ELECTROCHEMISTRY

- The study of the relationship between chemical change and electrical work

TERMS TO REMEMBER

ELECTROLYSIS
- The process of passing an electric current through a solution of an electrolyte or
through a molten electrolyte to cause a chemical reaction

ELECTROLYSIS CELL
- It is the apparatus in which electrolysis reactions are carried out

ELECTROCHEMICAL CELL
- A system that incorporates a redox reaction to produce or use electrical current

ELECTROLYTE
- A substance that conducts a current when it dissolves in water
- A mixture of ions in which the electrode of an electrochemical cell are immersed

ELECTRODE
- The part of an electrochemical cell that conducts the electricity between the cell
and the surroundings

ANODE
- The electrode at which oxidation occurs in an electrochemical cell
- Electrons are given up by the reducing agent and leave the cell at the anode

CATHODE
- The electrode at which reduction occurs in an electrochemical cell
- Electrons enters the cell and are acquired by the oxidizing agent at the cathode

SALT BRIDGE
- An inverted U-tube containing a solution of non-reacting electrolyte that
connects the compartments of a voltaic cell and maintains neutrality by allowing
VOLTAIC CELL ions to flow between compartments
- An electrochemical cell that uses a spontaneous reaction to generate electric
energy
- Also known as galvanic cell
OVERVIEW OF THE ELECTROCHEMICAL CELL
Mg2+(aq) + 2 e‒ → Mg(s) (cathode; reduction)
VOLTAIC CELL/GALVANIC CELL 2 Br (aq) → Br2(l) + 2 e
‒ ‒ (anode; oxidation)
- Uses a spontaneous reaction (∆G<0) to generate electrical energy Mg2+(aq) + 2 Br‒(aq) → Mg(s) + Br2(l)
- In the cell reaction, the difference in chemical potential energy between higher
energy reactants and lower energy products is converted into electrical energy 3. ELECTROLYSIS OF WATER AND NON – STANDARD HALF – CELL POTENTIAL
- The system does work on the surroundings 2 H2O(l) → O2(g) + 4 H+(aq) + 4 e‒ (cathode; reduction)
- Used to operate the load (CD player, car starter motor, flashlight bulb and other 2[2 H2O(l) + 2 e → H2(g) + 2 OH‒(aq)] (anode; oxidation)
‒

electrical device) 2 H2O(l) → O2(g) + 4 H+(aq) + 4 e‒

4 H2O(l) + 4 e‒ → 2 H2(g) + 4 OH‒(aq)
ELECTROLYTIC CELL 6 H2O(l) → 2 H2(g) + O2(g) + 4 H2O(l)
- Uses electrical energy to drive a nonspontaneous reaction (∆G>0) 2 H2O(l) → 2 H2(g) + O2(g)
- In the cell reaction, electrical energy from an external power supply converts
lower energy reactants into higher energy products 4. ELECTROLYSIS OF AQUEOUS IONIC SOLUTIONS AND THE PHENOMENON OF
- The surroundings do work on the system OVERVOLTAGE
- Electroplating and recovering metals from ores - Aqueous salt solution are mixtures of ions and water and we have to compare
the various electrode potentials to predict the electrode products
PREDICTING THE PRODUCT OF ELECTROLYSIS - When two half – reactions are possible at an electrode, the REDUCTION with
the LESS NEGATIVE (MORE POSITIVE) electrode potential occurs and the
1. ELECTROLYSIS OF PURE MOLTEN SALTS OXIDATION with the LESS POSITIVE (MORE NEGATIVE) electrode potential
- Is simple because the cation will be reduced and the anion oxidized occurs
- Electrolysis of molten calcium chloride
2 Cl‒(l) → Cl2(g) + 2 e‒ ELEMENTS THAT CAN BE PREPARED ELECTROLYTICALLY FROM AQUEOUS
Ca2+(aq) + 2 e‒ → Ca(s) SOLUTIONS OF THEIR SALTS
Ca2+(aq) + 2 Cl‒(l) → Ca(s) + Cl2(g)
1. Cations of less active metals are reduced to the metal including gold, silver,
2. ELECTROLYSIS OF MIXED MOLTEN SALT copper, chromium, platinum and cadmium.
- Electrolyte is a mixture of molten salts which is then electrolyte to obtained a 2. Cations of more active are not reduced including those in Group 1A, 2A and Al.
particular metal Water is reduced to H2 and OH‒ instead.
- The MORE EASILY OXIDIZED SPECIES (STRONGER REDUCING AGENT) reacts 3. Anions that are oxidized because of overvoltage from O2 formation, include the
at the ANODE, and the MORE EASILY REDUCED SPECIES (STRONGER halide except F‒.
OXIDIZING AGENT) reacts at the CATHODE 4. Anions that are not oxidized include F‒ and common oxoanions such as SO42‒,
- Rely on the knowledge of periodic trends to predict which of the ion present CO32‒, NO3‒ and PO43‒ because the central nonmetal, these oxoanions is already
gains or loses electrons more easily in its highest oxidation state. Water is oxidized to O2 and H+.

SAMPLE PROBLEM STOICHIOMETRY OF ELECTROLYSIS

A chemical engineer melts a naturally occurring mixture of NaBr and MgCl2 and - The charge flowing through an electrolytic cells yields products at the electrode
decomposes it in an electrolytic cell. Predict the substances formed at each - Determined experimentally by Michael Faraday and referred to as Faraday’s
electrode and write balanced half-reactions and the overall cell reaction. Law of electrolysis (the amount of substances produced at each electrode is
Possible oxidizing agents: Na+ and Mg2+ directly proportional to the quality of charge flowing through the cell)
Possible reducing agents: Br‒ and Cl‒
 - Each balanced half – reaction shows the amount (mole) of reactants electrons 1. DRY CELL OR LECLANCHE’ CELL
and product involved in the change - Invented in 1860s and became a familiar household item during the first three –
- The SI unit of current is ampere (1 A = 1 Coulomb/second) quarters of the 20th century
- Charge = Current x time - The anode is zinc that housed a mixture of MnO2 and a weakly acidic electrolyte
paste consisting of NH4Cl, ZnCl2, H2O and starch
TO APPLY FARADAY’S LAW - Powdered graphite is used to improve conductivity
1. Balance the half – reaction to find the number of moles of electrons needed per - The cathode is an inactive graphite rod (the cathode half – reaction involved the
mole of product reduction of MnO2(s) to Mn2O3(s) and an acid – base reaction between NH4+ and
2. Use the Faraday constant (F = 9.65 x 104 C/mol e‒) to find the corresponding OH-)
charge - At a high current drain, the generated ammonia gas which could build up and
3. Use the molar mass to find the charge needed for a given mass of product cause a serious voltage drop
- The zinc anode reacted with the acidic NH4+ ions which shorten it shelf life
- Powers portable radios, toys, and flashlight

2. ALKALINE BATTERY
- Use the same materials as dry cell for an electrode (zinc and manganese) but the
electrolyte is a paste of KOH and water
Amount
Mass (g) of
(mole) of
AMount - The use of the KOH paste eliminates the ammnonia build up and maintain the
subs.
substanced
(mole) of
Charge (C)
Current (A or zinc electrode
oxidized or electrons C/s)
oxidized or
reduced transferred
reduces (Anode) Zn(s) + 2 OH‒(aq) → ZnO(s) + H2O(l) + 2 e‒
(Cathode) MnO2(s) + 2 H2O(l) + 2 e‒ → Mn(OH)2(s) + 2 OH‒(aq)
Zn(s) + MnO2(s) + H2O(l) → ZnO(s) + Mn(OH)2(s) Ecell = 1.5 V

- Powers portable radios, toys, flashlights and is safe and comes in many sizes
- Has no voltage drop, longer shelf life and better performance in terms of power
SAMPLE PROBLEM capability and stored energy
1. How long does it take to produce 3.0 g of Cl2(g) by electrolysis of aqueous NaCl
using a power supply with a current of 12 A?

GALVANIC/VOLTAIC CELL
- An electrochemical cell that uses a spontaneous reaction to generate electric
energy

TYPES OF GALVANIC CELL

A. PRIMARY CELL (NONRECHARGEABLE BATTERIES)

- Cannot be charged (discarded when the components have reached their
equilibrium concentration – the cell is “dead”)
Alkaline Battery
3. MERCURY AND SILVER (BUTTON) BATTERIES (Anode) 3.5 Li(s) → 3.5 Li+ + 3.5 e‒
- Are quite similar with each other (Cathode) AgV2O5.5 + 3.5 Li+ + 3.5 e‒ → Li3.5AgV2O5.5
- Both use a zinc container as the anode (reducing agent) in a basic medium Overall (cell) reaction AgV2O5.5 + 3 Li(s) → Li3.5AgV2O5.5
- The mercury battery employs HgO as the oxidizing agent, the silver uses Ag2O,
and both use a steel can around the cathode
- The solid reactants are compacted with KOH and separated with moist paper

(Anode) Zn(s) + 2 OH‒ (aq) → ZnO(s) + H2O(l) + 2 e‒

(Cathode – Hg) HgO(s) + H2O(l) + 2 e‒ → Hg(l) + 2 OH‒(aq)
Overall (cell) reaction Zn(s) + HgO(s) → ZnO(s) + Hg(l) Ecell = 1.3 V

(Anode) Zn(s) + 2 OH‒ (aq) → ZnO(s) + H2O(l) + 2 e‒

(Cathode – Ag) Ag2O(s) + H2O(l) + 2 e‒ → 2 Ag(s) + 2 OH‒(aq)
Overall (cell) reaction Zn(s) + Ag2O(s) → ZnO(s) + 2 Ag(s) Ecell = 1.6 V

- Both cells are manufactured as small button – sized batteries

- The mercury cell is used in calculators
- The silver cell is used in watches, cameras, heart pacemakers and hearing aids
- Major disadvantages are toxicity of discarded mercury and high cost of silver
cells

Lithium Battery

B. SECONDARY (RECHARGEABLE) BATTERIES

- Battery is recharged when it runs down by supplying electrical energy to
reverse the cell reaction and re – form reactants
- Most widely used is the common car battery
Silver Button Battery
1. LEAD – ACID BATTERY
4. PRIMARY LITHIUM BATTERY
- A typical lead – acid car battery has six cells connected in series, each of which
- Widely used in watches and implanted medical devices delivers about 2.1 V for a total of about 12 V
- Offers an extremely high energy/mass ratio (producing 1 mol of e‒ ‒ 1 F from - Each cell contains two lead grids loaded with the electrode materials: high –
less than 7 g of metal) surface – area Pb in the anode and high – surface – area PbO2 in the cathode
- The anode is lithium metal foil (requires a nonaqueous electrolyte) - The grids are immersed in an electrolyte solution of ~ 4.5 M H2SO4
- The cathode is one of several metal oxides in which lithium ions lie between - Fiberglass sheets between the grids prevent shorting due to physical contact
oxide layers - When the discharges, it generates electrical energy as a voltaic cell
- Some implantable medical devices have silver vanadium oxide (SVO; AgV2O5.5)
(Anode) Pb(s) + HSO4‒ (aq) → PbSO4(s) + H+(aq) + 2 e‒
cathode and can provide power for several years but at a low rate (energy (Cathode) PbO2(s) + 3 H+(aq) + HSO4‒ (aq) + 2 e‒ → PbSO4(s) + 2 H2O(l)
storage is limited) Overall (cell) reaction (discharge): PbO2(s) + Pb(s) + 2 H2SO4(aq) → 2 PbSO4(s) + 2 H2O(l)
- Both half – reactions produce Pb2+ ions, ne through the oxidation of Pb and the 2. NICKEL – METAL HYDRIDE (Ni – MH) BATTERY
other through the reduction of PbO2 - Replace the nickel – cadmium battery because of toxicity concerns
- When the cell is recharged, it uses electrical energy as an electrolytic cell, and - The anode half – reaction oxidizes the hydrogen absorbed within a metal alloy
the half – cell and overall reactions are reversed (designated M) in a basic (KOH) electrolyte while nickel (III) in the form of
NiO(OH) is reduced at the cathode
Overall (cell) reaction (recharge): 2 PbSO4(s) + 2 H2O(l) → PbO2(s) + Pb(s) + 2 H2SO4(aq)
(Anode) MH(s) + OH‒(aq) → M(s) + H2O(l) + e‒
- Car and truck owners have relied on the lead – acid battery to provide the large (Cathode) NiO(OH) + H2O(l) + e‒ → Ni(OH)2(s) + OH‒(aq)
burst of current to the starter motor needed to the engine in both hot and cold Overall (cell) reaction NiO(OH) + MH(s) → M(s) + Ni(OH)2(s) Ecell = 1.4 V
weather
- Main problems with the lead – acid battery are loss of capacity and safety - The cell reaction is reversed during recharging
concerns - Common in cordless razors, camera flash units and power tools
- Loss of capacity include corrosion of the positive (Pb) grid, detachment of active - Lightweight, has high power and nontoxic (may discharge excessively during
material as a result of normal mechanical bumping and the formation of large long – term storage)
crystals of PbSO4 (makes recharging more difficult)
- Older batteries had a cap on each cell for monitoring electrolyte density and
replacing water lost on overcharging (during recharging, some water could be
electrolyzed to H2 and O2, which could explode if sparked and splatter H2SO4)
- Modern batteries are sealed (do not require addition of water during normal
operation) and use flame attenuators to reduce the explosion hazard

Nickel – Metal Hydride Battery

3. LITHIUM – ION BATTERY

- The anode is lithium but the atoms lie between sheets of graphite (designated
LixC6)
- The cathode is a lithium metal oxide (such as LiMn2O4 or LiCoO2) and a typical
electrolyte is 1 M LiPF6 in an organic solvent (mixture of dimethyl carbonate
and methylethyl carbonate)
- Electrons flow through the circuit while solvated Li+ ions flow from anode to
cathode within the cell

(Anode) LixC6 → x Li+ + x e‒ + C6(s)

(Cathode) Li1-x Mn2O4(s) + x Li+ + x e‒ → LiMn2O4(s)
Lead – acid Battery Overall (cell) reaction LixC6 + Li1-x Mn2O4(s) → LiMn2O4(s) + C6(s) Ecell = 3.7 V

- The cell reaction is reversed during recharging

- Not as powerful as the primary lithium battery, but it can powers countless
laptop computers, cell phones and camcorders
- Key drawbacks are expensive and the flammability of the organic solvent
 - At the cathode, an O2 molecule adsorbs onto the catalyst, which provide an e‒ to
form O2‒ (one H3O+ donates its H+ to the O2‒, forming HO2;HO–O)
- The O–O bond stretches and breaks as another H3O+ gives its H+ and the catalyst
provides another e‒ ‒ the first H2O has formed (another step form the second
H2O molecule)
- Both water molecules desorb and leave the cell

2. HYDROGEN FUEL CELL

- Have been used for years to provide electricity and pure water during space
flights (in the very near future, similar ones will supply electric power for
transportation, residential, and commercial needs)
- Produce no pollutants and convert about 75% of the fuel’s bond energy into
useable power

Lithium – Ion Battery

C. FUEL CELLS
- Sometimes called the flow battery
- The reactants (usually a combustible fuel and oxygen) enter the cell and the
products leave, generating electricity through the controlled oxidation of the
fuel
- Use combustion to produce electricity
- The reactions of the fuel cells have much lower rates than those in other
batteries (require an electrocatalyst to decrease the activation energy)

1. PROTON EXCHANGE MEMBRANE (PEM) Hydrogen Fuel Cell

CORROSION
- Uses H2 as the fuel and has an operating temperature of around 80°C
- The cell reactions are - The natural redox process that oxidizes metals to their oxides and sulfides
- The reverse of isolating metal from its oxides or sulfide ore (chemical terms)
(Anode) 2 H2(g) → 4 H+(aq) + 4 e‒ - Its component resemble those of a voltaic cell:
o Anodic and cathodic regions are separated in space
(Cathode) O2(g) + 4 H+(aq) + 4 e‒ → 2 H2O(g)
Overall (cell) reaction 2 H2(g) + O2(g)→ 2 H2O(g) Ecell = 1.2 V o The regions are connected via an external circuit through which the
electrons travel
- The electrodes are composites consisting of nanoparticles of a Pt – based o In the anodic region, iron behaves like an active electrode, whereas in
the cathodic region, it is inactive
catalyst deposited on graphite [embedded in a polymer electrolyte membrane
o The moisture surrounding the pit functions somewhat like a salt bridge
having a perfluoroethylene backbone (–[F2C–CF2–]n) with attached sulfunic acid
groups (RSO3‒) tha play a key role in ferrying protons from anode to cathode) (a means for the ions to ferry back and forth and keep the solution
neutral)
- At the anode, two H2 molecules adsorb onto the catalyst and are split and
oxidized - Occurs in the presence of oxygen and moisture and increased by high hydrogen
ion concentration (low pH), high ion concentration (salt) or contact with a less
- From each H2, two e‒ travel through the wire to the cathode, while two H+
become hydrated and migrate through the electrolyte as H3O+ active metal such as copper
PREVENTING/LIMITING CORROSION 3. Half – cell compartments usually appear in the same order as in the half –
1. CATHODIC PROTECTION reaction and electrodes appear at the far left and right of the notation.
- Making iron behave like a cathode [if the iron makes contact with a more active 4. A double vertical line separates the half – cells and represents the phase
metal (stronger reducing agent) such as zinc, the iron becomes cathodic and boundary on either side of the salt bridge (the ions in the salt bridge are omitted
remains intact, while the zinc acts as the anode and loses electrons] because they are not part of the reaction).

2. GALVANIZING PROCESS SAMPLE PROBLEMS

- Coating steel with a “sacrificial” layer of zinc [in addition to physical contact 1. Diagram, show balanced equations and write the notation for a voltaic that
with H2O and O2, the zinc is “sacrificed” (oxidized) instead of the iron] consists of one half – cell with a Cr bar in a Cr(NO3)3 solution, another half – cell
with a Ag bar in an AgNO3 solution, and a KNO3 salt bridge. Measurement
3. SACRIFICIAL ANODES indicates that the Cr bar electrode is negative relative to the Ag electrode.
- Use of aluminum and magnesium (more active than iron) as an anode (the iron
act as the cathode) 2. In one compartment of a voltaic cell, a graphite rod dips into an acidic solution
- Employed to protect iron and steel structures (pipes, tanks, oil rigs) in marine of K2Cr2O7 and Cr(NO3)3; in the other compartment, a tin bar dips into Sn(NO3)2
and moist underground environments solution. A KNO3 salt bridge joins them. The tin electrode is negative relative to
the graphite. Diagram the cell, write the balanced equations and show the cell
CONSTRUCTION AND OPERATION OF A VOLTAIC CELL notation.
- By convention, the oxidation half – cell (anode compartment) is shown on the
left and the reduction half – cell (cathode compartment) on the right 3. Write the cell notation for the voltaic cell that incorporates the redox reaction
- In any voltaic cell, the anode is the negative and the cathode is positive Al(s) + Cr3+(aq) → Al3+(aq) + Cr(s).
- For example, Zn/Cu2+
4. Write a balanced equation of the cell notation:
(Oxidation) Zn(s) → Zn2+(aq) + 2 e‒ Mn(s) )∣ Mn2+ (aq) ∥ Cd2+ (aq)∣Cd(s).
(Reduction) Cu2+(aq) + 2 e‒ → Cu(s)
Overall reaction Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) CELL POTENTIAL: OUTPUT OF A VOLTAIC CELL
- Its purpose of the voltaic cell is to convert the free energy change of a
NOTATION FOR A VOLTAIC CELL spontaneous reaction into the kinetic energy of electrons moving through an
- A shorthand notation that describes the components of a voltaic cell external circuit
- The unit for the voltaic cell is voltage (V) – [1 V = 1 J/C]
KEY PARTS OF THE NOTATION
1. The components of the anode compartment (oxidation half – cell) are written on CELL POTENTIAL (Ecell)
the left of the components of the cathode compartment (reduction half – cell). - The difference in the electrical potential between the two electrodes
2. A vertical line represents a phase boundary. For example, Zn(s)∣ Zn2+(aq) - Also called the voltage of the cell or electromotive force (emf)
indicates that the solid Zn is a different phase from the aqueous Zn2+. A comma
separates the half – cell compartments that are in the same phase. For example, POSITIVE CELL POTENTIAL
the notation for the voltaic cell housing the reaction between I‒ and MnO4‒ (in - The cell operates spontaneously (Ecell > 0)
the cathode compartment, H+, MnO4‒, Mn2+ ions are all in aqueous solution with - The more positive the Ecell is, more work the cell can do and the farther the
solid graphite immersed in it). reaction proceeds to the right

graphite ∣ I‒(aq)∣I2(s) ∥ H+(aq), MnO4‒ (aq), Mn2+(aq)∣graphite

NEGATIVE CELL POTENTIAL DETERMINING 𝑬°𝒉𝒂𝒍𝒇− 𝒄𝒆𝒍𝒍: THE STANDARD HYDROGEN ELECTRODE
- Associated with nonspontaneous cell reaction (Ecell < 0) - Standard reference half – cell has its standard electrode potential defined as
- The reaction will proceed to the left °
zero (𝐸𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 ≡ 0.00 𝑉)
- Standard hydrogen electrode which consists of a specially prepared platinum
ZERO CELL POTENTIAL
electrode immersed in a 1 M aqueous of a strong acid, H+(aq) or H3O+(aq),
- The reaction has reached equilibrium and the cell can do no more work
through which H2 gas at 1 atm is bubbled
(Ecell = 0)
°
2 H+(aq; 1 M) + 2 e‒ ⇌ H2(g; 1 atm) 𝐸𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 = 0.00 𝑉
STANDARD CELL POTENTIAL (𝑬°𝒄𝒆𝒍𝒍 )
- The measured potential of a voltaic cell affected by the changes in concentration ° °
as the reaction proceeds and by the energy losses due to heating of the cell and - With 𝐸𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 defined as zero, the overall 𝐸𝑐𝑒𝑙𝑙 allows the finding of the
°
the external circuit unknown standard electrode potential, 𝐸𝑢𝑛𝑘𝑛𝑜𝑤𝑛
- The potential measured at a specific temperature (298 K) with no current - When H2 is OXIDIZED, the REFERENCE HALF – CELL is the ANODE and the
flowing and all components are in their standard states (1 atm for gases, 1 M for REDUCTION occurs at the UNKNOWN HALF – CELL
° ° °
solutions, the pure solid for electrodes) 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
- The difference between the standard electrode potential of the cathode °
= 𝐸𝑢𝑛𝑘𝑛𝑜𝑤𝑛 °
− 𝐸𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒
(reduction) half – cell and the standard electrode potential of the anode °
= 𝐸𝑢𝑛𝑘𝑛𝑜𝑤𝑛 − 0.00 𝑉
(oxidation) half – cell °
= 𝐸𝑢𝑛𝑘𝑛𝑜𝑤𝑛

𝑬°𝒄𝒆𝒍𝒍 = 𝑬°𝒄𝒂𝒕𝒉𝒐𝒅𝒆 (𝒓𝒆𝒅𝒖𝒄𝒕𝒊𝒐𝒏) − 𝑬°𝒂𝒏𝒐𝒅𝒆 (𝒐𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏) - When H+ is REDUCED, the REFERENCE HALF – CELL is the CATHODE and the
OXIDATION occurs at the UNKNOWN HALF – CELL
STANDARD ELECTRODE (HALF – CELL) POTENTIALS (𝑬°𝒉𝒂𝒍𝒇− 𝒄𝒆𝒍𝒍) °
𝐸𝑐𝑒𝑙𝑙 °
= 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 °
− 𝐸𝑎𝑛𝑜𝑑𝑒
- The potential associated with a given half – reaction (electrode compartment) °
= 𝐸𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 °
− 𝐸𝑢𝑛𝑘𝑛𝑜𝑤𝑛
when all the components are in their standard states °
= 0.00 𝑉 − 𝐸𝑢𝑛𝑘𝑛𝑜𝑤𝑛
- By convention, a standard electrode potential always refers to the half – reaction °
= −𝐸𝑢𝑛𝑘𝑛𝑜𝑤𝑛
written as a reduction

° ° SAMPLE PROBLEMS
Zn2+(aq) + 2 e‒ → Zn(s) 𝐸𝑍𝑖𝑛𝑐 (𝐸𝑎𝑛𝑜𝑑𝑒 ) (reduction) 1. A voltaic cell has the Zn/Zn2+ half – reaction in one compartment and the H+/H2
°
Cu2+(aq) + 2 e‒ → Cu(s) 𝐸𝑐𝑜𝑝𝑝𝑒𝑟 (𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒
°
) (reduction) half – reaction in the other. The zinc electrode is negative relative to the
° °
hydrogen electrode. The measured 𝐸𝑐𝑒𝑙𝑙 is +0.76 V. find the value of 𝐸𝑧𝑖𝑛𝑐 .
- The overall cell reaction involves the oxidation of zinc at the anode, not the
reduction of Zn2+, so the zinc half – reaction is reverse 2. A voltaic cell houses the reaction between aqueous bromine and zinc metal:
°
Br2(aq) + Zn(s) → Zn2+(aq) + Br‒ (aq) 𝐸𝑐𝑒𝑙𝑙 = 1.83 𝑉
Zn(s) → Zn2+(aq) + 2 e‒ (Oxidation)
Cu2+(aq) + 2 e‒ → Cu(s) (Reduction) ° °
Calculate 𝐸𝑏𝑟𝑜𝑚𝑖𝑛𝑒 , given 𝐸𝑍𝑖𝑛𝑐 = −0.76 𝑉.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑜𝑝𝑝𝑒𝑟
°
− 𝐸𝑧𝑖𝑛𝑐
 3. A voltaic cell based on the reaction between aqueous Br2 and vanadium(III) ions STEPS IN WRITING SPONTANEOUS REACTIONS
°
has 𝐸𝑐𝑒𝑙𝑙 = 1.39 𝑉: 1. Reverse one of the half – reactions into an oxidation step such that the
Br2(aq) +2 V3+(aq) + 2 H2O(l) →2 VO2+(aq) + 4 H+(aq) +Br‒ (aq) difference of the electrode potentials (cathode minus anode) gives a positive
° °
𝐸𝑐𝑒𝑙𝑙 . When the half – reaction is reverse, the sign of the 𝐸ℎ𝑎𝑙𝑓− 𝑐𝑒𝑙𝑙 is not reverse.
°
What is 𝐸𝑣𝑎𝑛𝑎𝑑𝑖𝑢𝑚 , the standard electrode potential for the reduction of VO2+ to 2. Add the rearranged half – reactions to obtain a balanced overall equation. Be
V ?
3+ sure to multiply coefficients so the e‒ lost equals e‒ gains and to cancel species
common to both sides.
RELATIVE STRENGTHS OF OXIDIZING AND REDUCING AGENTS
- Ranking the relative oxidizing strengths for a given reactions can be done by EXAMPLE
writing each half – cell reaction as a gain of electrons (reduction) with its Ag+(aq) + e‒ → Ag(s) 𝐸 ° = 0.80 𝑉 (cathode)
corresponding standard electrode potential (the more positive the E° value, the Sn2+(aq) + 2 e‒ → Sn(s) 𝐸 ° = −0.14 𝑉 (anode)
more readily the reaction occurs)
Sn(s) → Sn2+(aq) + 2 e‒ 𝐸 ° = −0.14 𝑉
KEY POINTS 2 Ag+(aq) + 2 e‒ → Ag(s) 𝐸 ° = 0.80 𝑉
1. All values are relative to the standard hydrogen (reference) electrode: Sn(s) + 2 Ag+(aq)→ Sn2+(aq) + Ag(s) °
𝐸𝑐𝑒𝑙𝑙 °
= 𝐸𝑠𝑖𝑙𝑣𝑒𝑟 °
− 𝐸𝑡𝑖𝑛 = 0.94 𝑉
°
2 H+(aq; 1 M) + 2 e‒ ⇌ H2(g; 1 atm) 𝐸𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 = 0.00 𝑉
2. By convention, the half – reactions are written as reductions, which means that SAMPLE PROBLEMS
ONLY REACTANTS are OXIDIZING AGENTS and ONLY PRODUCTS are 1. Combine the following three half – reactions into three balanced equations for
REDUCING AGENTS. °
spontaneous reactions, and calculate 𝐸𝑐𝑒𝑙𝑙 . Rank the relative strengths of the
°
3. The more positive the 𝐸ℎ𝑎𝑙𝑓− 𝑐𝑒𝑙𝑙 , the more readily the half – reactions occurs. oxidizing and reducing agents.
4. Half – reactions are shown with an equilibrium arrow because each can occur as (A) NO3‒ (aq) + 4 H+(aq) + 3 e‒ → NO(g) + 2 H2O(l) 𝐸 ° = 0.96 𝑉
a reduction or an oxidation (take place at the cathode and anode, respectively) (B) N2 (g) + 5 H (aq) + 4 e → N2 H5 (aq)
+ ‒ + 𝐸 ° = − 0.23 𝑉
°
depending on 𝐸𝑐𝑒𝑙𝑙 of the other half – reaction. (C) MnO2 (s) + 4 H+(aq) + 2 e‒ → Mn2+ (aq) + 2 H2O(l) 𝐸 ° = 1.23 𝑉
5. The strength of the OXIDIZING AGENT (REACTANT) INCREASES GOING UP 2. Use the following half – reactions to write three spontaneous reactions, calculate
(BOTTOM TO TOP) and the strength of the REDUCING AGENT (PRODUCT) °
𝐸𝑐𝑒𝑙𝑙 for each reaction, and rank the strengths of the oxidizing and reducing
INCREASES GOING DOWN (TOP TO BOTTOM). strengths.
(A) Al3+(aq) + 3 e‒ → Al(s) 𝐸 ° = −1.66 𝑉
WRITING SPONTANEOUS READOX REACTIONS (B) N2O4 (g) + 2 e → NO2 (aq)
‒ ‒ 𝐸 ° = 0.867 𝑉
- Every redox reaction is the sum of two half – reactions, so there is a reducing (C) SO42‒ (aq) + H2O(l) + 2 e‒ → SO32‒ (aq) + 2 OH‒-(aq) 𝐸 ° = 0.93 𝑉
agent and oxidizing agent
- The stronger oxidizing and reducing agents reacts spontaneously to form a RELATIVE PROPERTIES OF METALS
weaker oxidizing and reducing agents - The activity series of the metals ranks metals by their abilities to “displace” one
- The stronger oxidizing agent (species on the left) has a half – reaction with a another from aqueous solution
larger (more positive or less negative) E° value, and the stronger reducing
agent (species on the right) has a half – reaction with a smaller (less positive 1. METALS THAT CAN DISPLACE H2 FROM ACID
or more negative) E° value - The standard hydrogen half –reaction represents the reduction of H+ ions from
- For a spontaneous reaction to occur, the half – reaction HIGHER in the list an acid
proceeds at the CATHODE AS WRITTEN, and the half reaction LOWER in the 2 H+(aq) + 2 e‒ → H2(g)𝐸 ° = 0.00 V
list proceeds at the ANODE IN REVERSE.
- To see which metals reduce H+ from acids, choose a metal, write its half – 4. METALS THAT CAN DISPLACE OTHER METALS FROM SOLUTION
reaction as an oxidation, combine this half – reaction with the hydrogen half – - Any metal that is lower in the list in Appendix D can reduce the ion of a metal
° that is higher up and thus displace that metal from solution
reaction and see if 𝐸𝑐𝑒𝑙𝑙 is positive
- The metals Li through Pb that lie below the standard hydrogen (reference) half –
°
reaction in Appendix D, give a positive 𝐸𝑐𝑒𝑙𝑙 when reducing H+ Zn(s) → Zn2+(aq) + 2 e‒ 𝐸 ° = − 0.76 V
Fe+(aq) + 2 e‒ → Fe(s) 𝐸 ° = − 0.44 V_
°
Fe(s) → Fe2+(aq) + 2 e‒ 𝐸 ° = − 0.44 V Zn(s) + 2 Fe (aq) → Zn (aq) + Fe(s) 𝐸𝑐𝑒𝑙𝑙
2+ 2+ = 0.32 V
2 H+(aq) + 2 e‒ → H2(g) 𝐸 ° = 0.00 V________
Fe(s) + 2 H+(aq) → Fe2+(aq) + H2(g) °
𝐸𝑐𝑒𝑙𝑙 = 0.44 V FREE ENERGY AND ELECTRICAL WORK

- The lower the metal in the list, the stronger it is as a reducing agent; the more STANDARD CELL POTENTIAL AND THE EQUILIBRIUM CONSTANT
positive its half – cell potential when the half – reaction is reversed, and the - A spontaneous reaction has a negative free energy change (∆G < 0) and that a
°
higher the 𝐸𝑐𝑒𝑙𝑙 for its reduction of H+ to H2 spontaneous electrochemical reaction has a positive cell potential (𝐸𝑐𝑒𝑙𝑙 > 0)
- °
If 𝐸𝑐𝑒𝑙𝑙 for the reducing of H+ is more positive for metal A than it is for metal B, - The signs of ∆G and 𝐸𝑐𝑒𝑙𝑙 are opposite for a spontaneous reaction and these two
metal A is a stronger reducing agent than metal B and more active metal indications of spontaneity are proportional to each other

2. METALS THAT CANNOT DISPLACE H2 FROM ACID ∆G ∝ − 𝐸𝑐𝑒𝑙𝑙

- Metals that are above the standard hydrogen (reference) half – reaction cannot
reduce H+ from acids - We determine this proportionality constant by focusing on the electrical work
°
- When we reverse the metal half – reaction, the 𝐸𝑐𝑒𝑙𝑙 is negative done (w, in joules) which is the product of the potential (𝐸𝑐𝑒𝑙𝑙 , in volts) and the
amount of charge that flows (in coulombs)
2 Ag(s) → 2 Ag+(aq) + 2 e‒ 𝐸 ° = 0.80 V
w = 𝐸𝑐𝑒𝑙𝑙 x charge
2 H+(aq) + 2 e‒ → H2(g) 𝐸 ° = 0.00 V___
°
2 Ag(s) + 2 H+(aq) → Ag+(aq) + H2(g) 𝐸𝑐𝑒𝑙𝑙 = − 0.80 V - The value used for 𝐸𝑐𝑒𝑙𝑙 is measured with no current flowing, therefore no
°
energy lost to heating the cell (𝐸𝑐𝑒𝑙𝑙 is the maximum voltage the cell can generate
- The higher the metal in the list, the more negative is its 𝐸𝑐𝑒𝑙𝑙 for the reduction of and the maximum work the system can do on the surroundings)
H+ to H2, the lower is its reducing strength and the less active it is - For no current to flow and the process to be reversible, 𝐸𝑐𝑒𝑙𝑙 must be opposed by
an equal potential in the measuring circuit (a reversible process means that the
3. METALS THAT CAN DISPLACE H2 FROM WATER opposing potential is infinitesimally smaller, the reaction goes forward; if it is
- Metals that lie below the half – reaction for the reduction of water infinitesimally larger, the reaction goes backward)
2 H2O(l) + 2 e‒ → H2(g) + 2 OH‒-(aq) E = − 0. 42 V 𝑤𝑚𝑎𝑥 = 𝐸𝑐𝑒𝑙𝑙 𝑥 charge = − ∆G
∆G = −𝐸𝑐𝑒𝑙𝑙 𝑥 charge
- The alkali metals (Group 1) and the larger alkaline earth metals (Group 2) can
displace H2 from H2O - The charge that flows through the cell equals the number of moles of electrons
(n) transferred times the charge of 1 mole of electrons (F)
2 Na(s) → 2 Na+(aq) + 2 e‒ 𝐸 ° = − 2.71 V
2 H2O(l) + 2 e‒ → H2(g) + 2 OH‒ (aq) E = − 0. 42 V___ charge = nF
2 Na(s) + 2 H2O(l) → 2 Na+(aq) + H2(g) + 2 OH‒(aq) 𝐸𝑐𝑒𝑙𝑙 = 0.29 V
- The charge of 1 mol of electrons is the Faraday constant and because 1 V = 1 J/C,
and 1 C = 1 J/V
° Reaction at standard – state
𝐽 ∆G° K 𝐸𝑐𝑒𝑙𝑙
F = 9.65 x 104 𝑉𝑚𝑜𝑙𝑒 − condition
<0 >1 >0 Spontaneous
- Substituting for charge, the proportionality constant is nF 0 1 0 At equilibrium
>0 <1 <0 Nonspontaneous
∆G = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
° 𝑅𝑇
- It is common practice to simplify equation 𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹 ln K in calculations by:
- When all the components are in their standard states, we have - Substituting the known value of 8.314 J/mol rxn.K for the constant R
𝐽
°
- Substituting the known value of 9.65 x 104 for the constant F
∆G° = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 𝑉𝑚𝑜𝑙𝑒 −
- Substituting the standard temperature of 298.15 K for T, but keeping in mind
that the cell can run at other temperature
- Using the relationship, we can relate the standard cell potential to the
- Multiplying by 2.303 to convert from natural to common (base – 10) logarithms
equilibrium constant of the redox reaction
- Thus, when n moles of e- are transferred per mole of reaction in the balanced
°
∆G° = − RT ln K equation, the simplified equation between 𝐸𝑐𝑒𝑙𝑙 and K gives

° 𝑅𝑇 𝑅𝑇
- Substituting for ∆G° 𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹 ln K = 2.303 𝑛𝐹 log K

°
−𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = − RT ln K 8.314
𝐽
(298.15 𝐾)
= 2.303 𝑚𝑜𝑙 𝑟𝑥𝑛 𝑘
𝑛 𝑚𝑜𝑙 𝑒− 𝐽 log K
(9.65 x 104 )
𝑚𝑜𝑙 𝑟𝑥𝑛 𝑉𝑚𝑜𝑙𝑒−

° 0.0592 𝑉 𝑛𝐸 °
𝐸𝑐𝑒𝑙𝑙 = 𝑛
log K or log K = 0.0592
𝑐𝑒𝑙𝑙
𝑉
at (298 K)
°
- Solving for 𝐸𝑐𝑒𝑙𝑙
SAMPLE PROBLEMS
°
𝐸𝑐𝑒𝑙𝑙
𝑅𝑇
= 𝑛𝐹 ln K 1. Lead can displace silver from solution:
Pb(s) + 2 Ag+(aq) → Pb2+(aq) + Ag(s)

∆G° As a consequence, silver is a valuable by – product in the industrial extraction of

lead from its ore. Calculate K and ∆G° at 298 K for this reaction.

°
∆G° = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 ∆G° = − RT in K
2. When cadmium metal reduces Cu2+ in solution, Cd2+ forms in addition to copper
°
metal. If ∆G° =−143 kJ, calculate K at 25°C. What is 𝐸𝑐𝑒𝑙𝑙 of a voltaic cell that uses
this reaction?

°
𝐸𝑐𝑒𝑙𝑙 K
° 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = ln K
𝑛𝐹
THE EFFECT OF CONCENTRATION ON CELL POTENTIAL SAMPLE PROBLEMS
- Most cell do not start with all components in their standard states and even if 1. In a test of a new reference electrode, a chemist constructs a voltaic cell
they did, the concentrations change after a few moment of operation consisting of a Zn/Zn2+ half – cell and H2/H+ half – cell under the following
- Based on the relation between free energy and concentration, we can derive an conditions:
expression for the relation between cell potential and concentration [Zn2+ ] = 0.010 M [H+] = 2.5 M PH2 = 0.30 atm
- ∆G equals ∆G° (the free energy change when the system moves from standard – Calculate 𝐸𝑐𝑒𝑙𝑙 at 298 K.
state concentrations to equilibrium) plus RT in Q (the free energy change when
the system moves from nonstandard – state to standard state concentrations) 2. Consider a voltaic cell based on the following reaction: Fe(s) + Cu2+(aq) →
Fe2+(aq) + Cu(s). If [Cu2+] = 0.30 M, what must [Fe2+] be to increase 𝐸𝑐𝑒𝑙𝑙 by 0.25
∆G = ∆G° + RT ln Q °
V above 𝐸𝑐𝑒𝑙𝑙 at 25°C?
°
- ∆G is related to 𝐸𝑐𝑒𝑙𝑙 and ∆G° to 𝐸𝑐𝑒𝑙𝑙 , so we substitute for them and get CHANGES IN POTENTIAL DURING CELL OPERATION

° Changes in 𝐸𝑐𝑒𝑙𝑙 and Concentration

−𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 + RT ln Q
Stage in cell Relative [P] 0.0592 𝑉
Q log 𝑄
- Dividing both side by – nF, we obtain the Nernst equation operation and [R] 𝑛
1. E > E° <1 [P] < [R] <0
𝑅𝑇
°
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln Q 2. E = E° =1 [P] = [R] =0
𝑛𝐹
3. E < E° >1 [P] > [R] >0
- The equation says that a cell potential under any conditions depends on the cell 4. E = 0 =K [P] >> [R] = E°
potential at standard – state concentrations
- °
When Q < 1 and thus [reactant] > [product], ln Q < 0, so 𝐸𝑐𝑒𝑙𝑙 > 𝐸𝑐𝑒𝑙𝑙 - The cell potential in terms of the starting Q/K ratio:
° - If Q/K < 1, 𝐸𝑐𝑒𝑙𝑙 is positive for the reaction as written. The smaller the Q/K ratio,
- When Q = 1 and thus [reactant] = [product], ln Q = 0, so 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙
° the greater the value of 𝐸𝑐𝑒𝑙𝑙 , and the more electrical work the cell can do.
- When Q > 1 and thus [reactant] < [product], ln Q > 0, so 𝐸𝑐𝑒𝑙𝑙 < 𝐸𝑐𝑒𝑙𝑙
- If Q/K = 1 and 𝐸𝑐𝑒𝑙𝑙 = 0. The cell is at equilibrium and can no longer do work.
- If Q/K >1, 𝐸𝑐𝑒𝑙𝑙 is negative for the reaction as written. The reverse reaction will
- To obtain a simplified form of the Nernst equation for use in calculation, we
take place, and the cell will do work until Q/K equals 1 at equilibrium.
substitute the known values for R and F and operate the cell at 298.15 K, and
convert to common (base – 10) logarithms:
CONCENTRATION CELL
° 𝑅𝑇 𝑅𝑇 - If you mix a concentrated solution of a salt, the final concentration equals some
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑛𝐹 ln Q = 2.303 𝑛𝐹 log Q intermediate value
- A concentration employs this phenomena to generate electrical energy
8.314
𝐽
(298.15 𝐾) - The two solutions are in separate half – cells so they do not mix rather their
= 2.303 𝑚𝑜𝑙 𝑟𝑥𝑛 𝑘
𝑛 𝑚𝑜𝑙 𝑒− 𝐽 log Q concentrations become equal as the cell operates
(9.65 x 104 )
𝑚𝑜𝑙 𝑟𝑥𝑛 𝑉𝑚𝑜𝑙𝑒−
- In a concentration cell, the half reaction are the same but the concentrations are
° 0.0592 𝑉 different
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log Q (at 298 K) °
𝑛 - As a result, even though 𝐸𝑐𝑒𝑙𝑙 equals zero, the nonstandard cell potential, 𝐸𝑐𝑒𝑙𝑙 ,
does not equal to zero because it depends on the ratio of the concentration
- The expression for Q contains only those species with concentrations (and/or
pressures) that can vary
EXAMPLE
A concentration cell has 0.10 M Cu2+ in the anode half – cell and 1.0 M Cu2+ in the
cathode half – cell. Calculate for the value of 𝐸𝑐𝑒𝑙𝑙 .

Solution:
Cu(s) → Cu2+(aq; 0.10 M) + 2 e-
Cu2+(aq; 1.0 M) + 2 e- → Cu(s)_______________
Cu2+(aq; 1.0 M0 → Cu2+(aq; 0.10 M) 𝐸𝑐𝑒𝑙𝑙 = ?

° 0.0592 𝑉
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑛
log Q
° 0.0592 𝑉 [𝐶𝑢2+ ]
= 𝐸𝑐𝑒𝑙𝑙 − log 2+
𝑛 [𝐶𝑢 ]
0.0592 𝑉 0.10 𝑀
= 0 V – ( 2 log 1.0 𝑀 )
0.0592 𝑉
= 0 V – [ 2 (− 1.00)]
= 0. 0296 V

SAMPLE PROBLEMS
1. A concentration cell consists of two Ag/Ag+ half – cells. In half – cell A, electrode
A dips into 0.010 M AgNO3; in half – cell B, electrode B dips into 4.0 x 10-4 M
AgNO3. What is the cell potential at 298 K? Which electrode has a positive
charge?

2. A concentration cell is built using two Au/Au3+ half – cells. In half – cell a, [Au3+]
= 7.0 x 10-4 M and in half – cell B, [Au3+] = 2.5 x 10-2 M. What is 𝐸𝑐𝑒𝑙𝑙 , and which
electrode is negative?