Cruise School: Gebriel campus

Individual Assignment

Subject: Chemistry
Grade: 12

Total weight: equivalent to 6th model / mid exam

Submission date: on the day school reopen.
Assignment should be submitted in hard copy.
Assignment should be presented individually.

April 2020
 Grade 12 Chemistry

Unit 4

Electrochemistry

Contents
4.5.3 Standard reduction potential

4.5.4 Electromotive force (Emf)

4.5.5 Dependence of emf on concentration

4.5.6 Batteries

4.5.7 Corrosion of metals

At the end of this lesson the students will be able to

 Measure the cell potential of Zn-Cu cell using volt meter.

 Define electrode potential cell potential.
 Explain how standard electrode potential is measured.
 Describe the reactivity of metal from its position in the activity series or electromotive
series.
 Calculate cell potential.
 Describe whether a given redox reaction is spontaneous or not.
 Explain the effect of concentration on cell potential.
 Mention the difference types of voltaic cell.
 Give examples of each types of Galvanic cell.
 Describe how a hydrogen-oxygen fuel cell operates.
 Distinguish between primary and secondary cell.
 Identify the cathode, anode and electrolyte of a given Galvanic cell.
 Compare and contrast electrolytic and Galvanic cell.
 Explain the negative effect of corrosion.
 Explain metallic corrosion in terms of redox reaction.
 Explain the different methods of the prevention of corrosion.
4.5.3 Standard reduction potential

 Cell potential is the difference between two electrode potentials, one associated with
cathode and the other associated with the anode.
 Standard cell potential (E0cell) – is the standard reduction potential at the cathode reaction
minus the standard reduction potential at the anode reaction.

E0cell = E0red(cathode) – E0red (anode)

 By convention a standard electrode potential always refers to the half reaction written as
a reduction.
Example for Zn – Cu galvanic cell
Zn2+ + 2e-  Zn
Cu2+ + 2e-  Cu
 Reduction potential:- is a measure of tendency of a species to gain electrons in a redox
half reaction or the measure of the ability of the species to act as an oxidizing agent.
 Oxidation potential:- is a measure of the tendency of a species to lose electrons in a
redox half reaction or the measure of the ability of a species to act as reducing agent.
 It is not possible to directly measure the standard reduction potential of a half reaction.
However if we assign a standard reduction potential to a certain reference half reaction
we can then determine the standard reduction potentials of the other half reactions,
relative to that reference. The reference half-reaction is the reduction of H +(aq) to H2(g)
under the standard conditions which is given a standard reduction potential of exactly
0.0volt.
2H+(aq) + 2e-  H2(g, 1atm): E0red = 0.0v
 An electrode designed to produce this half – reaction is called a standard hydrogen
electrode. (SHE), it consists of plantinium wire connected to a piece of platinium foil
covered with finely-divided platinium that serves as an inert surface for the reaction.
The spontaneous reaction in the above figure is the oxidation of zinc and the reduction of H +.

Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)

In the above figure the Zn2+lZn electrode is the anode and the SHE is the cathode, the cell
voltage is 0.76v.

- By using the defined standard reduction potential of H+, we can determine the standard
reduction potential for Zn2+lZn half reaction.
E0cell = E0red(cathode) – E0red(anode)
0.76 = 0.0v - E0red(anode)
E0red(anode) = -0.76v

Therefore a standard reduction potential of -0.76v can be assigned to the reduction of Zn 2+ to Zn

Zn2+ + 2e-  Zn: E0red = -0.76

Note that we write the reaction as a reduction, even though it occurs in reverse as oxidation.
Whenever; we assigned a potential to a half – reaction, we write the reaction as a reduction.

 The following information are used during your calculations

1. The more positive E0red is the greater the tendency for the substance to be reduced
Example F2 + 2e-  2F-, E0red = +2.87v
Li+ + 1e-  Li; E0red = -3.05v
 Since the reduction of F2lF- has the highest positive E0red then F2 is more easily reduced
than Li+ ion, therefore; F2 is the strong oxidizing agent.
2. Under standard stage conditions any species on the left of a given cell reaction reacts
spontaneously with a species that appears on the right of any half-cell reaction. This
principle is sometimes called the diagonal rule.
Example Cu2+(1M) + 2e-  Cu(s); E0red = +0.34v
Zn2+ + 2e-  Zn(s); E0red = -0.76v
The substance on the left of the first half-cell reaction is Cu 2+, and on the right in the second
half-cell reaction is Zn. Therefore; Zn spontaneously reduces Cu 2+ to form Zn2+ and Cu.
3. Changing the stoichiometric coefficients of a half-cell reaction does not affect the value of
E0red, because electrode potentials are intensive properties. This means that the value of E 0red
is unaffected by the size of the electrode or the amount of solution present but it
dependent on the concentration of the solutions and the pressure of a gas (if any)
Example F2(g) + 2e-  2F-(1M), E0red = +2.87v
 But E0red does not change (not affected) if we multiply by 2
2F2(g) + 4e-  4F-(1M), E0red = +2.87v
4. The sign of E0red changes but its magnitude remain the same when we reverse a reaction.
E0red = - E00x
Cu2+(aq) + 2e-  Cu(s), E0red = +0.34v
CU(s)  Cu2+(aq), E00x = -0.34v
5. The more negative the reduction potential, the greater the tendency to donate an electron.
As a result, when two half-cell, reaction are coupled, the reaction with higher (more
negative) reduction potential proceeds as oxidation, while the other proceeds as Reduction.
Example Ni2+(aq) + 2e-  Ni(s), E0red = -0.25v
Fe2+(aq) + 2e-  Fe(s), E0red = -0.44v
Therefore; Fe(s) has the greater tendency to donate electron than Ni(s). So, Fe
spontaneously reduces Ni2+ to form Fe2+ and Ni(s).
Fe(s) + Ni2+(aq)  Fe22+(aq) + Ni(s)
E0cell = E0red(cathode) - E0red(anode)
E0cell = -0.25v – (-0.44v) = 0.29v
Exercise 4.9
1. What is the standard emf (E0cell) of Galvanic cell which is made of a Cd electrode in 1.0M
Cd(NO3)2 solution and a Cr electrode in a 1.0M Cr(NO3)3 solution at 250C.
E0Cd2+lCd = -0.41v
E0Cr3+lCr = -0.74v
2. Given the following over all reaction
Cu2+(1M) + Mg(s)  Cu(s) + Mg2+(1M)
a. Sketch the Galvanic cell based on the reaction.
b. Identify the cathode and anode
c. Show the direction of electron flow through the external circuit.
3. A solution in an electrolytic cell contains Cu2+( E0 = +0.34v), Ag+( E0 = 0.80v) and Zn2+( E0 =
-0.76v). If the voltage is initially very slow and slowly increased in order will the metals be
plated out on to the cathode?
A. Zn2+ > Cu2+ > Ag+ C. Ag+ > Zn2+ > Cu2+
B. Cu2+ > Zn2+ > Ag+ D. Ag+ > Cu2+ > Zn2+
4. Consider the standard voltaic (galvanic cell) Fe, Fe2+ versus Au, Au2+. Which answer
identifies the cathode and gives the E0red for the cell?
E Au E Fe
(Given Au
3+ ¿ 0
¿ = 1.5v, 2+ ¿ 0

Fe
¿ = -0.44v)
 A. Fe, -0.44v B. Au, 1.06V C. Au, 1.94v D. Fe, 1.94v
4.5.4 Electromotive force (emf)
 Emf is the driving force that pushes electron from anode to cathode or negative terminal
to positive terminal through the external circuit due to potential difference between the
two electrodes.
 The energy of the moving electron is used to overcome resistance in the external circuit,
and it can be used to do various forms of electrical work. Electrical work is used for
starting cars, running watches, radios and computers, etc.
 A spontaneous electrochemical reaction has a positive cell potential (E 0cell > 0). The sign of
G and Ecell are opposite for a spontaneous reaction. This two indication of spontaneity
are related as
Gα = Ecell
 Cell potential (Ecell) is the maximum work in joules doing by the system per unit of charge
in coulombs that flow the circuit. (Since the work is done by the system in the
surrounding its sign is negative)
−W max
Ecell = ⟹W max=−QE cell
Q

But the charge that flow through the cell is equal to the number of moles of electron transferred
in a balanced redox reaction times the charge of one mole of electron (F)

Q = nF

Wmax = -QEcell =  Wmax = -nFEcell

Welectrical work = Wmax = -nF Ecell

- On the other hand free energy change G, it the maximum work that can obtain from a
spontaneous process.
G = Wmax = -nF Ecell
- At standard state condition
G = -nF Ecell
 Ecell = -G/nF
G = -nF Ecell
Both n and F are positive quantities, G is negative (G < 0) for a spontaneous process so Ecell
must be positive. (Ecell > 0)

- When E0cell related to the equilibrium constant (K) of a redox reaction. The standard free
energy change G, for a reaction is related to equilibrium constant as follows.
  We can also predict reaction direction by comparing the value of reaction quotient (Q)
and equilibrium constant (K).
- If Q < K, (Q/K < 1), The reaction proceeds to the right.
- If Q > K, (Q/K > 1), The reaction proceeds to the left.
- If Q = K, (Q/K = 1), The reaction proceeds to the equilibrium.
 The sign of G and magnitude of Q/K are related as follows:
- If Q/K < 1, then lnQ/K < 0,  the reaction proceeds to the right (G < 0)
- If Q/K > 1, then lnQ/K > 0,  the reaction proceeds to the left (G > 0)
- If Q/K = 1, then lnQ/K = 0,  the reaction proceeds to the equilibrium (G = 0)
- The sign of G and lnQ/K are identical for a given reaction direction.
- In fact the sign of G and lnQ/K are proportional to each other and made equal through
the constant RT
Gα lnQ/K
G = RTlnQ/K, where RT – is a proportionality constant
At equilibrium Q = K, So G = 0
G = RT/n – RTlnK

When all the concentration is 1.0M and pressure is 1atm

G = G0 and Q = 1

G0 RTln1 – RTlnK

If K > 1, G0 < 0

G0 = -RTlnk
If K < 1, G0 < 0

If K = 1, G0 = 0

Let us consider how E0cell related with the equilibrium constant.

E0cell = -G0/nF or G0 = -nF E0cell

 -nFE0cell = -RTlnK
 nFE0cell = RTlnK
RTlnK
 E0cell = , where, R = universal gas
nF
T = 298K
F = 96,500C
 J
8.314 ×298 lnK
 E cell =
0
mol . K
=
0.0257 vlnK
n × 96500C n
But lnK = 2.303logK
2.303× 0.027 logk
 E0cell = n
0.0592logk
 E0cell = n
Relationship among G0, K and E0cell

G00 K E0cell Reaction under standard state condition

Negative >1 Negative Favors the formation of product
Positive <1 Positive Favors the formation of reactant
Zero =1 Zero Reactant and products are equally favored
Exercise
1. Will the following reaction occur spontaneously a 250C, given that (Fe2+) = 0.60M and
[Cd2+] = 0.010M?
(Hint the Nernst equation)
Cd(s) + Fe2+(aq)  Cd2+(aq) + Fe(s)
2. Complete the following table; state whether the cell reaction is spontaneous, non-
spontaneous or at equilibrium.

E G Cell reaction
>0
>0
=0
3. Which one of the following indicates the Ecell for the reaction
Zn(s) + Cu2+ (aq)  Zn2+(aq) + Cu(s), if it run under the conditions such that
G = -532KJ
A. +2.76v B. +1.10v C. 3.16v D. -0.03v
4. The two standard electrode potential involved in the nickel cadmium rechargeable
cell are given below. Calculate the G0 in KJ of the cell?
NiO2(s) + 2H2O(l) + 2e-  Ni(OH)2(s) + 2OH-(aq) E0 = +0.49v
Cd(OH)2(s) + 2e-  Cd(s) + 2OH-(aq), E0 = -0.76v
A. -184 B. -153 C. 241 D. -206
5. Calculate G for the following reaction at 25 C.
0 0

2Al3+(aq) + 3Mg(s) ⇌ 2A(s) + 3Mg2+(aq)

E Al
Given ; Al
3+ ¿ 0
=−1.66 v ¿
 E Mg 2+ ¿ 0
=−2.37 v¿
Mg

4.5.5 Dependence of emf on concentration

- A change in concentration affects the change of cell potential which is a result of free
energy change. Most reaction do not with all components in their standard state, by
substituting the relationship between G0, and K in to the expression for (K) we obtain a
relationship that applies to any starting concentrations.
G = RTlnQ – RTlnK
G = RTlnQ + G0
G0 = G0 + RTlnQ
Where; Q is the reaction quotient, and Q is used to calculate the effect of concentration
on G.
Since G = -nFE0cell and G0 = -nFE0cell
-nFE0cell = -nFE0cell + RTlnQ
0 RTlnQ
 Ecell =Ecell − ln
0.257
 Ecell =E0cell − lnQ
n
0.0592
 Ecell =E0cell − logQ
n
 At equilibrium, there is no net transfer of electron. So, E cell = 0 and Q = K, where K is the
equilibrium constant.
Example; consider a Zn – Cu galvanic cell
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
Note that the concentration of solid and liquid is constant does not appear in the
equilibrium constant expression.
0.0592 v
Ecell =E0cell − logQ , but Q=¿ ¿
2
0.0592 v
Ecell =E0cel l− log ¿ ¿
2
 If ¿ ¿
 Ecell > E0cell,  Ecell is greater than that of E0cell
 If ¿ ¿
 Ecell < E0cell,  Ecell is less than that of E0cell
 If ¿ ¿
 Ecell = E0cell
Exercise
1. Consider the reaction, Cu2+(aq) + Fe(s)  Fe2+(aq) + Cu(s) E0 = 0.78v, what is the value of E
when [Cu2+] is equal to 0.040M and [Fe2+] = 0.40M?
2. The standard cell potential (E0) for the reaction below is 1.10v. What is the cell potential
for this reaction when [Cu2+] = 1 x 10-5M and [Zn2+] = 1M
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
4.5.6 Batteries
 Galvanic cell or voltaic cell can be classified as primary cell, secondary cell fuel cell.

Primary cell Secondary cell Fuel - cell

 The cell is not  The cell can be - Reactants are
rechargeable rechargeable continuously supplied
 The electrode reaction  The electrode reaction from outside and the
cannot be reversed can be reversed products formed
Example Example removed from the cell.
i. Zn – carbon dry cell - Lead – acid storage Example
(Leclanche cell) battery (car battery) O2 – H2 fuel cell
ii. Zn – MnO2 cell - Ni – Cad battery
(Alkaline battery)
iii. Zn – CuO cell
iv. Zn – Ag2O cel

 Zn – carbon dry cell (Leclanche cell)

In this cell Zn(s) acts as anode while carbon or graphite acts as cathode.
The electrolytes are moist paste ammonium chloride.
NH4Cl, (abola 80%), MnO2 and ZnCl2
 Anode Zn(s)  Zn2+(aq) + 2e-
Since the reaction is very complicated it can for a side reaction.
NH+4(aq) + OH-(aq)  NH3(g) + H2O(l)
The formation of ammonia gas NH3(g) disrupts the dangerous for the battery, ammonia gas
formed become removed by reacting with Zn2+ in the cell.
NH3(g) + Zn2+(aq) + 2Cl-  Zn(NH3)2Cl2(s)
 Cathode 2MnO2(s) + 2e-  Mn2O3(s)
Balance the charge using H+ ion since the media is acidic
2H+(aq) + 2MnO2(s) + 2e-  Mn2O3(s) + H2O(l)
  Cell reaction Zn + 2NH4Cl + 2MnO2(s)  Mn2O3(s) + Zn(NH3)2Cl2 + H2O
 Alkaline battery (Zn – MnO2 cell)
In this battery, Zn(s) acts as anode and MnO2(s) acts as cathode, KOH or NaOH(aq)
acts as electrolyte solution.
Anode, Zn(s)  Zn2+(aq) + 2e-
Cathode, MnO2 + H2O + 2e-  Mn2O3 + OH-
Cell reaction, Zn(s) + MnO2(s) + H2O(l)  Zn(OH)2(aq) + Mn2O3

Exercise

Do the same thing for Zn – CuO cell and Zn – Ag 2O cell.

Secondary cell

i) Lead – acid storage battery

 In this battery, spongy lead (Pb) acts as anode while lead (Iv) oxide, PbO 2, acts as
cathode.
 Dilute solution of sulfuric acid, H2SO4, acts as electrolyte solution
Anode Pb(s) + SO2-4(aq)  PbSO4(s) + 2e-
Cathode PbO2(s) + SO2-4(aq) + 2e-  PbSO4(s)
PbO2(s) + 4H+(aq) + SO2-4(aq) + 2e-  PbSO4(s) + 2H2O(l)
Cell reaction Pb(s) + PbO2(s) + 2H2SO4(aq) ⇌ 2PbSO4(s) + 2H2O(l)
 Pb(s) + PbO2(s) + 2H2SO4(aq)  2PbSO4(s) + 2H2O(l)
(discharging process)
 2PbSO4(s) + 2H2O(l)  Pb(s) + PbO2(s) + 2H2O4(aq)
(charging process)
 The common product at the anode and cathode half reaction is lead sulfate,
PbSO4(s)

Note; whether the battery is working or not, it can be monitored by measuring the
density of aqueous solution (water) suing hydrometer.

Exercise

Do the same for Ni – Cad battery.

  Fuel cell – is a continuous supply of reactants from outside (in the form of gases)
to produce electricity. It consists of two inert electrodes and hot NaOH or KOH as
electrolyte.

Anode; H2(g)  2H+(aq) + 2e-

Cathode; 2H2O + O2(g) + 4e-  4’OH-
Cell reaction; 2H2(g) + O2(g) + O2(g)  2H2O(l)
 At the anode H2(g) oxidized to H+ ion, while at the cathode O2(g) is reduced to OH-
ion.
4.5.7 Corrosion of metals
Corrosion of iron
 Iron does not rust in dry air, moisture must be present.
 Iron does not rust in air – free water, oxygen must be present.
 The lose of iron and the depositing of rust often occurs at different place on the
same object.
 Iron rust more quickly at low PH (at high [H+])
 The oxidation of iron (Fe) to Fe2+(anodic region) and the following half – reaction occurs.
Fe(s)  Fe2+(aq) + 2e- once the iron lose electron the damage to the object to be done
and a pit forms where the iron is lost. The free electron move through the external
circuit, the piece of iron itself until they reach region of relatively high O 2 concentration
near the surface of a surrounding water droplet (At the cathodic region, the electron
released from the iron atom reduces O2 molecule).
Cathodic region; O2(g) + 4H+(aq)  2H2O(l)
Overall reaction: 2Fe(s) + O2(g) + 4H+(aq)  2Fe2+(aq) + 2H2O(l)
 The Fe2+ ion formed originally at the anodic region disperses through the
surrounding water and react with O2 often at some distance from the pit.
2Fe2+(aq) + ½ O2(g) + (2 + n) H2O(l)  Fe2O3, nH2O(l) + 4H+(aq)
 (The inexact coefficient n for H2O in the above equation appears because of
rust from, (Fe2O3. nH2O), is a form of iron (iii) oxide with variable number of
water of hydration)
 Adding the previous two equation together show the overall equation.
2Fe(s) + O2(g) + 4H+(aq)  2Fe2+(aq) + 2H2O(l)
2Fe2+(aq) + ½ O2(g) + (2 + n) H2O(l)  Fe2O3 nH2O(l) + 4H+(aq)
3
2Fe(s) + O2(g) + n(H2O)  Fe2O3. nH2O(s)
2

We cancel, H+ ions to emphasize that they act as a catalyst, that is they are used up in one step
of the overall reaction and created in another as a result of this action, rusting is faster at low PH
(high [H+]).

 In many ways the components of the corrosion process resembles those of a

galvanic cell.
i. Anodic and cathodic regions are separated in space.
ii. The regions are connected by an external circuit through which the electrons
travel.
iii.In anodic region iron (Fe) behaves like an active electrode whereas the cathodic
region, it is in active.
iv.The moisture surrounding the pit function somewhat like a salt bridge, a means
for ions to ferry back and forth and keep the solution neutral.

Activity
Discuss in group on prevention of corrosion.