Chapter 17 Electrochemistry

Electrochemistry  Electrochemistry is the study of batteries

GCC CHM152 and the conversion between chemical and
electrical energy.
 Based on redox (oxidation-reduction)
reactions in which one substance gains
electrons and another loses electrons.
 These two processes MUST happen together.
 Single replacement, combustion,
combination and decomposition rxns are all
examples of redox reactions.

Oxidation Numbers (Chapter 4). Ox # examples

 Free elements: ox # = 0 (H2(g), Hg(l), etc.)  Find ox numbers for all the atoms in HCO3-
 Ions in binary ionic compounds: ox # = charge.
 H: ox # = +1 O: ox # = -2
 Ex. For Al2S3, ox # for Al = +3, ox # for S = -2.
 H: ox # = +1, except when H is with alkali  1H + 1C + 3O = -1
metals it is -1 (LiH, NaH, etc.)  + 1 + C + 3x(-2) = -1
 O: ox # = -2, except in peroxides it is -1 (H2O2,
 Ox # for C = +4
K2O2)
 The sum of the oxidation numbers of all the  What is the ox # for Cr in Cr2O72-?
atoms in a molecule = 0  2Cr + 7O = -2
 For polyatomic ions, the sum of the oxidation  2Cr + 7(-2) = -2
numbers must equal the charge on the ion.
 Cr = +6

Redox: LEO the lion goes GER Zn(s) + Cu(NO3)2(aq)  Zn(NO3)2(aq) + Cu(s)
 Oxidation: loss of electrons; ox # , more +
 Reduction: gain of electrons; ox # , more − Zn(s)  Zn2+(aq) + 2e-
 oxidizing agent: substance that is reduced; it
caused oxidization of other substace. Zn(s) dissolves

 reducing agent: substance that is oxidized; it

caused reduction of other substance. Cu2+(aq) + 2e-  Cu(s)
 Zn(s) + Cu(NO3)2(aq)  Zn(NO3)2(aq) + Cu(s)
Cu plates on electrode
 Identify atom oxidized, atom reduced,
oxidizing agent and reducing agent.

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 Redox Reactions Balancing Redox Reactions
 What is oxidized/reduced, give the specific atom.  Cr3+(aq) + Be(s)  Cr(s) + Be2+(aq)
 Agents: give the whole substance as an answer.  First, break it up into two half reactions,
 MnO4-(aq) + 8H+(aq) + 5Fe2+(aq)  the oxidation and reduction half reactions.
Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)  Balance charge by adding electrons (e-) to
 For this reaction: the more positive side for each reaction.
 What is oxidized?  Oxidation: Be(s)  Be2+(aq) + 2e-

 What is reduced?  Reduction: Cr3+(aq) + 3e-  Cr(s)

 What is the oxidizing agent?

 What is the reducing agent?

Balancing Redox Rxns contd Types of Cells

 Balance electrons by multiplying each half  Galvanic cell (also called voltaic cell)
reaction by an integer so that the # electrons
gained = # electrons lost. Electrochemical cell in which a
spontaneous reaction generates electricity.
 Oxidation: (Be(s)  Be2+(aq) + 2e-)x3
 Reduction: (Cr3+(aq) + 3e-  Cr(s))x2
 Electrolytic cell
Electrochemical cell in which an electrical
 2Cr3+(aq) + 3Be(s)  2Cr(s) + 3Be2+(aq)
current is used to drive a nonspontaneous
reaction.

Batteries Galvanic Cells: Figure17.2

 Batteries are examples of galvanic cells we use

in everyday life.
 For a Voltaic cell the voltage keeps dropping as
the spontaneous reaction proceeds right.
 Battery is dead when Ecell = 0 (at equilibrium)
 Bigger batteries only last longer, they don’t
have more volts. Volts are determined by the
chemical reaction that occurs.

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 Galvanic Cells Dr. Lisa’s cell Mnemonic
 Oxidation occurs at the anode - both vowels  Fat red cat eats electons! e-
mass of anode decreases - it is dissolving as metal
atoms lose electrons to form ions in solution
 Reduction occurs at the cathode - both consonants
mass of cathode increases as metal ions are reduced
to form atoms that plate onto the cathode.  Anorexic ox spits them out!
 External Circuit - electrons flow from the anode to
the cathode via an external wire. e-
 Salt bridge - soluble salt solution in a bridge that
connects the two half cells; ions flow through the
bridge to complete the electrical circuit. Cathode is reduced (gains e-) & mass (plating)
Anode is oxidized (loses e-) & mass (dissolves)

What happens in Salt Bridge? Short-hand Notation

 Migration of ions maintains charge Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
neutrality in both compartments: Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
 Anions move into the anode where Anode | anode ion || cathode ion | cathode
excess + charge builds up as metal | indicates a phase boundary between two
cations are formed by oxidation. phases in the same cell.
 Cations move into the cathode where
|| denotes the salt bridge between the cells.
excess (-) charge builds up as the metal
 anode is always on the left side, and the cathode
cations are reduced to form neutral
on the right side.
metal atoms.
 Electrodes are always on the two ends

Shorthand Notation for Galvanic Cells Inert Electrodes

Anode half-reaction: Zn(s)  Zn2+(aq) + 2e-  Pt and graphite are typically electrodes for gas
phase and aqueous reactions.
Cathode half-reaction: Cu2+(aq) + 2e-  Cu(s)
 Ex. Standard Hydrogen Electrode (SHE) uses
Overall cell reaction: Zn(s) + Cu2+ (aq)  Zn2+(aq) + Cu(s) Pt electrode. (figure 17.4)
Salt bridge  SHE consists of Pt electrode in contact with 1
Anode half-cell cathode half-cell M H+ solution and H2 gas at 1 atm pressure
 H2(g)  2H+(aq) + 2e-
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

Phase boundary
Chapter 17/17 © 2012 Pearson Education, Inc.

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 Galvanic Cells - Pt electrode Electromotive Force
emf = Ecell = cell voltage:
 Figure 17.4 Electromotive force is the cell potential
measured in volts. This is the driving force that
pushes electrons away from the anode and
towards the cathode.
Joules = Coulombs x Volts
Ecell is measured in volts: V = J/C
coulomb - the quantity of charge that passes a
point in 1 sec when a current of 1 ampere flows.

Free Energy and Emf Standard Cell Potential, Eo

DG = -nFE  Gases at 1 atm, Solutions at 1 M,
n = number of moles of e- transferred Temperature at 298 K (25oC)
E = Emf of cell
 Standard potential for any galvanic cell is
F = Faraday's constant the sum of the half-cell potentials.
96500 Coulombs 96500 J
1F    Eocell = Eoox + Eored
1 mol e  V  mol e 
 All cell potentials are compared to hydrogen
spontaneous reaction: DG < 0 and E > 0 (SHE: standard hydrogen electrode)
nonspontaneous reaction: DG > 0 and E < 0  2H+ + 2e-  H2(g) Eored = 0 V
At equilibrium: DG = 0 and E = 0

Reduction Potentials Calculating Cell potentials

  
 We can use the table of Standard Reduction Ecell  Ered (cathode)  Eox (anode)
Potentials for reduction half reactions to
determine the cell potential of a galvanic cell. For the oxidation reaction at the anode,
 Table 17.1: All potentials are listed as make sure you reverse the reaction and
reduction potentials. change the sign for Eox, then add the
reduction and oxidation potentials.
 Oxidation potentials: reverse the reaction
 
and Eox (anode)   Ered (cathode)

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 Strength of Oxidizing Agents
 Oxidizing Agents:
 F2(g) + 2e-  2F-(aq) Eored = 2.87 V
 F2 has the most positive Eored value.
 F2 is the easiest to reduce. (It wants e-
the most!)
 Thus F2 is strongest oxidizing agent.

 As Eored, strength ox agent 

Strength of Reducing Agents Table 17.1 info continued

 Li+(aq) + e-  Li(s) Eored = -3.04 V  Active metals tend to be good reducing
agents. (red agent = ox = lose e-)
 Li has the most negative Eored value, so it
 Active nonmetals tend to be good oxidizing
is the easiest to oxidize.
agents. (ox agent = red = gain e-)
 Li(s) is strongest reducing agent.  E° is intensive; it does not depend on # of
 Li(s) wants to lose electrons, so reverse moles involved. Don't need to multiply E°
reaction occurs: by factor if coefficients of reaction are
changed.
 Li(s)  Li+(aq) + e- Eoox = +3.04 V

Cell Potentials Cell Potentials

 Based on their Eored values, determine the  Ni(s) is the easiest to oxidize, best
best oxidizing agent, best reducing agent, reducing agent.
worst oxidizing agent, and worst reducing  Au3+ is the easiest to reduce, best
agent. oxidizing agent.
 Au3+ + 3e-  Au(s) Eored = 1.50 V  Au(s) is the hardest to oxidize, worst
 Br2(l) + 2e  2Br (aq)
- - Eored = 1.07 V reducing agent.
 Pb2+ + 2e-  Pb(s) Eored = -0.13 V  Ni2+ is the hardest to reduce, worst
 Ni + 2e  Ni(s)
2+ - Eored = -0.25 V oxidizing agent.

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 Cell Potentials Cell Potentials in Reactions
What will Eocell be if we react Ni(s) with Au3+?
 Positive Eocell means the reaction is product-
favored and spontaneous.
 A negative Eocell means the reaction won’t
happen in the forward direction.
What will Eocell be if Pb2+ reacts with Br -?
 Therefore, we want two half reactions that
yield the most positive Eocell value.
 Assign rxn with more + Eored as cathode! Calculate Eocell for the following cell
 Eocell = Eored + Eoox Ni(s) | Ni2+(aq) || Br2(l), Br -(aq) | Pt(s)

Which are spontaneous?

Example: Cl2(g) + Zn(s) Cell Potentials of Reactions

For a spontaneous reaction (+ Eocell), write the If we were to make a Galvanic cell from
appropriate anode and cathode reactions: the following metals, which would act as
Cl2 (g) + 2 e- → 2 Cl- (aq) E°red = 1.36 V the anode and which as the cathode?
Zn2+ (aq) + 2 e- → Zn (s) E°red = -0.76 V Refer to table 17.1. Write the half-cell
 Cl2 (g) has more + E°red, so it’s the cathode reaction reactions and the overall balanced
reaction for each cell. Calculate Eocell for
Cathode: Cl2 (g) + 2 e- → 2 Cl- (aq) E°red = 1.36 V each one.
 Zn reaction is reversed for the anode:  Also calculate Eocell for each one.
Anode: Zn (s) → Zn2+ (aq) + 2 e- E°ox = +0.76 V  Fe(s) and Ni(s)
 The E°ox reaction is flipped so the sign is the opposite!  Cu(s) and Ag(s)
 Eocell = 1.36 + .76 = 2.12 V

The Nernst Equation: Calculate emf for

nonstandard conditions Standard emf & K
Recall: DG = DGo + RT ln Q  At equilibrium, E = 0 and Q = K (plug these
 Plugging in DG = - nFE and DGo = - nFEo conditions into Nernst Equation)
-nFE = -nFEo + RT ln Q RT RT
0  E  ln K E  ln K
RT nF nF
Nernst Equation: E  E  ln Q
nF J J
R  8.314 , F  96500
2.303RT J J K  mol V  mol e 
E  E  logQ R  8.314 , F  96500
nF K  mol V  mol e 
 At 298 K, E   0.0592 V log K
0.0592 V n
At 298 K: E  E  n
logQ

 Both [ ]’s & P’s can be plugged into Q; V = volts (unit)

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 Calculations Cell Potentials Summary
Calculate DGo for the Ni(s) + Au3+ reaction. (#4a)
 Positive Eocell value
 DGo is negative
 K is large
Calculate K at 25oC for Ni(s) + Br2 cell (#4c):  Reaction is product-favored

Ni(s) | Ni2+(aq) || Br2(l), Br -(aq) | Pt(s)  Negative Eocell value

 DGo is positive
 nFE    nE  
     K is small
 RT  or  0.0592 V 
   
K e K  10  Reaction is reactant-favored

The Nernst Equation Corrosion

A galvanic cell utilizes the following reaction:  The oxidative deterioration of a metal (i.e.,
2Ag+ + Pb(s)  Pb2+ + 2Ag(s) solid metal converted to ions).
a) Write the half reactions and calculate Eocell.  Rust formation is the corrosion of iron.

b) Write the short-hand notation for this cell.  Metals can be plated with non-reactive
metals to protect them (chromium, tin, or
c) Calculate the cell potential if [Pb(NO3)2] =
zinc are common).
0.88 M and [AgNO3] = 0.14 M.

Electrolysis Electrolysis of Water

 Electrolytic Cell: Electrical energy from an external
source (outlet or a battery) is used to force a
 Water doesn’t naturally decompose into
nonspontaneous redox reaction to proceed. hydrogen and oxygen.
 Molten salt: 2NaCl(l)  2Na(s) + Cl2(g)  2H2O(l)  2H2(g) + O2(g) Ecell = -1.23 V

 Cathode: 2Na+(l) + 2e-  2Na(s)

Anode: 2H2O(l) → O2(g) + 4H+(aq) + 4e-
 Anode: 2Cl-(l)  Cl2(g) + 2e-
 Ecell = - 4 V Cathode: 4H2O(l) + 4e- → 2H2(g) + 4OH-(aq)
 This reaction naturally wants to run in reverse
The electrodes are the still the same for
direction. We need more than 4 volts to drive this
electrolysis: (oxidation at anode, reduction at
reaction forward. Salts don’t normally decompose
cathode).
into elements.

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 Electrolysis Calcs Electrolysis Calculations
 Used to find mass or volume  How many grams of Cu can be collected in 1.00
of product produced by hour by a current of 1.62 A from a CuSO4 solution?
passing current through cell.  Reduction reaction: Cu2+ + 2 e-  Cu(s)
 Current: measured in Amps  Calculate coulombs: Current (C/s) x time (s) = C
A = C/s  C  mol e-  mol solid  g solid
1.62C 1 mol e  1 mol Cu 63.5g
 ampere: unit of electric current; 3600s     = 1.92 g Cu
s 96,500C 2 mol e  mol
rate of flow of e-.
 charge = current x time
 coulombs = amps x seconds  Worked Examples 17.10, 17.11; Problems 17.22, 17.23

Batteries Household batteries

 Lead storage (i.e., car batteries)  Dry-cell (or Laclanche) batteries

9V battery – sum of 1.5 Volts Ni-Cad Batteries - rechargeable

Positive
electrode:
NiOOH

Negative
electrode:
Cd

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Lithium Ion Batteries Fuel Cell
 Used for space travel, and in hydrogen fuel cars
 Reactants are stored external to the cell and
Positive electrode: introduced to the electrodes as they are
Lithium cobalt oxide needed.
 The reactants are usually gaseous, such as O2
and H2, or O2 and CH4, or O2 and NH3.
Negative electrode:  H2 + 2OH-  2H2O + 2e- Eo = 0.83 V
 O2 + 2H2O + 4e-  4OH- Eo = 0.40 V
Carbon
 2H2 + O2  2H2O Eo = 1.23 V
 Fuel cells in action

Fuel
Cell