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Chapter 10

Electrochemistry
ELECTROCHEMISTRY

10.1 10.2 10.3


GALVANIC CELL NERNST EQUATION ELECTROLYTIC CELL
LEARNING OUTCOMES:

At the end of this topic, students should be able to:


a) Define oxidation, reduction redox reaction and
electrode potential
b) Draw a Voltaic/ Galvanic cell.
c) Describe the operation of a voltaic cell
d) State the function of salt bridge
e) Write half-cell equation and the overall cell reaction
equation
f) Write cell notation for a Galvanic cell
LEARNING OUTCOMES:
g) Define :
i. standard reduction/electrode potential, Eo
ii. Standard cell potential, Eo cell
h) Draw and explain the standard hydrogen electrode
(SHE)
i) Describe the method used to determine standard
reduction/electrode potentials
j) Use the standard reduction/electrode potential values
to:
i. Compare the relative strength of oxidizing agents
or reducing agents
ii. Calculate standard cell potential using the Eovalues
iii. Predict the spontaneity of a redox reaction
10.1 GALVANIC CELL
Electrochemistry
-study of the relationship between electricity
and chemical reaction

Electrochemical Cells

Galvanic/VoltaicCell Electrolytic Cell

Chemical Electrical Electrical Chemical


Energy Energy Energy Energy

spontaneous Non- spontaneous

Cathode= terminal positive Cathode= terminal negative

Anode =terminal negative Anode =terminal positive


REDOX REACTION

REDUCTION OXIDATION

Gain of electron loss of electron


Oxidation no. decrease Oxidation no. increase
Reaction at cathode Reaction at anode
Gain hydrogen, lost Gain oxygen, lost
oxygen hydrogen

Remember
RED CAT
= REDuction
RED at CAThode
CAT
Example:
Example:
Mg Mg2+ + 2e-
Cu2+ + 2e- Cu

Oxidation no. Oxidation no.


Galvanic cell

Voltmeter
e-
e-

Cu
Zn
electrode
electrode

Cathode
Anode (terminal POSITIVE)
(terminal NEGATIVE) Zn2+ Cu2+
CuSO4(aq)
ZnSO4(aq)
solution
solution
Salt bridge
Salt bridge

An inverted U tube containing a gel


permeated with solution of an inert
electrolyte such as KCl,KNO3, Na2SO4,
NH4NO3

Functions

to maintain electrical neutrality


completes the circuit by allowing ions carrying
charge to move from one half-cell to the other.
How does the cell maintains its electrical neutrality?

Left Cell Right Cell

Zn (s) Zn2+ (aq) + 2e- Cu2+ (aq) + 2e- Cu (s)

Zn2+ ions enter the solution. Cu 2+ ions leave the solution.


Causing an overall excess of tve Causing an overall excess of
charge. -ve charge.

SO4- ions from salt


bridge move into Zn half Na+ ions from salt bridge
cell move into Cu half cell

Electrical neutrality is maintained


What happens at the electrode?

Left Cell Right Cell

Zn (s) Zn2+ (aq) + 2e- Cu2+ (aq) + 2e- Cu (s)

Zn is more electropositive Electron moving from Zn


than Cu electrode Cu electrode
release electrons accept electrons.
Zinc dissolves. Copper is deposited.
Oxidation occurs Reduction occurs
Zn2+ ions enter ZnSO4 terminal positive- (cathode)
solution.
terminal negative-
( anode).
EXERCISE 1:

Write the overall cell reaction for galvanic cell?


e e

Cl- K+
Zn C u
A n o d e (- v e ) c a th o d e (+ ve )

s a lt b r id g e

Z n 2 + (a q ) C u 2 + (a q ) ,1M
,1M

Cathode : Half-cell
reaction
anode :
Overall cell
reaction :
Write the cell notation

Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)

Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s)


anode cathode

2. Include the concentration of the electrolyte

Zn (s) | Zn2+ (aq,1M) || Cu2+ (aq,1M) | Cu (s)


anode cathode
Example:

For the cell below, write the reaction at anode and


cathode and also the overall cell reaction.
Cell notation
Zn (s) | Zn2+(aq) || Cr3+ (aq) | Cr (s)

Anode : 3 Zn(s) Zn
3 (aq) + 2e
2+ 6e- X3

Cathode : 2 Cr3+(aq) + 3e- 6e Cr(s)2 X2


Overall cell 3Zn(s) + 2Cr3+(aq) + 3Zn2+ (aq) +2Cr(s)
reaction:
Exercise 2:
Write the cell notation for the voltaic cell that incorporates each
of the following redox reaction:

a) Al (s) + Cr3+ Al3+ + Cr (s)

b) 2Al (s) + 3Fe2+ (aq) 3Fe (s) + 2Al 3+ (aq)

c) Co (s) + 2H+ (aq) Co 2+ (aq) + H2 (g)


Answer :
a)

b)

c)
Exercise 3:
Write a balance chemical equation for each cell notation :

a) Mn (s) | Mn2+ (aq) || Cd2+ (aq) | Cd (s)

b) Mg (s) | Mg2+ (aq,1M) || Sc3+ (aq,1M) | Sc (s)

c) Pt (s) | Cu+ (aq) , Cu2+ (aq) || Ag+ (aq) | Ag (s)


Answer :
a.)

b)

c)
Exercise 4:

In the following cell notation, draw a voltaic cell and write


the anode and cathode half-reaction and overall reaction
for the following galvanic cell :

Al (s) | Al3+ (aq) || Pb2+ (aq) | Pb (s)


Answer :
Answer :

Anode :
cathode :

Overall :
Electrode Potential

A measure of the ability of a half-cell to attract electrons


towards it.
Cu2+(aq) + 2e Cu(s) Eored = +0.34 V
Zn2+(aq) + 2e Zn(s) Eored = -0.76 V
Standard reduction
potential
The more positive Eo, the stronger attraction for electrons.

Tendency for reduction


Cu - cathode
The more negative Eo, tendency for oxidation

Zn - anode
CELL POTENTIAL (Ecell)

The difference in electrical potential between the anode and


cathode is called:
cell voltage
electromotive force (emf)
measured by a voltmeter
cell potential

Acts as electrical pressure that pushes


electron through the wire.
STANDARD CELL POTENTIAL (E o
)
cell

-electromotive force of the cell measured under standard


conditions, that is, 298.15 K, 1 atm pressure and
concentration of 1 M for all aqueous solutions.

E0cell = E0cathode - E0anode

or
E0cell = E0red + E0 ox

Standard states : Pressure 1 atm for gases


Concentration-1 M for of electrolyte
Temperature- 25oC or 298.15 K
Example: Method 1

Cu2+(aq) + 2e Cu(s) Eored = +0.34 V

Zn2+(aq) + 2e Zn(s) Eored = -0.76 V

Method 1
Eocell = Eocathode Eoanode
= +0.34-(-0.76)
=+ 1.10 V
Method 2
Half-cell equation at:

Anode : Zn (s) Zn2+ (aq) + 2e- Eoox = +0.76 V

Cathode : Cu2+ (aq) + 2e- Cu (s) Eored = +0.34 V

Method 2
Eocell = Eored + Eoox
= +0.34 +(+0.76)
=+ 1.10 V
Standard Electrode Potentials (Eo)
Standard Electrode Potentials (Eo)

Cl2(g) + 2e- 2Cl-(aq) E0 = +1.36 V

~ The sign of E o changes when the reaction is reversed


Example:

Cl-(aq) Cl2(g) + e- E0 = -1.36 V

~ Changing the stoichiometric coefficients of a half-cell


reaction does not change the value of E o

Example:

Cl2(g) + e- Cl-(aq) E0 = +1.36 V


Standard Hydrogen Electrode (SHE)
Made up of a platinum electrode, immersed in an aqueous
solution of H+ (1 M) and bubbled with hydrogen gas at 1 atm
pressure, and temperature at 25oC

H2 gas
at 1 atm

H+ (aq) Pt
1M electrode
The standard reduction of SHE is 0 V
The direction of half-reaction of SHE depends on the
other
half-cell connected on it.
The cell notation for SHE is either:
H+(aq) | H2(g) | Pt(s) when it is cathode

Pt(s) | H2(g) | H+ (aq) when it is anode

In either case, E0 of SHE remains 0


Standard reduction potential of Zinc half cell is
measured by setting up the electrochemical cell as
below.
E0 = +0.76 V e-
e- - + E 0
=0
+
-
H2(g), 25OC, 1 atm
Zn
e
e
e H+(aq), 1M
Zn2+
e

ZnS04 (aq), 1M Pt
Zn (s) | Zn2+ (aq,1 M) || H+ (aq,1M) | H2 (g,1 atm) | Pt (s)

Anode : Zn (s) Zn2+ (aq) + 2e-


Cathode : 2e- + 2H+ (aq) H2 (g)

Cell reaction Zn (s) + 2H+(aq) Zn2+(aq) + H2 (g)

Eocell = Eocathode - Eoanode


Eocell = EoH+/ H2 EoZn2+ / Zn

0.76 V = 0 EoZn2+ / Zn
EoZn2+ / Zn = -0.76 V
Zn2+(aq) + 2e- Zn(s) E0 = -0.76 V
Standard reduction potential of Copper half cell is
measured by setting up the electrochemical cell as
below.

E0 cell = 0.34V
e-
e- + - E0 = 0
-
+
H2 (g) 25oC, 1 atm
Cu electrode
H+(ag), 1M
Cu2+

CuSO4(aq), 1M Pt electrode
Pt (s) | H2 (g,1 atm) | H+ (aq,1 M) || Cu2+ (aq,1 M) | Cu (s)

Anode : H2 (g) 2H+(aq) + 2e-


Cathode : 2e- + Cu2+ (aq) Cu (s)

Cell reaction H2(g)+ Cu2+(aq) Cu (s) + 2H+(aq)

Eocell = Eocathode - Eoanode

Eocell = EoCu2+/Cu Eo H+/H


0.34 V = EoCu2+/Cu 0

EoCu2+/Cu = + 0.34 V
Cu2+ (aq) + 2e- Cu (s) E0 =+0.34V
OXIDIZING AGENT
The substance that accepts electron in a redox
reaction and undergoes a decrease in oxidation number

REDUCING AGENT
The lose of electrons by a species, accompanied
by a increase in oxidation number.

Example :
Zn(s) + 2H+(g) Zn2+(aq) + H2(g)
Oxidation 0 +1 +2 0
number

Oxidizing agent : H+
Reducing agent : Zn
RELATIVE STRENGTH OF OXIDIZING AND
REDUCING AGENTS
Refer to the list of Standard Reduction Potential:

Example :

Increase Increase
Mg2+ (aq) + 2e- Mg (s) E0 = -2.37 V
strength strength
as Na+ (aq) + e- Na (s) E0 = -2.71 V as
oxidizing Ca2+ (aq) + 2e- Ca (s) E0 = -2.87 V reducing
agent Oxidation Reducing agent
agent agent
Strength of oxidizing agent :
Mg2+ > Na+ > Ca2+
Strength of reducing agent :
Ca > Na > Mg
Oxidizing Agent Reducing Agent

Eored more +ve Eored more -ve

Process occur- reduction Process occur- oxidation

In the standard reduction potential table :


Oxidizing agent reactant only
Reducing agent product only
Exercise 5 :

Arrange the 3 elements in order of increasing


strength of reducing agents

X3+ + 3e- X E0 = -1.66 V

Y2+ + 2e- Y E0 = -2.87 V

L2+ + 2e- L E0 = +0.85 V

Answer :
SPONTANEOUS REACTION
-reaction that occurs of its own accord at room conditions without
requiring energy input for it to occur.

Spontaneous Non-Spontaneous At Equlibrium


1.12 V -0.01 V

Ecell > 0 Ecell < 0

Ecell = 0

More positive

More negative
Example :

Predict whether the following reactions occur spontaneously or


non-spontaneously under standard condition.

Zn(s)+ Sn4+(aq)
Sn2+(aq) + Zn2+(aq)

[ Eo Zn2+/Zn = -0.76V , Eo Sn4+/ Sn2+ = +0.15V ]


Method 1 :

Anode : Zn2+(aq) + 2e Zn(s)

Cathode: Sn4+(aq) + 2e Sn2+(aq)

Eocell = Eocathode - E0anode


Eocell = Eo - E o
Sn4+/Sn 2+
Zn2+/Zn

= +0.15 (-0.76 )

= +0.91 V

spontaneous
Method 2 :

Anode : Zn(s) Zn2+(aq) + 2e


Cathode : Sn4+(aq) + 2e Sn2+(aq)
Zn(s) + Sn4+ (aq) Zn2+(aq) + Sn2+(aq)
Eocell= Eored + Eoox

= (+0.15) + (0.76)
= +0.91 V

spontaneous
Exercise 6:

Calculate the E0 cell for the reaction :


Mg(s) | Mg2+(aq) || Sn4+(aq,Sn2+(aq) | Pt(s)
Given :

Mg2+(aq) + 2e Mg(s) E = -2.38 V


Sn4+(aq) + 2e Sn2+(aq) E= +0.15 V
ANSWER :

anode :
cathode :
Overall:

Ecell =
Exercise 7 :

A cell is set up between a chlorine electrode and a hydrogen


electrode.

Pt | H2(g, 1 atm) | H+(aq, 1M) || Cl2(g, 1atm) | Cl-(aq, 1M) | Pt

E0cell = +1.36 V

I) Draw a diagram to show the apparatus and chemicals


used.
II) Discuss the chemical reactions occurring in the
electrochemical cell.
* discuss : 1)Show the process occur at anode and
cathode (half-cell)
2) Overall reaction
Answer

e- e-
- +

- +
Answer :
Reduction (cathode)

Oxidation(anode)

Eocell =

So the standard reduction potential for Cl2 is:

Eo =
Exercise 8 :

Calculate the standard cell potential of the following


electrochemical cell.

Co(s) | Co2+(aq) || Ag+(aq) | Ag(s)

Method 1 :
Method 2 :
Exercise 9:

Predict : Spontaneous or non-spontaneous?

Pb2+(aq) + 2Cl-(aq) Pb(s) + Cl2(g)


Answer :
Pb 2+
(aq) + 2Cl -
(aq) Pb(s) + Cl 2 (g)
Pb 2+
(aq) + 2Cl (aq) Pb(s) + Cl2(g)
-

cathode:
anode:

Eocell=
Exercise 10:

Predict whether the following reactions occur


spontaneously :
2Ag(s) + Br2(aq) 2Ag+(aq) + 2Br-(aq)

E0Ag+ /Ag = +0.8 V standard reduction


potential
E02Br /Br- = +1.07 V
Answer :
Exercise 11:

A cell consists of silver and tin in a solution of 1 M


silver ions and tin (II) ions. Determine the spontaneity
of the reaction and calculate the cell voltage of this
reaction.

Anode : Sn(s) Sn 2+(aq) + 2e-


Cathode: Ag+(aq) + e- Ag(s)

[ EoAg+/ Ag= +0.80V , EoSn2+/ Sn= - 0.14V ]


Answer :
10.2 NERNST EQUATION
LEARNING OUTCOMES:
At the end of this topic, students should be
able to:

a) Use Nerst equation, Ecell = E cell RT ln Q.


nF
to determine :
i) cell potential (emf)
ii) concentration or partial pressure of a species
iii) equilibrium constant, K when E cell = 0.
NERST EQUATION
Nernst equation can be used to calculate the E cell for
any chosen concentration :

Ecell = Eocell RT ln [ product ]x


nF [ reactant]y
Ecel: cell potential
Eocell: standard cell potential
R : universal gas constant ( 8.314 J K -1mol-1 )
n : no. of e- transferred in balanced redox reaction
Q : reaction quotient (focus on substance in gaseous and aqueous
state)
T : absolute temperature (at 298 K)
F : charge of 1 mol of e- ( 1 F = 96500 C )
Ecell = Eocell 0.0257 2.303 log [ product ]x
n [ reactant]y

Ecell = Eocell RT ln [ product ]x


nF [ reactant]y

[ product]x
= Q
[ reactant] y

Ecell = Eocell 0.0592


log Q
n
Example:

Calculate the Ecell for the following cell

Zn(s) l Zn2+ (aq, 0.02M) ll Cu2+(aq, 0.40 M) l Cu(s)

Answer:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Eocell = Eocathode Eoanode


= +0.34 V - (- 0.76 V)
= +1.10 V
Ecell = Eocell 0.0592 log [ Zn2+] ,n=2
n [ Cu2+]

Ecell = +1.10 V 0.0592 log (0.02 )


2 ( 0.40)

= +1.10 V (-0.0385)
= +1.14 V
At equilibrium:
~ No net reaction occur (Q=K)
~ Ecell = 0

Ecell = Eocell 0.0592


log K
n

0 = Eocell 0.0592
log K
n

Eocell = 0.0592
log K
n
Example :

Calculate the equilibrium constant (K) for the


following reaction.

Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)

[ EoAg+/ Ag= +0.80V , Eo Cu2+/ Cu


= + 0.34V ]
Answer:

Eocell = Eocathode-Eoanode

= 0.80 0.34
= + 0.46V

Eocell= 0.0592 log K

n
+0.46V = 0.0592 log K
2
0.46 = 0.0296 log K
K = 3.47 x 1015
EXERCISE 12:

A galvanic cell consists of a lead anode


immersed in a 1.00 M solution of Pb(NO3)2 and
a platinum cathode that has gaseous hydrogen
bubling over it at a pressure of 1.00 atm. The
hydrogen ion concentration of the solution is
1.30 x 10-5M.
i. Write the cell notation for this reaction.
ii. Calculate the cell potential, Ecell.
iii. Predict the spontaneity of the reaction.

[EPb
2+
= -0.13V , EH /H = +0.00V]
/Pb +
2
Answer:
i.

ii.
Ecell =

Ecell=

iii
10.3 ELECTROLYTIC
CELL
LEARNING OUTCOMES:
At the end of this topic, students should be able to:

a) Draw an electrolytic cell


b) Describe the operation of an electrolytic cell.
c) Explain the influence of the following factors on the
selective discharge of a species at the electrode :
i) standard reduction/electrode potential of the
species
ii) concentration of the species
iii) nature of electrodes
LEARNING OUTCOMES:
d) Explain the electrolysis of the following
electrolytes using inert electrode:
i) molten salt
ii) water
iii) concentrated and dilute aqueous NaCl
iv) aqueous Na2SO4
e) Predict the products of electrolysis using approriate
examples.
f) Define Faradays first law of electrolysis.
g) Apply Farady's first law in calculation
Electrolytic Cell

+ -

Oxidation Reduction

Electrolyte (M+X-)

X-,OH- M+,H+

anion cation
Electrode

as circuit connectors
as sites for the precipitation of insoluble
products
example: Platinum ,Graphite/carbon(inert electrode)

Electrolyte

a liquid that conducts electricity due to the presence of


+ve and ve ions
must be in molten state or in aqueous solution so
that the ions can move freely
example: KCl(l), HCl(aq), CH3COOH(aq)
Comparison Electrolytic Cell & Galvanic Cell

Electrolytic Cell Galvanic/voltaic Cell


+ -

e -
e - e- e-
- +
+ - Salt brige

Anode Cathode Anode Cathode

electrolyte electrolyte
Factor influencing electrolysis products

1. Reduction/oxidation potential of the species in electrolyte


2. Concentrations of ions
3. Types of electrodes used active or inert

When two half-reaction are possible at an electrode :


Cathode : reduction with more positive E o occurs
Anode : oxidation with more negative E o occurs
ELECTROLYSIS AQUEOUS AT ANODE
OXOANION

Example: CO32-, NO3-, PO43-,SO42-

It will not oxidize at anode.


It is because oxidation state of central atom is the highest.
H2O will be chosen.
Anode: 2H2O (l) O2 (g) + 4H+ (aq) + 4e-

HALIDE

Example: F-
It will not oxidize at anode.
It is because Eo very positive.

Example: Cl-, Br-


It can oxidize.
ELECTROLYSIS AQUEOUS AT CATHODE

ACTIVE METAL
- Group 1 and Group 2
Example: Na, Li, Mg

It cannot be reduced at cathode.


It is because Eo is very negative.
H2O will be chosen.

Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq)

LESS ACTIVE METAL


Example: Cu, Cr, Fe, Zn

It can oxidize.
MOLTEN NaCl

Pt Carbon electrode
electrode

anode cathode
species Cl- (l) Na+ (l)
Chosen Eo Cl-(l) Na+ (l)
Observation Cl2 (g) bubble is Na(s) metal deposited
observe

Cathode : Na+ (l) + e- Na (s)


2Na+ (l) + 2e- 2Na (s)
Anode : 2Cl- (l) Cl2(g) + 2e-
Overall : 2Na+ (l) + 2Cl-(l) Cl2(g) + 2Na(s)
DILUTED NaCl
Pt Pt
electrode electrode

Cl-(aq) NaCl Na+(aq


(aq)
H2O (l) H2O (l)

anode cathode
species H2O (l) H2O (l)
Chosen Eo

Eo more negative or lower Eo more positive


Observation O2 (g) bubble is observe H2(g) bubble is observe

Anode: 2H2O (l) O2 (g) + 4H+ (aq) + 4e-


Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq)
4H2O (l) + 4e- 2H2 (g) + 4OH- (aq)
Overall: 2H2O(l) O2(g) + 2H2(g)
Concentrated or Aqueous NaCl
Pt Pt
electrode electrode

Cl-(aq) NaCl Na+(aq


(aq)
H2O (l) H2O (l)

anode cathode
species Cl- (l) H20 (l)

Chosen Eo High concentration Eo more positive


Observation Cl2 (g) bubble is observe H2 (g) bubble is observe

Anode: 2Cl- (aq) Cl2 (g) + 2e-


Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq)

Overall: 2H2O(l) + 2Cl- (aq) Cl2(g) + H2(g) + 2OH-(aq)


Aqueous Na2SO4

Pt Pt
electrode electrode

SO42-(aq) Na2SO4 Na+(aq


(aq)
H2O (l) H2O (l)

anode cathode

species H2O (l) H2O (l)


Chosen Eo

Eo more negative or lower Eo more positive


Observation O2 (g) bubble is observe H2(g) bubble is observe

Anode: 2H2O (l) O2 (g) + 4H+ (aq) + 4e-


Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq)
4H2O (l) + 4e- 2H2 (g) + 4OH- (aq)
Overall: 2H2O(l) O2(g) + 2H2(g)
Active Electrode

CuSO4
Cu electrode Fe
(aq)
electrode

anode cathode
Observation Mass Cu electrode Cu metal is deposited
decrease and mass Fe electrode
increase
Anode: Cu (s) Cu2+ (aq) + 2e-
Cathode: Cu2+ (aq) + 2e- Cu (s)
Overall: Cu(s) + Cu2+ (aq) Cu2+(aq) + Cu(s)
Faradays Law of Electrolysis

Describes the relationship between the amount of


electricity passed through an electrolytic cell and
the amount of substances produced at electrode.

Faradays First Law


States that the quantity of substance formed at
electrode is directly proportional to the quantity
electric charge supplied.
Faradays 1st Law

mQ
Q = electric charge in coulombs (C)
m = mass of substance discharged
Q = It
Q = electric charge in coulombs (C)
I = current in amperes (A)
t = time in second (s)

Faraday constant (F)


is the charge on 1 mole of electron

1 F = 96 500 C
Example :

An aqueous solution of CuSO4 is electrolysed using a


current of 0.150 A for 5 hours. Calculate the mass
of copper deposited at the cathode.

Answer :

Electric charge, Q = Current (I) x time (t)


Q = (0.150 A) x ( 5 x 60 x 60 )s
Q = 2700 C

1 mole of electron 1 F 96 500 C


2700
No. of e- passed through = = 0.028 mol
96 500
Cu2+ (aq) + 2e- Cu (s)

From equation:
2 mol electrons 1 mol Cu

0.028 mol electrons 0.014 mol Cu

Mr for Cu = 63.5

Mass of Copper deposited = 0.014 x 63.5


= 0.889 g
Exercise 13:

An aqueous solution of copper (II) nitrate


was electrolysed using a current of 1.5 A
for 60 minutes at 25C and 1 atm. Calculate:

(a) The mass of copper metal deposited at the


cathode.
(b) The volume of gas evolved at the anode.

( Molar mass: Cu = 63.5 gmol-1)


Answer :
ANSWER:

(b)

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