Electrogravimetry and

Coulometry

Distinguishing Characteristics
Electrochemical reaction carried out to
completion
If analyte is deposited, weighed
electrogravimetry
If analyte is consumed by current
coulometry (Chemical analyses through the
passage of current)

Precision
Very precise (0.1% or better) but time-consuming
mass can be measured to 0.01mg (and atomic
weights are known to 3 ppm or better
charge can be measured accurately, and the
Faraday is known to be 96484.560.27 C/mol

Electrogravimetry
Typically, a metal is electroplated onto a
previously weighed electrode
The initial applied potential is usually slightly
higher than that predicted for the reduction to
account for anode and cathode overvoltage, and
resistive losses
Voltage adjusted to maintain a current flow of
several amperes

Apparatus
for Electrogravimetry

ControlledPotential
Electrolysis

Electrodeposition of Copper
Cu2+ + 2 e Cu(cathode) E = +0.34 V
H2O O2 + 2 H+ + 2 e (anode) E = +1.23 V
2 H+ + 2 e H2(unwanted)
E = +0.00 V
Easy reaction carried out at electrode to
suppress hydrogen evolution:
NO3 + 10 H+ + 8 e NH4+ + 3 H2O (depolarizer)
Thus, Cu often plated in a nitrate medium to
prevent spongy deposits

Controlled-Potential Coulometry
Measure charge consumed by electrolysis of
analyte
qM
Faradays Law: w

nF

w = weight of product in grams

q = charge in coulombs
M = atomic weight in g/mol
n = # of electrons transferred
F = Faradays constant in C/mol

Measurement of Charge (q)

t

q i dt
0

Direct Coulometric Titration at

Constant Current
Analyte is consumed at either anode or cathode
Auxiliary reactions maintain electrolytic
efficiency (=prevent side reactions)
Endpoint is determined by another method, e.g.
potentiometry, photometry, amperometry
Analyte is quantified by amount of charge
consumed

Determination of Fe(III) in HBr

Fe(III) consumed at cathode:
Fe3+ + e Fe2+ (desired)
2 H+ + 2 e H2 (undesired)

Toward end of reaction H+ will be easier to reduce

than Fe3+
Auxiliary reaction prevents this:
TiO2+ + 2 H+ + e Ti3+ + H2O (auxiliary)
Ti3+ + H2O + Fe3+ TiO2+ + 2 H+ + Fe2+ (net)

Indirect Coulometric Titration at

Constant Current
Titrant is generated at
generator electrode
Endpoint is detected by
another method, e.g.,
potentiometry or
voltammetry
Analyte quantified by
charge consumed

Determination of As(III) with I2

Analyte added to solution of buffered NaI
Generator electrode (Pt): 2 I I2 + 2 e
Titration Reaction: I2 + As(III) 2 I + As(V)
Endpoint can be detected colorimetrically with
starch (I2-starch complex is blue)

Coulometric Titrants

SOAL :
The purity of a sample of Na2S2O3 was determined by a
coulometric redox titration using I as a mediator, and I3
as the titrant. 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.

Answer : 98.73% w/w Na2S2O3

QUIZ 3
The purity of a sample of picric acid, C6H3N3O7, is
determined by controlled-potential coulometry,
converting the picric acid to triaminophenol,
C6H9N3O.
A 0.2917-g sample of picric acid is placed in a 1000mL volumetric flask and diluted to volume. A 10.00mL portion of this solution is transferred to a
coulometric cell and diluted till the Pt cathode is
immersed. The exhaustive electrolysis of the sample
requires 21.67 C of charge.
Report the purity of the picric acid.