Finding the Equilibrium Constant of a Non-Redox Rxn from the SRP

From the following values of SRP: E°(Br2(l)/Br-) = + 1.078 V and

E°(Br2(aq)/Br-) = + 1.098 V,
calculate the equilibrium constant, Ks, for solubility of liquid Br2 in water at 25°C.
Solution:
Equilibria involved: Br2(l) Br2(aq) (dissolution of Br2 in water; non-redox rxn)
Br2(aq) + 2 e- 2 Br-(aq); E°Br2(aq)/Br- = + 1.098 V (redox)
Overall rxn: Br2(l) + 2 e- 2 Br-(aq), E°Br2(l)/Br- = + 1.078 V
For solubility of Br2(l) in water, Ks = [Br2(aq)].
For the redox rxn, write the Nernts eqn.:
E = E°Br2(aq)/Br- - (0.0592/2) log K = E°Br2(aq)/Br- - (0.0592/2) log ([Br-]2/[Br2(aq)] ) =
= 1.098 – 0.0296 log ([Br-]2) + 0.0296 log [Br2(aq)] ;
Substituting expression for Ks:
E = 1.098 - 0.0296 log ([Br-]2) + 0.0296 log Ks
By definition, E = E°Br2(l)/Br- when [Br-] = 1.00 M.
Hence, 1.078 = 1.098 – 0.000 + 0.0296 log Ks;
- 0.020 = 0.0296 log Ks; log Ks = - 0.676;
Ks = 0.211
 Potentiometry
(Chapter 21)
• Potentiometric methods of analysis are based on measuring the potential of an
electrochemical cell without drawing current.
• Potentiometry is often used to determine the concentration of unknown analyte
from the measured cell potential.
• The simplest electrochemical (voltaic) cell applied in potentiometry uses two
electrodes: an indicator electrode and a counter electrode called reference
electrode.
• Indicator electrode (called also a working electrode) is the electrode whose
potential is a function of the analyte’s concentration.

• Reference electrode is the electrode whose potential remains constant

(does not vary with the analyte concentration) and against which potentials of
other electrodes can be measured.
 By convention, reference electrode is always written on the left in the cell
notation:
Reference electrode Salt bridge Analyte solution Indicator electrode

Eref Ej Eind

Ej is a liquid junction potential, which is a potential that develops at the

interface between two ionic solutions that differ in composition, because
of a difference in the mobilities of the ions.
For example,
- +
H+ - +
0.1 M HCl 0.01 M HCl 0.1 M HCl - + 0.01 M HCl
Cl- - +

Diffusion of ions through porous membrane; Excess of Cl - Excess of H +

the mobility of H+ is larger than that of Cl- The potential between two membrane
interfaces with aq. solutions is Ej
Ej is usually an unknown value, but it must be accounted for:
Ecell = Eind – Eref + Ej
A cell for potentiometric
determinations
 Common Reference Electrodes

• Standard hydrogen electrode (SHE), E = 0.00 V

Pt(s) H2(g, 1 atm) H+ (aq, a = 1.00 M)
2 H+(aq) + 2 e- H2(g)

• Saturated calomel electrode (SCE), E(25°C) = + 0.244 V

Hg(l) Hg2Cl2 (satd.), KCl (aq, satd.)
Hg2Cl2(s) + 2 e- 2 Hg(l) + 2 Cl-
calomel
Saturated calomel electrode (bulk, lab-made)
 Commercial saturated calomel
electrode

Walking away from bulk version:

a salt bridge is “incorporated” into
the electrode
• Silver/silver chloride reference electrode, E(25°C) = + 0.199 V
Construction is analogous to the SCE:
an Ag-electrode is immersed in a solution saturated with both AgCl
and KCl
Ag(s) AgCl(satd.), KCl(satd.)
AgCl(s) + e- Ag(s)
Indicator electrodes:
 Metal electrodes – develop a potential in response to a redox- rxn that
takes place on the metal surface. Metals are used as indicator electrodes
to determine their own ions by potentiometry.
Examples: Zn(s), Cu(s), Pb(s)

 Inert electrodes – used when both reactant and product of a redox half-
rxn are species in solution or they are liquids or gases.
Examples: Pt(s), Pd(s), C(s)

 Ion-selective electrodes – are not based on a redox-process and respond

to a change of concentration of only a particular ionic species.

The most common ion-selective electrode is a glass electrode

for measuring the pH.
 Electrolytic Methods of Analysis:
Electrogravimetry and Coulometry
(Chapter 22)
Fundamentals of Electrolysis
Electrolysis is splitting of a substance by the input of electrical energy.
In industry, electrolysis is often used to decompose a compound
into its elements to produce pure metals and non-metals (for example,
halogens).
Just a reminder: Electrolytic cell drives a non-spontaneous reaction (DG > 0,
E < 0) at expense of a potential applied from an external source.
In an electrolytic cell, same as in a voltaic cell, oxidation takes place at the
anode and reduction takes place at the cathode;
however, in contrast to a voltaic cell, the anode has (+) charge, while the
cathode has (–) charge.
During electrolysis, cations migrate to (-) cathode, and anions migrate to
(+) anode.
Hence, the cation is reduced at the cathode; the anion is oxidized at the anode.
 Electrolysis of a molten salt (for example, NaCl)
Predicting the products
of electrolysis:

• The ions (cation and anion)

move towards the oppositely
charged electrodes:
Cation (Na+) → Cathode (-)
Anion (Cl-) → Anode (+)

• Cation is reduced at the

cathode:
Na+ + e- → Na(s)
Anion is oxidized at the
anode:
2 Cl- → Cl2(g) + 2e-

Therefore, the products of electrolysis of molten NaCl are

metallic Na (at the cathode) and gas Cl2 (at the anode).
 Quantitative Aspects of Electrolysis:
Faraday’s Law

Faraday’s law of electrolysis: The amount (in moles) of a substance

produced at each electrode during electrolysis is directly proportional
to the quantity of charge flowing through the cell.

Q = nFN where Q is total charge in coulombs;

n is the number of moles of electrons involved in
the redox-reaction;
F is Faraday’s constant: F = 96,485 C/mol;
N is the number of moles of reduced/oxidized analyte.

On the other hand, Q = It where I is the current (in amperes) passing through
the cell; t is time of electrolysis in seconds.

nFN = It ; hence, moles of compound produced:

It
N=
nF
Problem 1:
How many kg of Al(metal) can be produced on the cathode in
24.0 h by passing a constant current of 500.0 A through an
electrolytic cell with molten Al2O3?

Solution:
It
Moles of compound produced N =
nF
The cathode half-reaction (reduction of Al3+):
Al3+ + 3 e– → Al(s); n = 3 mol e–/mol Al
t = 24.0 h = 24 × 60 × 60 = 86400 s
Moles of Al = (500.0 A × 86400 s)/(3 mol × 96485 C) = 149.2 mol
Mass of Al = 149.2 mol × 27.0 g/mol = 4029.0 g = 4.03 kg
Problem 2:
A layer of silver is electroplated by applying a constant current of
0.100 A to an electrolytic cell with solution containing Ag+.
(a) On which of the electrodes will silver be deposited?
(b) How much time (in hours) is required to deposit 3.00 g of silver?

Solution:
(a) Ag will be deposited on the cathode: Ag+ + e– → Ag(s).
It
Moles of compound produced N =
nF
Solving the formula for time: t = (NnF)/I
Moles Ag = 3.00 g/(107.9 g/mol) = 0.0278 mol
For reduction of Ag+ to Ag(s),
n = 1 mol e–/mol Ag.
F = 96485 C/mol e– = 96485 (As)/mol e–
t = (0.0278 mol × 1 mol e–/mol Ag × 96485 As/mol e–)/0.100 A =
= 26827 s = 447 min = 7.45 h.
 Electrogravimetry (Chapter 22-C)
Electrogravimety is based on a direct
measurement of the amount of analyte
deposited on the electrode during
electrolysis by finding the difference of
mass of the electrode before and after
the electrolysis.

The electrolysis is performed by

passing constant current through the
electrolytic cell.
Example of electrogravimetric analysis:
A solution containing 0.40249 g of CoCl2 × x H2O was exhaustively electrolyzed to
deposit 0.09937 g of metallic cobalt on a platinum cathode:
Co2+ + 2e- → Co(s).
Calculate the number of moles of water, x, per mole of cobalt in this reagent.

Solution:
grams of Co deposited
Grams of CoCl2 in the sample = (FW of CoCl2) =
at. weight of Co
0.09937
= x 129.839 = 0.21893 g
58.933

Grams of water in the sample = 0.40249 – 0.21893 = 0.18356 g

moles of H2O 0.18356 /FW of H2O
= = 6.043
moles of Co 0.0099
0.099 37 /At. mass of Co
37

Therefore, x = 6:
CoCl2 × 6H2O