REDOX PROCESSES

ELECTROCHEMICAL CELLS
 ESSENTIAL IDEA
Energy conversions between electrical
and chemical energy lie at the core of
electrochemical cells.
NATURE OF SCIENCE (3.1)
Employing quantitative reasoning – electrode
potentials and the standard hydrogen electrode.
NATURE OF SCIENCE (4.5)
Collaboration and ethical implications – scientists
have collaborated to work on electrochemical cell
technologies and have to consider the environmental
and ethical implications of using fuel cells and
microbial fuel cells.
 INTERNATIONAL-MINDEDNESS
Many electrochemical cells can act as
energy sources alleviating the world’s
energy problems but some cells such as
super-efficient microbial fuel cells
(MFCs) (also termed biological fuel
cells) can contribute to clean up of the
environment. How do national
governments and the international
community decide on research
priorities for funding purposes?
 UNDERSTANDING/KEY
IDEA 19.1.A
A voltaic cell generates an
electromotive force (EMF) resulting in
the movement of electrons from the
anode (negative electrode) to the
cathode (positive electrode) via the
external circuit. The EMF is termed
the cell potential (E◦).
 STANDARD ELECTRODE
POTENTIALS
• Voltaic cells generate an electromotive (emf) measured
in volts as electrons flow from the half-cell with the more
negative potential to the half-cell with the more positive
potential.
• The magnitude of this voltage depends upon the
difference in the tendencies of the 2 half-cells to undergo
reduction.
• No one half-cell can be measured in isolation.
• We need a fixed reference point that acts as a standard
for measurement – Standard Hydrogen Electrode.
 UNDERSTANDING/KEY
IDEA 19.1.B
The standard hydrogen electrode (SHE)
consists of an inert platinum electrode in
contact with 1 mol/dm3 hydrogen ion
and hydrogen gas at 100 kPa and 298 K.
The standard electrode potential (E◦) is
the potential (voltage) of the reduction
half-equation under standard conditions
measured relative to the SHE. Solute
concentration is 1 mol/dm3 or 100kPa for
gases. (E◦) of the SHE is 0V.
 STANDARD HYDROGEN
ELECTRODE
• The standard hydrogen electrode is assigned an
electrode
potential of 0V.
• The concentration of the HCl
is 1.0 mol/dm3.
• The H2 gas is at 298K
and 100 kPa.
• The metal is platinum.
• Platinum is chosen because it is a fairly inert metal that
will not ionize.
• The reaction on the electrode happens rapidly as the
large surface area helps with the adsorption of hydrogen
gas.
• Adsorption only occurs on the surface.
• As the electrode is immersed in the acid, an equilibrium is
set up between the adsorbed layer of H2 gas and the H+
ions.
2H+(aq) + 2e- → H2(g)
• The reaction is reversible, occurring as the reduction of
H+ (forward rxn) or the oxidation of H2 (backward rxn)
depending upon the electrode potential of the half-
cell to which it is linked.
• The hydrogen half-cell is arbitrarily assigned an
electrode potential of 0V. This gives us a means to
measure and compare the electrode potential of any
other half-cell to which it is connected.
 STANDARD CONDITIONS
• The following variables must be controlled to compare
standard electrode potentials:
• All solutions must be 1.0 mol/dm3
• All gases must have a pressure of 100kPa
• All substances must be pure.
• Temperature is 298K or 25˚C.
• If the half-cell does not include a metal, platinum must
be used as the electrode.
 STANDARD ELECTRODE
POTENTIAL E˚
• Half-cells under the conditions listed previously are
known as standard half-cells.
• When the standard hydrogen electrode is connected
to another standard half-cell, the emf generated is
known as the standard electrode potential (E˚) of that
half-cell.
• E means electrode potential and ˚ means carried out at
standard conditions.
• Positive values for E˚ mean that electrons flow from
hydrogen to the metal electrode.
• The hydrogen is oxidized (anode) and the metal is reduced
(cathode).
• Negative values for E˚ mean that electrons flow from the
metal to the hydrogen electrode.
• The hydrogen is reduced (cathode) and the metal is
oxidized (anode).
• Let’s refer back to our previous activity series to make
sense of all of this.
Mg -2.37 V strongest reducing agent
Al -1.66 V (most readily oxidized)
Zn -0.76 V
Fe -0.44 V
Pb -0.13 V
Hydrogen falls here 0.00 V
Cu +0.34
Ag +0.80 weakest reducing agent
(least readily oxidized)
Notice that H2 would be the cathode for the metals
above it and the anode for the metals below it on the
series.
• The more negative the E˚ the stronger the reducing agent
and the more readily it loses electrons or becomes oxidized.
• The more positive the E˚ the more it tends to be reduced.
• In a voltaic or galvanic cell, electrons always flow from
the half-cell with the more negative electrode potential
to the half-cell with the more positive electrode
potential.
• The more negative (lower) E˚ is always the anode and the
more positive (higher) E˚ is always the cathode.
 APPLICATION/SKILLS

Be able to calculate cell

potentials using standard
electrode potentials.
 CALCULATING CELL
POTENTIALS
• Electrons always flow towards the half-cell with the
highest or most positive E˚.
• The standard electrode potentials are listed in your IB
Data booklet.
• All values listed are reduction potentials so you will
have to reverse one of the values for the species
being oxidized.
• For a galvanic or voltaic cell, E˚ will always be positive
indicating a spontaneous reaction.
• Oxidation occurs with the E˚ of the more negative or
lower value.
• Reduction occurs with the E˚ of the more positive or
higher value.
• Do not multiply the E˚ by a factor as you do in Hess’s
law even if you had to multiply the equations by a
factor to get the electrons to cancel out.
 USES OF THE E˚ DATA
• You can predict spontaneity by using the reaction as it
is given and calculating E˚.
• You can also calculate the emf of a voltaic cell.
• You can be given 2 half reactions and be expected to
draw the cell, write the overall reaction and determine
E˚cell.
• You can compare oxidizing and reducing power of
half cells. (The more positive or higher E˚ is the strongest
oxidizing agent.)
 APPLICATION/SKILLS

Be able to predict whether a

reaction is spontaneous or not
using electrode potential (E◦)
values.
• If your calculations give you a positive E˚cell, then the
reaction is spontaneous.
• Remember that even though the E˚ can give you the
feasibility of a reaction, it does not give you any
information on the rate of the reaction.
• The activation energy may be too high for the reaction
to occur at any appreciable rate.
• Remember this on fundamental fact: Electrons
ALWAYS flow to the half-cell with the highest or most
positive value for E˚.
 UNDERSTANDING/KEY
IDEA 19.1.C
ΔG◦ = -nFE ◦ . When E is positive,
ΔG◦ is negative indicative of a
spontaneous process. When E ◦ is
negative, ΔG◦ is positive indicative
of a non-spontaneous process.
When E ◦ is 0, ΔG◦ is 0.
 APPLICATION/SKILLS

Be able to determine the standard

free-energy changes ΔG◦ using
standard electrode potentials.
• We now have 2 ways to measure the spontaneity of a
reaction, E ◦ and ΔG◦
• They are related by the equation
ΔG◦ = -nFE ◦
Where n is the number of moles of
electrons.
F (Faraday’s constant) is the
charge carried by 1 mol of electrons =
96,500 C/mol
• This equation allows us to calculate the free-energy
change of a reaction from standard electrode
potential data.
• The more positive the value for E, the more favorable
the reaction or more negative the delta G.
• A voltmeter is an indirect measure of free-energy
change as well as electrode potential.
 UNDERSTANDING/KEY
IDEA 19.1.D
When aqueous solutions are
electrolyzed, water can be
oxidized to oxygen at the anode
and reduced to hydrogen at the
cathode.
 APPLICATION/SKILLS

Be able to explain the products

formed during electrolysis of
aqueous solutions.
• The electrolysis of an aqueous solution involves ions
from the solvent water as well as the ions from the ionic
compound.
• More than one type of ion then migrates to the anode
and the cathode.
• Selective discharge is a process by which certain ions
are discharged at each electrode.
• The products of electrolysis are determined by the
following factors that influence the discharge of ions:
• The relative E˚ of the ions
• The relative concentrations of the ions in the electrolyte
• The nature of the electrode.
 ELECTROLYSIS OF WATER
• When electrolysis is carried out in an aqueous solution,
predicting the products is more difficult because water itself
can be oxidized or reduced.
• At the cathode, H2O can be reduced to H2:
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E˚= -.83V
• At the anode, H2O can be oxidized to O2:
2H2O(l) → 4H+(aq) + O2(g) + 4e- E˚= -1.23V
• The ionization of pure water is very low.
• However, the addition of ions increases its conductivity
so some ionic compound like NaOH is added when
electrolysis is performed.
• 1. Ions present: NaOH(aq) → Na+ + OH-
cathode anode
• 2. At the cathode:
• The possible reactions are:
• 2H2O(l) + 2e- → H2(g) + 2OH-(aq)
• Na+(aq) + e- → Na(s)
• E˚ for Na+ is -2.71V and E˚ for H2O is -.83V
• H2O is preferentially reduced because lower on the table (less
negative number); therefore, H2 is discharged.

2H2O(l) + 2e- → H2(g) + 2OH-(aq)

• 2. At the anode:
• The possible reactions are:
• 4OH-(aq) → 2H2O(l) + O2(g) + 4e-
• 2H2O(l) → 4H+(aq) + O2(g) + 4e-
• E˚ for OH- is -.40V and E˚ for H2O is -1.23V
• OH- is preferentially oxidized because it is higher on the table; less
negative when reversed.
• 3. The overall equation:
2H2O(l) → 2H2(g) + O2(g)
• 4. The observed changes at electrodes:
• A colorless gas evolved at both electrodes –
• O2 at anode and H2 at cathode
• The ratio of volume of gases is 2H2 to 1O2.
• The pH at the anode decreases as OH- is discharged (taken
away from the solution).
• The pH at the cathode increases as H+ is discharged (taken
away from the solution).
 ELECTROLYSIS OF
NACL(AQ)
• NaCl(aq) is known as brine.
• The electrolysis of brine leads to the production of H2,
Cl2 and NaOH.
• The electrolysis of NaCl(aq) and NaCl(l) are different
processes leading to different products.
• 1. Ions present: NaCl(aq) → Na+ + Cl-
cathode anode
• 2. At the cathode:
• Na+ and H+ accumulate.
• 2H2O(l) + 2e- → H2(g) + 2OH-(aq)
• Na+(aq) + e- → Na(s)
• E˚ for Na+ is -2.71V and E˚ for H2O is -.83V
• H2O is preferentially reduced and H2 is discharged.
• At the Anode:
• Cl- and OH- accumulate. The E˚ for OH- is lower than Cl- so we
would expect OH- to be preferentially oxidized, but it is more
complicated.
• When the concentration of Cl- is low, OH- is discharged leading to
the release of O2.
• But when the concentration of NaCl is greater than 25% by mass of
the solution, Cl- is discharged leading to the release of Cl2. 2Cl- →
Cl2 + 2e-
• The industrial electrolysis of brine uses saturated solutions of
aqueous NaCl to produce Cl2.
• 3. The overall equation when Cl- is discharged:
2NaCl(aq) + 2H2O(l) → 2H2(g) + Cl2(g) + 2Na+ +
2OH-
• 4. The observed changes at electrodes:
• A gas evolves at both electrodes –
• Cl2 at anode and H2 at cathode
• Cl2(g) is identified at the anode through its strong smell and
bleaching effect on blue litmus paper.
• An increase in pH of the electrolyte occurs due to the loss of H+.
 ELECTROLYSIS OF
• CuSO4(aq) CUSO
is bright blue due to the hydrated Cu ion.
2+
4(AQ)
• The electrolysis leads to different products depending
upon the nature of the electrodes: either carbon or
copper.
• 1. Ions present: CuSO4 (aq)→ Cu2+ + SO42-
cathode anode
(A) With Carbon (graphite) as the electrodes
2. At the cathode:
• Cu2+(aq) + 2e- → Cu(s)
• 2H2O(l) + 2e- → H2(g) + 2OH-(aq)
• E˚ for Cu2+ is +0.34V and E˚ for H2O is -0.83V
• Cu2+ is preferentially reduced and Cu(s) is discharged. Cu2+(aq)
+ 2e- → Cu(s)
At the Anode:
• SO42- and OH- accumulate. The E˚ for OH- is lower than SO42- so
OH- is discharged.
4OH-(aq) → 2H2O(l) + O2(g) + 4e-
• 3. The overall equation is:
2Cu2+(aq) + 2H2O(l) → 2Cu(s) + O2(g) + 4H+
• 4. The observed changes at electrodes:
• Pinky-brown color develops as copper is deposited on the
cathode.
• A colorless gas O2 is evolved at the anode.
• A decrease in pH of the electrolyte occurs due to the loss of OH-.
• Loss of intensity of blue color as Cu2+ is discharged.
(B) With copper as the electrodes
2. At the cathode:
• Cu2+(aq) + 2e- → Cu(s)
• 2H2O(l) + 2e- → H2(g) + 2OH-(aq)
• E˚ for Cu2+ is +0.34V and E˚ for H2O is -0.83V
• Cu2+ is preferentially reduced and Cu(s) is discharged.
Cu2+(aq) + 2e- → Cu(s)
At the Anode:
• The Cu electrode itself is oxidized, supplying electrons for the
reaction and dissolving as Cu2+.
Cu(s) → Cu2+(aq) + 2e-
• 3. So the net reaction is the movement of Cu2+ from
where it is produced at the anode to the cathode where
it is discharged as Cu(s).
• 4. The observed changes at electrodes:
• Pinky-brown color develops as copper is deposited on the
cathode.
• Disintegration of the Cu anode.
• No change in pH.
• No change in intensity of blue color as the concentration of Cu2+
remains constant.
 UNDERSTANDING/KEY
IDEA 19.1.E
Current, duration of electrolysis
and charge on the ion affect the
amount of product formed at the
electrodes during electrolysis.
 APPLICATION/SKILLS

Be able to determine the relative

amounts of products formed
during electrolytic processes.
• The three factors influencing the amount of products
are:
• The charge on the ion
• The current
• The duration of the electrolysis
• There are two types of problems involving electrolysis.
• Solve for amount of product.
• Solve for time.
 STEPS TO SOLVE FOR AMOUNT OF
PRODUCT IN ELECTROLYSIS
PROBLEMS
• Step 1: Multiply your current by your time.
1 ampere (amp) = 1 C/s where
C = coulomb and time
needs to be in seconds.
• Step 2: Multiply coulombs by mole e-/96500 C
to get moles of electrons
• Step 3: Divide by moles of electrons in the process.
• Step 4: Multiply by molar mass to get grams.
 GUIDANCE

Faraday’s constant = 96,500

C/mol is found in the data
booklet.
 EXAMPLE
• How much copper will be plated out when a current
of 10.0 amps is passed through a solution of Cu2+ ions
for 30.0 minutes? Cu2+ + 2e- → Cu(s)
• Step 1: Multiply your amps by your time (must
convert minutes to seconds first)
• 10.0 amps = 10.0 C/s x 30.0 min x 60 sec/min = 1.80 x 104 C
• Step 2: Multiply coulombs by 1 mol e-/96500 C to get
moles of e-
• 1.80 x 104 C x 1mol e-/96500 C = 1.87 x 10-1 mol e-
• Step 3: Divide by moles of electrons in equation.
• .187 mol e- x 1 mol Cu/2 mol e- = .0935 mol Cu
• Step 4: Multiply by molar mass to get grams
• .0935 mol Cu x 63.55g/mol = 5.94 g Cu
 SOLVING FOR TIME IN
ELECTROLYSIS
• Step 1: Divide grams by molar mass to
get moles.
• Step 2: Multiply by moles of electrons.
• Step 3: Multiply moles of electrons by
96500 C/moles e-
• Step 4: Divide by amps and convert to
minutes.
• How long must a current of 5.00 A be applied to a
solution of Ag+ to produce 10.5 g of silver?
• Step 1: Divide by molar mass to get moles.
• 10.5 g x mol/107.9g = .0973 mol
• Step 2: Multiply by moles of electrons.
• .0973 mol Ag x 1 mol e-/1 mol Ag = .0973 mol e-
• Step 3: Multiply by Faraday’s constant to get
Coulombs
• .0973 mol e- x 96500 C/mol e- = 9390 C
• Step 4: Divide by the given amps and convert to
minutes
• 9390 C x s/5.00C x min/60s = 31.3 min
 UNDERSTANDING/KEY
IDEA 19.1.F
Electroplating involves the
electrolytic coating of an object
with a metallic thin layer.
 APPLICATION/SKILLS

Be able to explain the process of

electroplating.
 ELECTROPLATING
• Electroplating is the process of using electrolysis to
deposit a layer of metal on top of another metal or
conductive substance.
• It must have the following features:
• An electrolyte containing the metal ions which are to be
deposited
• The cathode made of the object to be plated
• The anode can be the same metal if it is used to replenish
the supply of ions in the electrolyte.
• Process can be controlled by altering the current and
time according to how thick a layer of metal is desired.
 PURPOSES OF
ELECTROPLATING
• Decorative purposes
• Corrosion control
• Improvement of function
 CITATIONS
International Baccalaureate Organization. Chemistry
Guide, First assessment 2016. Updated 2015.
Brown, Catrin, and Mike Ford. Higher Level Chemistry.
2nd ed. N.p.: Pearson Baccalaureate, 2014. Print.
ISBN 978 1 447 95975 5
eBook 978 1 447 95976 2

Most of the information found in this power point comes

directly from this textbook.

The power point has been made to directly complement

the Higher Level Chemistry textbook by Brown and Ford
and is used for direct instructional purposes only.