Coulometry

Sheryl Lozel Arreola

Types of Electroanalytical Methods
Phenomena
that occur in
the bulk of
the solution
Coulometry

 An electrochemical method in which the current

required to quantitatively oxidize or reduce the
analyte is measured

 Based on an exhaustive electrolysis of the analyte

– the analyte is completely oxidized or reduced at the
working electrode or that it reacts completely with a
reagent generated at the working electrode.
Two forms of coulometry

 Controlled-potential coulometry
apply a constant potential (potentiostatic) to the
electrochemical cell

 Controlled-current coulometry
– pass a constant current (amperostatic) through the
electrochemical cell
Fundamental requirement for both methods is 100% current efficiency
- all e- go to participate in the desired electrochemical process
- If not, then takes more current  over-estimate amount of analyte
Electrolysis

The total charge, Q, in coulombs, passing

through the electrochemical cell is proportional to
the absolute amount of analyte by Faraday’s law

Q=nFnA

Where
n is the number of electrons per mole of analyte,
F is Faraday’s constant (96485 C mol–1), and
nA is the moles of analyte.
Coulometry


Coulometry

 When passing a constant current, i, the total

charge is
Q=ite where te is the electrolysis time
 To determine the moles of analyte,
Q=nFnA
 To obtain an accurate value for nA, all the current
must be used to oxidize or reduce the analyte
 Current efficiency
Controlled-Potential Coulometry

 The easiest way to ensure

100% current efficiency is
to hold the working
electrode at a constant
potential

 As electrolysis progresses
the analyte’s concentration
decreases, as does the
current.
Selecting a Constant Potential
Coulometric method for Cu2+ using Pt
cathode working electrode.

The potential needed for a quantitative

reduction of Cu2+ can be calculated
using the Nernst equation

Quantitative reduction means 99.99% of

the Cu2+ is reduced to Cu
Selecting a Constant Potential

If [Cu2+]0 is 1.00 x 10–4 M, the cathode’s

potential must be more negative than
+0.105 V versus the SHE to achieve a
quantitative reduction of Cu2+ to Cu

at this potential H3O+ is not reduced to

H2, maintaining a 100% current
efficiency.
Electrogravimetry

 If the product of controlled-potential coulometry forms a

deposit on the working electrode, then the change in the
electrode’s mass as the analytical signal.

 If a potential is applied that reduces Cu2+ to Cu at a Pt

working electrode, the difference in the electrode’s mass
before and after electrolysis is a direct measurement of the
amount of copper in the sample.
Controlled-Potential Coulometry
Controlled-Current Coulometry

 Use a constant current

which produces the
current-versus-time profile
Controlled-Current Coulometry

Advantages over controlled-potential coulometry

1. Analysis time is shorter

 current does not decrease over time.
 <10 min vs 30–60 min
2. Total charge is simply the product of current
and time Q=ite
no need to integrate the current-time curve in
Controlled-Current Coulometry

Limitation

a method for determining when the analyte's

electrolysis is complete is needed
Controlled-Current Coulometry

Application: Coulometric Titrations

• titration of analyte in solution by using coulometry

at constant current to generate a known quantity
of titrant electrochemically potential set by
contents of cell

• To detect endpoint, use 2nd electrode to detect

buildup of titrant after endpoint
 Controlled-Current Coulometry
Example:
Coulometric Titration of Cl-
use Ag electrode to produce Ag+
Ag (s) Ag+ + e-
Ag+ + Cl- AgCl (ppt.)

• measure Ag+ in solution by 2nd electrode

• only get complete circuit when Ag+
exists in solution
• only occurs after all Cl- is consumed
• by measuring amount of current and
time required to complete reaction can
determine amount of Cl-
Controlled-Current Coulometry
Application: Coulometric Titrations
a) Acid-Base Titrations
- Acid titration:
2H2O + 2e- ↔ 2OH- + H2 titrant generation reaction
- Base titration

H2O ↔ 2H+ + ½ O2 + 2e- titrant generation reaction

b.) Complexation Titrations (EDTA)

HgNH3Y2- + NH4+ + 2e- ↔ Hg + 2NH3 +HY3-
HY3- ↔ H+ + Y4-
c.) Redox Titrations
Ce3+ ↔ Ce4+ + e-
Ce4+ + Fe2+ ↔ Ce3+ + Fe3+
Quantitative Applications

Constant current of 0.800 A used to deposit

Cu at the cathode and O2 at anode of an
electrolytic cell for 15.2 minutes. What
quantity in grams is formed for each
product?

Cu+ + e-  Cu (s)
H2O  4e- + O2(g) + 4H +
Find total charge.

Find the number of moles of Cu and O2.

Find the mass of Cu and O2.

Quantitative Applications
The purity of a sample of Na2S2O3 was determined by a
coulometric redox titration. A sample weighing 0.1342 g is
transferred to a 100-mL volumetric flask and diluted to volume with
distilled water. A 10.00-mL portion is transferred to an
electrochemical cell along with 25 mL of 1 M KI, 75 mL of a pH 7.0
phosphate buffer, and several drops of a starch indicator solution.
Electrolysis at a constant current of 36.45 mA required 221.8 s to
reach the starch indicator end point. Determine the purity of the
sample.
Ans:98.73% Na2S2O3