Instrumental Analysis

Fundamentals of Electrochemistry

Tutorial 4

Electricity from the Ocean Floor

Bacteria oxidizes organic matter using SO42- ions available in the sediment layer. As a result, HS is released and acts as one of the reactant in the electrochemical cell. The other reactant is dissolved O2 molecules available at the sediment-water interface.

Oceanographic instruments can be powered by making a battery between the water and sediment layers.

Summary of Symbols, Units, and Relationships

Relation between Charge charge and (coulombs, C) moles

z
moles of e

F
C/mol

F is the Faradays constant (96500 C/mol). z is the total no. of moles of electrons passes in the circuit E is the electric potential difference, E is the work (J) needed to move a coulomb of positive charge from one point to the other. n is the moles of charge moved under a potential difference, E.

Relation between work and voltage

Work
Joules, J

E
Volts, V

coulombs

Relation between free energy and potential difference

(G =
J/mol

nFE E
Volts V

I
Ohms Law Current A

R
resistance Ohm, ;

I is the electric current, measured in ampere (A). It is the coulombs per second moving pas a point in the circuit. P is the work per unit time done by electricity moving through a circuit.

Electric Power

P = work/s Power J/s (Watt, W)

= E . I V A

Relation between Current and rate of chemical reaction

I
A (C/s)

n . F . Rate
C/mol mol/s

n is the number of moles of e per 1 mole of reactant and rate is the rate of electrochemical reaction in mol/s E is the reduction electrode potential and Er is the standard reduction electrode potential when the activities of all reactants and products are unity. n is the number of electrons in the half-cell reaction. a is the activity of reactant or product of the electrochemical reaction of the 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 species, K is the activity coefficient, c is the concentration of chemical species

Nernst equation Relation between potential of the electrode and activity of ions

0.05916 V aB Q E!E  log a n aA

Relation between activity and concentration

a !K c

Example (Charge)
If 3.2 g of O2 were reduced in the overall reaction with HS:
1 2

O2  2 H   2e p H 2O

HS   1 O2  H  p S  H 2O 2
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 O2 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

HS p S  H   2e

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 Solution
oxidation occurs is the anode while the electrode at which reduction occurs is the cathode

HS 
o. of moles of e  / s !

S H

4.24 mmol HS  1 mol HS  2 mol e  1h v 3 v v ! 2.356 v 10  6 moles e  / s   1h 10 mmol HS 1 mol HS 3600 s

Current !

ch arg e coulombs moles coulomb ! ! . time sec ond sec ond mol  couloms  6 moles e ! 2.356 v10 v 96500 ! 0.227 A s mole e 

Generally, the current may be related to the rate of electrochemical reaction by:

I ! n . F . rate

2e 
n

Rate of consumption of reactants in 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 ! n . F ! (2.4 v10 3 mol) (96500 C/mol) ! 2.3 v10 2 C Electrical Work ! E . q ! (0.70 )(2.3 v10 2 C) ! 1.6 v10 2 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 (Ohms 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

I!

E 3.0V ! ! 0.030 A R 100 ;

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

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

a  ne - m bB
E aB T r ln [ a ] E  nF aA
b

We usually calculate half-reactions at 25 C, substituting that in with the gas constant and to base 10 log gives:

0.05916 V a log B a E ! Er  n aA
Where a is the activities of species A and B.

Example (Nernst Equation)

Write the Nernst equation for the reduction of O2 to water:
1 2

O 2  2H   2e - m H 2 O
! 1.23 
[ H 2O ] 0.05916 log 1 2 PO2 2 [H  ]2
0.05916 1 log 2 [ H  ]2

E r ! 1.23 V

Note that: asolid =1, agas = pressure aH2O =1, aion = molarity

E ! 1.23 

E !1

16

H

! 1.23  0.05916 log [ H  ]

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

O 2  4H   4e - m 2H 2 O
! 1.23 
0.05916 l 4 HO PO 2 H 
4

E r ! 1.23 V

E ! 1.23  0.05916 log [H  ]

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+ electrode

Ag   e  m Ag (s)
E ! 0.799  0.05916 l 1

r E ! 0.

1 ! 0.781 V 0.50
r E ! 0.402 V

For Cd/Cd2+ electrode

Cd 2  2e  m Cd ( s)
E ! 0.402 

0.05916 1 log ! 0.461 V 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.

2 g  2e  m 2 g(s) Cd m Cd 2  2e

Cd(s)  2Ag m Cd 2  2 g(s)

Q cell

cell

0.05916 [Cd 2  ][ Ag ]2 log  [Cd ][ Ag  ]2 2

Q Cd / Cd 2

cell

cell

cell

[Cd 2  ] 0.05916 log )  !(  2 [ Ag  ]2 0.05916 [0.01] log ! (0.799  (0.402 ))  2 [0.5]2 0.05916 [0.01] log ! 1.201  2 [0.5]2 ! 1.242 V
Q Ag / Ag 

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 ( SC = 0.241 V) into 0.10 M CuSO4 solution ( rCu/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?
Electrode connected to the positive terminal of the potentiometer is the cathode and the other is the anode

solution

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

2-

3-

0.05916 log [Cu 2 ] 2 0.05916 ! 0.339  log (0.10 ) ! 0.309 V 2

0

cell

Cu/Cu2+

SC

= 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. ( rAg/Ag+ = 0.799 V) b) xplain 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) p AgCl(s). quivalence 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+A:

[ Ag  ] [Cl  ] ! K sp
so ? Ag+ A = Ksp / Cl = 8.5 x 10-9 M

where Ksp is the solubility product of insoluble AgCl Ag+ depends on the concentration of Cl ion

= 1.8 x 10-10 M / 0.0212 M

The cell voltage is therefore: Ag electrode reaction: Ag+ + e!

Ag/Ag+
Q

Ag+
1 !  [ Ag ]
Q

0.05916 [ Ag ] ! log  1 [ Ag ]

 0.05916 log

 0.05916 log [ Ag  ]

= 0.799 + 0.05916 log (8.5 v 10-9) = 0.322 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.
K sp E Ag/Ag  ! E Q  0.05916 log [Ag  ] ! E Q  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(N )
r = 1.35 V

If the power required to operate the pace maker is 0.010 W, how many kilogram of HgO (atomic 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(N / Pt(s) ) (b) Hg(N / Hg2Cl2(s) / KCl(0.060 M) // KCl(0.040 M) / Cl2(g, 0.50 bar) / Pt(s) ) ( rFe/Fe2+ = 0.44 V, rBr2/Br = 1.078 V, rHg/Hg2Cl2 = 0.268 V, rCl2/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 14- 14- 14- 14- 14-12, 14-14, 14-17, 14-18, 14Harris text book, p308-310 p308If 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)