2.

3 Electrochemistry
Engr. Aaron Joseph J. Peñano

1
 Panalanging Ekumeniko ng URS
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Rizal System at sa buong sambayanan.

Gabayan po ninyo kami upang magampanan namin ang aming mga

tungkulin na ipinagkatiwala ninyo sa amin sa diwa ng tapat na
paglilingkod.

2
 Panalanging Ekumeniko ng URS
Ibuhos po ninyo sa amin ang mga biyaya upang lumago kami sa
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Itulot po ninyo na kayo ay manatili sa aming diwa, salita, at gawa sa

tuwina.
3
2.3 Electrochemistry
Engr. Aaron Joseph J. Peñano

4
Outline
2.3.1 Electrochemistry
2.3.2 Electrolytic Cell
2.3.3 Electrical Units
2.3.4 Faraday’s Laws
2.3.5 Voltaic or Galvanic Cell
2.3.6 The Nernst Equation
2.3.7 Equilibrium Constant from Redox Equations

5
2.3.1 Electrochemistry
▪ Electrochemistry - study of electricity and how it relates to chemical reactions
- electricity can be generated by movements of electrons from
one element to another in a reaction known as redox or
oxidation-reduction reaction1

Two Types of Electrolytic Conductance2,7

1. Electrolytic Cells - electrical energy causes
chemical reaction
2. Voltaic or Galvanic Cells - chemical reaction
produces energy

6
2.3.1 Electrochemistry

7
2.3.1 Electrochemistry

8
 2.3.1 Electrochemistry
Direction of Direction of
Current, I Current, I

Salt Bridge
Voltaic or Galvanic Cells Electrolytic Cells
- maintains electrical porous membrane Driver for the reaction to occur
neutrality salt bridge
- prevents cell from
rapidly reaching
equilibrium

glass tube salt bridge

Driver to
produce
electricity.

(-) because it is where e-
(+) because it draws to
the ions in the solution “feed” the reduction.
losses/transfers their e- It is inherently (+)
i.e. electroplating
spontaneous nonspontaneous The battery pumps e- The battery pumps e- into the
away from the anode cathode (making it negative)
(making it positive)
Electric current carried by electrons in wires and electrodes while by ions in the cell.

9
 2.3.2 Electrolytic Cell
Electric current, consisting of a flow of electrons, is Electrodes
passed through the cell. The cation (Na+) moves toward the
cathode. At this electrode, Na+ ions accept electrons to
form sodium metal:
Reduction at Cathode + -
At the anode, the anion (Cl-) loses electrons, to form
chlorine gas (Cl2):
Anode: Oxidation
In the cell, electrons move from the anode through the
external circuit to the cathode. The anions move toward the
anode, where oxidation takes place. The cations move
toward the cathode where reduction takes place.
These reactions only takes place because of the conducts current
electrical energy supplied to the system. Also, both
oxidation and reduction must take place in the cell:
electrons lost by one substance must be gained by another.

10
2.3.2 Electrolytic Cell
Sample Reactions
Anode Reactions (Oxidation) Cathode Reactions (Reduction)
1. Oxidation of an anion to an element 1. Reduction of cation to a metal

2. Oxidation of an anion or cation in solution to 2. Reduction of an anion or cation in solution to

an ion of higher oxidation state an ion of lower oxidation state

3. Oxidation of a metal anode 3. Reduction of a nonmetal to an anion

4, Oxidation of H2O to produce oxygen 4. Reduction of H2O to produce hydrogen gas

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2.3.2 Electrolytic Cell
In particular electrolytic cells, there are often possible reactions that could
take place. For example, in any aqueous solutions there is always the possibility
of the water being oxidized or reduced more readily than the cation or anion
present.

Hydrogen gas produced at the cathode and chlorine gas at the anode.

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 2.3.3 Electrical Units2
▪ Resistance - offered when current passes through a conductor
- hindrance to the flow of charge affected by the length
of the wire (length of travel), cross-sectional area of
the wire (flow area) and the material of the
conductor4
- the greater the resistance, the poorer the conductance Conductor - electrons of outermost shell are attracted by
weak electrostatic force3
Water - offers high resistance; poor conductor - electrons jump from one atom to another3
HCl - low resistance; good conductor
Cu - good conductor
S - practically a nonconductor

▪ The SI derived unit for electrical resistance R is the ohm (Ω)

Positive charges move with the electric field while

electrons move in opposition.5

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 2.3.3 Electrical Units2
▪ Current - flow of charges from one region to another4,5
- rate at which a certain quantity of charge Q passes through a cross
sectional area (such as a wire) in a certain amount of time t.5
Q
I=
t
where: I = electric current in ampere (A in SI)
Q = quantity of electricity (C in SI or Ampere-second or A-s)
= current of one ampere flowing for one second
▪ Electrical Potential
For current to pass from one point to another through a conductor, a
difference of potential or electromotive force (emf or E) must exist. Electricity will
pass from a region of high potential to one of lower potential.
E where: E = electrical potential or electromotive force (V in SI)
I= = potential which will drive current of 1 A through a
R resistance of 1 Ω Conductor - electrons of outermost shell are attracted by
R = electrical resistance (Ω in SI) weak electrostatic force3
- electrons jump from one atom to another3

14
2.3.3 Electrical Units2
Factors Affecting Resistance
▪ Temperature
▪ resistance increases with temperature probably due to increased vibrations of metal-ions about their lattice
positions (solids)
▪ metal conductance increases at lower temperatures (solids)
▪ for electrolytic solutions (liquid), increase in temperature causes increase in kinetic energy of the ions offering
less resistance to their movement

▪ Concentration of Ions
▪ for electrolytic solutions, the conductance depends on the molality of ions:
▪ interionic attractions (greater in concentrated solutions than in dilute)
▪ solvation of ions
▪ solvent viscosity
▪ ionic charge
In an electrolytic solution, there is an equal charge of anions and cations to give electrical neutrality. During electrolysis,
there is some concentration built up near the respective electrodes–anions at the anode and cations about the cathode.

15
 2.3.4 Faraday’s Laws2
According to Michael Faraday (1833),
During electrolysis:
1. the quantities of substances produced at the electrodes are directly proportional to the quantity of electricity
passing through a solution 𝑦 𝐴+𝑎
(𝑎𝑞) + 𝑧 𝑒
−
→ 𝑥 𝐴(𝑠) i.e. electroplating of metal A on an electrode by
reduction of metal ions (A+a)
mM α Q
2. when a given quantity of electricity is passed through solutions of several electrolytes, the weights of substances
formed at the electrodes are directly proportional to their equivalent weights
MM where: Q = amt. of charge in C
mM α M E ME = z mM = mass of an atom/molecule/ion, g
z = number of electrons transferred (gained/lost)
Faraday’s two laws of electrolysis may be combined into a single expression = mol of e- transferred/x mol A(s)
Q α mM 1 Q = total change of oxidation number (abs. number)
stoich. factor from chem. equation mM = F × MEQ I = t ; Q = It = equivalents/mol of M (matter, atom/ion/molec.)
units: Cαg (1 equivalent = 1 mole of e-)
MEQ ME = equivalent weight
x mol A(s) 1 mM = F = qNA = 96,485 C /mol e - MM = molec./atomic/ionic wt. of M
Getting mM for A(s): mM = MM∙ z mol e− ∙ F ∙ Q F (atom/molec./ion)
q = charge of 1 e-
MM Q F = Faraday’s constant (1 F = 96,485 C)
g A(s) mol A(s) mol e− = 1.60217662×10-19 C/e-
mol A(s) ∙ mol e− ∙ 96,485 C ∙ C
units: g = mM = N = Avogadro’s constant
= amt. of electricity carried by 1 mol of e-
zF A
23 -
-
- = 96,485 C/mol e , 96,485 C/6.022x10 e
23 -
= 6.0221415×10 e /mol e

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 2.3.4 Faraday’s Laws2
Sample Problem 1 𝑦 𝐴+𝑎
(𝑎𝑞) + 𝑧 𝑒
−
→ 𝑥 𝐴(𝑠)
Calculate the equivalent weight of each of the following:
(a) Aluminum x=1
(b) Fe, in the reaction Fe → Fe2+ + 2e- 𝑔𝑀
(c) Fe, in the reaction Fe3+ + 3e- → Fe MM 𝑚𝑜𝑙 27.0 𝑔 𝑀 1 𝑚𝑜𝑙 𝑀
ME = = 𝑧 𝑚𝑜𝑙𝑀𝑒− = ×
(d) Fe, in the reaction Fe3+ + e- → Fe2+ z 𝑚𝑜𝑙 𝑀 𝑧 𝑚𝑜𝑙 𝑒 −
1 𝑚𝑜𝑙 𝑀
Solution (Problem was not specific if equivalent weight of atom or ion, x or y but it’s usually the atom; one with no charge):
(a) Al → Al3+ + 3e- (Al always release 3 e-), z=3; x=1: 1 equivalent = 1 mole of e- Al → Al3+ + 3e- Al3+ + 3e- → Al
27.0 𝑔 𝐴𝑙 1 𝑚𝑜𝑙 𝐴𝑙
ME = 𝑚𝑜𝑙 𝐴𝑙 × 3 𝑚𝑜𝑙 𝑒 − = 9.00 g/mole e- or 9.00 g/equivalent y=1 z=3 x=1
(b) z = 2; x =1: Fe → Fe2+ + 2e- Fe2+ + 2e- → Fe
55.8 𝑔 𝐹𝑒 1 𝑚𝑜𝑙 𝐹𝑒
ME = 𝑚𝑜𝑙 𝐹𝑒 × 2 𝑚𝑜𝑙 𝑒 − = 27.9 g/mole e- or 27.9 g/equivalent y=1 z=2 x=1
(c) z = 3; x= 1: Fe3+ + 3e- → Fe
55.8 𝑔 𝐹𝑒 1 𝑚𝑜𝑙 𝐹𝑒
ME = 𝑚𝑜𝑙 𝐹𝑒 × 3 𝑚𝑜𝑙 𝑒 − = 18.6 g/mole e- or 18.6 g/equivalent y=1 z=3 x=1
(d) z = 1; x=1: y=1:
55.8 𝑔 𝐹𝑒 2+ 1 𝑚𝑜𝑙 𝐹𝑒 2+ 55.8 𝑔 𝐹𝑒 3+ 1 𝑚𝑜𝑙 𝐹𝑒 3+
ME = × = 55.8 g/mole e- or 55.8 g/equivalent ME = × = 55.8 g/mole e-
𝑚𝑜𝑙 𝐹𝑒 2+ 1 𝑚𝑜𝑙 𝑒 − 𝑚𝑜𝑙 𝐹𝑒 3+ 1 𝑚𝑜𝑙 𝑒 −

17
 2.3.4 Faraday’s Laws2
Sample Problem 1
Calculate the equivalent weight of each of the following:
(a) Aluminum Al → Al3+ + 3e-
(b) Fe, in the reaction Fe → Fe2+ + 2e-
(c) Fe, in the reaction Fe3+ + 3e- → Fe
(d) Fe, in the reaction Fe3+ + e- → Fe2+
1 equivalent = 1 mole of e-
Since 1 F is necessary for the transfer of 1 mol of e-, it is the amount of electrical energy necessary to produce
1 equivalent of any substance.
Therefore from the problem, it would take 1F or 96,485 Coulombs to produce 9.00 g of Al, 27.9 g of Fe from
FeCl2, 18.6 g of Fe from FeCl3, and 55.8 g Fe2+(portion of FeCl2). We can also use relationships directly between
equivalents and moles, as follows:
1 mol Al = 3 equivalents Al
1 mol Fe = 2 equiv. Fe (from FeCl2)
1 mol Fe = 3 equiv. Fe (from FeCl3)
1 mol Fe2+ = 1 equiv. Fe2+ (from FeCl3)
18
 2.3.4 Faraday’s Laws2
Sample Problem 2
In the electroplating of nickel from a solution containing Ni2+ ions, what weight of nickel metal will be produced at
the cathode by a current of 4.02 amp flowing for 100 min?

Solution: 𝑦 𝐴+𝑎
(𝑎𝑞) + 𝑧 𝑒
−
→ 𝑥 𝐴(𝑠)
Ni2+ + 2e- → Ni x = 1; y = 1; z = 2
I = 4.02 A t = 100min (60s/min)

MNiQ 58.71 g Ni
mass of Ni deposited: mNi = MNi = mol Ni
zF
(58.71g Ni/mol Ni)(4.02C/s)(100min)(60s/min) (58.71g Ni/mol Ni)(4.02A)(100min)(60s/min)
m= m=
(2 mol e−/mol Ni)(96,485C/mol e−) (2 mol e−/mol Ni)(96,485C/mol e−)(1 A−s/C)
m = 7.34 g 1 A = 1 C/s
58.71g Ni 1 mol Ni mol e− 4.02 C 60 s
m = mol Ni × 2 mol e− × 96,485 C × s ×100 min× min = 7.34 g

19
 2.3.4 Faraday’s Laws2
Sample Problem 3
A Na2SO4 solution is electrolyzed with a current of 1.00 amp flowing for 5 minutes. The anode half-reaction is
2 H2O → O2 + 4H+ + 4e-
Calculate (a) the grams of O2 produced, (b) the volume of O2 produced, (c) the equivalents of O2 liberated, (d) the
number of coulombs used, and (e) the amount of Faradays used.

Solution:
(a) m = ? (b) V of O2? (c) equivalents of O2 liberated = ? (d) Q = ? (e) Faradays used = ?
Ideal Gas Equation: 𝑃𝑉 = 𝑛𝑅𝑇
Given: I = 1 A or 1 C/s t = 5 min × 60s/min z = 4 mol e-/mol O2 𝑉 0.08206(273) 𝐿
𝑉 𝑅𝑇
Vm = 𝑛 = 𝑃 At STP: 𝑛 = 1
= 22.4 𝑚𝑜𝑙
(a) M Q M It 𝐿∙𝑎𝑡𝑚

mass of O2 produced: m = O2 = O2 = (32 g/mol O2)(1 C/s)(5min)(60s/min) = 0.0249 g R = 0.08206 𝑚𝑜𝑙∙𝐾

zF zF − −
(4 mol of e /mol O2)(96,485C/mol e )
(b) V of O produced: VO MQ Vm = VmIt = (22.4 L/mol O2)(1 A)(5min)(60s/min) = 0.0174 L or 17.4 ml
2 2= zF M zF (4 mol of e−/mol O2)(96,485A−s/mol e−)
V of gas = (mass/M)(Molar Volume, Vm of a gas at STP) At STP: 1 mole of gas = 22.4 L; Vm = 22.4 L/mol
Q It (1 C/s)(5min)(60s/min)
equivalents of O2 liberated: equiv. O2 = F = F = = 0.00311 mol e- or 0.00311 equivalents
(c) (96,485C/mol e−)
1 equivalent = 1 mol e-

20
 2.3.4 Faraday’s Laws2
Sample Problem 3
A Na2SO4 solution is electrolyzed with a current of 1.00 amp flowing for 5 minutes. The anode half-reaction is
2 H2O → O2 + 4H+ + 4e-
Calculate (a) the grams of O2 produced, (b) the volume of O2 produced, (c) the equivalents of O2 liberated, (d) the
number of coulombs used, and (e) the amount of Faradays used.

Solution:
(a) m = ? (b) V of O2? (c) equivalents of O2 liberated = ? (d) Q = ? (e) Faradays used = ?
Given: I = 1 A or 1 C/s t = 5 min × 60s/min z = 4 mol e-/mol O2
(d) Q = It = (1 C/s)(5min)(60s/min) = 300 C

1F
(e) Faradays Used = 300 C × 96, 485 C = 0.00311 F

21
 2.3.5 Voltaic or Galvanic Cell
In a voltaic or galvanic cell, the chemical reaction produces electrical energy. The redox reaction is carried out in such a
way that the electrons being transferred from the RA to the OA travel through a wire, producing electric current.

If the reaction is carried out in such a way that the zinc metal does not come in contact
with the Cu2+ ions, the energy given off may be obtained as electricity.

Solution containing the Cu2+ ions is separated from solution with zinc metal. The two
solutions are separated by a salt bridge containing an ionic substance and allows ions to
pass from a solution in one container to a solution in another container. Oxidation Half: Reduction Half:

When the switch in internal circuit is closed, the reaction will begin to take place since
electrons can then pass through from the anode to the cathode.

22
2.3.5 Voltaic or Galvanic Cell2
Standard Hydrogen Electrode (SHE)
Thermodynamic Std. State Conditions
Every oxidation must be accompanied by a reduction. So, it is impossible
to determine experimentally the potential of any single electrode. We
established an arbitrary standard then.
▪ Standard Hydrogen Electrode (SHE)
- contains a piece of metal electrolytically coated with a grainy black
surface of inert platinum metal, immersed in a 1 M H+ solution. Hydrogen, H2,
is bubbled at 1 atm pressure through a glass envelope over the platinized
electrode.
- by convention, E0 = 0 V.
H2 → 2 H+ + 2 e− E0 = 0 V
2 H+ + 2 e− → H2 E0 = 0 V
We then construct a standard cell consisting of an SHE and some other
standard electrode (half-cell). Because the defined electrode potential of the
SHE contributes 0 V to the sum, the voltage of the overall cell then lets us
determine the standard electrode potential of the other half-cell.
▪ Standard Electrode Potential
- potential with respect to the SHE, measured at 25°C when the
concentration of each ion in the solution is 1 M and the pressure of any gas
involved is 1 atm.

23
2.3.5 Voltaic or Galvanic Cell2
E0 > 0 = Spontaneous Reaction
E0 < 0 = Nonspontaneous Reaction
E0 = 0 Reaction at Equilibrium

Samples
1. Mg2+ + Zn → Zn2+ + Mg
Reduction Half: Mg2+ + 2 e− → Mg E0 = -2.36 V
Oxidation Half: Zn → Zn2+ + 2 e− E0 = +0.76 V
Mg2+ + Zn → Mg + Zn2+ E0 = -1.60 V Nonspontaneous
Reverse: Mg + Zn2+ → Mg2+ + Zn E0 = +1.60 V Spontaneous
Potentials are not multiplied by the coefficients

2. 3 Mg + 2 Al3+ → 3 Mg2+ + 2 Al
Reduction Half: 2(Al3+ + 3e− → Al) E0 = -1.66 V
Oxidation Half: 3(Mg → Mg2+ + 2e-) E0 = +2.36 V
2Al3+ + 3Mg → 2Al + 3Mg2+ E0 = +0.70 V Spontaneous

24
 2.3.5 Voltaic or Galvanic Cell2
Which reaction is preferred?
◦ Elements having higher reduction potential will gain
electrons and that having lower reduction potential will
Lower Reduction
Potential (E0) lose electrons.
Increasing Ease of Reduction

Increasing Ease of Oxidation

Stronger Reducing Agent
Stronger Oxidizing Agent

Sample
1. Mg2+ + Zn → Zn2+ + Mg
Ge-ROA

Mg2+ + 2 e− → Mg E0 = -2.36 V

Le-ORA
Reduction Half:
Oxidation Half: Zn → Zn2+ + 2 e− E0 = +0.76 V
Mg2+ + Zn → Mg + Zn2+ E0 = -1.60 V Nonspontaneous
Reverse: Mg + Zn2+ → Mg2+ + Zn E0 = +1.60 V Spontaneous

Mg (E0=−2.36V) displaces Zn2+ (E0=−0.76V) in the compound (i.e. ZnSO4).

Zn2+ + 2 e− → Zn Higher Reduction Potential E0 − preferred reduction reaction

Mg2+ + 2 e− → Mg Lower Reduction Potential E0 − NOT preferred reduction reaction
Higher Reduction
Potential (E0)

25
 2.3.5 Voltaic or Galvanic Cell2
Which reaction is preferred?
◦ Elements having higher reduction potential will gain
electrons and that having lower reduction potential will
Lower Reduction
Potential (E0) lose electrons.
Increasing Ease of Reduction

Increasing Ease of Oxidation

Stronger Reducing Agent
Stronger Oxidizing Agent

Samples Potentials are not multiplied by the coefficients

3+ 2+
2. 3 Mg + 2 Al → 3 Mg + 2 Al
Ge-ROA

E0 = -1.66 V

Le-ORA
Reduction Half: 2(Al3+ + 3e− → + Al)
Oxidation Half: 3(Mg → Mg2+ + 2e-) E0 = +2.36 V
2Al3+ + 3Mg → 2Al + 3Mg2+ E0 = +0.70 V Spontaneous

Mg (E0=−2.36V) displaces Al3+ (E0=−1.66V) in the compound (i.e. Al2(SO4)3).

Al3+ + 3 e− → Al Higher Reduction Potential E0 − preferred reduction reaction
Mg2+ + 2 e− → Mg Lower Reduction Potential E0 − NOT preferred reduction reaction

Higher Reduction
Potential (E0)

26
 2.3.6 The Nernst Equation
All the potentials used in the previous section involved solutions in which the concentration of the ions was 1 M. This
is known as the standard state. As the concentration changes, potential for the half-reaction also changes according to the
Nernst Equation:
Digression:
log10a
ln a=logea =
RT log10e
E = E 0 − zF ln Q 2.303RT
E = E0 − log Q
J zF
J ∙K
V = C − mol erxn
mol
−
∙K
C
∙ aA + bB → cC + dD wA + xB → yC + zD
mol rxn mol e−
where: E0 = potential under the standard conditions, V (J/C)
𝐶𝑐𝐷𝑑
E = potential under the nonstandard conditions, V (J/C) Q = reaction quotient = 𝐴𝑎𝐵𝑏
← gaseous and aqueous only
z = number of electrons transferred (gained/lost)
= mol of e- transferred/mol of reaction Samples: Activity - of component of an ideal mixture is the ratio of its
concentration or partial pressure to a standard concentration (1 M)
F = Faraday’s constant (96,485 C/mol e-)
= amt. of electricity carried by 1 mol of e- 2Al3+(aq) + 3Mg(s) → 2Al(s) + 3Mg2+(aq) or pressure (1 atm). For now, we can consider the activity of each
species as dimensionless.
R = universal gas constant (8.31447 J/mol∙K)
Mg2+ 3
Pure Solid/Pure Liquid: a = 1
Components of Ideal Solutions: a = [Conc. in M]/[Standard: 1 M]
T = temperature (if standard, T = 298.15 K) Q= 2 Gases in Ideal Mixture: a = Partial Pressure p in atm/[Standard: 1 atm]
Al3+

At Standard Conditions (25°C): NO−3 (aq) + 10H+(aq)+ 8e− →NH+4 (aq) + H2O (l)
1
0.025693 0.05916 NH+4
E = E0 − ln Q E = E0 − log Q Q=
z z 1
NO−3 H+ 10

27
 2.3.6 The Nernst Equation
Sample Problem
For the reaction 2Al + 3Cu2+ → 2Al3+ + 3Cu, calculate the potential if the [Cu2+] is 1x10-4 M and the [Al3+] is 1x 10-3 M.
Solutions:
Can be solved as two separate steps or as overall reaction
a. Two separate steps
RT
Cu2+ + 2 e− → Cu E0 = +0.34 ECu2+, Cu = E 0 − zF ln Q

8.31447 J (298.15K)
1 mol rxn∙K 1
Q= ECu2+, Cu = 0.34 − −
2 mol e ∙96,485 C ln = 0.221681 V
[1x 10−4]1 [1x 10−4]1
mol rxn mol e−

RT
Al→ Al3+ + 3 e− E0 = +1.66 EAl, Al3+ = E 0 − zF ln Q

8.31447 J (298.15K)
Q = [1x 10−3]1 mol rxn∙K
EAl, Al3+ = 1.66 − −
3 mol e ∙96,485 C ln [1x 10−3]1 = 1.719160 V
mol rxn mol e−

Eoverall = 0.221681 V + 1.719160 V = 1.94 V

Cu2+ + 2 e− → Cu Higher Reduction Potential E0 − preferred reduction reaction
Al3+ + 3 e− → Al Lower Reduction Potential E0 − NOT preferred reduction reaction

28
 2.3.6 The Nernst Equation
Sample Problem
For the reaction 2Al + 3Cu2+ → 2Al3+ + 3Cu, calculate the potential if the [Cu2+] is 1x10-4 M and the [Al3+] is 1x 10-3 M.
Solutions:
Can be solved as two separate steps or as overall reaction
b. Overall Reaction - from the sum of 2 half-reactions, 6 e- are involved

2Al → 2Al3+ + 6e− E0 = +1.66 V

3Cu2++ 6e− → 3Cu E0 = +0.34 V
2Al + 3Cu2+ → 2Al3++ 3Cu E0 = +2.00 V

z = 6 mole e-/mole rxn [1x 10−3]2

Q=
[1x 10−4]3
8.31447 J (298.15K) [1x 10−3]2
Eoverall = 2.00 − mol rxn∙K ln = 1.94 V
−
6 mol e ∙96,485 C [1x 10−4]3
mol rxn mol e −

Cu2+ + 2 e− → Cu Higher Reduction Potential E0 − preferred reduction reaction

Al3+ + 3 e− → Al Lower Reduction Potential E0 − NOT preferred reduction reaction

29
 2.3.7 Equilibrium Constants from Redox Equations
We now want to consider the case where the potential is zero. This means that neither the forward nor reverse
reactions will take place spontaneously, that is, the reaction has reached a point of equilibrium. Therefore, at equilibrium
the Q will be constant, called Keq or often called Kredox. Putting this into Nernst equation gives

RT
E = E 0 − zF ln Q

RT
0 = E 0 − zF ln Keq

zFE 0
ln Keq = RT
Digression:
eln a = a
zFE0 10𝑙𝑜𝑔10 𝑎 = 𝑎
Keq = e RT

At Standard Conditions (25°C):

0.025693 zE0 0.05916 zE0
E = E0 − ln Q Keq = e 0.025693 E = E0 − log Q Keq = 10 0.05916
z z

30
 2.3.7 Equilibrium Constants from Redox Equations
Sample Problem
1. Calculate the Keq for the reaction Zn + Cu2+ ↔ Zn2+ + Cu.
E0 = +0.76 V + +0.34 = 1.10 V
zFE0
Keq = e RT
z = 2 mole e-/mole rxn
2(96485)(1.10)
Zn → Zn2+
+ 2e− E0 = +0.76 V Keq = e 8.31447(298.15)
Cu2++ 2e− → Cu E0 = +0.34 V
Zn + Cu2+ → Zn2++ Cu E0 = +1.10 V
Keq = 1.54 × 1037

2. Calculate the concentration of Zn2+ in equilibrium with 0.30 M Cr3+ from the reaction
3 Zn2+ + 2 Cr → 2 Cr3+ + 3 Zn
At equilibrium:
E0 = -0.76 V + +0.74 = -0.02 V zFE0
z = 6 mole e-/mole rxn
Keq = e RT Cr3+
2
0.30
2
Keq = 9.3667 × 10-3= 3
6(96485)(−0.02) Zn2+
3
Zn2+
3[Zn2++ 2e− →
Zn] E0 = -0.76 V
2[Cr → Cr3+ + 3e−] 0
E = +0.74 V Keq = e 8.31447(298.15)
Zn2+ = 2.126 M
3Zn2+ + 2Cr → 2Cr3++ 3Zn E0 = -0.02 V Keq = 9.3667 × 10-3

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Questions?

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References
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