom. It is only a formalism, but a very useful one! For purely ionic compounds the oxidation state does equal the formal charge For example NaCl (Na+ and Cl ), CaBr2 (Ca2+ and Br ) not HCl and Cl2 The oxidation number refers to an atom, not to a molecule or polyatomic ion Examples of Different Oxidation States of Nitrogen

N has 5 valence electrons (Ox=0)

E.N.(N) >E.N.(H) All shared electrons goes to N N now has total of 8 electrons 3 more than neutral Ox =3

E.N.(O) >E.N.(N) All shared electrons goes to O N only has 2 electrons left 3 less than neutral Ox =+3

E.N.(O) >E.N.(N) All shared electrons goes to O N has no electrons left 5 less than neutral Ox =+5

Identical atoms, no "winner" Electrons are equally shared N only has 5 electrons Same as neutral Ox =0

E.N.(N) >E.N.(H) The electrons in NH bond goes to nitrogen Between identical N atoms, no "winner" Electrons are equally shared in NN bond Each N has 7 electrons 2 more than neutral Ox =2

1. In compounds, sum of oxidation numbers equals molecular charge 2. Oxidation state of free element is 0 3. For ions composed of only one atom, oxidation number equals charge 4. The alkali metals (row 1) in compounds are assigned and oxidation state of +1 5. The alkali earth metals metals (row 2) in compounds are assigned and oxidation state of +2

6. Fluorine is assigned oxidation state of 1 7. Hydrogen has an oxidation state of +1 except when bonded to metals in binary compounds when it is 1

8. Oxygen is assigned oxidation state of 2 except in peroxides when it is 1 9. In any binary (two-element) compound with metals, group VIIA have oxidation state of 1 group VIA have oxidation state of 2 group VA have oxidation state of 3

Use rules in order! Trends in oxidation states

Example 1

Oxidation States CO2 NH+ 4 SO2 4 SnBr4 NaClO4 P2 O5

Petrucci 5.4

Identifying redox reactions Assign oxidation numbers. If they change the reaction is a redox reaction Oxidation of zinc by Copper(II) ions: Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s) Oxidation of zinc by oxygen: 2 Zn (s) + O2 2ZnO (s)

Example 2

Identifying Redox Reactions Identify which of the following reactions are redox reactions 1. Ca (s) + Cl2 (g) CaCl2 (s)

2. CaCl2 (s) Ca2+ (aq) + 2 Cl (aq)

3. CH3 COOH (aq) + NaOH (aq) H2 O (l) + NaCl (aq)

4. 2Fe2 O3 (s) + 3 C (s) 4 Fe (s) + 3 CO2 (g)

Half reactions A redox reaction consists of two half-reactions: An oxidation reaction that produces electrons and a reduction reaction consumes electrons For example: Oxidation Zn (s) 2+ Reduction Cu (aq) + 2 e Overall Zn (s) + Cu2+ (aq) Zn2+ (aq) + 2 e Cu (s) Zn2+ (aq) + Cu (s)

Disproportionation Reactions Redox reactions where the same compound is being oxidized and reduced. Example: Reaction to prepare bleach 2NaOH (aq) + Cl2 (g) NaCl (aq) + NaClO (aq) + H2 O (l) In this case Cl2 acts both as oxidizing and reducing agent
Ox. Red. 1/2 Cl2 (g) + NaOH (aq) + OH (aq) 1/2 Cl2 (g) + NaOH (aq) + e 2NaOH (aq) + Cl2 (g) NaClO (aq) + H+ (aq) + e NaCl (aq) + OH (aq) NaCl (aq) + NaClO (aq) + H2 O (l)

Petrucci 5.5

How to balance Redox reactions in acidic environment 1. Write half reactions Identify oxidized and reduced species 2. Balance elements other than H or O, if any. 3. Balance O by adding H2 O molecules. 4. Balance H by adding H+ . 5. Balance charge by adding electrons. 6. Add the two half reactions 7. Cancel common terms 8. Recheck!!
Example 3

Balancing redox reactions Balance the following reation in acidic environment Fe2+ (aq) + Cr2 O7 2 Fe3+ (aq) + Cr3+ (aq) Ox. reaction: Red. reaction: (Fe2+ Fe3+ (aq) + e ) 6 Cr2 O2 + 14H+ + 6e 2 Cr3+ + 7H2 O 7

Cr2 O2 + 14H+ + 6Fe2+ 6Fe3+ + 2 Cr3+ + 7H2 O 7 How to balance Redox reactions in basic environment Balance reaction as in acidic solution To both sides of the equation, add OH to equal the number of H+ Form H2 O from H+ + OH , eliminate H2 O molecules that appear on both sides of the equation.
Example 4

Balance redox reaction in basic environment Balance the following reation in basic environment Fe2+ (aq) + Cr2 O7 2 Fe3+ (aq) + Cr3+ (aq) Cr2 O2 + 7 H2 O + 6Fe2+ 6Fe3+ + 2 Cr3+ + 14OH 7

Example 5

Balancing Disproportionation Reaction Balance the following redox reaction is basic solution ClO2 (aq) Cl (aq) + ClO (aq) 3 Ox. reaction: ClO2 + H2 O ClO + 2 H+ + e add OH : ClO2 + H2 O+ 3 2OH ClO + 2 H+ + 2 OH + e Neutralize: ClO2 + 2OH ClO + 3 3 H2 O + e Red. reaction: ClO2 + 4H+ + 5e Cl + 2 H2 O add OH : ClO2 + 4H+ + 4OH + 5e Cl + 2 H2 O+ 4 OH Neutralize: ClO2 + 2H2 O+ 5e Cl + 4 OH 6ClO2 + 6OH 5ClO + Cl + 3H2 O 3 Electrochemical Cell

Cu 2+ + 2 e Cu Zn Zn 2+ + 2 e cathode reduction anode oxidation

Petrucci 19.1

An electrochemical cell consists of two electrodes, an anode and a cathode Oxidation occurs at the anode (by denition) Reduction occurs at the cathode Saltbridge required so "counter ions" ow into half cells to maintain neutral charge as electrons ow from one cell to the other. Electrons move from anode (oxidation) to cathode (reduction). compensate for this movement of negative charge: negative counter ions move from cathode to anode positive counter ions move from anode to cathode. Simple salt bridge can be wet lter paper (allows diffusion) 10 To

Anode & Cathode How to remember?

Red Cat

An Ox

Reduction at Cathode

Anode oxidation

Galvanic cell: Spontaneous redox reaction generate electricity Spontaneous G < 0 Electrons build up where they are generated, i.e. at the anode anode is negative for a galvanic cell Electrons are consumed in reduction reaction, i.e. at the cathode cathode is postive for a galvanic cell Produces electricity (Batteries, fuelcells, etc.) Electrolytic cell: Non-spontaneous redox reaction is driven by electric current NON-spontaneous G > 0 DRIVEN by electricity. Electrons must be added to electrode where reduction is driven to occur cathode is negative for an electrolytic cell Electrons must be removed to electrode where oxidation is desired anode is positive for an electrolytic cell Charging of batteries, electroplating, etc Measuring Cell Potentials The production and consumption of electrons at the anode and cathode, respectively, builds up a potential between the electrodes that can be measured with a voltmeter

11

Measuring Height Differences

Petrucci 19.2

Cell Potential (Ecell )

Cell voltage: Ecell = Eox + Ered e pulling potential (Ered ) Cu2+ + 2 e Cu (s) e pushing potential (Eox ) Zn (s) Zn2+ + 2e

12

Standard Electrode Reduction Potentials It would be very convenient to be able to assign a potential to every halfreaction. In that way we could always calculate Ecell for any given reaction as Ecell = Eox + Ered No need to know absolute potential, we only need it relative to a standard. All half cell potentials are measured relative to the standard hydrogen electrode (SHE) Half cell potentials depends on concentration. Table values are for reactions at standard conditions.
From table values we can calulate the the standard cell potential, Ecell : Ecell = Eox + Ered

Standard Hydrogen Electrode The half-cell potential is arbitrarily set to zero for the standard hydrogen electrode (SHE) Pt electrode Bubble Hydrogen gas at 1 bar pressure H+ activity = 1 (a = 1, c 1M)

2 H+ (a = 1) + 2 e H2 (g, 1 bar) Oxidation vs. Reduction Potential If a reaction is inverted the (half) cell potential changes sign

Zn(s) Zn 2+ (aq) + 2 e Cu 2+ (aq) + 2 e Cu(s) Zn(s) + Cu 2+ (aq) Zn 2+ (aq) + Cu(s)

E = 0.763V E = 0.340V Ecell = 1.103V

Zn 2+ (aq) + 2 e Zn(s) Cu(s) Cu 2+ (aq) + 2 e Zn 2+ (aq) + Cu(s) Zn(s) + Cu 2+ (aq) 13

E = 0.763V E = 0.340V Ecell = 1.103V

Table values (usually) listed as reduction potentials It is attempted by convention to make the table values reduction potentials only. To get the oxidation potential for the reaction occurring at the anode the sign must be inverted. The formula Ecell = Ecat Ean uses the reduction potentials for both reactions The formula is hence identical to the formula Ecell = Ered + Eox which refers to the oxidation potential for the reaction occuring at the anode. Use whichever form you like, just make sure you understand the difference. Measuring Half cell reduction potentials

Cu2+ (aq) + 2e Cu (s)

ECu2+ /Cu = +0.34 V

Cu2+ (aq) + H2 (g) Cu (s) + 2 H+ (aq) spontaneous at standard conditions

Zn2+ (aq) + 2e Zn (s) EZn2+ /Zn = 0.763 V

Zn2+ (aq) + H2 (g) Zn (s) + 2 H+ (aq) NON-spontaneous at standard conditions

14

15

Example 6

Redox Potentials

What is the stronger oxidizing agent, I2 (s) or Br2 (l)?

Is the oxidation of Fe2+ by O2 spontaneous at standard conditions?

Example 7

The Behavior of Metals Toward Acids Which metals can be oxidized by H+ ?

Example 8

The oxidation of Ag by Nitric Acid Explain why Ag can be oxidized by HNO3 , but not by HCl

Cell Diagrams

Zn | Zn2+ (1M) || Cu2+ (1M) | Cu (s)

Single line (|) denotes phase boundary Double line (||) denotes boundary between half compartments (salt bridge) Different species in same phase are separated by commas 16

 Anode always at the left Remember A(node) comes before C(athode)

Example 9

Cell diagram for Calomel electrode Write the cell diagram for the cell shown in the picture

Oxidation Reduction Overall

2 Hg (l) + 2 Cl (aq) Hg2+ (aq) + 2 e 2

Hg2 Cl2 (s) + 2 e 2 Hg (l)

Example 10

Cell diagram for standard hydrogen electrode Write the cell diagram for the following cell:

Oxidation Reduction Overall

1/2 H2 (g) 3+ Co (aq) + e 1/2 H2 (g) + Co3+ (aq)

H+ (aq) + e Co2+ (aq) H+ (aq) + Co2+

17

Example 11

Electrochemical Cell An electrochemical cell is based on the following reaction: 2 Ag (s) + Mg(NO3 )2 (aq) Mg (s) + 2 AgNO3 (aq) 1. What reaction occurs at the anode? 2. What reaction occurs at the cathode?
3. What is the cell potential, Ecell ?

4. Is this an electrolytic or galvanic cell? 5. Write the cell diagram (a) Draw the cell (b) Show the direction of electrons (c) Designate anode and cathode and the sign of each electrode (d) Show the direction of ions
Petrucci 19.3

Thermodynamics Electrochemistry Gr is the maximum amount of non-expansion work which can be extracted from a closed system welec = nF Ecell =

F is Faradays constant which is the charge per mol electrons (96,485 C/mol) n is the number of electrons transferred in the reaction Gr = nF Ecell
G = nF Ecell r

Gr is an extensive property (depends on the size of system, and hence how the reaction is balanced)
Ecell is an intensive property and does NOT depend on the size of the system

To determine n look at how many electrons are transferred in the half reactions that add up to the overall equation

18

Example 12

How to determine n Balance the following reactions and determine n: 1. 2 Fe2+ (aq) + Cl2 (g) 2 Fe3+ (aq) + 2 Cl (aq) 2. CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2 O (l)

Extensive vs intensive properties Intensive properties DOES NOT vary with size of system

Extensive properties DOES vary with size of system

G vs. Ecell Gibbs free energy depends on how the reaction is balanced, the cell potential does not. H2 (g) + 1 O2 (g) H2 O(g) 2
G = G (H2 O(g)) (G (H2 (g)) + 1/2G (O2 (g))) r f f f
Ecell

n=2

= 228.6 kJ/mol G (228.6 kJ/mol) r = = = 2.36 V nF 2 96485 C/mol

2 H2 (g) + O2 (g) 2 H2 O(g)

G = 2G (H2 O(g)) (2G (H2 (g)) + G (O2 (g))) r f f f
Ecell

n=4

= 457.2 kJ/mol G (457.2 kJ/mol) r = = 2.36 V = nF 4 96485 C/mol

19

 Relationship between the cell potential Ecell , Gibbs free energy G , and the r equilibrium constant K

Example 13

Zincs reaction with Iodide Determine the EMF (electromotoric force = cell potential) and G for the folr lowing reaction under standard conditions Zn (s) + I2 (s) Zn2+ (aq) + 2I (aq) what is the equilibrium constant for the reaction? Use the table of reduction potentials in your textbook.

Petrucci 19.4

What about non-standard conditions? Gr = G + RT ln Q r Substitute cell potential

G = nF Ecell r

Gr = nF Ecell

nF Ecell = nF Ecell + RT ln Q

Rearrange and you get the Nernst equation:

Ecell = Ecell

RT ln Q nF ln Q = 2.3 log Q

Change bases for the logaritm

Ecell = Ecell

RT (2.3) log Q nF

20

At room temperature (T = 298 K): 0.0592V log Q n This is the way it was originally written by Nernst in 1889.
Ecell = Ecell

As a cell operates its potential decreases Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s) 0.0592V log Q n

Ecell = Ecell

Example 14

Electrochemical cell at non-standard conditions What is the cell potential for the following electrochemical cell? Pt (s) | Fe3+ (1 M), Fe2+ (0.2 M)|| Ag+ (0.1 M) | Ag (s)

Compare with example 199 in book: Pt (s) | Fe3+ (0.10 M), Fe2+ (0.2 M)|| Ag+
(1.0 M) | Ag (s) Ecell = 0.011V

21

Concentration Cells A concentration cell has the same half cells, only with different concentrations

Petrucci 19.5

Batteries Voltaic cells put in series so their individual voltage add together Egyptian Battery Anode: Cathode: Zn Zn + 2 e 2 H+ + 2 e H2
2+

Connecting Electrochemical Cells

Connecting cells in series (+ to ) voltages add up 22

 Connecting cells in parallel (+ to + and to ) current add up) Same as making the cell bigger Batteries Primary (non-rechargeable) batteries Alkaline, Mercury, Silver, Lithium Secondary (rechargeable) batteries Cell can be recharged by driving cell reaction backwards by applying electrical current Lead-acid, Nickel-Metal Hydride, Lithium ion Fuel cells Also called ow batteries These cells are not self contained, requires fuel to run Hydrogen cells Non-rechargable Battery Dry cell or Leclanche Cell In an acidic dry cell, the reduction reaction occurs within the moist paste comprised of ammonium chloride (NH4 Cl) and manganese dioxide (MnO2 ): 2 NH+ + 2 MnO2 (s) + 2 e Mn2 O3 (s) + 2 NH3 (aq) + 4 H2 O (l) The zinc cylinder serves as the anode and it undergoes oxidation: Zn (s) Zn2+ + 2 e The battery cannot be recharged because of the following reaction Zn2+ + NH3 (aq) + 2 Cl (aq) Zn(NH3 )Cl2 (s) In the alkaline version, the ammonium chloride is replaced by KOH or NaOH and the half-cell reactions are: Zn (s) + 2 OH (aq) 2 MnO2 (s) + 2 e + H2 O (l) ZnO + H2 O (l) + 2 e Mn2 O3 (s) + 2 OH (aq)

The alkaline dry cell lasts much longer as the zinc anode corrodes less rapidly under basic conditions than under acidic conditions.

23

Lead-acid Battery

An. Cat.

Pb (s) + HSO (aq) 4 PbO2 (s) + (aq) + + 3 H3 O (aq) + 2 e HSO 4

PbSO4 (s) + H+ (a) + 2 e PbSO4 (s) + 2 H2 O (l)

E = 0.296 V E = 1.628 V

Why does the cell not need separate anode and cathode compartments?

Why does electrodes have large surface area?

How come the lead-acid battery can be recharged?

Fuel Cells Fuel + Oxygen Oxidized product Fuel can for example be gasoline, methane (CH4 ), Hydrogen, metals Combustion of methane is a highly exothermic reaction CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2 O (l) + energy
An. Cat.
Petrucci 19.6

CH4 (g) + + 2 H2 O (l) 2 O2 (g) + 8H+ (aq) + 8e

CO2 (g) + 8 H+ (aq) + 8 e 4 H2 O (l)

Corrosion

Unwanted voltaic cell! Oxidizes metal to its oxide or sulde Not only iron can rust.

An. (ox.) Cat. (red.)

2 Fe (s) O2 (g) + 2H2 O (l) + 4 e 2 Fe (s) + O2 (g) + 2H2 O (l) 24

2 Fe2+ + 4 e E = 0.440 V 4 OH (aq) E = 0.401 V 2 Fe2+ + 4 OH (aq) Ecell = 0.841 V

 Rust (Fe2 O3 nH2 O) is not formed by the direct reaction between iron and air but by a series of reactions Fe2+ (aq) + 2 OH (aq) Fe(OH)2 (s) 4 Fe(OH)2 (s) + O2 (g) + 2 H2 O (l) Fe(OH)3 (s) 2 Fe(OH)3 (s) Fe2 O3 H2 O(s) + H2 O (l)

Iron can only rust if water is present Loss of iron and depositioning of rust often happens at different places on same object Iron rusts faster at low pH (high [H+ ]) Protection from Corrosion Iron rusts faster in contact with a less active metal (e.g. Cu) and slower in contact with a more active metal (e.g. Zn)

25

Petrucci 19.7

Electrolysis

Electrical energy drives non-spontaneous reverse reaction. The applied eld must be at least the cell potential In practice, the applied voltage must be much greater than the cell potential, called an overpotential. The extra voltage is needed to overcome kinetic barrier. Electrolysis of Water

Extremely pure water is hard to electrolyze because no ions are present to conduct the current Volume of H2 at Cathode is twice that of O2 at Anode

An. (ox.) Cat. (red.)

2 H2 O (l) ( 2 H2 O(l) + 2 e 2 H2 O (l)

O2 (g) + 4 H+ + 4 e H2 (g) + 2 OH (aq) )2 H2 (g) + O2 (g)

E = 1.229 V E = 0.828 V E = 2.057 V

Electroplating Electrolysis can cause metal plating on the cathode.

26

Cat. (red.) Ag+ + e Ag (s) Battery pushes electrons to cathode

E =0.800 V

The number of electrons "pushed" by the battery determines amount of product plated on the electrode Current time I t = Faraday s constant F Battery does not "supply" electrons. Oxidation reaction occurring at anode does. ne =
Example 15

Plating Copper What is the mass of Cu(s) plated at cathode when a 10.0 amp current ows for 30.0 min in the following setup? What reaction occurs at the Pt anode?

27

Example 16

Electrolysis of molten NaCl Two inert electrodes are placed in molten NaCl (melting point 801 C) a a voltage is applied to drive the reaction 2 NaCl (l) 2 Na (s) + Cl2 (g) 1. Write the half reactions and specify which one occurs at the anode and cathode, respectively 2. What is the minimum voltage required to drive the reaction assuming that no over potential is needed? 3. Draw the cell and show the direction of ions and electrons 4. Label anode and cathode with signs 5. How long does it take to produce 1.00 g of Na (s) at 10.0 A? 6. What reaction would occur if an aqueous solution of NaCl was used instead of molten NaCl?

28

Example 17

Cell diagram For the cell: Cu (s) | Cu 2+ || Br2 (g, 1 atm) | Br (1.0 M) | Pt (s) 1. Write the anode half reaction 2. Write the cathode half reaction 3. Draw the galvanic cell and show (a) the direction of electron ow (b) the direction of positive and negative counter ions (c) which electrode is positive and negative, respectively

Example 18

Cell Diagram from Reaction Write the cell diagram for a cell that uses the reaction: Mg (s) + 2H+ (aq) H2 (g) + Mg2+ (aq) A platinum electrode is used with the H+ /H2 couple and a salt bridge separates the two compartments Anode: Mg (s) Mg2+ = 2e Cathode: H+ + 2e H2 Mg(s)|Mg2+ (aq)|| H+ (aq) | H2 (g) | Pt(s)

Example 19

Write Reactions from Cell Diagram Write the chemical equation for the reaction corresponding to the cell Pt(s) | H2 (g) | H+ (aq) || Co3+ (aq), Co2+ (aq) | Pt (s)

Example 20

Galvanic Cell A working galvanic cell is based on the following half-reactions: Fe2+ (aq) + 2e Fe (s) MnO (aq) + 5e + 8H+ Mn2+ (aq) + 4 H2 O (l) 4 1. What is the cell reaction?
2. What is the cell potential, Ecell ?

E = 0.44 V E = +1.51 V

3. Write the cell diagram 4. Draw the cell 5. Show the direction of electrons 6. Designate anode and cathode 7. Show the direction of ions

29

Overview of Electrochemistry Review of redox reactions OILRIG Oxidation states Electrochemical cells Galvanic vs electrolytic cell Anode & cathode Saltbridge Cell diagram Cell potential Standard half cell reduction potential half reactions How to balance redox reactions in acidic and basic solution

The connection between Ecell , G , and K r

Spontaneous change Electrical work Concentration Cells Non-ideal conditions Batteries Primary vs secondary cells Dry cells Corrosion Corrosion protection Electrolysis Electroplating

Nernst equation

Measuring Ksp

Lead-acid battery Fuel cells

Quantitative calculations

30