TEMA 5.

ELECTROLYSIS OF POLLUTANTS
1. Direct and indirect electrolysis
2. Mineralization
a) Incineration
b) Wet Air Oxidation (WAO)
c) Chemical oxidation with strong oxidants
d) Electrochemical mineralization
3. Thermodynamics of electrochemical mineralization
4. Direct electromineralization
5. Indirect electromineralization
a. Reversible processes
b. Irreversible processes

The type of the oxidative process involved in the removal of a pollutant by

electrochemical processes is a function of the material of the anode, and application of
different anodic materials with different electrocatalytic properties can affect reactor
treatment efficiencies. Two different process can occur at the electrode as a function of
the anodic material.
On anodes having a high electrocatalytic activity, such as platinum, direct oxidation can
take place. Other materials can be involved in the production of redox mediators that, in
the bulk solution, can undergo a reaction with a pollutant, setting for an indirect
electrochemical oxidation. It has been shown that on dimensionally stable anodes (DSA),
oxidation of organics can occur only under conditions of simultaneous oxygen evolution,
which can be accomplished either by electrochemical oxidation of physically adsorbed
hydroxyl radicals or by electrochemical oxidation of the surface itself, followed by the
release of oxygen in a chemical decomposition step.

Anodes on which electrocatalytic mineralization is favoured are those at which the

formation of hydroxyl radicals can be fast, thus having many active sites and low oxygen
vacancies in the oxides. Anodes composed of metallic oxides at the highest possible
oxidation level and/or which contains excess of oxygen can be considered suitable to
conduct mineralization, and thus may be suitable for application during industrial
wastewater treatment for the complete destruction of organic substances.
For electrochemical processes occurring via a direct reaction of the pollutant at the
electrode surface, the term DIRECT ELECTROLYSIS is generally used. INDIRECT
ELECTROLYSISS refers to those processes in which a redox couple, whose oxidized
form is being continuously renewed by an anodic heterogeneous reaction, is involved in
a homogeneous phase reaction with the pollutant. Indirect electro-oxidation can be
conducted when chloride, ferric or silver ions are present, the first the most important
from the point of view of practical applications, as chlorides are common constituent of
several industrial wastewaters.
DIRECT ELECTROLYSIS
The Figure below explains the concept of a direct electrochemical reaction applied for
the pollutant abatement, using the anodic process as example. As it can be seen oxidation
occurs directly on an electrode by the application of appropriate potential, without the
involvement of other substances.

The pollutant at the surface will release one or more electrodes

INDIRECT MINERALIZATION
Figure en los apuntes de clase mirar ahí

OUR GOAL IS TO COMPLETE THE MINERALIZATION OF THE POLLUTANTS

Por mineralización entendemos: you completely transform your pollutant into CO2 and
H2O or eteroatoms
MINERALIZATION IS CLASSIFIED IN THREE MAIN CATHEGORIES (Referred to
the traditional methods).
a) Incineration (It takes place at temperatures around 800-1000ºC It’s basically a
combustion in presence of excess of air).
It’s nearly an instantaneous process. You have byproducts that are gases: NOx,
SO2,HCl,ashes)

Good: COD>100g/L

b) Wet Air Oxidation

It is oxidation of organics in an aqueous medium
It is carried out by oxygen (from air) and the temperature required is around 300
ºC and the pressure around 100-150 bar.
 You need a catalyst which is usually Cu2+. Efficiency of this process is around
99.9 %
It can give several byproducts (acetones, methanol, ethanol, methane, sulfuric
acid)

Good: 50 g/L>COD>15 g/L

c) Chemical oxidation with strong oxidants (Usually O3 or H2O2)

Reactions usually occur at room temperature
Often a catalyst is needed or UV irradiation
Good: COD<5g/L

In additional to these classical approaches of mineralization, we have

ELECTROCHEMICAL MINERALIZATION which is in competition with a)
INCINERATION because we are using the same chemicals (Cl2, O3, H2O2,
O2…)
Good: for diluted waters with COD< 5g/L

THERMODYNAMICS OF ELECTROCHEMICAL MINERALIZATION

Reacciones en los apuntes de clase.
Meaning of these reactions: Chemical identity of pollutants is known. So, you can
calculate the minimum of anode to know the one for the pollutants (the voltage is
known a priori).

FIGURES OF MERIT IN ELECTROCHEMICAL MINERALIZATION

As several reactions can occur simultaneously at the electrode surface, including
the parasite reactions of solvent decomposition, the current delivered to the reactor
will be used only in part for the reaction in which a pollutant of interest is involved.
IMPORTANT PARAMETERS IN ELECTROCHEMICAL
MINERALIZATION.
a) Instantaneous current efficiency
The ratio between the charge used for a given transformation and the total
charge applied determines the current efficiency.

In case of the process of electrochemical treatment of polluted effluents is

followed by monitoring the parameter of chemical oxygen demand (COD),
the current efficiency can be evaluated, assuming a four-electron reaction
during COD destruction:
 𝐶𝑂𝐷𝑡 − 𝐶𝑂𝐷𝑡−∆𝑡
𝐼𝐶𝐸𝐶𝑂𝐷 = ∙ 𝐹 ∙ 𝑉𝑠
8 ∙ 𝐼 ∙ ∆𝑡

We have the volume of the water, the faraday constant, and the current you set
in the electrolyzer.
The total difference in COD is considered with respect to the current given.
K2CR2O7 IN H2SO4 → When you want to measure COD by adding
K2CR2O7 in H2SO4 into the waters.

K2CR2O7 will oxidize any organic material. After this reaction has occurred,
you measure the unreated by titration because you know at time=0 how much
you added, so, you cam determine the excess. COD units mg/L.

b) Electrochemical Oxidability Index (EOI).

ICE that was just seen, is an instantaneous parameter which means that changes
with time. HOW CAN YOU EVALUATE THE AVERAGE OF THE PROCESS?
You plot the ICE parameter versus time and you plot it.
APUNTE: Anodic oxidation is a very powerful tool for breaking up the most
resilient organic compounds. The result is the reduction of the COD and enhanced
biological degradability measured by the BOD.
The ease of electrochemical oxidation of organic species can be estimated by the
EOI. The EOI is the average current efficiency from the initial concentration of
pollutants at time sigma, when the pollutant is nearly zero. Calculation of the
index requires knowing the ICE which is the efficiency at any time during the
electrolysis. The EOI is defined as:
Common destruction pathways include direct, and indirect electrolysis. An
important routine for electrochemical destruction of organics is: “electrochemical
combustion method” where the organics are completely oxidized to CO2 and
H2O. This procedure can be used as tertiary method following biological
treatment.
The highest the EOI the easiest is to decontaminate the specific waters you are
getting. NH3 high EOI
Low EOI can be due to: -SO3H,-COOH (because functional groups tend to retain
electrons). The pollutants are not oxidized easily

c) Electrochemical Oxygen Demand (EOD)

Mirar formulas en los apuntes.
If all the current circulating in the electrolytic cell was used to produce oxygen at
the anode (only oxidation reaction) we could calculate the theoretical number of
moles of oxygen produced.
In presence of organic species, we have only a fraction of the current which is
used to produce oxygen.

We compare the current that is used to oxidize the organic compounds to the
theoretical current if we don’t oxidize anything. By doing this comparison, we can
express the efficiency related to the oxidation or organics.
When we have the EOD we can calculate the degree of oxidation of organics by
any by-product.
X=EOD/COD*
If EOD is low respect to COD*, we won`t get close to mineralization.
Primary degradation: 20%
Final degradation: 70% it’ also called COMPLETE MINERALIZATION
PUNTO 4. DIRECT ELECTROMINERALIZATION
Pollutants react directly in the anode. There are not intermediates. Electrodes should not
corrode. Very positive values.
It’s not easy to predict the electrostability under real conditions. However we know the
metals Ir, Rn are very stable but too expensive. For this reason another alternative is Ni,
Pb. It’s also possible to use vitreous carbon reticule GC, Graphite, titanium, stainless
steel,…
WE HAVE TO TAKE INTO ACCOUNT WHAT HAPPENS IN THE ANODE →
DIFFERENT ANODIC MATERIALS WILL PRODUCE DIFFERENT PRODUCTS.
SP IT’S IMPORTANT TO CONSIDER THE NATURE OF THE BY-PRODUCTS.

a) Phenols
Produced by variety of wastewaters.
If the concentration is high, the are treated by chemicals.

Using anodes that have high overpotential for oxygen evolution. FOR
EXAMPLE:
PbO2, Graphite, Ti/TiO2, or Ti/SnO2.

This means that we can polarize this material with positive potential without
produce oxygen.
The by-products will give polymeric materials at the films on the electrode and
they will also slow down oxidation of the pollutant.

b) Aromatic amines
They react due to hemoglobine. They are found in wastewater from perfumes.
Paper, petroleum, rubber industry,…

Example in the notes of class.

CONCLUSION: MINERALIZATION PROCESS IS REALLY SENSITIVE
WITH THE PH.

c) Halogenated and nitroderivatives

Pesticides belong to this cathegory.
Methods used to treat this:
- Concentration by membrane separation
- Absorption
- Chemical oxidation
- Biological treatment
From electrochemical point of view, it can be treated by the use of micelles.

d) Waste biomass
 This can be oxidized using led anodes in sulfuric acid
Electrochemical incineration (Mineralization is over 90%). Not producing
undiserable gases. Generally incineration produces CO, NO,NO2,CH4,NH33
which in this case they are not produce (ADVANTAGE FROM
ELECTROCHEMICAL INCINERATION).

e) Cyonides

They are treated by Cl2 or ClO

This approach gives several toxic byproducts. [CN-] >0.2 and the solution is
alkaline.
We will never add acid with cyonides because volatile compounds are produced.
For example we can use: RnO2 + TiO2 or PbO2.

PUNTO 5 - INDIRECT ELECTROMINERALIZATION

Reversible: Ag+/Ag2+, Fe2+/Fe3+,CO2+/CO3+,OH∙
Irreversible: H2O2, O3, ClO-,Cl2