Instrumental

Instrumental Analysis
Analysis
Fundamentals
Fundamentals of
of Electrochemistry
Electrochemistry

Tutorial 4
 Electricity from the Ocean Floor

Oceanographic
instruments can be
Bacteria oxidizes organic matter powered by making a
using SO42- ions available in the
battery between the
sediment layer. As a result, HS
is released and acts as one of the
water and sediment
reactant in the electrochemical layers.
cell. The other reactant is
dissolved O2 molecules available
at the sediment-water interface.
 Summary of Symbols, Units, and Relationships
F is the Faraday’s constant q = z . F Relation between
(96500 C/mol). Charge moles C/mol charge and moles
z is the total no. of moles of (coulombs, C) of e
electrons passes in the circuit
E is the electric potential
difference, E is the work (J) Relation between
needed to move a coulomb of Work = E . q work and voltage
positive charge from one point to Joules, J Volts, V coulombs
the other.
n is the moles of charge moved ** G = ─ W = ─ n F E Relation between free
under a potential difference, E.J/mol energy and potential
difference
I is the electric current, I = E / R
measured in ampere (A). It is the Ohm’s Law
Current Volts resistance
coulombs per second moving
pas a point in the circuit. A V Ohm, 

P is the work per unit time done

P = work/s = E . I
Electric Power
by electricity moving through a Power J/s V A
circuit.
(Watt, W)
** the minus sign in the equation indicates that the free energy of a system decreases
when the work is done on the surrounding
n is the number of moles of e- per I = n . F . Rate Relation between
1 mole of reactant and rate is the Current and rate
A C/mol mol/s
rate of electrochemical reaction in of chemical
(C/s)
mol/s reaction

E is the reduction electrode

potential and E is the standard
reduction electrode potential when
the activities of all reactants and Nernst equation
products are unity. n is the b
number of electrons in the half-cell0.05916 V a
E  E
reaction. a is the activity of

 log B a Relation between
reactant or product of the
n aA potential of the
electrode and
electrochemical reaction of the activity of ions
half-cell when written as reduction
Note: Nernst Equation can be
applied to one half cell as well
as to the reaction of the whole
cell.

a is the activity of a chemical Relation between

species,  is the activity coefficient, a  c activity and
c is the concentration of chemical concentration
species
Example (Charge)
If 3.2 g of O2 were reduced in the overall reaction with HS:

HS   S  H   2e 
1
2 O 2  2H   2e   H 2O
HS   12 O 2  H   S  H 2O

how many coulombs have been transferred from HS to O2 or how many
charges pass in the circuit?

Solution

3.2 g O 2 /32 g mol -1  0.1 mol O 2

Since 1
2 moles of O 2 gain 2 moles of e 
No. of moles of electrons  0.1 x 4  0.4 moles
q  z F  (0.4 mol) (96500 C/mol e - )  38,600 C
Example (Current)
If electrons are forced into a wire which acts as anode to oxidize HS  at a rate
of 4.24 mmol/hr, how much current passes through? Note: The electrode at which
oxidation occurs is the anode
while the electrode at which
Solution reduction occurs is the cathode

HS   S  H   2e 
n
No. of moles of e  / s 
4.24 mmol HS  1 mol HS  2 mol e  1h
 3 
 
  2.356  10 6 moles e  / s
1h 10 mmol HS 1 mol HS 3600 s

ch arg e coulombs moles coulomb

Current    .
time sec ond sec ond mol

 6 moles e couloms
 2.356  10  96500  0.227 A
s mole

Generally, the current may be related to the rate of electrochemical reaction by:
Rate of consumption of reactants in
I  n . F . rate a unit of mol/s
n is the number of moles of e- per 1 mole of reactant
Example (Work)
How much work can be done if 2.4 mmol of electrons go through a potential
difference of 0.70 V in the ocean-floor battery?

Solution

q  z . F  ( 2.4  10  3 mol ) (96500 C/mol )  2.3  10 2 C

Electrical Work  E . q  (0.70 V )( 2.3  102 C)  1.6  102 J

• The greater the difference in potential (V), the stronger the e will be
pushed around the circuit
• 12V battery “pushes” electrons through a circuit eight times harder than a
1.5V battery
 Example (E from free energy change)
Calculate the voltage that will be measured by the potentiometer in the figure,
Knowing that the free energy change for the net reaction is 150 kJ/mol of Cd.

Solution
Re duction : 2 AgCl(s )  2e   2 Ag(s )  2Cl  (aq )

Oxidation : Cd(s )  Cd 2  (aq )  2e 

Net Re action : Cd(s )  2 AgCl(s )  Cd 2  (aq )  2 Ag(s )  2Cl  (aq )

G   n F E
J
 150  10 3
G mol Cd
E    0.777 V ( J / C)
nF mol e  C
(2 ) ( 96500 )
mol Cd mol e 

A spontaneous chemical reaction of negative G produces a positive voltage.

Example (Ohm’s Law)
In the following circuit, a battery generates a potential difference of 3 V and
the resistor has a 100  resistance. How much current and power are
delivered by the battery?

Solution

E 3.0V
I   0.030 A
R 100 

P  E . I  ( 3.0 V)(0.030 A)  0.090 W

Nernst Equation
• The Nernst Equation relates the potential of the half cell to the activities of
the chemical species (their concentrations)
– For the reaction (written as reduction)

aA  ne -  bB

 RT aBb
E E  ln [ ]
nF aA a

– We usually calculate half-reactions at 25º C, substituting that in with the

gas constant and to base 10 log gives:

a b
0. 05916 V n is the no. of electrons
E  E  log B in either the electrode or
n a a cell reaction
A

Where a is the activities of species A and B.

Example (Nernst Equation)
• Write the Nernst equation for the reduction of O 2 to water:

• Note that multiplying the reaction by any factor does not affect either Eº or the calculated E:

1
O 2  2H   2e -  H 2O E  1.23 V Note that:
2
asolid =1, agas = pressure
0.05916 [ H 2O]
E  1.23  log 1
aH2O =1, aion = molarity
2 PO 2 2 [H  ]2

0.05916 1 0.05916
E  1.23  log E  1.23  log [ H  ]2
2 [H  ]2 2

E  1.23  0.05916 log [H  ]

O 2  4H   4e -  2H 2O E  1.23 V

0.05916 [H 2O]2
E  1.23  log E  1.23  0.05916 log [H  ]
4 PO 2 [H  ]4
Example (Ecell)
• Find the voltage for the Ag-Cd cell and state if the reaction is spontaneous if
the right cell contained 0.50 M AgNO3(aq) and the left contained 0.010 M
Cd(NO3)2(aq).

For Ag/Ag+ Ag   e   Ag(s ) E  0.799 V

electrode
0.05916 1
E   0.799  log  0.781 V
1 0.50

For Cd/Cd2+ Cd 2   2e   Cd(s ) E   0.402 V

electrode
0.05916 1
E   0.402  log  0.461V
2 0.010

For the Cell Ecell  E   E   0.781  ( 0.461)  1.242 V

  Note that you will get the same value of cell potential if you apply the
Nernst equation directly to the overall cell reaction.

2Ag   2e   2Ag(s)
Cd  Cd 2  2e 
Cd (s)  2Ag   Cd 2  2Ag(s)

0.05916 [Cd 2 ][ Ag]2

Ecell  Ecell  log
2 [Cd][ Ag  ]2
2
0 . 05916 [Cd ]
Ecell  (EAg / Ag   ECd / Cd 2 )  log
2 [ Ag  ]2
0.05916 [0.01]
Ecell  (0.799  ( 0.402))  log
2 [0.5]2
0.05916 [0.01]
Ecell  1.201  log
2 [0.5]2
 1.242 V
Since Ecell is found to be +ve quantity, the reaction as written is spontaneous
Example (Ecell)
A cell was prepared by dipping a Cu wire and a saturated calomel electrode
(ESCE = 0.241 V) into 0.10 M CuSO4 solution (ECu/Cu2+ = 0.339 V). The Cu wire
was attached to the positive terminal and the calomel to the negative terminal
of the potentiometer.
1- Write the half-cell reaction of Cu electrode.
2- Write the Nernst equation for the Cu electrode.
3- Calculate the cell voltage.
4- What would happen if the [Cu2+] were 4.864x10-4 M?

solution Electrode connected to the positive terminal of the potentiometer is the

cathode and the other is the anode

1- Cu2+(aq) + 2e-  Cu(s)

0.05916 2
2- E  E 0
 log [Cu ]
2
0.05916
E  0.339  log (0.10)  0.309V
2
3- Ecell = ECu/Cu2+  ESCE = 0.309 V  0.241 V = 0.068 V
Example (Ecell)
A 100.0 ml solution containing 0.100 M NaCl was titrated
with 0.100 M AgNO3 and the voltage of the cell shown in
the figure was monitored.
a) Calculate the voltage after the addition of 65.0 ml
of AgNO3. (EAg/Ag+ = 0.799 V, ESCE = 0.241 V)
b) Explain why a silver electrode can be used as an
indicator electrode for both Ag+ and for halides.
Solution: NaCl

a) The titration reaction is: Ag+(aq) + Cl(aq)  AgCl(s).

Equivalence point is reached upon addition of 100.0 ml titrant (in this case).

After addition of 65.0 ml of AgNO3, we can say:

(M V)reacted Cl- = (M V)Ag+ added (note that Ag+ and Cl react in the ratio of 1:1)

(M V)Cl- remains unreacted = (M V)total Cl-  (M V)Ag+ = (0.1 x 100)  (0.1 x 65)

(M V)Cl- remains unreacted = 3.5 mmole MCl- = 3.5 mmol/165 = 0.0212 mol/L
• To find the cell voltage we need to know Ag+:

[ Ag  ] [Cl  ]  K sp where Ksp is the solubility product of insoluble AgCl

so  Ag+  = Ksp / [Cl] [Ag+] depends on the concentration of Cl ion

= 1.8 x 10-10 M / 0.0212 M
= 8.5 x 10-9 M
• The potential of Ag electrode is given by:
Ag electrode reaction: Ag+ + e- Ag+
0.05916 [ Ag] 1
E  E  log  E   0.05916 log  E   0.05916 log [ Ag  ]
1 [ Ag  ] [ Ag  ]

EAg/Ag+ = 0.799 + 0.05916 log (8.5  10-9) = 0.322 V

• The cell potential: Ecell = ESCE  EAg/Ag+ = 0.241  0.322 =  0.081 V

b) We can see from the example that the silver electrode can act indirectly as halide
indicator electrode if solid insoluble silver halide is present. The solubility of silver
halide will be affected by whatever halide ion is present and in turn the concentration of
Ag+ ion as well as the potential of the Ag electrode.
 ]  E K sp
E Ag/Ag   E   0 .05916 log [ Ag  0.05916 log
Ag/Ag  Ag/Ag  [Cl  ]
Exercise 1
A mercury cell used to power heart pacemaker runs on the following reaction:
Zn(s) + HgO(s) ZnO(s) + Hg() E = 1.35 V
If the power required to operate the pace maker is 0.010 W, how many
kilogram of HgO (molar mass = 216.59) will be consumed in 365 days?

Exercise 2
Calculate the voltage of each of the following cells:
(a) Fe(s) / FeBr2(0.010 M) // NaBr(0.050 M) / Br2() / Pt(s)
(b) Hg() / Hg2Cl2(s) / KCl(0.060 M) // KCl(0.040 M) / Cl2(g, 0.50 bar) / Pt(s)
(EFe/Fe2+ = 0.44 V, EBr2/Br = 1.078 V, EHg/Hg2Cl2 = 0.268 V, ECl2/Cl = 1.360 V)

Try to solve problems 14-3, 14-4, 14-5, 14-7, 14-12, 14-14, 14-17, 14-18, and 14-19
Harris text book, p308-310
If you are unable to solve these problems or need to revise your answer, please refer to
the “Solution Manual for Quantitative Chemical Analysis”, by D.C. Harris (GUC library)