Electrochemical cell - HL

Cell representation
An electrochemical cell can be represented in short form

A Zn-Cu electrochemical cell can be written as

 Electrode potential
When a piece of metal is placed in
an aqueous solution of its cations,
a chemical equilibrium known as a
redox equilibrium is established
b/w metal and its cations

The position of equilibrium depends on the reactivity (reducing

strength) of the metal.

For example, when a piece of zinc, a relatively reactive metal, is

placed in an aqueous solution of zinc ions, the equilibrium lies to
the right-hand side:
Electrode potential
When Zn electrode is dipped in the salt
solution, the zinc electrode mass deceases
slightly as more atoms will form ions by
releasing electrons.

This makes the surface of the metal negatively

charged with respect to the solution.

A charge separation develops between the

zinc metal and its ions and this is known as
electrode potential
 Electrode potential
The opposite process occurs when copper,
a relatively unreactive metal, is placed in an
aqueous solution of copper(ii) ions.
In this reaction the equilibrium lies to the
left-hand side:

The mass of the original piece of copper increases slightly and

the concentration of copper(ii) ions in solution decreases slightly.

The overall reaction involves the deposition of copper(ii) ions as

copper atoms and so as a consequence the surface of the piece
of copper gains a positive charge.
 Electrode potential
When these two half-cells are connected by an external wire,
electrons will flow spontaneously from the zinc half-cell to the
copper half-cell because of their different electrode potentials.
 Standard electrode potentials
Electrode potentials measured under standard (298 K (25o C),
100 kPa for all gases and all concentrations of 1 moldm−3),
are always given for the reduction reaction and are sometimes
also known as standard reduction potentials.

Table 24 in data booklet give standard reduction potentials

Increasing
tendency to
occur as
reduction
 Standard Hydrogen Electrode (SHE)
Electrode potential of half cell cannot be determined as
oxidation and reduction occurs simultaneously
So, to determine the electrode potential of half cells, standard
hydrogen electrode is used

A Standard
hydrogen electrode
consists of a
platinum electrode in
contact with 1
moldm-3 hydrogen
ions and hydrogen
gas at 298K and
100kPa.
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 Standard Hydrogen Electrode (SHE)
In the standard hydrogen electrode, hydrogen gas at 1 atm
pressure is bubbled around a platinum electrode of very high
surface area in a solution of H+ ions of concentration 1 moldm−3.

Platinum is chosen as it is an inert metal, has very little tendency

to be oxidized and does not react with acid.

SHE can act as either electrode

As cathode
As anode

It is assigned a standard electrode potential (E ) of 0.00 V.

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 Using Standard Reduction Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

E0cell= EH0+/H2 - EZn
0 2+
/Zn
0 2+
EZn
0 2+ /Zn = -0.76 V
0.76 V = 0 - EZn /Zn
 Using Standard Reduction Potentials

0 = E0
Ecell 0
cathode - Eanode 0 2+
ECu /Cu = 0.34 V

Cu /Cu – EH +/H 2
0 = E 0 2+
Ecell 0

0 2+
0.34 = ECu /Cu - 0
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 Question
E⊝ for the Cu2+(aq)/Cu(s) half-cell is +0.34 V. What does the
positive sign for E⊝ indicate?

The positive sign for E⊝ indicates that:

◼Cu half-cell forms the positive electrode when connected to the
standard hydrogen electrode
◼Electrons flow from the hydrogen half-cell, which is oxidized, to
the Cu half-cell, which is reduced.
◼H2 is a better reducing agent than Cu
◼H2 is above Cu in activity series.

Anode (oxidation): H2(g) → 2H+(aq) + 2e–

Cathode (reduction): Cu2+(aq) + 2e– → Cu(s)
Overall reaction: Cu2+(aq) + H2(g) → 2H+(aq) + Cu(s)
Copper has a higher tendency to be reduced than H+.
 Electromotive Force (emf) - HL
• The potential difference between the anode and
cathode in a cell is called the electromotive force (emf).

• It is also called the cell potential, Ecell

Potential difference = voltage = EMF = cell potential Eocell

  (cathode) − Ered
 (anode)
Ecell = Ered
Remember - Eo values are given as
reduction potential and the
magnitude of cell voltage depends
on the difference in the tendencies
of the two half-cells to undergo
reduction
 Cell Potentials

• For the oxidation in this

 cell,
Ered = −0.76 V

• For the reduction,

 = +0.34 V
Ered


Ecell  (cathode) − E  (anode)
= Ered red

= +0.34 V − (−0.76 V)
= +1.10 V
 Standard electrode potential - Key points
•The standard electrode potential is always quoted for
a reduction reaction.

•The more positive the standard electrode potential,

the stronger the oxidizing agent.

•The more negative the standard electrode potential,

the stronger the reducing agent.
•The sign of E0 changes when the reaction is reversed
•Changing the stoichiometric coefficients of a half-cell
reaction does not change the value of E0
 Question
◼ Which statement is correct about the value of Eο?

A. The more positive the value of Eο, the greater the

driving force for reduction.
B. The more negative the value of Eο, the greater the
driving force for reduction.
C.The more positive the value of Eο, the greater the rate
of reaction.
D.The more negative the value of Eο, the greater the rate
of reaction.
 Using standard electrode potential data

3 applications of using E⊝ data:

1. Calculating the cell potential, E⊝ cell
2. Determining spontaneity of a reaction
3. Comparing relative oxidizing and reducing power of
half-cells

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Copper half-cell will be reduced (higher E⊝ value), and zinc
half-cell will be oxidized. Electrons flow from zinc (anode) to
copper (cathode).
E
cell = E  (cathode) − E  (anode)
red red
 Write balance equations and calculate the standard emf of
an electrochemical cell made of a Cd electrode in a 1.0 M
Cd(NO3)2 solution and a Cr electrode in a 1.0 M Cr(NO3)3
solution?
Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V Cd is the stronger oxidizer
Cr3+ (aq) + 3e- Cr (s) E0 = -0.74 V Cd will oxidize Cr

Anode (oxidation): Cr (s) Cr3+ (aq) + 3e- x 2

Cathode (reduction): 2e- + Cd2+ (aq) Cd (s) x 3
2Cr (s) + 3Cd2+ (aq) 3Cd (s) + 2Cr3+ (aq)

0 = E0
Ecell 0
cathode - Eanode

0 = -0.40 – (-0.74)
Ecell
0 = 0.34 V
Ecell
Question - Use E⊝ values to deduce the reaction that occurs
when Cu(s) and Ag(s) are added to a solution that contains
Cu2+(aq) and Ag+(aq). Write the equation for this reaction and
calculate the EMF of the cell.

Ag+(aq) + e– ⇌ Ag(s) E⊝ = +0.80 V

Cu2+(aq) + 2e– ⇌ Cu(s) E⊝ = +0.34 V
Silver half-cell will be reduced (higher E⊝ value), and copper
half-cell will be oxidized. Electrons flow from copper to silver
◼ Anode (oxidation): Cu(s) → Cu2+(aq) + 2e–
◼ Cathode (reduction): 2Ag+(aq) + 2e– →2Ag(s)
◼ Overall reaction: Cu(s) + 2Ag+(aq) →2Ag(s) + Cu2+(aq)

E⊝cell = +0.80 – (+0.34) = +0.46 V

Question

1. Identify the reducing agent

Mg
2. Write over cell reaction

3. Calculate Eocell
Question
 2. Determining spontaneity of a reaction

A voltaic cell will always run in the direction that gives a

positive value for the E⊝ cell:

❑ If E⊝ cell is positive, the reaction is spontaneous as

written.

❑ If E⊝ cell is negative, the reaction is non-spontaneous,

and the reverse reaction is spontaneous.
 Question
Use E⊝ values to determine whether the reaction
Ni(s) + Mn2+(aq) → Ni2+(aq) + Mn(s)
will occur spontaneously under standard conditions.
Solution
Ni2+(aq) + 2e– ⇌ Ni(s) E⊝ = – 0.26 V
Mn2+(aq) + 2e– ⇌ Mn(s) E⊝ = –1.18 V
◼ In the reaction given, Ni is oxidized and Mn2+ is reduced.
◼ Substituting in the equation:
◼ E⊝cell = E⊝Ni2+ – E⊝Mn2+
◼ E⊝cell = –1.18 – (–0.26) = –0.92 V
◼ The negative sign for E⊝cell tells us that this reaction
will NOT happen spontaneously!
 Question
Consider the following standard electrode potentials.
Zn2+(aq) + 2e– ⇌ Zn(s) EO = –0.76 V
Mg2+(aq) + 2e– ⇌ Mg(s) EO = –2.37 V
What will happen when zinc powder is added to an aqueous
solution of magnesium chloride?

A. No reaction will take place.

B. Chlorine gas will be produced.
C. Magnesium metal will form.
D. Zinc chloride will form.
 E⊝cell and ΔG⊝
Two quantitative measures of the spontaneity of a reaction:
E⊝cell and ΔG⊝

The two are related as

ΔG⊝ = – n F E⊝cell
n = number of moles of electrons transferred in the reaction;
F = Faraday constant (= 96500 C mol–1). It is the charge carried
by 1 mole of electrons

Important - For a reaction to be spontaneous

E⊝cell Should be +ve
ΔG⊝ Should be -ve
 Question

Calculate the standard free-energy change at 298 K for

the zinc–copper voltaic cell, which has a standard cell
potential of +1.10 V.

First write the equation for the overall cell reaction, as

we need to know the number of electrons transferred.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
ΔG⊝ = – nFE⊝
ΔG⊝ = – 2 (mol) . 96 500 (C mol–1) x 1.10 (V)
ΔG⊝ = – 212,000 J = –212 kJ

Note that J = C x V
 Question
Use the standard electrode potentials to calculate the Eo
and ΔGo values for the following reaction:

State whether the reaction is spontaneous under

standard conditions.
 Summary
▪ Half-cell with the more negative (lower) electrode
potential (–) is the anode as oxidation occurs there.

▪ Half-cell with the more positive (higher) electrode

potential (+) is the cathode as reduction occurs there.

▪ Electrons always flow through the external circuit in a

voltaic cell from the half-cell with the more
negative/lower E⊝ value (anode) to the half-cell with
the more positive/higher E⊝ value (cathode).
 3. Comparing relative oxidizing &
reducing power of half-cells
• Strong oxidizing agents have high positive Eo
values and undergo reduction easily by gaining
electrons.

• Strong reducing agents have high negative Eo

values and undergo oxidation easily by losing
electrons.

• Therefore, the Eo values can be used to

compare the relative tendencies of half-cells to
undergo oxidation or reduction.
3. Comparing relative oxidizing &
reducing power of half-cells
 Question
From the following data
Cu2+(aq) + 2e– ⇌ Cu(s) E⊝ = +0.34 V
Mg2+(aq) + 2e– ⇌ Mg(s) E⊝ = –2.37 V
Zn2+(aq) + 2e– ⇌ Zn(s) E⊝ = –0.76 V
Identify the strongest oxidizing agent and the strongest
reducing agent.
Strongest oxidizing agent = Cu2+
The species with the higher E⊝ is the most easily reduced. Cu2+
is the most easily reduced, so is the strongest oxidizing agent.

Strongest reducing agent = Mg

The species with the lowest E⊝ is the hardest to reduce but its
reverse reaction will have the species that is the most easily oxidized.
Mg is the species most easily oxidized, so is the strongest reducing
agent.
 Question
Identify the stronger oxidizing agent

Cr2O72− has a more positive standard electrode

potential than I2, and therefore Cr2O72− is a stronger
oxidising agent than I2 and will oxidise I− to I2.

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 Question
Use the standard electrode potentials on page 23 of the IB
Chemistry data booklet to arrange the following oxidizing agents in
increasing order of oxidizing strength (under standard conditions):
• Potassium manganate(vii) (in acidic solution)
• Iodine
• Iron(iii) ions
• Oxygen (in acidic solution)

The standard electrode potentials are:

iodine, iron(iii) ions, oxygen (in acidic solution) and potassium

manganate(vii) (in acidic solution).
 Question
A solution containing potassium manganate(VII) and conc.
hydrochloric acid reacts to form chlorine gas. Identify the
strongest oxidizing agent in the solution and calculate the
standard cell potential.

First extract the relevant half-equations from table 14 in the

IB data booklet

Cl- is being oxidized to Cl2 and MnO4- is being reduced

Reaction is spontaneous and MnO4- is the stronger oxidizing

agent as it has the higher value for E⊝ so it will be reduced.