Electrochemistry and

Its Application
TEKNIK KIMIA – UNIVERSITAS PERTAMINA 2019

Agung Nugroho
Electrochemistry and Its Applications
Contents
Application of electrochemistry in:
 Water Treatment
 Battery
 Corrosion Prevention
Objectives
 Able to understand application of
electrochemistry in water treatment
process
 Able to understand application of
electrochemistry in battery technology
 Able to understand application of
electrochemistry in corrosion
prevention
Electrochemistry
application on
water treatment
Process in water treatment
 Unit processes in water treatment

 Coagulation
 Sedimentation
To remove particles
 Flotation
 Filtration

 Biological processes
 Advanced oxidation
 Adsorption To remove organic
compounds
 Membrane processes
 Disinfection
 Electrochemical Methods

Benefit
 Electrocoagulation
 High efficiency
 Electrodeposition
 Easy operation
 Electroflotation
 Safety
 Electrooxidation
 Compact facilities
 Electrodisinfection
 Selectivity
 Less chemical used
 Environmental compatibility
“
Electrocoagulation
”
 Introduction to coagulation

- Coagulation and flocculation are two consecutive process (i.e. occur one after the other) that are used to
remove colloidal particles from water.

- Colloidal particles found in wastewater :

- Net negative surface charge
- 0.001 to 1 µm in size (turbidity and color causing particles)
- Attractive body forces between particles < repelling forces
- This stable conditions, Brownian motion (i.e. random movement) keeps the particles in suspension.
- Examples of colloids: soil particles, bacteria, viruses and color causing materials. These colloids are
stable in solution and theoretically will stay there for ever unless an action is done to destabilize them.
- Coagulation is the process of destabilizing colloidal particles so that particle growth can occur as a result
of particle collisions
Suspended Solids and colloids
properties
Colloidal particle
 Chemical coagulation

 Chemical coagulation  all reactions and mechanisms involved in the

chemical destabilization of particles and in the formation of larger particles
through flocculation (aggregation of particles in the size range from 0.01 to 1
µm)
 Coagulant  chemical that is added to destabilize the colloidal particles in
wastewater so that floc formation can occur.
 Flocculant  chemical, typically organic, added to enhance the flocculation
process.
 Flocculation  the process of increasing the size of particles as a result of
particle collisions.
Coagulation and Flocculation

Raw waste Floc Formation Settle floc

 Destabilization of colloid

 Destabilization of colloidal particles

takes place by following ways

1. Double layer compression

2. Charge neutralization
3. Bridging
4. Colloid entrapment
 Electrical Double Layer

An Electric Double Layer consists of three parts:

 Surface charge - charged ions (commonly negative)
adsorbed on the particle surface.
 Stern layer - counter ions (charged opposite to the
surface charge) attracted to the particle surface
and closely attached to it by the electrostatic force.
 Diffuse layer - a film of the dispersion medium
(solvent) adjacent to the particle. Diffuse layer
contains free ions with a higher concentration of the
counter ions. The ions of the diffuse layer are
affected by the electrostatic force of the charged
particle.
 Electrical Double Layer Compression
Mechanism

 Zeta potential  a measurement of the magnitude of electrical charge

surrounding the colloidal particles.
 The zeta potential is the amount of repulsive force which keeps the particles in
the suspension.
 If the zeta potential is large, then more coagulants will be needed.
 When coagulants are added into the water it changes ionic concentration.
 Which compresses double layer and weakens repulsive forces.
 The basic goal of coagulation is to reduce the net repulsive force.
Mechanism
Charge Neutralization
 Colloidal entrapment

 Sufficient amount of coagulants

(Al2(SO4)3, FeCl3, MgCO3, and Ca(OH)2)
can generate rapid precipitates (Al(OH)3,
Fe(OH)3, Mg(OH)2 and CaCO3) and
colloids may become enmeshed in these.
 Colloid become enmeshed in the
growing precipitate
 Flocculation

 After destabilization (i.e. Coagulation), particles will be ready to a

tract and agglomerate and form flocs.
 Flocculation is a process of forming aggregate of flocs to form
larger settleable particle.
 The process can be described as follows:
 Mutual collision of small floc resulting in bigger size.
 Usually slow speed or gentle mixing is used so as not to break the
large flocs due to shear.
 Polymer or large molecular wt compound is added to enhance
floc build up.
 Coagulant

 The chemicals added to water to destabilize colloids are called Coagulants.

 The most common Coagulants used in water treatment are:
1. Metal coagulants :
- Aluminum Sulfate (Alum): Al2(SO4)3.14H2O
- Ferric Chloride : FeCl3 . xH2O
- Ferric sulfate : Fe2(SO4)3 . xH2O
2. Organic polymer coagulants : Polyacrylamide, Chitosan, Moringa olifeira
Alginates (brown seaweed extracts)
Coagulation-flocculation

 Coagulation is the step where colloidal particles

are destabilized.
 Flocculation is the step where destabilized colloidal
particles are accumulated into aggregates.
 Coagulants: cause the neutralization of pollutants
 repulsive forces between pollutant species
disappear
 Flocculants: cause the aggregation of the
destabilized colloidal particles
 Coagulant is always added before flocculants
Chemical coagulation and
flocculation
Chemical coagulation and
flocculation
Coagulation flocculation
 Electrocoagulation

Generation of coagulant
species in situ by electrolytic
oxidation of sacrificial anode
materials

Electrocoagulation consists of
delivering metallic hydroxide
flocs to the water by
electrodissolution of the
electrodes.
 History of Electrocoagulation

 Using electricity to treat water was first proposed in the UK in 1889

 Electrocoagulation with aluminium and iron electrodes was patented in the US in 1909
 During this period, several water treatment plants were operating in the UK using
electrochemical techniques, for example in Salford, England, a plant was commissioned to
use iron electrodes with seawater as the source for chlorine disinfection.
 Because of the large capital investment and expensive electricity, coupled with the
availability of chemical coagulant, electrochemical treatment of water did not much
applicable.
 During 1970s and 1980s significant and growing interest was generated by Russian scientists
to use electrocoagulation for a variety of water treatment processes.
 Today electrochemical technologies have reached such a state of consideration that they
are considered a reliable and effective technology.
 Application of electrocoagulation for
treatment of water containing:
 Heavy metals
 Foodstuffs
 Oil wastes
 Textile dyes Ability to remove a wide range
of contaminants make
 Organic matter from landfill leachate
increasing interest from the
 Suspended particles industrial sector in investigating
the feasibility of the
 Chemical and mechanical polishing wastes
electrocoagulation process.
 Aqueous suspensions of ultrafine particles
 Arsenic [74]
 Refractory organic pollutants including lignin and EDTA
 Electrocoagulation process

Advantages Disadvantages

 Equipment for the electrocoagulation process is simple  The use of electricity increase
and easy to operate. energy cost.
 Can be carried out in small and compact treatment
facilities.
 Occurrence of an oxide or passive
film on the surface of the
 Relatively low cost electrodes can lead to a loss in the
 Possibility of process automation efficiency of the process.
 No moving parts and controlled electrically  less  high conductivity of the solutions is
maintenance cost required
 No need to use chemical coagulants minimize
secondary pollution
 Low sludge production
 Solar power can be used
 Principles of Electrocoagulation

 The electrocoagulation technique uses an electrochemical cell to treat the water.

 An electrochemical cell consists of:

 Anode
 Cathode
 Electrolyte
 Electrical circuit which includes a
current source and control
device,
 Electrocoagulation Process

 The chemical processes occurring in the cell are oxidation (in anode) and reduction
reactions (in cathode).
 The metal ions spontaneously undergo hydrolysis in water (depending on the pH)
 Sacrificial aluminum or iron anodes are the most common:
Al – 3e-  Al3+
Al3+ + 3OH-  Al(OH)3 (at alkaline conditions)

 These metal ions are effective coagulants for the pollutants

 Hydrogen gas released at the cathode helps to float the formed flocs out of the water
 Principles of Electrocoagulation

3 Stages of
Electrocoagulation
Process
 Reactions at the electrodes

 At Cathode

 At Anode
 For Fe as anode
 Mechanism 1

 Mechanism 2  in presence of dissolved oxygen

 Faraday Law

The amount of metal dissolves from anode is depend on the quantity of

the electricity passed through the electrolyte solution

𝐼𝑡 M = atomic weight
𝑚𝑜𝑙 = W = mass of metal ion dissolved from anode
𝑛𝐹 n = valence
I = current in Ampere
𝐼𝑡𝑀
𝑊= t = time in seconds
𝑛𝐹 F = Faraday constant (96485 C/mol)
The generation of oxygen and
hydrogen
Flotation
 Factors affecting electrocoagulation

 Electrode Materials
 Electrode Arrangement
 Current density
 Electrolyte conductivity
 pH solution
 Electrode Materials

 The electrode material determines the electrochemical reactions

that take place in the electrocoagulation process.
 The selection depends on
 the pollutants to be removed
 the chemical properties of the electrolyte.
Katal, R., & Pahlavanzadeh, H. (2011). Influence of
different combinations of aluminum and iron electrode on
electrocoagulation efficiency: Application to the treatment
of paper mill wastewater. Desalination, 265(1-3), 199–
205. doi:10.1016/j.desal.2010.07.052
 Electrode Arrangements

 A typical electrocoagulation cell consists of plate electrodes and the water flows through the
space between the plates
 Current density

 The applied current density affects the rate of the electrochemical

reactions that generate the coagulant and the size and the number
of hydrogen bubbles.
 In addition, it has an influence on the electrode potential, which
determines the reactions taking place on the electrode surface.
 Higher current density sometimes indicate other reactions at the
anode
 Electrolyte conductivity

 The presence of supporting

electrolyte (eg. NaCl, Na2SO4, NH4Cl
etc) significantly increase
conductivity

Akbal, F., & Camci, S. (2011). Copper, chromium and

nickel removal from metal plating wastewater by
electrocoagulation. Desalination, 269(1), 214-222.
 pH solution
Dissolved ion equilibrium in solution
 The speciation of metal cations, such as Al3+ and Fe3+, present in solution at a given pH can be
shown in distribution diagrams.
Akbal, F., & Camci, S. (2011).
Copper, chromium and
nickel removal from metal
plating wastewater by
electrocoagulation.
Desalination, 269(1), 214-222.
 Electrocoagulation

Different kind of cell designs have been applied

Batch and continuous

Hakizimana, J. N., Gourich, B., Chafi, M.,
Stiriba, Y., Vial, C., Drogui,P., & Naja, J.
(2017). Electrocoagulation process in
water treatment:A review of
electrocoagulation modeling
approaches. Desalination, 404, 1-21.
 Electrocoagulation Vertical Flow
Horizontal Flow

Different kind of cell designs

have been applied

Wang, Hung & Shammas, Handbook of

Environmental Engineering, Advanced
physicochemical treatment technologies,
Humana Press Inc. 2007
“ Electrochemical
oxidation (EO)
”
 Chemical Oxidation Process

Chemical Oxidation Process  a method by which water is treated by using oxidizing

agents.
Generally, two forms.
1. Conventional oxidation processes
- Use common oxidizing agents such as ozone, chlorine without production of highly
reactive species

2. Advanced Oxidation processes (AOPs)

- Produce highly reactive species, hydroxyl radicals (HO·) using oxidizing agents and
catalysts.
 Chemical Oxidation Process

 The result of such reaction it typically the precipitation of contaminants

(especially in the case of inorganic pollutants such as heavy metals) or their
conversion to a much less toxic form (e.g., an organic waste mineralized to
CO2 and H2O)
 Common Oxidation Agents Used in Wastewater Treatment:
• Sodium hypochlorite ...................... NaClO
• Calcium hypochlorite ..................... Ca(ClO)2
• Chlorine ........................................... Cl2
• Potassium permanganate .............. KMnO4
• Hydrogen peroxide ......................... H2O2
• Ozone............................................... O3
• Oxygen............................................. O2
Typical Applications of Chemical
Oxidation to Wastewater Pollutants

 Inorganic Pollutants
• Heavy metals
• Cyanides
 Organic Pollutants
• phenol and chlorophenols
• pesticides
• ammonia nitrogen and amines
 Example 1: Cyanide Removal

 Cyanide (CN-) is a common pollutant found in many industrial applications, especially metal plating
 Chemical treatment of cyanide typically involves its oxidation with a strong oxidizing agent to
cyanate (CNO-), followed by the oxidation of the cyanate to carbon dioxide, nitrogen, water and NaCl

Oxidizing Agent Reaction

Sodium hypochlorite 2 NaCN + 5 NaOCl + H2O ⇋ N2 + 2 NaHCO3 + 5 NaCl
Calcium hypochlorite 4 NaCN + 5Ca(OCl)2 + 2 H2O ⇋ 2N2 + 2 Ca(HCO3)2 + 3 CaCl2 + 4 NaCI
Chlorine 2 NaCN + 5 CI2 + 12 NaOH ⇋ N2 + 2 Na2CO3 + 10 NaCI + 6 H2O
Potassium permanganate NaCN + 2 KMnO4 + 2 KOH ⇋ 2 K2MnO4 + NaCNO + H2O
Hydrogen peroxide NaCN + H2O2 ⇋ NaCNO + H2O
Ozone NaCN + O3 + H2O ⇋ NaCNO + O2
 Example 2: Fe and Mn Removal

• Soluble ferrous (Fe2+) and manganous (Mn2+) ions are removed by precipitation as Fe(OH)3 and MnO2,
respectively via oxidation

• As oxidation agents oxygen (O2), chlorine (Cl2), or permanganate (MnO4- ) are typically used

Oxidizing Agent Reaction

2 Fe2+ + 1/2 O2+ 5 H2O ⇋ 2 Fe(OH)3 + 4 H+
Oxygen
Mn2+ + 1/2 O2+ H2O ⇋ MnO2 + 2 H+
Fe2+ + 1/2 CI2 + 3 H2O ⇋ Fe(OH)3 + Cl- + 3 H+
Cl2
Mn2+ + Cl2 + 2 H2O ⇋ MnO2 + 2 Cl- + 4 H+
3 Fe2+ + MnO4- + 7 H2O ⇋ 3 Fe(OH)3 + MnO2 + 5 H+
Potassium permanganate
3 Mn2+ + 2 MnO4- + 2 H2O ⇋ 5 MnO2 + 4 H+
 Chemical Oxidation of Organic
Pollutants
 Overall reaction for reducing COD for example:
Intermediate
Organic 𝑂3 oxygenated
𝑂3 Simple end product
molecule (COD) (CO2, H2O)
molecule
 In general, overall reaction rate are usually too slow to be applicable.

Typical dosage for Chemical

Oxidation for BOD and COD
reduction process
 Electrochemical oxidation (EO)
Electrochemical oxidation (Electro-
Oxidation, EO) also known as anodic
oxidation,
Electrochemical oxidation (EO) has been used
for the removal of organic compounds from
wastewater produced in/by
 distilleries
 agrochemical industries,
 pulp and paper mills
 textile industries
 Oilfields
 pharmaceutical industries
 Pesticides industries
 Electrochemical oxidation (EO)

During the last two decades, research works have been focused on
 Efficiency in oxidizing various pollutants on different electrodes,
 Improvement of the electrocatalytic activity and electrochemical stability of electrode
materials,
 Investigation of factors affecting the process performance,
 Exploration of the mechanisms and kinetics of pollutant degradation
 Electrochemical oxidation (EO)

Indirect EO processes
 Chlorine and hypochlorite generated anodically
 Electrochemically generated hydrogen peroxide
 Mediated EO where metal ions are oxidized on an anode to form high valence reactive
species, which attack pollutants or generate hydroxyl radicals
Direct EO Processes
 Generation of physically adsorbed “active oxygen” (adsorbed hydroxyl radicals) or
chemisorbed “active oxygen” (oxygen in the oxide lattice)
 Physically adsorbed “active oxygen” causes combustion of organic pollutants
 Chemisorbed “active oxygen” participates in the formation of selective oxidation products
 Power supply

e-

Electrochemical
oxidation (EO) pollutant
a) Direct electrolysis

Electrode (Anode)
product

inert1 inert2
pollutant
electroactive
Product
b) Indirect electrolysis
inert
pollutant
electroactive
Product
 Electrochemical oxidation (EO)

pollutant Direct
 Oxidation of the pollutant on the electrode
surface

H2 O
pollutant
Indirect
e- OH·
 With some anode materials it is possible the
PO43- generation of OH·
 On the electrode surface several oxidants can be
+ formed from the salts contained in the salt
P2O84-
pollutant
Electrochemical oxidation (EO)

Direct oxidation process Indirect oxidation process

Interfase Interfase Interfase

Electrolyte Electrolyte
H2O Cred
R R R
e- R R e-
Electrolyte
OH · Cox Cox
e-

Anode (+)
RO RO Anode (+) Anode (+)
RO RO RO
Electrochemical Mass Electrochemical Mass Electrochemical Mass
Reaction Transport Reaction Transport Reaction Transport

Kinetic or mass Kinetic

transport controlled
controlled
 Electrochemical oxidation (EO)

Oxidants: Important parameters:

 Hydroxyl radicals (direct oxidation)  Electrolyte solution (conductivity,

composition of ions)
 Ozone and H2O2 (indirect oxidation)
 Current density (mA/cm2)
 Chlorine and hypochlorous acid (indirect)
 pH
 Electric field (direct)
 Pollutant concentration
 Oxygen
 Electrode material
Formation potentials of different
oxidants

 2 H+ + 2 e-  H2 E0 = 0.0 V
 2 H2O  O2 + 4 e- + 4 H+ E0 = + 1.23 V
 2 Cl-  Cl2 + 2e- E0 = + 1.36 V
 Cl- + H2O  HOCl + 2 e- + H+ E0 = + 1.49 V
 3 H2O  O3 + 6 e- + 6 H+ E0 = + 1.51 V
 2 H2O  H2O2 + 2 e- + 2 H+ E0 = + 1.77 V
 O2 + H2O  O3 + 2 e- + 2 H+ E0 = + 2.07 V
 H2O  OH• + e- + H+ E0 = + 2.85 V
Indirect EO
Process
Different oxidation reactions
on the surface of the anode
 e- Organic
pollutant Direct EO Process
intermediates
(aromatics,  Direct electrolysis consists of the direct oxidation of a
pollutant on the surface of the anode. To be oxidized the
carboxylic organic must arrive to the anodic surface and interact
acids)
... with this surface. This means that electrocatalytic
properties of the surface towards the oxidation of organics
e- can play an important role in the process. Likewise, it
CO2 means that in certain conditions mass transfer can control
the rate and the efficiency of the electrochemical
+ process
H2 O  The potentials required for the oxidation of organics are
usually high. This implies that water can be oxidized and
the generation of oxygen is the main side reaction. This is
a non desired reaction and it influences dramatically on
O2 the efficiencies

Cl-  Frequently the potential is high enough to promote the

formation of stable oxidants, through the oxidation of
other species contained in the wastewater. This can have
a beneficial effect on the efficiency as these oxidants can
Cl2 oxidize the pollutant in all the volume of wastewater
Direct EO Process
e- Organic
pollutant Organic
2. Mass transport, which can pollutant
be promoted by a proper cell
design

...
e-
CO2
1. Electrode material, which influences
+ on the nature of the products and on the
importance of the side reactions
H2 O

3. The presence of compounds in the

O2 wastewater that can be transformed into
Cl-
oxidants, promoting mediated
electrochemical oxidation processes

Cl2
 Electrode material

Platinum
Metals Stainless stell
DESIRABLE PROPERTIES:
 MECHANICAL STABILITY.
 CHEMICAL STABILITY Grafite
Carbon Boron Doped
material
 MORPHOLOGY. diamond
 ELECTRICAL CONDUCTIVITY (BDD)
 CATALYTIC PROPERTIES oxides DSA
Ti/SnO2
 RATIO PRICE/ LIFETIME.
Ti/PbO2

Drawbacks of High efficiency electrodes: low efficiency electrodes

BDD : large price
PbO2/SnO2: Dissolution of toxic species High efficiency electrodes
 Example: ammonia removal using
indirect EO

NH4+

Cl-
N2

e-
Cl2 H2O ClO-

OH-
+
if the chloride content in the raw wastewater is low, a large
amount of salt must be added to increase the process
efficiency
Example: Effect of Electrode material and
NaCl conc. on COD removal of wastewater

Without NaCl

Panizza, M. (2000). Electrochemical

NaCl = 5 g/l treatment of wastewater containing
polyaromatic organic pollutants. Water
Research, 34(9), 2601–
2605. doi:10.1016/s0043-
1354(00)00145-7