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Chapter 20
Electrochemistry
Electrochemical Cell
Consists of electrodes which dip intoan electrolyte & in which a chem. rxn.uses or generates an electric current
Voltaic (Galvanic) Cell
Spont. rxn. - produces electrical energy
- current supplied to external circuit
Electrolytic Cell
electrical energy is used to drivean otherwise nonspont. rxn.
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I) Oxidation - Reduction Rx’s (Redox)
Involves loss of e! by one element & gain of e! by another element
Oxidation: lose e!
(inc. in oxidation #)
Reduction: gain e!
(dec. in oxidation #)
Oxidizing agent: substance that(oxidant) is reduced
Reducing agent: substance that(reductant) is oxidized
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Zn + Br2 Zn Br2
Zn Zn2+ + 2 e!
Zn lost e! Y oxidized
Br2 + 2 e! 2 Br!
Br gained e! Y reduced
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A) Oxidation Numbers
“Charge” an atom would have if both e! in each bond are assigned to the more electronegative atom.
1) Elemental Form
Cu, H2, O2, S8
ox. # = 0 (zero)
2) Monatomic Ion
ox. # = charge
Na+, Zn2+, Al3+, O2!, Br!
Group IA | + 1 (Always)
Group IIA | + 2 (Always)
Group IIIA | + 3 (usually)
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3) Hydrogen
H | + 1 (usually)
exceptions
hydrides, H | !1NaH , CaH2
4) Oxygen
O | !2 (usually)
exceptions
peroxides, O22! O | !1
H2O2 Na2O2
superoxides, O21! O | !1/2
KO2
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5) Fluorine
F | !1 Always
6) Halogens: Cl, Br, I
&1 except when combinedw. a more E.N. element
CBr4 : Br | !1
can be : !1, 0, +1, +3, +5, +7
ClO4! : +7
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7) Sum of ox. no.’s of atomsin neutral cmpds. =
0 (zero)
8) Sum of ox. no.’s of atomsin a polyatomic ion =
charge
9) Ox. no. can not be:
more positive than the group #
or
more negative than (group # ! 8)
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B) Examples
1) Ex 1: What is ox. # of N in NH3 ?
# xN + 3(+1) = 0
# xN = ! 3
2) Ex 2: What is ox. # of N in NO3! ?
# xN + 3(!2) = !1
# xN = + 5
3) Ex 3: What is ox. # of N in NO2! ?
# xN + 2(!2) = !1
# xN = + 3
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C) Redox Reactions
Involves transfer of e! betweenspecies or change in ox. # of atoms
Oxidation: inc. in ox. #(lose e!)
Reduction: dec. in ox. #(gain e!)
1) Ex 1: Combustion
CH4 + 2 O2 CO2 + 2 H2O
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2) Ex 2: What is being oxidized andreduced? What is the oxidizingagent and reducing agent? Howmany electrons are transferred?
P4 + 10 HClO + H2O 4 H3PO4 + 10 HCl
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III) Voltaic (Galvanic) Cells
Consists of 2 half-cells connectedby an external circuit.
Half-cell
portion of an electrochem. cellin which a ½-rx occurs
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Cell rxn : net rxn. which occursin the voltaic cell
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A) Half-cell Rxns
1) Anode (!)
Anode : electrode at whichox. occurs
ox. half-rx
Zn (s) Zn2+ (aq) + 2 e!
Zn2+ ions produced at electrode
- move away leaving e! behind
e! flow out of anode
(towards the cathode)
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2) Cathode (+)
Cathode : electrode at whichred. occurs
red. half-rx
Cu2+ (aq) + 2 e! Cu (s)
Cu2+ ions discharged at electrode
- removes e! from electrode
e! flow into the cathode
(appears to attract e!)
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Soln. on right has a ! chg.
Soln. on left has a + chg.
anions must move from
lt. rt.
Accomplishes 2 things
1) Carry chg.
2) Preserves electrical neutrality
Salt Bridge
tube of electrolyte in a gelconnected to the half-cells
- allows flow of ions but preventsmixing of the diff. solns.
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B) Cell Notation
Shorthand description of cell
1) Ions in soln.
Zn(s) * Zn2+(aq) 2 Cu2+(aq) * Cu(s)
anode salt cathode bridge
* vertical line is a phase boundary
begin & end w. electrodes
anode :
cathode :
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2) Gaseous Reactant or Product
use inert electrode
Zn(s) * Zn2+(aq) 2 Cl2(g) * Cl!(aq) * Pt(s)
anode salt cathode bridge
anode :
cathode :
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3) Ions in Diff. Ox. States
use inert electrode
Sn(s) * Sn2+(aq) 2 Sn4+(aq), Sn2+(aq) * Pt
anode salt cathode bridge
anode :
cathode :
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IV) Standard Cell (Electrode) Potentials
A) Electromotive Force
Work req. to move a charge froma region of low electric pot. energyto a region of high electric pot. energy.
w = charge × )P.E.
Joules = Coulombs C Volts
1 J = 1 C C V
)P.E. (V) : diff. in electric potential between 2 points
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work done by a voltaic cell tomove n moles of e! is given by:
wmax = ! n F Ecell
F : faraday constant, 9.65 x 104 C
charge on 1 mole of e!
Ecell : electromotive force (emf)
max. potential diff. between electrodes of a cell
)G = ! n F Ecell
NOTE : Spont. rxn.
)G < 0 Ecell > 0
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B) Cell (Electrode) Potentials
Ecell = Ered + Eox
Eox = ! Ered for reverse rxn.
Tabulate reduction pot.called electrode pot., Ered
Zn(s) Zn2+(aq) + 2 e! Eox = !EZn
Cu2+(aq) + 2 e! Cu(s) Ered = ECu
Ecell = ECu + (!EZn)
= ECu ! EZn
Ecell = Ecathode ! Eanode
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C) Standard Reduction Potentials
Standard emf : Eocell
emf of a cell understandard-state conditions
Standard reduction pot. Eored
reduction (electrode) pot. when conc.of solutes are 1 M & gas pressuresare 1 atm, at a specified temp.
- measured relative toa reference electrode
- standard H electrode (SHE)
2 H+ (aq) + 2 e! H2 (g)
EoH2
= 0.00 V
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D) Strengths of Ox. & Red. Agents
Arranged in table w. greatesttendency for red. at top
Strongest ox. agents are at theupper left (F2, S2O8
2!, H2O2)
Strongest red. agents are at thelower right (Li, Na, Mg, Al)
Note
For a spont. rxn the strongerox. & red. agents will bethe reactants
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1) Ex 1 : Which will be the strongerred. agent under standardconditions, Sn2+ (to Sn4+)or Fe (to Fe2+)
Eored (V)
Sn4+(aq) + 2 e! Sn2+(aq) + 0.154
Fe2+(aq) + 2 e! Fe(s) ! 0.440
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E) Calc. Cell emf’s from Std. Pot.
Eored (V)
Pb2+(aq) + 2 e! Pb(s) ! 0.13
Ag+(aq) + e! Ag(s) + 0.80
1) rxn. is spont. w. stronger red. agent(one most easily ox.) on left (asreactant), Pb
Reverse of Pb electrode rxn.
NOTE: For a voltaic cell the cathode must be rxn. w. more + Eo
red
- Ag electrode in this case
Pb(s) Pb2+(aq) + 2 e!
Ag+(aq) + e! Ag(s)
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2) Multiply rxn. 2 (Ag rxn) by 2to balance the e!
Eored NOT multiplied by factor
- intensive quantity
Pb(s) Pb2+(aq) + 2 e!
2 Ag+(aq) + 2 e! 2 Ag(s)
3) Add eqns to get overall cell rxn
Pb(s) + 2 Ag+(aq) Pb2+(aq) + 2 Ag(s)
Pb(s) * Pb2+(aq) 2 Ag+(aq) * Ag(s)
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4) Calc. cell potential, Eocell
Eocell = Eo
cathode ! Eoanode
= EoAg ! Eo
Pb
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