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ELECTROCHEMISTR

LEARNING OUTCOMES :
Students should be able to;
explain the redox processes and cell

diagram (cell notation) of the Daniell cell;


construct redox equations.
describe the standard hydrogen electrode;
use the standard hydrogen electrode to
determine standard electrode potential
(standard reduction potential), E;
calculate the standard cell potential using
the E values, and write the redox
equations;

Def: Is a study of the relationship between electricity and


chemical reaction
Chemical reaction involved in electrochemistry is REDOX
reaction (OIL RIG)
REDuction OXidation
Gain electron - Loss of electron
Oxidation no decrease

At cathode
RED CAT
2eAka: reduction at cathode
- Eg : Cu2+ + 2eCu

- Oxidation no increase
At anode
- Eg:Mg

Mg 2++

Reduction & oxidation in electrochemical reaction

are called half cell rxs


Combination of 2 half rxs is called cell rx
Red : Cu 2+ (aq) + 2e Ox : Zn(s)

Cu(s)

Half cells

Zn 2+ (aq) + 2e -

Overall cell reaction:

Cu 2+(aq) + Zn(s)
(aq)

Cu(s) + Zn 2+

Redox Reaction in terms of Electron (e-) Transfer


Constructing redox equation using half equation
- combine the [ox] and Rd half equation.
- one or both equation are multiplied by some integer
to
make no e- gained equal no of e- lost.
Eg : redox rx between acidified potassium manganate (VII) & ethanol
Step 1: Write [ox] & Rd equation

[ox] : C 2 H 5 OH

CH 3 CHO + 2H + + 2e-

[Rd] : MnO 4- + 8H+ + 5e-

Mn2+ + 4H 2 O

Step 2 : Combine equation. No of e- lost no egained

Therefore, 2MnO 4- 10e-

5C 2 H 5 OH

5 x [ox] + 2 x [ R ]
6
5 C 2 H 5 OH + 2MnO 4- + 16H+ + 10e5 C H 3 CHO + 10H+ + 10e- + 2Mn2+ + 8H2O
Cancel H + and e- on both side of equation
lost of H (Ox)
5 C 2 H 5 OH + 2MnO 4- + 6H+
5 C H 3 CHO + 2Mn2+ +
8H2O

lost of O (R )

Balancing Redox equation in acidic


solution:
Eg: Cr 2 O 7 2- + Fe 2+
Cr 3+ + Fe 3+
Solution:
1) Classify => 1) Cr 2 O 7 2-

Cr 3+

11) Fe 2+
Fe 3+
2) Balance element except O and H
Coefficient
i. Balance O with H 2 O(in the other
side)
ii. Balance H with H + (in the other side)
Cr 2 O 7 22Cr 3+ + 7H 2O

3) Balance charges with e- on side with bigger


charges
R => Cr 2 O 7 2- + 14H+ + 6e2Cr 3+ + 7H
2O
-2+(+14)= +12+6e- =+6
+6
Ox => Fe 2+
Fe 3+ + e+2 +3 + 1e- = +2
4) Balance no. of e6 x [ox] => 6Fe 2+
6Fe 3+ + 6e5) Add two equations =>
Cr 2 O 7 2- + 14H+ + 6Fe 2+
3+
2O + 6Fe

2Cr 3+ + 7H

Balancing Redox equation in basic solution:


Eg:

Cl 2 + Cr 3+

Cl - + Cr O 4 2-

Solution : Steps 1 to 5, according to balancing Redox in acidic solution


3Cl 2 + 2Cr 3++ 8H2O 2Cr O 4 2- + 16H+ + 6Cl
6) Add XOH on both side (follow n H+):
3Cl 2 + 2Cr 3++ 8H2O+ 16OH2Cr O 4 2- + 16H+ + 6 Cl +
16OH7) Cancel H 2 O
3Cl 2 + 2Cr 3++ 8H2O+ 16OH16OH-

2Cr O 4 2- + 16H+ + 6 Cl +

8
16H 2 O
3Cl 2 + 2Cr 3++ 16OH
i) 3Cl 2 + 6eii) 2Cr 3++ 8H2O

2Cr O 4 2- + 6 Cl + 8H2O

6 Cl (R )
2Cr O 4 2- + 16H+ + 6e- (Ox)

Eg 2 : HNO 3 + I 2
answer: 10HNO 3 + I 2
+ 4H 2 O

HIO3 + NO 2
10NO 2 + 2HIO3

Solution:
i)

HNO3

ii)

I2

NO 2
HIO3

HNO3 + H+ + e- NO2 + H2O


I2 + 6H2O 2HIO3 + 10 H+ + 10e(Rd)=> 10HNO3 + 10H+ + 10e- NO2 + 10H2O
+ [ox] => I2 + 6H2O 2HIO3 + 10H+ + 10e-

Daniel cell/Galvanic cell


Zn electrode
Cu electrode

Cu
electrode

ZnSO4(aq)
Porous pot

Zn electrode

CuSO4(aq)

CuSO4

salt bridge

ZnSO4

porous pot

Function:
Maintains electrical neutrality
Completes the circuit by allowing ions carrying
charge to move from one cell to the other

Zn(s) + Cu 2+ (aq)
Cu(s)

Zn 2+(aq) +

Cell notation (aka : cell diagram):cathode (red)


rxt

pdt

rxt

pdt

Zn(s) / Zn 2+(aq) // Cu 2+ (aq) / Cu(s)


phase boundary
anode(ox)
salt bridge
e- flow

Eg:
Given;
anode : Mg(s)
Mg2+(aq) + 2ecathode : Ag+(aq) + eAg (s)
1)Write cell notation
2)Write the overall cell rx

Solution
1)Mg(s) / Mg2+(aq) // Ag+(aq) / Ag (s)
2)Mg(s) + 2 Ag+(aq)
Mg2+(aq) +
2Ag (s)
(ox) = Mg(s)
(Rd ) = (Ag+ + e= 2Ag + 2e-

Mg2+(aq) + 2eAg )2
2Ag

The difference in electrical potential


between the anode and cathode is called ;
Cell voltage
Eletromotive force (emf)
Cell potential

measured by a
voltmeter

* Acts as electrical pressure that pushes ethrough the wire.

Electrode potential = a measure of the


ability of a half cell to attract etoward it.
Depends on factors:
[ions] in aqueos solution
Pressure of gas
T of the expt.

To measure a standard electrode potential,


standard condition is obtained:
i.all [solution] = 1.0 M
ii.all gases, P = 1.0 atm
iii.all materials, T at 25 0C
iv.Pt as inert electrode when the cell does
not contain metal electrode
*its is impossible to measure directly the electrode potential
of a single electrode system, because rx cant occur
without simultaneous rx in another electrode system.

STANDARD HYDROGEN POTENTIAL : measure std


e/trode potentials

Set up of electrochemical cell to measure std electrode


potential, E of Mg metal half cell

Std electrode potential is always


refer to as a half rx of reduction ,
aka std reduction potential aka std
redox potential, E
Calculation of cell potential , Ecell
E cell = E cathode E anode
( C IA)

Eg 1 : Given half cells


Cu2+ (aq) + 2eCu(s) E red =
+ 0.34V
Zn 2+(aq) + 2eZn(s) E red =
-0.76V
Calculate E cell
RedPoC
at
more positive E, sps

undergo reduction, act


cathode

as

Solution:
E cell = E cathode E anode
E

cell

= +0.34 (-0.76) = +1.10v

cell equation :
anode = Zn(s)

Zn2+(aq) + 2e-

(reverse) [Ox]
cathode = Cu2+(aq) + 2e-

Eg 2 : calculate the std cell potential of


the following electrochemical cell
Co(s) / Co2+(aq) // Ag+/Ag(s)
Solution:
Ag+ + eAg
E = +0.80V
Co2+ + 2eCo
E = -0.28V
Cat(Rd) : Ag+ (aq) + eAg(s)
Anode(Ox) : Co(s)
Co2+(aq ) + 2eE = E cathode - E anode
= +0.80 (-0.28) = +1.08V

Eg 3 : when a voltaic cell is in operation, the


following overall rx occurs;
Fe2+(aq) + Ag+(aq)
Fe3+(aq) + Ag(s)
i. Determine the positive and negative electrode of
this cell and direction of electrons flow.
ii. Write the cell diagram
Solution:
Half equation:

1) Fe2+

Ox
2) Ag++ eOIL RIG
Ox is loss of e-

Fe3+ + e-

Ag

Red
red

is

gain of e-

Therefore;
+ve electrode = Ag (cathode),
-ve electrode = Pt in solution Fe2+ , Fe3+
(anode)
:. e- flow from Pt in Fe2+ , Fe3+ to Ag in the
external circuit.
ii) Pt(s) / Fe2+(aq), Fe3+ (aq) // Ag+(aq) /Ag(s)

--------- anode ----------

---- cathode ----

Eg 4:
A cell is constructed by putting a
Pt electrode in a solution
containing Fe2+ and Fe3+ ions. It is
then connected by means of a
porous pot to another cell
containing a Pt electrode in a
solution of Mn2+, MnO 4- and H+ ions.
Volume of solution are 1.0 M and at
a T of 25C.

1.Referring to std red potential table,


a) determine the positive and negative
electrodes of this cell
b) calculate the emf of this cell
2.Write the equation for:
a)1/2 rx at positive elctrode
b)1/2 rx at negative electrode
c)the overall cell rx.

porous pot
Mn2+ ,MnO4- ,H+
Pt

Fe2+ , Fe3+

1.a)+Ve = Pt in solution of Mn2+,

MnO4- ,
H+ ions
-Ve = Pt in solution of Fe2+ , Fe3+
b) E = Ecathode Eanode

2. a) MnO 4- + 8H++ 5e4H2O


b) Fe2+

Mn2+ +

Fe3+ + e-

c) MnO 4- + 8H++ 5Fe2+


Mn2+ + 4H2O + 5 Fe3+

LEARNING OUTCOMES :
Students should be able to;
predict the stability of aqueous ions from

E values;
predict the power of oxidising and
reducing agents from E values;
predict the feasibility of a reaction from
Ecell value and from the combination of
various electrode potentials: spontaneous
and nonspontaneous electrode reactions.

Uses of Std E/trode


Potential
a)Compare relative strenght

of [ox] agt & [Rd] agt


b)Predict stability of
aqueous ions
c)Predict feasibility of a rx

a) Metals react by releasing e-.

The easier it is to loose e-,


the more electropositive the
metal. Its place is higher in
the ESC due to the more ve
E value
Ni metal (E = -0.25 V) is
more electropositive than Pb
(E = -0.13 V)

Co2+ + 2e- Co
Ni2+ + 2e- Ni
Sn2+ + 2e- Sn
Pb2+ + 2e- Pb
Fe3+ + 3e- Fe
2H+ + 2e- H2 (g)
S + 2H+ + 2e- H2S (g)
Sn4+ + 2e- Sn2+
Cu2+ + e- Cu+

-0.28
-0.25
-0.14
-0.13
-0.04
0.00
+0.14
+0.15
+0.16

SO42+ + 4H+ + 2e- SO2 (g) + 2H2O

+0.17

Cu2+ + 2e- Cu
2H2O + O2 + 4e- 4OH-

+0.34
+0.40

strenght as reducing agent

strenght as oxidizing agent

Std Red Potentials (partially)


Half rx
E0

b) Higher a sps in ECS (more ve E

value), the stronger as reducing


agent or the lower (more +ve E
value), the stronger as oxidising
agent.
Eg : Sn2+/Sn & Pb2+/Pb half rxs
Strenght of Rd agt : Sn > Pb
Strenght of ox agt : Pb2+ > Sn2+
Eg : Br2/2Br- & Cl2/2Cl- half rxs
Strenght of Rd agt : Br- > ClStrenght of ox agt : Cl2 > Br2

An ox agt at lower position in ECS,

can oxidise a Rd agt above it.


Ni2+ + 2e- Ni ; E= -0.25 V
Sn2+ + 2e- Sn ; E = -0.14 V
Pb2+ + 2e- Pb ; E = -0.13 V
Sn2+ can oxidise Ni metal but not
lead but Pb2+ can oxidise tin metal &
nickel.

The strength of oxidizing and reducing


agents
1)The most powerful Ox agent in SEP
has the most +ve value of E,
whereas the least powerful Ox agent
has the most ve value of E and vice
versa for red agents.
In other words, the strongest red
agents loose e- easily, readily and the
strongest Ox agents has strongest

Eg 1 : Arrange the following sps in


order of increasing order of oxidizing
and reducing strength
Zn2+ + 2e- Zn
E= - 0.76 V
I2 + 2e- 2I E= +0.54 V
VO2 + 2H - +e- VO2+ + H2O
E= +1.00 V
Fe3+ + e- Fe2+
E= +0.77 V
MnO4 - + 8H+ + 5e- Mn2+ + 4H2O
E= + 1.52 V

Solution:
Sps on the left side of red rx = ox
agents
Sps on right hand side of red rx =
red agents
Most +ve E0 value, most powerful ox
agent and most ve, least powerful.
1)[Ox] agents: Zn2+ < I2 < Fe3+<
VO2< MnO4
2)[Rd] agents :

< Zn

Mn2+ < VO2+ < Fe2+< I

b) Stability of Aqueous Ions


Certain elements (esp transition

elmts) exhibit variable oxidation


state.
Eg : Co ; Co2+, Co3+
Cobalt (III) chloride added to
water, pink cobalt (II) ions are
produced
Shows Co2+ (aq)> Co3+ (aq)

E values :

O2 + 4H+ + 4e- 2H2O E=


+1.23 V
Co3+ + e- Co2+
E= +1.82
V
Shows water can reduce Co3+

(aq) to Co2+ (aq) & water is


oxidised by Co3+

c) Feasibility of a Reaction
SPONTANEOUS AND NONSPONTANEOUS RXS:
1)DEF: Spontaneous Rx = a process that
occur by itself outside influence or an
external energy.
NON-spontaneous rx = a rx that must be
driven by an external source of energy.
Most rxs occur non-spontaneosly

2) Predicting the feasibility of a rx from the E


cell value.
E cell +Ve= Rx is feasible; ie occurs
spontaneously under std condition
E cell Ve = Rx is not feasible; ie not
occurs spontaneously under std conditions.

Eg 1 : By using E from the std Rd


potential table, calculate the E cell
for the following rxs and predict
whether the rxs can proceed
spontaneously under std condition:
a)Zn + Cu2+
Zn2+ + Cu
b)MnO2 + 2Cl - + H +
Mn2+ + 2H2O

+ Cl2
c)2Cu +

Cu 2+ +Cu

Solution:
S1: identify which sps undergo [Ox] and Rd from the
Rx en
S2: substitute E of each sps in the formula (C I A) to
calculate E cell
S3: determine whether value of E cell +ve or ve
a)Zn
Zn2+ +2e- (Ox) Anode E = -0.76 V
Cu2+ + 2eCu (Rd) Cathode E = +0.34 V
E cell = +0.34 (-0.76) = +1.10V
* Rx is feasible => occur spontaneously !

b) MnO2 + 4H ++ 2eMn2+ + 2H2O


E= +1.23 V(cathode)
2ClCl2 + 2e- E=+1.36
V(anode@Ox)
E

cell

= +1.23 (+1.36)
= -0.13 v

* E cell is negative value, so Rx is not


feasible

c) Cu + + eCu E=
+0.52v(Rd@cat)
Cu +
Cu 2++ e- E=
+0.15v(Ox@anode)
E cell = +0.52-(+0.15)
= +0.37v
* Rx is feasible, will occur
spontaneously

redox rx :
3Ag(s) + Al3+(aq) 3Ag+(aq) +
Al(s)

E0cell = -2.46 V
:. Rx not feasible

And another one


Sn4+ + 2I- Sn2+ + I2
Ans : NOT FEASIBLE !!! ( Ecell = -0.39 V)
Solutn :
Break up overall eqn :Sn4+ + 2e- Sn2+ E0 = +0.15 V(Red = cat)
2I- I2 + 2eE0 = +0.54 V(Ox = and)

LEARNING OUTCOMES :
Students should be able to;
calculate the non-standard cell
potential, Ecell, of a cell using the
Nernst equation.
describe the importance of the
development of more efficient
batteries for electric cars in terms of
smaller size, lower mass and higher
voltage, as exemplified by hydrogenoxygen fuel cell.

Nernst Equation
To calculate cell potential (E

)from

cell

[solution] not at std condition


E

cell

=E

cell

0.059
z

Where :

E
E

cell

[Products ions]c
log
[Reactants ions]a

= electrode potential

cell

= std electrode potential

z = no of moles of etransferred

Eg. 1 :
The case of a Daniell cell:
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)
with cell diagram ;
Zn(s) / Zn2+(1.8M) // Cu2+(0.5M) / Cu(s)
What is the emf of the cell above?

Solutn :

1)

1Cu2+(aq) + 2e- Cu(s) &


Zn(s) 1Zn2+(aq) + 2e-

2) Ecell = cathode anode = 0.34 (0.76)


= + 1.10V
3) Ecell = 1.10 - 0.059 log (1.8)1
2
(0.5)1
= 1.08V #

Eg 2 : E cell is 0.48V for the galvanic cell


based on the rx :
2Al(s) + 3Mn2+(aq) 2Al3+(aq) +
3Mn(s)
whereby [Mn2+] = 0.5M & [Al3+] =
1.50M
What is the cell potential for these
concentrations?

Ox : 2Al(s) 2Al3+(aq) + 6e:. Z = 6


Rd : 3Mn2+(aq) + 6e- 3Mn(s)

Ecell = +0.48 - 0.059 log [(1.5)2 /


(0.50)3]
6
= +0.47V #

Eg. 3 :
A cell with rxs :
VO2+ + 2H+ + e- VO2+ + H2O E0 =
+1.00V
Zn2+ + 2e- Zn
E0 =
-0.76V
is set up where T = 250C,
[VO2+] = 2.0M, [H+] = 0.50M,
[VO2+] = 1.0x10-2M, [Zn2+] = 1.0x10-1M
Calculate the cell potential.

Solutn :
Ox : Zn Zn2+ + 2eRd : 2VO2+ + 4H+ + 2e-
2VO2+ + 2H2O

Ecell = 1.00 (-0.76) = +1.76V


Ecell = Ecell - 0.059
z

log [VO2+ ]2[Zn2+]


[VO2+]2[H+]4

= +1.76 - 0.059 log (1.0x102 2


) (1.0x10-1)
2
(2.0)2(0.50)4

For a voltaic cell, Cd(s)/Cd2+(aq)//Cu2+


(aq)/Cu(s),
determine :
i) std cell potential at 25 0C
ii) E cell @ 25 0C if [Cd2+] = 1.0 M
& [Cu2+] = 0.5 M
Answers :
i)
+0.74 V
ii) +0.731 V

Calculate emf of the fllwg cell:


1) Pt(s)/Sn2+(0.6M),
Sn4+(1.1M)//Fe3+(2.0M), Fe2+(1.6M)/Pt(s)

2)
Zn(s)/Zn2+(0.024M)//Zn2+(2.4M)/Zn(
s)
Answers :
1) +0.618 V
2) +0.059 V

Electric cars
The ideal battery :
i) Compact
ii) Lightweight
iii) High voltage
iv) Cheap
v) Long driving range
vi) Quick recharge
vii)Endurance

Advantage : no emission of

pollutants
Disadvantage : time consuming to
recharge the batteries