TEMA 2.

ELECTROCHEMICAL DETECTION OF POLLUTANTS

Brief introduction to the topic

Chromatography and atomic spectrometry are the most competitive techniques
comparing them to electrochemical methods for water analysis.
We will choose one or the others depending on two factors:
 Number and concentration of pollutants
 Properties of the water
Sometimes we can find chromatography, atomic spectroscopy and electrochemical
methods combined together. (Electrochemical located first, them the others).

There are two features that characterize electrochemical technologies compared to

the other two:
1. Easily implemented in feed
2. More cost effective
3. Some main drawbacks (Incovenientes)
 May have problems due to fouling (ensuciamiento)
 When we have a mixture of pollutants (metals) you cannot differentiate
the concentration of each single ion (You just can see there is a mixture).
This è suffers from sensitivity.
 Sometimes electrochemical techniques to work need electrical current to
flow. So possible reaction at the è. So you might modify the composition
of the water during the analysis.

Classification of electrochemical technologies:

1. Potentiometric methods
2. Coulometric methods
3. Amperometric methods
4. Voltammetric methods
Techniques such as voltammetry are also useful for first defining the electrochemical
behaviour of a specified pollutant.
1 Potentiometric method.
Brief introduction to this topic
In potentiometry we measure the potential of an electrochemical cell under static
conditions. Because no current—or only a negligible current—flows through the
electrochemical cell, its composition remains unchanged.
It does not require current to flow, so you do not modify the composition of your
water. (I  0)
Two electrodes are necessary to make a potential measurement, which usually are:
Indicator electrode: which selectively responds to changes in the activity of the analyte
being measured.
Reference electrode: which must be constructed so that its composition is fixed and its
response stable over time, with observed changes in measured potential due solely
changes in analyte concentration.

The standard reduction potential, or E0, allows you to predict the ease with which a half-
cell reaction occurs relative to other half-reactions. Values of E0 are most often reported
as the potential measured in an electrochemical cell for which the standard hydrogen
electrode is used as a reference.

The standard hydrogen electrode, or SHE, is composed of an inert solid like platinum
on which hydrogen gas is adsorbed, immersed in a solution containing hydrogen ions at
unit activity. The half-cell reaction for the SHE is given by
−¿↔ H2 ( g)¿

2 H +¿ (aq )+2 e ¿

and the half-cell potential arbitrarily assigned a value of zero (E0 = 0.000 V).

Practical application of the SHE is limited by the difficulty in preparing and maintaining
the electrode, primarily due to the requirement for H2 (g) in the half-cell. Most
potentiometric methods employ one of two other common reference half-cells – the
saturated calomel electrode (SCE) or the silver-silver chloride electrode (Ag/AgCl).
Basic components needed for the analysis

1  REFERENCE ELECTRODES (gives reference for potential measurement)

a. Calomel Reference electrode

b. Silver/Silver chloride electrode

2  INDICATOR ELECTRODES (where species of interest is measured)

a. Metallic Indicator Electrode

i. First Kind
ii. Second Kind
iii. Third Kind
iv. REDOX indicators
b. Membrane indicator electrodes
i. Glass membrane electrode / pH meter
ii. Cristalline membrane electrode
iii. Liquid membrame electrode

c. Molecular selective electrodes systems

i. Gas sensing probes
ii. Biocatalytic membrane electrodes
1 REFERENCE ELECTRODES (Instead of SHE: Standard hydrogen electrodes)
Desired characteristics:

o The potential is known and constant (It’s fixed)

o A constant response is obtained
o It must be insensitive to composition of the waters that are being studied
o Reversible

It means that if you reverse the direction of the current reactions occur in both
directions:
A↔B
You simple reverse the reactions on the electrode (Most of the times is not like
that).

o Obeys the Nerst equation

When we analyse water, we measure the activity. In some cases, we can
approximate activity to concentration by assuming a=1.
Example to see the difference between the concept’s activity and concentration.
When you add a certain amount of NaCl in the water when you cook this is
concentration. Them the ions will interact among themselves in the water.
Sometimes the concetration will give a higher value. APPARENT
CONCENTRATION: activity is higher which means ions will be more active
than what they should be
Activity: ions will be less or more active than what they should be
mathematically.
Example: We bubble hydrogen close to a platinum plate.
The TESTER is the deviced used to measure the potential difference.
Anode: occurs the oxidation (pierdes electrones)
First the hydrogen dissolves into the water
H 2 ( g ) → H 2 (l)

Second this reaction occurs in the platinum plate:

1
H 2 → H +¿+1 è¿
2
On the other side we have silver. Both plates are immersed in a solution which is
0.01 M HCl which is a saturated solution (When you have a stable precipitate 
Solution saturated with AgCl).
Cathode: reduction occurs at the cathode

Ag+¿+1 è→ Ag ¿
The overall reaction would be (Chemical REDOX reaction):
+ ¿(aq) ¿

2 AgCl (s)+ H 2 ( g) →2 Ag(s )+ 2Cl−¿(aq)+2 H ¿

So, we can define the equilibrium constant (K) of the overall reaction:
K=a aCl ∙a ¿ 2
¿
¿
H ∙
Ag(s )

2
¿
a H ( g)∙ a
2 AgCl (s )

The activity of solids is equal to 1, so:

K=a ¿ aCl ¿
¿
H ∙ ¿
a H ( g)
2

EQUILIBRIUM WHEN STABLE SITUATION

With this configuration you produce electrical current, so this is not an
equilibrium situation. So, any battery is not an equilibrium situation.
So how can we define something that is not an equilibrium situation? By taking
the instantaneous activity of the species:
Q=¿¿ ¿
The Gibbs energy of the process is:
∆ G=RTlnQ−RTlnK
R: 8.3145 J/mol-1/K-1
We also know that:
∆ G=−nF E cell

We can combine these two different equations, and finally get:

 RT RT
Ecell (V )= ∙lnK − ∙ lnQ
nF nF
F: 96485 C/mol
Ecell is the voltage of the battery.

At the end we can arrange to. This is the Nernst equation that relates the cell
potential to the standard potential and to the activities of the electroactive
species. Notice that the cell potential will be the same as E° only if Q is unity.
RT
Ecell =E0cell − ∙lnQ
nF
The more the process goes on the more the voltage reduces its potential:
RT
Ecell =E0cell − ∙ ln ¿
nF
Types
1a) Calomel reference electrode

The SCE is a half cell composed of mercurous chloride (Hg2Cl2, calomel) in contact
with a mercury pool. These components are either layered under a saturated solution of
potassium chloride (KCl) or within a fritted compartment surrounded by the saturated
KCl solution (called a double-junction arrangement). A platinum wire is generally used
to allow contact to the external circuit. The half reaction is described by:
Hg| Hg2 Cl2 , KCl ( x , m )|∨half reaction
−¿¿

HgCl 2 ( s )+2 e−¿↔ 2 Hg ( l) +2 Cl ¿

Tmax=40 ºC
Electrochemical reactions are written in the sense if reduction, mercury is required.
IF KC los saturated  SATURATED CALOMEL ELECTRODE (SCE)
with an E0 value of +0.244 V. A common arrangement for the SCE is shown below, left
side. In this arrangement, a paste is prepared of the calomel and solution that is
saturated with KCl.
1b) Silver/Silver chloride ELECTRODE

The silver/silver chloride reference electrode is composed of a silver wire, sometimes

coated with a layer of solid silver chloride, immersed in a solution that is saturated with
potassium chloride and silver chloride. The pertinent half reaction is:
−¿ ¿

AgCl ( s )+ e−¿→ Ag ( s) +Cl ¿

Ag| AgCl (sat ), KCl ( sat )|∨¿

with a value for E0 of +0.222 V. The actual potential of the half-cell prepared in this
way is +0.197 V vs SHE, which arises because in addition to KCl, AgCl also
contributes to the chloride activity, which is not exactly unity.
2 INDICATOR ELECTRODES
2a) Metallic indicator electrode
In potentiometry the potential of the indicator electrode is proportional to the analyte's
activity. There are different classes of indicator electrodes which are used in
potentiometry. They can be subdivided in first, second, third and redox
i) Electrodes of the first kind:
If we place a copper electrode in a solution containing Cu2+:
−¿ →Cu(s )¿

Cu2+¿ (l) +2 e ¿

The electrode’s potential due to the reaction is determined by the activity of Cu2+:

Eind =E Cu 2+ ¿ 0
0.0592 1
− ∙log ¿
Cu 2 a Cu = ECu
2+¿ 2+¿ 0
0.0592
¿
− ∙ pCu¿
Cu 2

RT/F=0.0592 (At room temperature)

2 indicates the moles of electrons in the reaction
If the concentration of copper changes, the potential difference does too.
Electrodes of the first kind cab be chosen from the following metals: Ag, Cd, Cu, Hg,
Pb, and Zn.
ii) Electrodes of the second kind:
Metal electrodes assembly with the equilibrium potential being a function of the
concentration of an anion in the solution. Typical examples are the silver/silver-chloride
electrode and the calomel electrode. The potential of the metal is controlled by the
concentration of its cation in the solution, but this, in turn, is controlled by the anion
concentration in the solution through the solubility product of the slightly soluble metal
salt.
They answer to the anion activity which forms a precipitate or a stable complex with the
metallic electrode.
Example:
−¿ (l )¿

AgCl ( s )+ 1e−¿ → Ag (s )+Cl ¿

a Cl −¿(l)

K=a Ag(s ) ∙ remembering a of solids equal¿ 1

a AgCl( g)

K=aCl −¿(l)
¿

So, the electrodes potential is:

Eind =E Ag +¿ 0
0.0592
− ∙ log¿¿
Ag 1

DUDA SIGNO
The aim is to write the Nerst equation just dependant of the activity of one specie each
time. Whenever the voltage changes, it just changes the activity of one specie.
Another example: EDTA detection:
4−¿ ¿
−¿→ Hg (l )+ y

Hg y 2−¿+2 e
¿
¿

Eind =E Hg 2+ ¿ 0
0.0592
− ∙log ¿¿
Hg 2

aHgy2- is constant, it’s really stable so it does not change much. So, the voltage just
depends on the activity of ay4-.
E0:0.21 V (vs SHE)

iii) Electrodes of the third kind:

Electrode of the third kind is a metal electrode assembly with the equilibrium potential
being a function of the concentration of a cation, other than the cation of the electrode
metal, in the solution.
They answer to cations different than those of the electrode.
Example: Detect Ca by a complex with EDTA
Equilibrium reaction:
4−¿¿
2+¿+ Y ¿

CaY 2−¿ ↔Ca ¿

Eind =E Hg 2+ ¿ 0
0.0592
− ∙log ¿¿
Hg 2

Mirar apuntes
iv) Redox indicators:
Inert metal like Pt,Au,Pd which do not take part in the reaction just by being in the
solution, and its potential depends on the dissolution.
Example: Ce (IV)/Ce (III) //Pt.

0.0592 a 3 +¿

Eind =E 0Ce (IV ) − ∙ log Ce ¿

Ce ( III )
1 aCe ¿ 4+ ¿
2b) Membrane indicator electrode
The existence of this membrane potential led to the development of a whole new class
of indicator electrodes called ion-selective electrodes (ISEs).
By now you have learned that the identity of the membrane determines the selectivity of
the electrode. In other words, the type of membrane used dictates which analyte you can
detect. Therefore, different electrodes are used for different ions.
The membrane should also have:
- Low solubility in the analyte solution (We don’t want it to dissolve!!)
- Small electronic conductivity.
- Selective reactivity
There are three main types of membranes. The electrodes are classified by the
membrane material.
i. Glass membrane electrode
ii. Cristalline membrane electrode
iii. Liquid membrane electrode

i. Glass membrane electrodes/ Glass pH electrode

Most common type of ISE which utilizes a thin glass membrane that is responsive to
changes in H+ activity. Cremer observed the pH dependence of measured potential
across a thin glass membrane.
COMPLETAR
ii. Cristalline membrane electrode
The membrane is composed of an insoluble inorganic salt. An ion-exchange process
leads to the formation of a potential at the membrane.
Those can be manufactured from ionic compounds or a mixture of ionic compounds.
Most of them are nonconductive, but for this application we need a conductive one.

Example when you have the crystal called lanthanum trifluoride (LaF3) in the glass
(OUR CRISTAL MEMBRANE) in solution you have dissociation.
−¿(solution)¿
( glass) +F
La F3 ( glass ) ↔ La F +¿ ¿
2

You can see that the formation of LaF2+ creates a charge at the surface. The
equilibrium will be shifted to the right for the solution with a smaller F- concentration,
and the potential will become more positive relative to the other side of the membrane.
It is this potential difference across the LaF3 crystal membrane that is measured and
related to F- concentration. The fluoride electrode is extremely selective for F- but can
experience interference from OH- above pH 8. This electrode is used in one of the
experiments listed at the end of this learning module.
Single crystal LaF3 is widely used to determine F-. YOU CAN USE THIS
CRYSTAL TO DETECT CHLORIDES
A solid-state ion-selective electrode uses a membrane consisting of either a
polycrystalline inorganic salt or a single crystal of an inorganic salt. We can fashion a
polycrystalline solid-state ion-selective electrode by sealing a 1–2 mm thick pellet of
Ag2S—or a mixture of Ag2S and a second silver salt or another metal sulfide—into the
end of a nonconducting plastic cylinder, filling the cylinder with an internal solution
containing the analyte, and placing a reference electrode into the internal solution.
2−¿ ( aq ) ¿

Ag2 S ( s ) ↔2 Ag+ ¿ ( aq )+S ¿

What can we detect with this method? A list of cations and anions:
Br- Cd2+ Cl- Cu2+ CN- Pb2+ SCN-

iii. Liquid membrane electrode

It uses a porous plastic membrane. The membrane is placed in an inert solid covered by
a liquid ion exchanger. It’s usually an organometallic compound.
The potential of the electrode depends on the one of the membrane which depends on
the organometallic compound (which is exchanging ions with the solution) which is
covering the plastic disk.
One of the most famous liquid membrane electrodes has been used for calcium
determination. You can also detect NO3- ClO4- K+ Ca2+ Mg2+
2c Molecular selective electrodes systems
i.Gas sensing probes
They are done to detect dissolved gasses like CO2 or ammonia

It’s already an electrochemical cell.

You have a glass electrode in the tube which is connected to the external solution
through a glass membrane.
Around it, there is another tube which contains a solution which forms a tin fin in
between the gas-permeable membrane (the one that connects the cell to the external
world) and the glass membrane.
Example: when you want to detect CO2.
You measure the concentration of CO2 in water by measuring the pH of the solution
NaHCO2 + NaCl. Why?
You have CO2 in your analyte which is in equilibrium with the CO2 in the membrane
because it’s permeable. It will dissolve into the membrane and from the membrane will
go to the internal solution.
CO 2( analyte)↔ CO 2(membrane) ↔CO 2 (aq)(internal solution )

So, when you have CO2 aqueous and water, this happens:
+ ¿(aq) ¿
( aq ) + H
CO 2 ( aq )+ H 2 O ↔ H CO−¿ ¿
3

+ ¿( aq)¿
( aq ) +H
CO 2 ( analyte )+ H 2 O ↔ HC O−¿ ¿
3
El CO2 subrayado, goes into solution producing protons (pH key word)
K=a a HCO −¿ ( aq)
¿
+ ¿(aq) ∙
H
3
¿
aCO (analyte )
2

Which can be rewritten this way:

aH +¿ (aq )
K
= ¿
aCO (analyte)
2
aHCO −¿(aq) ¿
3

If the concentration of NaHCO3 is sufficiently high and you add a little bit of CO2. The
concentration of HCO3- will not change really much, so you can assume it constant:
aH +¿( aq)
=const ∙aCO (analyte )¿ 2

FALTA ALGO

ii. Biocatalytic membrane electrodes

They are really expensive because they work exploding the function of enzymes.
The analyte will undergo to a catalytic reaction with the enzyme. We will transform the
analyte into species like H+, H2O2 …

Analyte (+ Enzyme ) → CO2 , H + ¿, H 2 O2 ,… ¿

The concentration of the products is proportional to the concentration of the analyte.

The more hydrogen you produce, the more analyte you have.
Advantages:
 You can detect complex organic molecules (Also inorganic molecules which are
always easier to detect them).
 You can detect minimal analyte concentration
 It’s a very selective approach. REASON: Because you can choose the enzymes
which are characteristic for being very selective.

BREVE RESUMEN: YOU DO NOT HAVE CURRENT FLOWING INTO THE

SYSTEM, SO YOU DO NOT CHANGE THE COMPOSITION OF THE ANALITE
OR THE WATER. WHEN YOU HAVE CURRENT, YOU HAVE THE RISK OF
CHANGING THE COMPOSITION.

ACABAR TEMA COULOMETRY

2 Coulometric method.
Coulometry is based on an exhaustive electrolysis of the analyte. By exhaustive we
mean that the analyte is completely oxidized or reduced at the working electrode or that
it reacts completely with a reagent generated at the working electrode.
There are two forms of coulometry:
1. Potentiostatic coulometry: in which we apply a constant potential to the
electrochemical
2. Amperostatic coulometry: we pass a constant current through the
electrochemical cell
All the current must be used to oxidize or reduce the analyte. In other words,
coulometry requires 100% current efficiency—or an accurately measured current
efficiency established using a standard—a factor that we must be consider when
designing a coulometric method of analysis.

1 Potentiostatic coulometry
A three-electrode system is used to set the potential in controlled-potential coulometry.
The easiest way to ensure 100% current efficiency is to hold the working electrode at a
constant potential, chosen so that the analyte reacts completely without simultaneously
oxidizing or reducing an interfering species. As electrolysis progresses the analyte’s
concentration decreases, as does the current. The resulting current-versus-time profile
for controlled-potential coulometry is shown below. Integrating the area under the curve
(equation 11.27) from t = 0 to t = te gives the total charge.

2 Amperostatic coulometry
Amperostatic coulometry is sometimes called a coulometric titration because of its
similarity to a conventional titration.
In comparison to a conventional titration, a coulometric titration has two important
advantages. The first advantage is that electrochemically generating a titrant allows us
to use an unstable reagent. Although we cannot easily prepare and store a solution of a
highly reactive reagent, such as Ag2+ or Mn3+, we can generate them
electrochemically and use them in a coulometric titration. Second, because it is
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 conventional titration.