COULOMETRIC

Methods of
Analysis
Electrolysis
Fundamentals of Electrolysis

• the process by which a chemical reaction is forced to

occur at an electrode by an imposed voltage
cathode Cu2+ + 2e- = Cu (s) Eo = + 0.337 V
anode ½ O2 (g) + 2H+ + 2e- = H2O Eo = + 1.230 V

Cu2+ + H2O = Cu (s) + ½ O2 (g) + 2H+ Eocell = - 0.893 V

• We need to apply a potential of at least 0.893 V in

order to force the reaction
 Fundamentals of Electrolysis

Anode: Cathode:
H2O = ½ O2 (g) + 2H+ + 2e- Cu2+ + 2e- = Cu (s)
Fundamentals of Electrolysis

• The magnitude of the voltage that must be applied

to an electrolysis cell is:

Ecell = Ecathode – Eanode – OP – IR – CP

OP = overpotential
IR = ohmic potential
CP = concentration polarization
Fundamentals of Electrolysis
Ecell = Ecathode – Eanode – OP – IR – CP

1) Overpotential (OP)

• Voltage required to overcome the activation

energy of an electrode reaction

• A greater overpotential is required to drive a

reaction at a faster rate
Fundamentals of Electrolysis
Ecell = Ecathode – Eanode – OP – IR – CP

2) Ohmic potential (Eohmic = IR)

• Is that voltage needed to overcome internal

resistance of the cell

• The required voltage is a function of current

• Eohmic = V = IR
Fundamentals of Electrolysis
Ecell = Ecathode – Eanode – OP – IR – CP

3) Concentration polarization (CP)

• Occurs when the concentration of the

electroactive species near an electrode is not
the same as its concentration in bulk solution

• Concentration polarization is embedded in the

terms Ecathode and Eanode
Fundamentals of Electrolysis
• Overpotential (OP), ohmic potential (IR) and
concentration polarization(CP) always oppose the
desired reaction and require a greater voltage to be
applied for electrolysis

• Because of these factors, a voltage greater than

0.893 V is needed in order for electrolysis to occur
cathode Cu2+ + 2e- = Cu (s) Eored = + 0.337 V
anode ½ O2 (g) + 2H+ + 2e- = H2O Eored = + 1.230 V

Cu2+ + H2O = Cu (s) + ½ O2 (g) + 2H+ Eocell = - 0.893 V

Fundamentals of Electrolysis

• Knowing the current, I, flowing through the cell over a

period of time, t, allows us to calculate the total charge

Q=Ixt

,I = current in amperes (A = coulomb/s)

,t = time in seconds (s)
,Q = charge in coulombs (C)
Fundamentals of Electrolysis
Q=Ixt ; Q = nA (nF)
,I = current in amperes ,nA = mole of product
,t = time in seconds ,n = number of e- / molecule
,Q = charge in coulombs ,F = 96,500 C/mol

• analyte’s concentration
and current (I) decrease
over time (t)
Fundamental Equations

• Faraday’s law

Faraday’s law correlates

• total charge, Q [C], passed through a cell

• to the amount of product, N [mol]
• where F is Faraday’s constant, F = 96,485.3 C mol-1,
and
• n is the number of electrons transferred per mole
of product finding the number of electrons implicated in
an electrolytic process.
Faraday’s Law

Can be used in many applications:

ü Electrogravimetry - to find the amount of substance

deposited at an electrode

ü Coulometry - to find the total amount of electricity

required for complete electrolysis of a compound
- can also be used for finding the number
of electrons implicated in an electrolytic process.
 Fundamentals of Electrolysis
• Measurement of Q allows us to calculate the number of
moles (nA) of analyte and the number of moles of
electrons (n) involved in that specific half-cell reaction

Q = (nA) (nF) ; Q = It

moles reacted, nA = I x t
nF
, n = number of electrons per molecule
, F = Faraday constant, 96,485 coulombs (1 faraday)
is equal to one mole of electron
 Example
• A sodium sulfate solution was electrolyzed using inert Pt
electrodes. The cathode reaction was 2H2O = H2 + 2OH-.
If a current of 3.0 amp was used for 30 min, what weight
(g) of H2O (MM = 18.0) gas would be produced?
moles reacted, n = Ixt
Q = (nA) (nF) ; Q = It ; A
nF

moles reacted, nA = I x t
nF

2 H2O + 2e- = H2 + 2 OH-

Example
• A sodium sulfate solution was electrolyzed using inert Pt electrodes. The
cathode reaction was 2H2O = H2 + 2OH-. If a current of 3.0 amp was used for 30
min, what weight (g) of H2O (MM = 18.0) gas would be produced?

moles reacted, n = Ixt

Q = (nA) (nF) ; Q = It ; A
nF
moles reacted, nA = I x t
nF
2 H2O + 2e- = H2 + 2 OH-
grams H2O (g)
60 s 1 1 mol
= (3.0 A) (30 min x ) x x
min 2 e- 96,500 A s
x 18.0 g
mol
weight H2O (g) = 0.50 g
Fundamentals of Electrolysis
CONTROLLED-POTENTIAL
ELECTROLYSIS

• is conducted in a three-
electrode cell

• The potential of the working

electrode is measured with
respect to a reference
electrode to which negligible
current flows

• Current flows between the

working and auxiliary (or
counter) electrodes
Coulometry
Introduction ● Coulometry

ü An analytical method for measuring an

unknown concentration of an analyte in
solution by completely converting the
analyte from one oxidation state to another

ü Chemical analysis based on charge passed

(coulomb, Q = It) during electrolysis
Principle ● Coulometry

ü The main principle involved in the coulometry is the

measurement of the quantity of the electricity
which is directly proportional to the chemical
reaction at the electrode.

ü This is given by the Faraday's laws of electrolysis:

Q = amperes x seconds
 Principle ● Coulometry
ü Michael Faraday reported that the
mass, m, of elements deposited
at an electrode in g is directly
proportional to the charge, Q, in
coulombs
maQ
Q = It

• mass of the substance

deposited/liberated per unit Michael Faraday
charge.
Coulometry

• A dynamic technique, in which current passes

through the electrochemical cell

• Based on an exhaustive electrolysis of the analyte

• Exhaustive means:
1) the analyte is completely oxidized or reduced at
the working electrode, or
2) that it reacts completely with a reagent
generated at the working electrode
 Coulometry

• Based on the measurement of electrical charge that

passes through a solution during an electrochemical
reaction

• In coulometry, the number of moles of electrons

that participate in a chemical reaction are measured.

• Example:
H+ and OH- can be produced electrochemically
2 H2O + 2e- = H2 + 2 OH-

2 H2O = O2 + 4 H+ + 4 e-
 Coulometry
• Based on the stoichiometry associated with the conversion of
species from one oxidation state to another:

Cu2+ + 2e- → Cu (2 mole e-/mole Cu)

1 mol of e-: (1.6022 x 10-19 C/e-) (6.022 x 1023 e-)

= 96,485 C or 96,500 C

96,485 C = 1 faraday (F) (charge of 1 mole of elementary charges)

Two Forms of Coulometry

(1) Controlled potential coulometry

• constant potential (Potentiostatic, Vconstant)
• apply a constant potential to the
electrochemical cell

(2) Controlled-current coulometry

• constant current (Amperostatic, Iconstant)
• pass a constant current through the
electrochemical cell
Types of Coulometry

1 CONTROLLED-POTENTIAL COULOMETRY
• Is more selective than constant-current
coulometry, but slower

Electrons consumed in the reaction are measured

by integrating the current versus – time curve
1 Controlled Potential Coulometry
• Highly analogous to controlled potential
electrogravimetry

Advantages of coulometry over electrogravimetry:

(1) requires no weighing (requires current

measurement)

(2) reaction need not give rise to formation of a

solid product
1 Controlled Potential Coulometry
• this technique can be applied to systems that yield
deposits with poor physical properties as well as to
reactions that yield no solid product at all

Controlled-potential coulometry is carried out in

ü Small-volume electrochemical cells

ü Using electrodes with large surface areas

ü with high stirring rates

Electrogravimetry vs. Potentiostatic Coulometry

Electrogravimetry Potentiostatic Coulometry

1 Controlled Potential Coulometry
• Potentiostatic coulometry

• the working electrode will be kept at constant

potential that allows for the analyte’s reduction
or oxidation without simultaneously reducing or
oxidizing other species in the solution

•The current flowing through the cell is

proportional to the analyte’s concentration
1 Controlled Potential Coulometry
Current vs. Time profile
•With time the analyte’s
concentration as well as
the current will decrease

•The quantity of
electricity is measured
with an electronic
integrator
• Integrating the area under the curve
from t = 0 to t = te gives us the total
charge
(te is electrolysis time)
Selecting a Constant Potential
Cu2+ (aq) + 2e- = Cu (s) E0 = +0.324 V
• The potential is selected so that the desired
oxidation or reduction reaction goes to
completion without interference from redox
reactions involving other components or the
sample matrix
• The reaction is favored when the working
electrode’s potential is more negative than
+0.324 V
• To maintain a 100% current efficiency, the
potential must be selected so that the
reduction of H+ to H2 does not contribute
significantly to the total charge passed at the
electrode
1 Potentiostatic Coulometry: Instrumentation
• consists of potentiostat, electrolysis cell, chemical
coulometer for determining the number of coulombs and
placed in series with the working electrode
1 Potentiostatic Coulometry: Instrumentation
(1) CELL ASSEMBLY

• The cell assembly

consists of Pt gauze
working electrode, Pt
wire as counter
electrode, and SCE as
reference electrode
1 Potentiostatic Coulometry: Instrumentation
(1) CELL ASSEMBLY

• The cell assembly

consists of Pt gauze
working electrode, Pt
wire as counter
electrode, and SCE as
reference electrode
1 Potentiostatic Coulometry: Instrumentation
• a three-electrode potentiostat is used to set the
potential in controlled potential coulometry
(1) Working electrode
Usually one of two types:
(a) a Pt-electrode manufactured from a Pt-gauze
fashioned into cylindrical tube
- Pt is the working electrode of choice is we need to
apply a positive potential
(b Hg pool electrode
- Hg electrode of choice for an analyte requiring
negative potential
1 Potentiostatic Coulometry: Instrumentation
(1) Working electrode
1 Potentiostatic Coulometry: Instrumentation
(2) Auxiliary or Counter electrode
• Is part of the other half cell and it is made of the same
material as the working electrode; usually Pt wire
• Usually separated from the solution in contact with
the working electrode to prevent reaction between
species produced at auxiliary electrode and species in
the bulk of solution
• separation is necessary to prevent electrolysis products
generated at the auxiliary electrode from reacting with
the analyte and interfering in the analysis
1 Potentiostatic Coulometry: Instrumentation

(3) Reference electrode

serves as the reference electrode

• Saturated calomel electrode

• Ag/AgCl electrode
1 Potentiostatic Coulometry: Instrumentation
(2) POTENTIOSTAT
• maintains the potential if the working electrode at a constant
level relative to a reference electrode

• the practical circuit

shows the other
components of a
potentiostatic
coulometry

• the circuit includes a variable voltage source at the noninverting

input of the operational amplifier so that the potentiostat control
potential can be varied, a booster amplifier to supply the high
currents that are necessary, a recorder, and an integrator
1 Potentiostatic Coulometry: Instrumentation
(3) INTEGRATORS

• employed to determine the number of charge

(coulombs) as a function of time

• charge required to complete an electrolysis

• Efficient stirring is important for controlled

potential electrolysis, since all analyte species
must be swept up to the electrode surface, so
that the electrochemical reaction is completed
1 Potentiostatic Coulometry: Instrumentation

(4) DIGITAL READOUT

• the total charge at the end of electrolysis is

read directly from a digital readout
Gravimetric technique: ELECTROGRAVIMETRY

• if the product of controlled potential coulometry is

a deposit on the working electrode, then we can use
the change in the electrode’s mass as the analytical
signal

• apply a potential to reduce 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
1 Potentiostatic Coulometry: Applications
• majority of controlled-potential coulometric
analyses involve the determination of inorganic
cations and anions, including trace metals and
halide ions

• also used for the quantitative analysis of organic

compound

• example is the reduction of trichloroacetate to

dichloroacetate and dichloroacetate to
monochlroacetate
1 Potentiostatic Coulometry: Applications

(1) Inorganic Analysis

• widespread use in the determination of several metal ions

• As many as 55 elements in the periodic table can be

determined by the cathodic reduction of metal ions to
metallic state

• Most of them can form amalgams with Hg, an hence

controlled potential coulometry with Hg cathode is
usually preferred
1 Potentiostatic Coulometry: Applications

(2) Micro Analysis

• controlled potential coulometry is more popular than

the electrogravimetric methods since it avoids the final
step of weighing the product

• This technique is epically useful for the determination of

small amounts of analyte (0.01 – 1 mg) with an
accuracy of ± 0.5 %
1 Potentiostatic Coulometry: Applications

(3) Analysis of Radioactive Materials

• This technique si widely adopted for the determination

of uranium and plutonium and thus finds extensive use
in nuclear energy field

• Reduction of UO22+ to U4+ can be carried out in H2SO4

medium with Hg pool cathode (-0.6 V vs. SCE)

• Samples containing 7 - 75 mg of U have been analyzed

with an accuracy of ± 0.1 %
1 Potentiostatic Coulometry: Applications

(4) Electrolytic Determination of Organic Compounds

• A new step for the electrolytic determination of organic

compounds

• Trichloroacetic acid and picric acid are quantitatively

reduced at a Hg cathode

• Coulometric methods permit the analysis of these

compounds with an accuracy of 0.1%
2 Controlled Current Coulometry
Applications
• A technique using a constant
current in place of a constant
potential, which produces a
current versus – time profile

• Amperostatic coulometry or
Coulometric titration

• The time needed to complete

reaction measure the number
of electrons consumed
2 Controlled Current Coulometry
Applications
Two Advantages of Controlled-Current coulometry
over Controlled-Potential coulometry
(1) Analysis time is shorter
- Using constant current leads to more rapid analysis
since current does not decrease over time
- a typical analysis time for controlled-current
coulometry is less than 10 mins, compared to approx.
30-60 mins for controlled-potential coulometry
(2) Total charge
- With a constant current, the total charge is simply the
product of current and time
2 Controlled Current Coulometry
Applications
Problems with this technique

(1) we need a method for determining when the

analyte’s electrolysis is complete

(2) The current efficiency may be < 100 %, due to

secondary reactions
2 Amperostatic Coulometry: Instrumentation

• controlled-current
coulometry normally is
carried our using a two-
electrode galvanostat

• Consisting of a

(a) working electrode

and
(b) counter electrode
2 Amperostatic Coulometry: Instrumentation

(1) Working electrode

- Often a simple Pt electrode
- also called as the generator
electrode, since it is where
the mediator reacts to
generate the species that
reacts with the analyte

- Should have a large surface

area
2 Amperostatic Coulometry: Instrumentation
(2) Auxiliary or Counter electrode

- Usually Pt wire

- is isolated from the analytical

solution by a salt bridge or
porous frit to prevent its
electrolysis products from
reacting with the analyte
2 Amperostatic Coulometry: Instrumentation
Two Other Crucial Needs for Controlled-Current
coulometry instrument

(1) An accurate clock

- for the measurement of the electrolysis time, te

(2) The switch for starting and stopping the electrolysis

- The switch must control both the current and the
clock, so that we can make an accurate determination
of the electrolysis time
2 Amperostatic Coulometry: Instrumentation

Coulometric
Titration
5 Sources of Errors: Coulometric Titration

1) Variation in the current during electrolysis

2) Departure of the process from 100% current

efficiency

3) Error in the current measurement

4) Error in the measurement of time

5) Titration error due to the difference between the

equivalence point and the end point
2 Amperostatic Coulometry: Applications

• The use of mediator makes a coulometric titration a

more adaptable analytical technique than controlled-
potential coulometry

• for an analyte that is not easily oxidized or reduced, we

can complete a coulometric titration by coupling a
mediator’s oxidation or reduction to an acid-base,
precipitation, or complexation reaction involving the
analyte.
2 Amperostatic Coulometry: Applications
§ Neutralization Titrations

e.g. coulometric titration of weak and strong acids using

electrogenerated hydroxide
2H2O + 2e- ® 2OH- + H2(g) (at the cathode)

e.g. coulometric titration of weak and strong bases using

electrogenerated hydrogen ions
H2O ® ½O2(g) + 2H+ + 2e- (at the anode)
2 Coulometric Titration: Applications
§ Precipitation and Complex-Formation Titrations
e.g. coulometric titration of Ca2+, Cu2+, Zn2+, Pb2+
using electrogenerated complexing agent
HgNH3Y2- + NH4+ + 2e- ® Hg(l) + 2NH3 + HY3-

§ REDOX Titrations
e.g. coulometric titration of ascorbic acid using
electrogenerated iodine: 2I- ® I2 + 2e-
I2 + ascorbic acid ® dehydroascorbic acid + HI
Summary of Coulometric Titrations (Neutralization,
Precipitation and Complex formation Reactions

Species Generated Electrode Secondary Analytical

Determined Reaction Reaction
Acids 2H2O + 2e- = 2OH- + H2 OH- + H+ = H2O

Bases H2O = 2H+ + 1/2O2 + 2e- H+ + OH- = H2O

Cl-, Br-, I- Ag = Ag+ + e- Ag+ + X- = AgX (s)

Mercaptans (RSH) Ag = Ag+ + e- Ag+ + RSH = AgSR (s) + H+

Cl-, Br-, I- 2Hg = Hg22+ + 2e- Hg22+ + 2X- = Hg2X2 (s)

Zn2+ Fe(CN)63- + e- = Fe(CN)64- 3Zn2+ + 2K+ + 2Fe(CN)64- =

K2Zn3[Fe(CN)6]2 (s)

Ca2+, Cu2+, Zn2+, HgNH3Y2- + NH4+ 2e- = HY3- + Ca2+ = CaY2- + H+,
Pb2+ Hg(l) + 2NH3 + HY3- etc.
Summary of Coulometric Titrations Involving REDOX Reactions

Reagent Generated Electrode Substance Determined

Reaction
Br2 2Br- = Br2 + 2e- As(III), Sb(III), U(IV), Tl(I), I-, SCN-,
NH3, N2H4, NH2OH, phenol, aniline,
mustard gas, mercaptans, olefins

Cl2 2Cl- = Cl2 + 2e- As(III), I-, styrene, fatty acids

I2 2I- = I2 + 2e- As(III), Sb(III), S2O32-, H2S, ascorbic

acid

Ce4+ Ce3+ = Ce4+ + e- Fe(II), Ti(III), U(IV), As(III), I-,

Fe(CN)64-

Mn3+ Mn2+ = Mn3+ + e- H2C2O4, Fe(II), As(III)

Ag2+ Ag+ = Ag2+ + e- Ce(III), V(V), Ce(IV), U(VI)

• unstable reagents: Br2, Cl2 , l2 • highly reactive reagents: Ag2+ or Mn3+

Summary of Coulometric Titrations Involving REDOX Reactions

Reagent Generated Electrode Reaction Substance Determined

Fe2+ Fe3+ + e- = Fe2+ Cr(VI), Mn(VII), V(V), Ce(IV)

Ti3+ TiO2+ + 2H+ + e- = Ti3+ + H2O Fe(III), V(V), Ce(IV), U(VI)

CuCl32- Cu2+ + 3Cl- + e- = CuCl32- V(V), Cr(VI), IO3-

U4+ UO22+ + 4H+ + 2e- = U4+ + 2H2O Cr(VI), Ce(IV)

Conventional Titration vs. Coulometric Titration
Conventional Titration vs. Coulometric Titration
Advantages of Coulometric Titration
versus Conventional Titration

1) Electrochemically generating a titrant allows us to use an

unstable reagent and use them in coulometric titration.
Can prepare unstable reagents, since they react almost
as soon as they are generated e.g. Cl2, Br2, or highly
reactive reagents like Ag2+ or Mn3+

2) Relatively easy to measure a small quantity of charge, we

can use a coulometric titration to determine an analyte
whose concentration is too small for a convenient
titration
Conventional Titration vs. Coulometric Titration
con’t. Advantages of Coulometric Titration
versus Conventional Titration

3) No need to prepare, standardize, store standard

solutions. Standardization using primary standard
are not necessary

4) A single coulometric titration apparatus can be used

for redox, acid-base, precipitation and
compleximetric titrations
Conventional Titration vs. Coulometric Titration
con’t. Advantages of Coulometric Titration
versus Conventional Titration

5) Coulometric methods of analysis is accurate,

precise, sensitive, selective and not expensive, but
controlled-potential coulometry is relatively time
consuming analysis, with a typical analysis
requiring 30-60 min.

Coulometric titrations requires only a few

minutes
Volumetric Titration vs. Coulometric Titration

Volumetric Tritration Coulometric Titration

Standard solution Constant current source of
known magnitude

Buret and stopcock Timer and switch

Volume of standard Charge required to reach

solution required to reach an equivalence point is
an equivalence point is measured
measured

Moles of reagent Current x time

Karl Fischer Titration

• An important example of redox titrimetry

• Titration methods that used coulometric or

volumetric titration to determine trace amounts
of water in a sample

• Determination of water in substance such as

pharmaceutical preparation and raw material

• Invented in 1935 by the German chemist Karl

Fischer
Karl Fischer Titration

• The titrant for this analysis is known as Karl

Fischer reagent and consists of a mixture of
iodine (I2), sulfur dioxide (SO2), pyridine (py)
and methanol (CH3OH)

• Because the concentration of pyridine (py) is

sufficiently large, I2 and SO2 react with py to
form complexes py•I2 and py•SO2
Karl Fischer Titration

• When added to a sample containing water, I2 is

reduced to I- and SO2 is oxidized to SO3

py•I2 + py•SO2 + H2O = 2py•HI + py•SO3

Karl Fischer Titration

• Methanol is included to prevent further reaction of

py•SO3 with water

• Based on an iodine / iodide reaction

• The water reacts with iodine.

• The amount of I2 used to consume all the water

contained in the sample is measured
Karl Fischer Titration

• The endpoint of the

titration is reached
when all the water is
consumed.

• The titration end point is

signaled when the
solution changes from
the product’s yellow
color to the brown color
of the Karl Fischer
reagent
Coulometric Karl Fischer Titration

• Iodine is electrolytically generated

• The amount of iodine added to the sample is

determined by measuring the current needed for
the electrochemical generation of the iodine

• When reacting with water, the brown iodine is

reduced to the colorless iodide

• The coulometric method is suitable for samples

with low water content (10 ug to 100 mg)
Coulometric Karl Fischer Titration
Sample Calculation

1) The purity of a sample of Na2S2O3 (158.1 g/mol)

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.
Sample Calculation
1) The purity of a sample of Na2S2O3 (158.1 g/mol) 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

2S2O32- (aq) + I3- (aq) = S4O62- (aq) + 3I- (aq)

Q = It ; nA = Q / nF ; (nF) (nA) = I te
, nA = number of moles of analyte
, n = number of moles of electrons
transferred in the half-cell reaction
, F = 96,487 C mol-
` , te = electrolysis time

nF (g Na2S2O3 / MM Na2S2O3 ) = I te
Sample Calculation
1) The purity of a sample of Na2S2O3 (158.1 g/mol) 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.
Ixt
Q = (nA) (nF) ; Q = It ; moles reacted, nA =
nF
2S2O32- (aq) + I3- (aq) = S4O62- (aq) + 3I- (aq)
• oxidizing S2O32- to S4O62- requires one electron per S2O32- (n=1)

grams Na2S2O3
1 1 mol x 158.1 g
= (0.03645 A) (221.8 s) x x
1 e- 96,500 A s mol
weight Na2S2O3 (g) = 0.01324 g
Sample Calculation
1) The purity of a sample of Na2S2O3 (158.1 g/mol) 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.

2S2O32- (aq) + I3- (aq) = S4O62- (aq) + 3I- (aq)

• 0.01324 g represents the amount of Na2S2O3 in a 10.00 mL
portion of the sample
• Thus, 0.1324 g of Na2S2O3 is present in the original sample (in
100 mL)
0.01324 g Na2S2O3
% w/w Na2S2O3 = x 100
0.1342 g sample

= 98.66 % w/w Na2S2O3

Sample Calculation

2) A 0.3619-g sample of tetrachloropicolinic acid,

C6HNO2CI4 (260.8 g/mol), is dissolved in distilled
water, transferred to a 1000-mL, volumetric flask, and
diluted to volume. An exhaustive controlled-potential
electrolysis of a 10.00-mL portion of this solution at a
spongy silver cathode requires 5.374 C of charge.
What is the value of n for this reduction reaction?
Sample Calculation
2) A 0.3619-g sample of tetrachloropicolinic acid, C6HNO2CI4 (260.8 g/mol), is
dissolved in distilled water, transferred to a 1000-mL, volumetric flask, and
diluted to volume. An exhaustive controlled-potential electrolysis of a 10.00-mL
portion of this solution at a spongy silver cathode requires 5.374 C of charge.
What is the value of n for this reduction reaction?
Ixt
Q = (nA) (nF) ; Q = It ; moles reacted, nA =
nF
Solution.
mole = 1.39 x 10-5 mol
mole = 0.3619 g x
260.8 g
ü 10.00 mL portion of sample has 1.39 x 10-5 mole C6HNO2CI4
Q 5.374 C
n= =
nA F (1.39 x 10-5 mole) ( 96,500 C/ mole)
n = 4.01
Sample Calculation

n = 4.01

The reducing molecule, tetrachloropicolinic acid, C6HNO2CI4,

requires 4 electrons.

The overall reaction, which results in the selective

formation of 3,6-dichloropicolinic acid is,