Electrochemistry (New)

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ELECTROCHEMISTRY
2
Outline.

OUTLINE.

1. Redox reactions revisited


2. Electrolysis
3. Quantitative electrolysis (Faradays laws of
electrolysis)
4. Electrochemical cells
5. Standard electrode potentials, standard cell
potentials and the Nernst equation
6. Cell potential and Gibbs free energy.
3

Electrochemistry involves either…


 generating electricity by harnessing a spontaneous
chemical reaction – electrochemistry.
OR
 using electricity to force a chemical reaction to
occur - electrolysis

Understanding electrochemistry requires a


basic understanding of the processes called
“oxidation” and “reduction”.
4
1. Redox reactions

 Definitions of Reduction and Oxidation


in terms of;
 hydrogen

 oxygen
 electrons and
 oxidation number
? Redox reaction
? Disproportionation reaction
5
Cont…

Oxidation is…
 the loss of electrons
 an increase in oxidation state/number
 the addition of oxygen
 the loss of hydrogen

2 Mg + O2 ® 2 MgO

note that magnesium is losing


electrons/gaining oxygen
6
Cont…

Reduction is…
 the gain of electrons
 a decrease in oxidation state/number
 the loss of oxygen
 the addition of hydrogen

MgO + H2 ® Mg + H2O

Note: Mg2+ in MgO is gaining electrons/loosing oxygen


7
Cont…

 Redox reaction – a reaction in which oxidation


and reduction take place at the same time.
 Disproportionation reaction – a reaction in
which reduction and oxidation occur on the same
species/atom, simultaneously, in a chemical
reaction.
Example: 2H2O2 2H2O +
O2
 How do we know if a reaction is redox,
disproportionation or not?
 We use oxidation numbers/oxidation
8
Oxidation States

Oxidation number/states:
is a number assigned to an atom or ion
in a compound that describes how
oxidized or reduced it is.

Oxidation numbers can be thought of as


“imaginary” charges. They are assigned
according to the following set of rules:
9
Assigning Oxidation States/Numbers

 Each atom in a pure element has an oxidation


state of “0”. This is true for monoatomic, diatomic
and polyatomic structures

e.g. F2 O3 K N2 Fe
 For mono-atomic ions, the oxidation state is equal
to the charge on the ion.
e.g. F- Al3+ Fe2+ O2-
 In a compound, the more electronegative element
obtains a negative oxidation number and the
more electropositive element a positive oxidation
number.
10
Cont…

 The oxidation state of oxygen in compounds is always “-


2” except in peroxides where it is “- 1” and difluoride
monoxide, F2O, where it is “+2”.
 The oxidation state of hydrogen in a compound (e.g.
CH3OH) is always “+1” except in hydrides where it is “-
1”.
 Alkali metals have oxidation state +1, alkaline earth
metals +2 and fluorine -1 in their compounds.
 The sum of the oxidation states of all the
atoms/elements in a neutral compound must equal “0”.
 The sum of the oxidation states in a complex ion must
equal the charge on the complex ion.
Sli
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11

Question.

Assign oxidation numbers/states to all


underlined elements :
H2 SO3
SO42-

K+ NH3
MnO4-
Cr2O72- CH3OH
PO43-
12
More Definitions

 Oxidizing Agent
 a substance which brings about oxidation by removing
electrons from another atom or ion.

 an oxidizing agent always gets reduced in the reaction.

 Reducing Agent
 a substance which brings about reduction by donating
electrons to another atom or ion.

 a reducing agent always gets oxidized!


13
Identifying Redox Reactions

Using change in oxidation numbers, identify which of


the following reactions are redox:

(i) 2 Fe3+ + 2 I- ® 2 Fe2+ + I2

(ii) 2 H2O ® 2 H2 + O2

(iii) 2 AgNO3 + Cu ® 2 Ag + Cu(NO3)2

(iv) HCl + AgNO3 ® AgCl + HNO3


14
Question.

1. In each of the chemical reactions a to d identify:


(i) the species that gains electrons/is reduced
(ii) the species that looses electrons/is oxidised
(iii) the species that is an oxidising agent.
(iv) the species that is a reducing agent.
(a) CuCl2 + Fe FeCl2 + Cu
(b) Cu + Br2 Cu2+ + 2Br-
(c) PbO2 + SO2 PbSO4
(d) 5Fe2+ + MnO4- + 8H+ ® 5Fe3+ + Mn2+ + 4H2O
15
Balancing Redox Equations

 Redox reactions are often quite complicated


and difficult to balance. For this reason,
you’ll learn a step-by-step method for
balancing these types of reactions.
 Theprocedure is called the “Half-Reactions
Method” of balancing redox equations.
 Itstarts by identifying the substances being
reduced and oxidized in the reaction, and
then following the steps below:
16
Balancing Redox Equations; Half-
Reactions Method
 First split the original equation into two half-reactions, one for
“reduction” and the other “oxidation”.

In each half-reaction, follow these steps:


 First balance all elements except “H” and “O”.
 Balance the “O’s” by adding water, H2O.
 Balance the “H’s” by adding hydrogen ions, H+.
 Balance the electric charge by adding electrons, e-.
 Multiply the two equations by appropriate coefficients to make
the number of e- in the equations equal.
 Re-combine the two equations, canceling some spp. if needed.
17
Example - Balancing with Half-Reactions

 Fe2+ + Cr2O72- ® Fe3+ + Cr3+


Fe2+ ® Fe3+
Fe2+ ® Fe3+ + e-
6Fe2+ ® 6Fe3+ + 6e-

Cr2O72- ® Cr3+

Cr2O72- ® 2 Cr3+

Cr2O72- ® 2Cr3+ + 7H2O

Cr2O72- + 14H+ ® 2Cr3+ + 7H2O

Cr2O72- + 14H+ + 6e- ® 2Cr3+ + 7H2O


 Cr2O72- + 6 Fe2+ + 14 H+ ® 2 Cr3+ + 6 Fe3+ + 7 H2O
18
Question.

Balance the following redox reactions.


(i) C2O42- + MnO4- ® Mn2+ + CO2

(ii) Fe2+ + MnO4- ® Fe3+ + Mn2+

(iii) I- + H2O2 I2 + H2O

(iv) Cl- + MnO2 Cl2 + Mn2+


19
2. Electrolysis.

 Electrolysis is the decomposition of a


compound (an electrolyte) into its elements by
an electric current.
 Uses of electrolysis.
(i) It is used in extraction of very reactive metals
i.e. metals high in the reactivity series.
(ii) It is also used to produce non-metals such as
chlorine (electrolysis of brine)
(iii) It is used to purify some metals, e.g. copper
20
Electrolysis Cell

 An electrolysis cell consists of:


(i) An electrolyte: is the molten ionic compound or
aqueous solution of ions that is decomposed by
passing current through it.
(ii) Electrodes:-rods, made from either carbon
(graphite) or metal, that conduct electricity to
and from the electrolyte.
 Anode:- positive electrode where oxidation occurs
 Cathode:- negative electrode where reduction takes place.

(iii) Power supply:- source of current, must be a direct


current
21
Diagram of an electrolysis cell
22

 Duringelectrolysis, the positive ions move


towards the cathode, gain electrons and
get reduced, and the negative ions move
towards the anode, loose electrons and
get oxidised.
 Electrons,
in the external circuit, flow from
the anode to cathode and current flows in
the opposite direction.
23
Question.

(a) Explain why cations move towards the cathode


during electrolysis.
(b) When lead iodide, PbI2, is electrolysed, the
following reactions occur:
Pb2+ + 2e- Pb and 2I- I2 +
2e-
(i) Which of these equations describes the
reaction at the cathode? Explain your answer.
(ii) State the ox. no. change of each iodide
ion in the reaction: 2I-
-
24
Which ion is discharged at the electrode?

 Thenature of the ion discharged at the


electrode depends on:
(i) The position of the ion in the
reactivity series
 Theless reactive ion will be discharged in
preference to the more reactive ion.

 The
order of discharge of the anions is: X-, OH-,
NO3-, SO42- and for cations: H+ first
25
26

(ii) The concentration of the solution/ions.


 The ions in large concentration will be discharged in
preference to the less concentrated ions.
(iii) State of the electrolyte (molten or
aqueous solution)
 Molten electrolyte contains ions of the electrolyte only,
and they will be discharged at either electrodes.
 Aqueous solutions contain ions of the electrolyte plus
ions from water molecules, H+ and OH-. The water ions
must be considered in deciding the ions to be
discharged.
27
Electrolysis of Molten Sodium
Chloride
Anode: 2 Cl- ()  Cl2 (g) + 2 e-
Cathode: 2 Na+ () + 2 e-  Na()
Overall: 2 Cl- () 2 Na+ ()  Cl2 (g) + Na()

Molten sodium
metal is formed
at the cathode.

Chlorine gas
is formed at the
anode.
28
Questions.

1. Anaqueous solution of Na2SO4 is


electrolysed using carbon electrodes.
(a) Explain why hydrogen is formed
at the cathode and not
sodium.
(b) write a half-equation for the
reaction occurring at the anode.
29

2. Predict the electrolysis products at the anode and


cathode when the following are electrolysed: (give
equations in each case to justify your prediction)
(a) molten aluminium iodide
(b) a concentrated aqueous solution of
magnesium chloride
(c) a concentrated aqueous solution of
sodium bromide
(d) molten zinc oxide
30

3. A concentrated aqueous solution of hydrochloric


acid is electrolysed.
(a) Write half-equations to show the
reactions at:
(i) the cathode
(ii) the anode
(b) A very dilute solution of hydrochloric
acid is electrolysed. What
substance/substances are formed
at the anode? Explain your answer.
4. ESQ, qn. 10, pg. 435
31
3. Quantitative electrolysis

(i) Calculating mass/amount/volume of


substance deposited/produced during
electrolysis.
 The mass/amount/volume of a substance produced
during electrolysis is proportional to the quantity of
electricity (in coulombs) passing through the
electrolyte. (Faraday’s 1st Law)
 The quantity of charge in coulombs, C, is given by;
Q (C) = I (A) x t (s)
 The quantity of electricity is often expressed in
Faraday (F)
32
Cont…

 1 Faraday is the quantity of electric charge


carried by 1 mole of electrons.
 1 Faraday = 96,500 C.
 1 Faraday will deposit one mole of a unipositively
charged ion.
Qn. How many Faradays are required in each of the
following reactions?
(i) Ag+ + e- Ag(s)
(ii) Cu2+ + 2e- Cu(s)
(iii) 4OH-(aq) O2(g) + 2H2O(l) + 4e-
33
Calculations.

Steps:
(i) Write equation for the reaction
(ii) Calculate the charge transferred during
electrolysis
(iii) Find the number of coulombs required to
deposit 1 mole of product (from equation)
(iv) Calculate the required item
34
Cont..

1. Calculate the mass of lead deposited at the


cathode during electrolysis when a current of 1.50A
flows through molten lead (II) bromide for 20
minutes. (Ar for Pb = 207).
2. Calculate the volume of oxygen produced at r.t.p.
when a concentrated aqueous solution of H2SO4
is electrolysed for 30 minutes using a current of
0.50A.
(1 mole of a gas occupies 24dm3 at r.t.p.)
35
Cont…

3. Calculate the mass of silver deposited at


the cathode during electrolysis when a current of
1.80A flows through an aqueous solution of silver
nitrate for 45.0 minutes. (Ar for Ag = 108).

4. Calculate the volume of hydrogen produced at


r.t.p. when a concentrated aqueous solution of
H2SO4 is electrolyzed for 15 minutes using a
current of 1.40A.
36
Cont…

5. Calculate the volume of oxygen produced at r.t.p.


when a conc. aqueous solution of sodium sulfate
is electrolyzed for 55 min using a current of 0.70A.
6. ESQ, pg. 434, qn. 8
7. What mass of aluminum can be produced in
8.00 min by passing a constant current of
100A through a molten mixture of aluminum
oxide, Al2O3?
37
Questions.
38
Cont…
39
Cont…
40
Cont…
Quantitative Electrolysis 41

Q =It
Charge = Current x time
(Coulombs) (Amperes) (seconds)

1 F = 96,500 C/mol e-
42

(ii) Calculating Avogadro constant


 The Avogadro constant, L, is the number of
specified particles in one mole of a substance.
 It’s value is 6.02 x 1023, and it can be
determined by calculating the charge
associated with 1 mole of electrons.
 The formula is:
ch arg e on 1mole of e 
L
ch arg e on 1 electron
43
Cont…

 Steps to be followed when calculating


Avogadro constant:
(i) Write the equation for the reaction taking place
(ii) Calculate the quantity of charge ,Q, transferred
in an experiment.
(iii) Calculate the coulombs required to deposit 1
mole of a substance
(iv)Calculate charge carried by 1 mole of electrons
(v) Divide (iv) by the charge on 1 electron to get
Avogadro constant.
44
Questions.

1. A learner passed a constant electric current of 0.15A


through a solution of silver nitrate, using pure silver
electrodes, for 45 minutes exactly. The mass of the
anode decreased by 0.45g. Use this data to calculate
the charge on a mole of electrons. (ArAg = 108).
Note:
We normally use change in mass of the anode in
calculations as the metal discharged at the
cathode does not deposit well on the cathode.
(change/increase in mass of the cathode doesn’t
give an accurate figure)
45
Cont…

2. An accurate value of the Faraday


constant is 96485 C mol-1. An accurate value
of the charge on one electron is 1.6022 x
10-19C. Use these values to calculate a
value of the Avogadro constant to 5
significant figures.
46
Questions.

3. A current of 0.20A was passed through


a solution of copper for 34 minutes
and the mass of copper removed from
the anode was 0.13g. Calculate the
Avogadro constant. (The charge on
one electron is 1.60 x 10-19C and Ar of
Cu = 63.5g)
47
Cont…

4. ESQ pg. 433 qn. 7


48

4.
ELECTROCHEMICAL
CELLS
Sli
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49

Redox Reactions - What’s Happening?

 Zinc is added to a blue


solution of copper(II)
sulfate

 The blue colour


disappears…the zinc
metal “dissolves”, and
solid copper metal
precipitates on the zinc
strip

 Zinc is oxidized (loses


electrons)
Zn (s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s)
 Copper ions are reduced
(gain electrons)
50
Harnessing the Electricity
 During the spontaneous redox reaction, electrons
flow from the zinc atoms to the copper ions.
Zn ® Zn2+ + 2 e- (oxidation)
Cu2+ + 2 e- ® Cu (reduction)
 Electricity can be thought of as the “flow of electric
charge”.
 How can we make use of the flow of electrons from
the zinc atoms to the copper ions??
 Answer: SEPARATE the Cu2+ ions from the zinc
atoms. This will force the electrons from the zinc
atoms to travel through an external path to reach
51
Electrochemical Cells
52
Cont…

 Electrochemical Cell
a device that uses a spontaneous redox
reaction to produce electricity

 What are the components of an


electrochemical cell?
53
Components of an electrochemical
cell.
 Electrodes/Half-cells.
 Anode:- the electrode/half-cell where oxidation occurs
 Cathode:- the electrode/half-cell where reduction takes place.
 Salt Bridge
 It’s made using a strong electrolyte, e.g. a U-tube filled with salt
solution such as KNO3
 Functions: (i) It connects two “half-cells” to complete the
electric circuit.
(ii) It maintains an ionic balance
in the two half-cells
 Voltmeter
 Measures the voltage of the electrochemical cell
54
Types of electrodes (Half-
cells)
 There are three main types of half-cells;
(i) Metal/metal ion electrode
Formed by dipping a metal rod in a solution containing its ions.
(ii) Non-metal/non-metal ion electrode
Formed by bubbling a gas through platinum wire into a solution
containing its ions
(iii) Metal ion/metal ion electrode
Half-cellcontaining two ions of the same element but in different
oxidation states. E.g Fe2+/Fe3+
Check dgs.pg. 414 – 416 (figs. 20.9 – 20.15)
Qn. Why platinum is used in type (ii) and (iii) electrodes?
55

 Functions of platinum rod in half-cells:


(i) Its surface allows electron transfer
from one species to another
(ii) Provides electrical contact
56
Electrode potentials.

 A redox equilibrium exists between two chemically


related species that are in different oxidation
states.
E.g. Cu2+ (aq) + 2e- Cu(s)
 The redox equilibrium is established when the rate
of electron gain equals the rate of electron loss.
 The position of equilibrium is different for different
metals. For unreactive metals, the position of
equilibrium lies more to the right, and for reactive
metals it lies more to the left.
57
Cont…

 When a metal is put into a solution of its


ions, an electric potential (voltage) is
established between the metal and the
metal ion solution.
 We can not measure this potential directly,
but we can compare/measure the
difference in potential between
metal/metal ion systems.
 This value is called electrode potential.
58
Cont…

 Definition:
 Electrode potential, E, is the voltage measured
for a half-cell compared with another half-cell.
59
How do we measure electrode potentials?

 Weconnect the electrode system to a


Standard Hydrogen Electrode (SHE).
 TheSHE acts as a reference electrode,
and it’s electrode potential value is taken
as zero.
60

 When a zinc electrode is connected to the SHE as shown above, the


voltmeter reads: E°cell = + 0.76 V
 The positive sign means electrons are flowing from zinc to the
hydrogen cell. The zinc is being oxidized.
 Since E°SHE= 0 V, we can conclude that E°Zn = + 0.76 V . This is the
“oxidation potential” for the reaction: Zn ® Zn2+ + 2 e-
61

Standard Hydrogen Electrode (SHE)

2 H+ + 2 e- ® H2 E° = 0 V
Sli
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Definitions. 62

(i) Standard Hydrogen Electrode


(SHE)
 Standard Hydrogen Electrode is an
electrode formed by bubbling hydrogen
gas, at a pressure of 1 atmosphere and a
temperature of 298K, through a platinum
wire dipped in a solution containing 1.00
mol.dm-3 of H+ ions.
Sli
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Cont… 63

(ii) Standard electrode potential.


 Standard electrode potential for a half-
cell is the voltage measured under
standard conditions with a standard
hydrogen electrode as the other half-cell.
Sli
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Standard conditions. 64

 Standard conditions for the measurement of


electrode potentials are:
 Temperature: 25⁰C (298K)
 Pressure (for the gases): 1 atm (101 kPa)
 Concentration: 1 mol.dm-3 solutions
 The electrode should be connected to a SHE
 The electrode potentials measured under these
conditions are called Standard electrode
potentials and are denoted by EƟ
Question. 65

 ESQ, qn. 1, pg. 430

 ESQ, qn. 3 (a) - (c)


66
What do EƟ values tell us?

1. The ease of reduction/oxidation


 Thehalf-cell with more positive/less negative electrode
potential value readily undergoes reduction (thus it’s an
oxidizing agent), and the half-cell with more negative/less
positive value undergoes oxidation and it’s a reducing
agent.
2. The cathode/anode for a particular
electrochemical cell.
 Thehalf-cell with more positive value is the cathode and
the one with less positive value is the anode.
Note:
EƟ values are quoted for reduction, hence reduction
potentials
Table of Standard Reduction Potentials
67
68
Using Eθ values.

1. To predict the cell voltage.


 Electrochemical cells consist of at least two electron
conductors (usually metals) in contact with ionic conductors
(electrolytes).
The current flowing through electrochemical cells may be zero
or non-zero.
 We can use EƟ values to calculate the voltage of a cell.
 The voltage measured is the difference between the EƟ values
of the two half-cells and it’s called standard cell potential.
 The formula is:
EƟ cell = EƟ reduction – EƟ oxidation

EƟ cell = EƟ cathode - EƟ anode

 Qns 18 & 19, pg. 418


69
Questions.

(a) Draw a diagram of an electrochemical cell


consisting of a Cr3+/Cr half-cell and a Cl2/Cl-
half-cell.
(b) Use redox potential values to calculate the cell
voltage.
(c) Which half-cell is the positive pole?
70
Cont…

2. To predict the direction of electron flow


 We can deduce the direction of electron flow in
the external circuit by comparing the EƟ values of
the two half-cells.
 Electrons always flow from the electrode with
less positive electrode potential value to
the one with more positive value, i.e. they
flow from the anode to the cathode.

 Qn. 20, pg. 418


71
Question.

State the direction of the electron flow in the


electrochemical cells represented by the following
pairs of half-equations. Use standard electrode
potential values.
(a) F2 + 2e- 2F- and Mn2+ + 2e- Mn
(b) Sn4+ + 2e- Sn2+ and I2 + 2e- 2I-
(c) Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O and
Cu2+ + 2e- Cu
(d) Ni2+ + 2e- Ni and Fe3+ + 3e- Fe
Cont… 72

3. To predict the feasibility of a reaction.


 To tell whether a particular redox reaction is
feasible or not:
 Calculate the Ecell of the cell as given, and
If the Ecell is positive, the reaction is feasible
Ifthe Ecell is negative, the reaction is not
feasible
Ifthe Ecell is zero, the reaction is feasible and is
at equilibrium.
73
Cont…

Note:
 Feasibility of a reaction can be
determined from:
 ∆H of reaction
 ∆S (entropy change)
 ∆G (Gibbs free energy change)
 Eθcell

How???
74
Steps in determining feasibility of a reaction
from Ecell.

1. Write the equation for the suggested


reaction.
2. Calculate the Ecell as per the equation
3. Conclude as per the answer obtained.
75
Questions.

Use the electrode potential values to predict


whether or not the following reactions are
feasible. If a reaction does occur, write a
balanced equation for it.
(a) Can MnO4- ions oxidise Cl- to Cl2 in acidic
conditions?
(b) Can MnO4- ions oxidise F- ions to F2 in acidic
conditions?
(c) Can H+ ions oxidise V2+ ions to V3+ ions?
(d) Can H+ ions oxidise Fe2+ ions to Fe3+ ions?
76
Questions.

1. What is the feasible reaction, reduction of


nickel by zinc or reduction of zinc by
nickel? Explain your answer.
2. ESQ, pg. 432, qn. 5
3. ESQ, pg. 432, qn. 6
4. Qns. 22 Pg. 423
5. Qns. 24 & 25 pg. 424.
77
Cell Notation

An electrochemical cell needs to be described in a


more convenient way than drawing a diagram!
We use “line notation” to describe a cell. The zinc-
copper standard cell is described:
Zn(s)|Zn2+ (aq) // Cu2+(aq)|Cu(s)
 TheANODE is described/written before the
CATHODE.
 Concentrations of ions are indicated in brackets.
A vertical line represents a phase boundary.
A double vertical line represents the salt bridge.
78
Question.

(a) What is the feasible reaction, reduction of


nickel by zinc or reduction of zinc by
nickel? Explain your answer

(b) Give overall cell reaction and cell


notation for the feasible reaction.
79
The variation of the value of Eθ with ion
concentration.

 Standard conditions for measuring electrode


potentials are a temperature of 298K,
pressure of 1atm and a concentration of
1 mol.dm-3.
 This means, electrode potentials are affected
by these conditions. If any of these factors is
changed, electrode potential changes.
 Under non-standard conditions we use the
symbol ,E, for electrode potential and not Eθ.
80
How does concentration affect EƟ?

 Consider the following metal/metal ion equilibrium;


Zn2+ (aq) + 2e- Zn(s); Eθ = -0.76V
 If [Zn2+] is greater than 1 mol.dm-3, the value of E becomes
less negative/more positive.
 Because the equilibrium shifts more to the right and Zn
will have a higher tendency of undergoing reduction, i.e.
becomes a cathode.
 If [Zn2+] is less than 1.00 mol.dm-3, the value of E becomes
more negative/less positive.
 Because the equilibrium shifts more to the left and Zn will
have a higher tendency of undergoing oxidation, i.e.
becomes an anode.
81
What about for metal ion/metal ion half-cells?

 Consider the equilibrium:


Fe3+ + e- Fe2+; E = +0.77V
 If [Fe3+] is greater than 1.00mol.dm-3 (keeping
[Fe2+] = 1.00mol.dm-3), the value of E
becomes more positive. Why?
 Consider other possibilities and their effects
on E.
82
The Nernst equation.

 The Nernst equation is used to calculate


electrode potential value, E, of an electrode
or the cell potential, Ecell, under non-standard
conditions.

 The Nernst equation is also used to deduce


the effect of concentration and temperature
on the value of Ecell
83
Cont…

 For a given electrode, the electrode potential is given by;

RT [oxidised form ]


E E  ln
zF [reduced form ]
 Where:
 E = electrode potential under non-standard conditions
 Eθ = standard electrode potential
 R = molar gas constant, 8.314 J.K-1mol-1
 T = temperature in Kelvin
 Z = number of electrons transferred in the reaction
 F = Faraday constant in C mol-1
84
Cont…

 But, for a metal/metal ion electrode:


 Atstandard temperature the values of R, T and
F are constants.
 [Reduced form], i.e. the metal, is constant
(unity)
 Naturallog can be converted to normal
logarithm by the relationship, ln x = 2.303
log10x
 So the 0.059becomes;
equation

E E  log10[oxidised form ]
z
85
Ecell under non-standard conditions

 To calculate Ecell from Nernst equation, we use the


relationship:
 0.059 [Pr oducts ]
Ecell Ecell  log
z [Re ac tan ts ]

 Where;
 Ecell = cell potential under non-standard conditions
 EƟcell = cell potential under standard conditions
 Products and reactants are obtained from the
overall cell reaction.
86
Calculating Equilibrium Constants

 When an electrochemical cell operates, and the redox


reaction reaches equilibrium;
[Pr oducts ]
Kc
[Re ac tan ts ]
 Also when the cell reaches equilibrium; Ecell = 0.
 Combining these facts with the Nernst eqn;
 0.059 [Pr oduct ]
Ecell Ecell  log
z [Re ac tan t ]
 We get;
 0.059
0 Ecell  log Kc
z
87
Cont…

 This equation can be used to determine the


equilibrium constant of any reaction
occurring in an electrochemical cell.
 The Kc values obtained from such
calculations are very large indicating that
the reactions lie more to the right (product
side) i.e. reactions go to completion.
88
Questions.

1. Calculate the value of the electrode


potential at 298K of a Ni/Ni2+ electrode that
has a concentration of Ni2+ ions of
1.5mol.dm-3. Eθ = -0.25V
2. Calculate the electrode potential of a
silver/silver ion electrode at 0⁰C when the
concentration of Ag+ ions is 0.0002mol.dm-3.
Eθ = +0.80V
89
Cont…

3. Calculate the Kc value for the reaction that occurs


when Mg is added to a solution of AgNO 3.
 The net reaction is:
Mg(s) + 2Ag+(aq) Mg2+(aq) + 2Ag(s)
90
Cont…

4.Given the following:


Cu2+ + 2e- Cu; Eθ = +0.34V
Ag+ + e- Ag; Eθ = + 0.80V
(a) Construct a galvanic cell using the above
data.
(b) For what concentration of Ag + ions will the
Ecell of the cell be zero at 25⁰C,
if the concentration of Cu2+ is 0.01M?
91
Cont…

5. The standard electrode potential for Zn2+/Zn is –


0.76V and for Cu2+/Cu is +0.34V.
(i)Draw a cell diagram of a cell that can be formed
from Cu and Zn electrodes and show the direction of
electron flow in the external circuit.
(ii) Write the cell reaction and calculate the Ecell
under standard conditions.
(iii) Calculate the equilibrium constant for the
reaction.
(iv) Give the functions of a salt bridge in
electrochemical cells.
92
Relationship between Gibbs free energy, ∆G θ,
and Eθcell

 In a galvanic cell, where a spontaneous


redox reaction drives the cell to produce
an electric potential, the change in Gibbs
free energy must be negative.

 This is opposite of the cell potential, which


is positive when electrons flow
spontaneously through the electrochemical
cell.
93

 The relationship between ∆Gθ and Eθ is given by the


following equation:
∆Gθ = -nFEθ
 Where, n = number of moles of electrons
F = Faraday constant
Remember:
 If Eθcell > 0; the process is spontaneous (galvanic cell)
 If Eθcell < 0;the process is not spontaneous (the voltage
must be supplied, electrolytic cell)
94
Question.

 Calculate the change in Gibbs free energy


of an electrochemical cell where the
following redox reaction is taking place:
Pb2+ + Ni Ni2+ + Pb

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