Module-4 1BCHES102/202

Module-4: Chemical Sensors and Corrosion Control

Electrochemical Sensors: Introduction, Conductometry Sensor- Principle,
Instrumentation, and its application in the estimation of mixture of acids, numerical
problems on conductometry. Amperometry Sensor- Principle and its application in
the measurement of Dissolved Oxygen (DO).
Optical sensor- Introduction, Colorimetry- Principle, Instrumentation and its
application in the estimation of copper.
Biosensor-Principle and working mechanism for the detection of glucose in
biofluids.
Corrosion: Introduction, electrochemical theory of corrosion, types-differential
metal and differential aeration corrosion, corrosion control- Galvanization and
anodization, vapour corrosion inhibitors for protecting computer circuit boards,
corrosion penetration rate (CPR)- definition, importance, and numerical problems.
Self-Study Component: Electrochemical gas sensors for the detection of NOx & SOx
in air sample.

Chemical Sensors

A chemical sensor is a device that is capable of giving real time analytical information about a test
sample. It interacts with a specific chemical or biological analyte, detects it, and produces the
signal proportional to its quantity.

There are numerous ways to keep track of how the receptor and analyte are interacting. Each
method measures a different parameter, such as a change in potential, conductivity, current, mass,
heat, pH, color, etc. Each parameter is measured using a different kind of transducer. Depending
on the type of transducer being used, there are several types of sensors available, including
electrochemical sensors, conductometric sensors, thermometric sensors, and optical sensors,
among others.
Electrochemical sensors
Electrochemical sensors use electrodes as the transducer component. Main components of an
electro chemical sensor are working or sensing electrode, electrolyte, counter electrode, and a
reference electrode. The main steps involved in working of an electrochemical sensor are:
1. Diffusion of the analyte to the electrode/electrolyte interface (in the liquid phase)
2. Adsorption onto the electrode surface
3. Electrochemical reaction with electron transfer
4. Desorption of the products
5. Diffusion of the products away from the reaction zone to the bulk of electrolyte or gas
phase.

Applications of electrochemical sensors

1|Page
 Module-4 1BCHES102/202

Electrochemical sensors provide a low-cost and convenient solution for the detection of variable
analytes and are widely utilized in agriculture, food, and oil industries as well as in environmental
and biomedical applications. Few applications are listed:
 The oxygen sensor is employed to measure the concentration of dissolved oxygen in
hydrogen fuel, metal melts, glasses, and water boilers.
 They are employed in security and defense applications, including the detection of
poisonous gases and other military agents.
 They are employed in water analysis and environmental monitoring, such as measuring the
quantity of harmful metals in water, detecting nitric and sulfuric oxides, carbon monoxide
(CO), and water pH, among other things.
 They are utilized in diagnostic and healthcare applications, such as in situ monitoring of
blood Ca2+, Fe2+, Acetylcholine, and blood uric acid, glucose, and uric acid.
 They are employed in agricultural applications and the evaluation and analysis of soil
parameters.

Depending on the exact mode of signal transduction, electrochemical sensors can use a range of
modes of detection such as,

 Potentiometric sensors (measure voltage)

 Amperometric sensors (measure current)
 Conductometric sensors (measure conductivity)

1. Conductometric sensors
In conductometric sensor, determination of the concentration of analyte is based on measurement of
changes in electrolytic conductance of solution. Conductance of a solution is based on:
Conductance of a solution is based on:
 The quantity (concentration) of ions in a solution that affects its conductivity.
 The ion types of different mobility. The size of an ion affects its mobility. More mobility
and better electrolytic conductivity are associated with smaller sizes.

Working principle: Electrode used in the conductivity sensor is called as conductivity cell. It is
made of two platinum fails with unit cross sectional area and unit distance between them. 1 cm3 is
the volume between the two electrodes. Conductance of unit volume of the solution is called as
specific conductance. There will be change in specific conductance of solution when there is
change in number of ions or type of ion.
Specific conductance is given by, k=1/r x cell constant, where R is resistant of the solution.
The conductivity cell is attached to a conductance measuring equipment known as a conductivity
meter and is submerged in the electrolytic solution placed in a beaker to do the analysis.

2|Page
Module-4 1BCHES102/202

Applications
1. It is used to calculate the amounts of acids, bases, and their combinations in a sample.
2. It assesses the quantity of ionic contaminants in water samples.
3. It determines the alkalinity or acidity of freshwater and seawater.
4. Conductometric biosensors are used in biomedicine, environmental monitoring,
biotechnology, and agriculture.

Procedure: Determination of mixture of acids

Dip the clean conductivity cell into the acid mixture and connect it to the conductometer. Record
the initial conductance. Fill the burette with NaOH and add it in 0.5 cm³ increments, stirring and
noting the conductance after each addition. Continue until conductance changes from decreasing
to slowly, then steeply increasing, taking 5–6 readings beyond this point. Plot conductance vs.
volume of NaOH; the intersection of the lines gives the equivalence point.

The conductivity of a solution depends on the number and mobility of ions. During titration of an
acid mixture (HCl + CH₃COOH) with NaOH, conductance first decreases as H ⁺ ions are replaced
by less mobile Na⁺ ions. After neutralizing HCl, conductance increases as CH₃COOH dissociates
and forms its salt (sodium acetate). Once both acids are neutralized, conductance rises sharply due
to excess OH⁻ ions. The intersection point on the conductance vs. volume graph indicates the
neutralization points.

Calculation and Observation

(NV 1)NaOH A ×V 1
Normality of HCl= = =
V Acid Mixture 50 50

Weight of HCl per dm3 = NHCl × Equivalent weight of HCl

=B× 36.5 = _________ g/dm3

N × ( V 2−V 1) NaOH
Normality of Acetic acid= − A ׿ ¿
V Acid Mixture
3
Weight of C H 3 COOH per dm =N C H 3
COOH × Equivalent weight of C H COOH ¿
3
¿

= C × 60 =___________× 60 = __________ g/dm3

3|Page
Module-4 1BCHES102/202

Sample Numerical on conductometry………….

Problem 1: 50 cm³ of an acid mixture containing HCl and CH₃COOH is titrated with 0.1 N
NaOH. The first and second equivalence points are observed at 12.5 cm³ and 32.5 cm³ of NaOH
respectively. Calculate: a) Normality and weight of HCl per dm³. b) Normality and weight of
CH₃COOH per dm³. c) Predict the nature of Graph (Eq. wt. of HCl = 36.5, Eq. wt. of CH₃COOH
= 60)

Problem 2: In a conductometric titration, 0.05 N NaOH is added to 50 cm³ of an acid mixture.

The first break in the graph occurs at 10.0 cm³ and the second at 28.0 cm³.
Determine the normality and strength (g/dm³) of both acids and write the nature of graph.
(Eq. wt. of HCl = 36.5, Eq. wt. of CH₃COOH = 60)

Problem 3: A 50 cm³ mixture of nitric acid (HNO₃) and phosphoric acid (H₃PO₄) is titrated
with 0.1 N NaOH. The first neutralization point is reached at 14.0 cm³, and the second at 37.0
cm³.
Calculate the normality and strength (g/dm³) of both acids. Depict the nature of graph
(Eq. wt. of HNO₃ = 63, Eq. wt. of H₃PO₄ = 32.7) (Hint: Nitric acid is stronger acid than
phosphoric)

Problem 4: 50 cm³ of an acid mixture of sulfuric acid and oxalic acid is titrated with 0.5 N
NaOH. The first break in the titration curve appears at 9.0 cm³, and the second at 26.0 cm³ of
NaOH. Find: a) The normality of each acid. b) Their strengths in g/dm³. c) Write the nature of the
graph (Eq. wt. of H₂SO₄ = 49, Eq. wt. of H₂C₂O₄ = 63) (Hint: Sulfuric acid is stronger than
oxalic acid)

Problem 5: A student titrates 50 cm³ of a mixed acid solution (HCl + CH₃COOH) with 0.2 N
NaOH. The conductometric curve shows equivalence points at 15.0 cm³ and 40.0 cm³ of NaOH
added. Calculate :a)The normality of each acid. b) The mass of each acid present per dm³ of the
solution.

Amperometry Sensor
An amperometric sensor measures analyte concentration by detecting the current produced during
oxidation or reduction at an electrode. It operates with a constant potential between electrodes,
and the resulting current is proportional to analyte concentration. These sensors are widely used
for gas, biochemical, and pollutant detection due to their high sensitivity and quick response.

Electrochemical Sensors for the measurement of DO

In an electrochemical DO sensor, two electrodes used are of

dissimilar metals. Zinc or lead is used as anode and silver metal is
used as inert cathode. The difference in potential between the anode
and the cathode should be more than 0.5 V to reduce dissolved
oxygen without an external applied potential. The electrolyte solution
used is sodium chloride, or any other inert electrolyte. When the
electrode assembly is dipped in water to measure its DO, anode
undergoes oxidation liberation electrons.
2Zn 2Zn2+ + 4e-

4|Page
Module-4 1BCHES102/202

At cathode, DO undergoes reduction. Ag cathode is inert, it only passes electrons to oxygen for
reduction.
O2 + 2H2O + 4e- 4OH-
Overall reaction is
Zn2+ + O2 + 2H2O 2Zn (OH)2

The current generated by the reduction of oxygen at the cathode is proportional to the oxygen's
partial pressure in the water sample. Zinc hydroxide produced during the reaction precipitates in
the electrolyte, gradually affecting sensor performance. If the sensor readings become unstable,
the electrolyte solution and zinc anode must be replaced to restore proper function.

Optical Sensor
Spectrochemical methods analyze how electromagnetic radiation interacts with matter using UV,
visible, or IR light. Optical sensors work on absorption, emission, reflectance, or scattering of
light, depending on the analyte and wavelength. The analyte concentration is determined from
light intensity using optoelectronic instruments. A basic sensor includes a light source,
wavelength selector, photodetector, and display, operating on Beer-Lambert’s law to measure the
concentration of colored species by their light absorption or transmission.

Colorimetry is an instrumental analysis in which the amount of a substance in solution which are
themselves colored or which gives color with a suitable reagent is determined. The Colorimetric
method of analysis is based on Beer’s and Lambert’s Law.
Beer’s law - states that the intensity of the transmitted light decreases exponentially as the
concentration of the media increases arithmetically.
Lambert’s law- states that the intensity of the transmitted light decreases exponentially as the
path length of the media increases arithmetic.
Beer’s Lambert’s law states that when a monochromatic light is passed through a solution, part of
light is absorbed by the solution. The extent of absorption depends on the concentration of the
solution and the path length of the light through the solution.
A = εcl
A = absorbance c = concentration of the solution, l = path length ε = molar absorption
coefficient.
If the path length l of the cell is kept constant, absorbance A is proportional to the concentration
C.
AαC
Therefore, if absorbance of a series of solution are plotted versus their concentration, a straight
line graph result, which is called Beer’s-Lambert’s curve or calibration curve.

Instrumentation: A colorimetric sensor measures light absorption by colored species in a

solution. Polychromatic light is converted to monochromatic light, which passes through the
sample cuvette. Some light is absorbed, and the rest is transmitted. A photovoltaic detector
measures the absorbed light, amplifies it, and displays the result. The absorbance is set to zero
using a blank solution, and the analyte concentration is determined by plotting absorbance against
concentration.

5|Page
Module-4 1BCHES102/202

Procedure: Transfer the given stock solution of CuSO4 solution into a burette and draw 5, 10,
15, 20, 25 cm3 of solution into different 50 cm3 standard flasks. Add
5 cm3 of ammonia to each flask and dilute up to the mark with
distilled water and mix well. To the electroplating effluent given in a
50 cm3 standard flask add 5cm3 of ammonia and make up to the mark
and mix well. Using the blank solution (5ml of ammonia dilute to
50cm3) calibrate the colorimeterat 620 nm by setting the
transmittance to 100% or absorbance to zero. Record the absorbance
of the above solutions. Plot the graph of absorbance against volume
of CuSO4 to obtain the calibration curve. Using this calibration curve
find out the concentration of copper in the PCB test solution.
Calculation:
Weight of Cu per cm3 of stock solution = 1 mg (given)
Volume of the test solution from the graph (A) =_____ cm3
Concentration of the Cu in test solution (PCB solution)=
A x 1= ______ mg

Biosensor-Principle and working mechanism for the detection of glucose in biofluids.

Definition: A biosensor is an analytical device that combines a biological element (like an
enzyme, antibody, or microorganism) with a physicochemical detector to measure the
presence or concentration of specific substances.
Principle:
A glucose biosensor works on the principle of enzymatic oxidation of glucose catalyzed by
glucose oxidase (GOx). The enzyme reacts specifically with glucose in biological fluids (like
blood or saliva) to produce hydrogen peroxide (H₂O₂) and gluconic acid.
The electrochemical oxidation of H₂O₂ generates electrons that produce a current proportional to
the glucose concentration in the sample.
Enzyme Reaction:
 The enzyme glucose oxidase (GOx) catalyzes the oxidation of glucose.
 Reaction:
❑
Glucose +O2 → Gluconic acid +H2 O2
Electrochemical Detection:
 The produced H₂O₂ is oxidized at the electrode surface:
−¿¿
+ ¿+O +2 e ¿
H2 O2 → 2 H 2

 The electrons generated during this oxidation create a current.

6|Page
Module-4 1BCHES102/202

Transducer Function:
 The transducer converts the biochemical reaction (electron flow) into an electrical
signal.
Signal Processing and Display:
 The electrical signal is amplified, processed, and displayed as glucose concentration (e.g.,
in mg/dL).

Corrosion Chemistry

Corrosion is defined as “the destruction or deterioration of metals or alloys by the

surrounding environment through chemical or electrochemical changes.
The familiar examples of corrosion are,

i. Rusting of iron – A reddish brown scale formation on iron and steel objects. It is
due to the formation of hydrated ferric oxide.
ii. Green scales formed on copper vessels. It is due to the formation of basic cupric
carbonate [CuCO3 + Cu(OH)2].
The metals undergo corrosion due to the oxidation by losing electron and the resulting product is
called rust, which mainly contains oxides, sulphates, carbonates, and bicarbonates of the metals.
Due to corrosion, metals lose their valuable properties such as conductivity, strength, shining,
malleability, ductility etc.

Cause for corrosion: Each metal tries to get original state such as ore form (oxides, sulphates,
carbonates, and bicarbonates of the metals) which are more stable and lower energetic.
Therefore, corrosion is the reverse process of metallurgy.
Classification of corrosion

1. Chemical corrosion (Dry corrosion)

Chemical corrosion occurs due to the direct chemical reaction between the metal and the
gases present in the corrosion environment. This type of corrosion is generally observed in the
absence of moisture. Therefore, it is also known as dry corrosion.
Example: Oxidation of metals or alloys on exposure to oxygen in air.

2. Electrochemical corrosion (Wet corrosion)

Electrochemical corrosion involves reactions in aqueous medium and moist air. The
conducting surface of the metal undergoes an electrochemical reaction with the moisture and
oxygen present in the atmosphere. This process can be explained based on electrochemical
theory of corrosion.

Electrochemical theory of corrosion

Electrochemical theory of corrosion explains the corrosion based on galvanic cell formation.
According to this theory, corrosion of metal takes place due to the formation of anodic and
cathodic region on the same metal surface or when two different metals are in contact with each

7|Page
Module-4 1BCHES102/202

other in the presence of a conducting medium. At anodic region metal undergo oxidation by
losing its valence electron and gets corroded. While in the cathodic region reduction reaction
takes place. Thus, cathodic region is unaffected by the cathodic reaction.
The electrons liberated at the anodic region migrate to the cathodic region constituting
corrosion current. The metal ions liberated at the anode and the anions formed at the cathode
diffuse towards each other through the conducting medium and forms corrosion product.
When a part of the metal is dipped in an aqueous solution, the part which is exposed to lower
concentration of air (or oxygen) acts as anode, while the part which is exposed to higher
concentration of air (or oxygen) acts as cathode. (Because oxygen as greater tendency to absorb
electrons)

Corrosion reaction
At anode region metal undergo oxidation liberating electron.
M Mn+ + ne-
Fe Fe2+ + 2e-
Cathodic reaction depends on the nature of the corrosion environment.

a) If the surrounding environment is aerated and almost neutral, oxygen and water are
reduced to OH- ions.
1
O2 + H 2 O+2 e− →2OH −
2
b) If the surrounding environment is de-aerated and almost neutral the cathodic reaction
involves the liberation of hydrogen gas and hydroxyl ions.
2H2O + 2e- 2OH- + H2

c) If the surrounding environment is deaerated and acidic the cathodic reaction involves
the evolution of hydrogen gas.
2H+ + 2e- H2

Corrosion of iron produces Fe2+ ions and OH- ions at the anodic and cathodic region
respectively. These ions diffuse towards each other forming insoluble product Fe(OH)2
(ferrous hydroxide)

2Fe2+ + 4OH- 2Fe(OH)2

In an oxidizing environment ferrous hydroxide is oxidized to ferric oxide.

8|Page
Module-4 1BCHES102/202

4Fe (OH)2 + O2 + 2H2O 2[Fe2O3·3H2O] Rust

In the presence of limited oxygen, ferrous hydroxide is converted into magnetic oxide of iron
(Fe3O4) and is known as black rust.

Note: 1

(i) The cathodic and anodic process occurs at the same rate.
(ii) The formation of galvanic cells on the metal surface is due to the following reasons.
(a) Contact with other metal
(b) Difference in the concentration of air or oxygen.
(c) Stress and strain on the material.
(d) Precipitation at the grain boundaries.
Note: 2

An arrangement of metals in the order of their corrosion resistance in the given environment is referred
to as galvanic series.

Types of Corrosion
Differential metal Corrosion or Galvanic Corrosion:
When two dissimilar metals are in contact with each other in a corrosion conducting
medium, the metal with lower electrode potential becomes anodic and undergoes corrosion,
whereas the metal with higher electrode potential becomes cathodic and remains unaffected.
This kind of corrosion is called differential metal corrosion. The rate of corrosion depends
on the difference in electrode potential. The higher the difference, the faster the rate of
corrosion.
Example: When Zinc is in contact with Copper, Zinc metal being placed higher up in
the electrochemical series acts as anodic and gets corroded, whereas Copper metal which is
placed below Zn in electrochemical series is protected from corrosion.

This type of corrosion can be observed in the following.

(i) Steel pipe connected to copper plumbing.
(ii) Lead antimony solder around copper wires

9|Page
 Module-4 1BCHES102/202

Differential aeration corrosion

Differential aeration corrosion occurs when one part of the metal is exposed to lower
concentration of air when compared to other parts. When a metal is exposed to different
concentrations of air (O2), part of the metal exposed to lower concentration of O 2 will have
lower potential becomes anodic and undergoes corrosion. Other parts of the metal which are
exposed to higher concentration of O 2 become cathodic and remain unaffected. Thus, a
differential aeration of metal causes a flow of current called differential current.
Example: When an iron rod is partially immersed in water, the part exposed to
atmosphere is more oxygenated and forms cathode and the part immersed in water which is
less oxygenated forms anode.
Examples for differential aeration corrosion:
i. Part of the nail inside the wall being exposed to lower oxygen concentration than the
exposed part undergoes corrosion.
ii. Window rods inside the frame suffer corrosion but not the exposed parts.
iii. Metal surface under dirt, dust, scale, or water undergoes corrosion.
iv. Paper pins inside the paper get corroded and the exposed part is free from corrosion.
v. Partially buried pipeline in soil or water undergoes corrosion below the soil or water.
Whereas, the exposed part is free from corrosion.

1. Water line corrosion

Water line corrosion can be observed in steel tanks partially filled with water. The area above the
water line, which is more oxygenated acts as cathode and is unaffected by corrosion, where as
corrosion takes place along a line just beneath the level of water meniscus because it is exposed to
lower oxygen concentration. Mort intense corrosion is observed just below the water line, hence it
is called as water line corrosion.

1
O +H O+2 e− →2OH −
Metal 2 2 2 Cathode
Water line
Fe→ Fe 2+ +2 e− Anode
Water

Examples for differential aeration corrosion:

i. Part of the nail inside the wall being exposed to lower oxygen concentration than the
exposed part undergoes corrosion.
ii. Window rods inside the frame suffer corrosion but not the exposed parts.
iii. Metal surface under dirt, dust, scale or water undergoes corrosion.
iv. Paper pins inside the paper get corroded and the exposed part is free from corrosion.
v. Partially buried pipe line in soil or water undergoes corrosion below the soil or water.
Whereas the exposed part is free from corrosion.

2. Pitting corrosion

10 | P a g e
 Module-4 1BCHES102/202

Pitting corrosion results when small particle of dust particle or oil drop or moisture (water
drop) gets deposited on the surface of the metal. The portion covered is less aerated compared
to the large exposed area and thus acts as anode with respect to the surface exposed. Corrosion
takes place below the deposit resulting in the formation of pit. Once a pit is formed corrosion
rate accelerated due to further decrease in concentration of O2 within the pit.

Cathode Water drop (dust particle)

Anode Pit
Metal

Corrosion Control
Corrosion of metal is a natural spontaneous process, by which a metal is converted into a more
stable compound state. Therefore, corrosion control is more realistic than corrosion prevention.
The corrosion types are so numerous, the mechanism of corrosion is so different and conditions
under which corrosion takes place are so varied that no single method can be used to control all
possible corrosion cases. Some of the important methods used in controlling corrosion of metals
are,

1. Protective Coating
The Protective coating protects the metal from corrosion by acting as a barrier
between the metal and the corrosive environment. The principal types of coating applied on
the metal surface are,
Metal Coating: The process of covering the base metal with a layer of another metal is
known as metal coating. By this method the base metal can be protected. Metal coating can
be anodic metal coating or cathodic metal coating.

Anodic Coating: Anodic coatings are produced by coating a base metal with more active metals
which are anodic to the base metal such as Zn, Al, Mg, etc.,
The important characteristics of anodic coating are that, even if the coating is ruptured, the base
metal does not undergo corrosion. The exposed surface of the base metal is cathodic w.r.t. the
coating metal and the coating metal preferentially undergoes corrosion. The protection is
ensured if the anodic coating metal is still present on the surface. Therefore, anodic metal
coating is also known as sacrificial coating.
Example: Galvanizing is a familiar anodic coating and is extensively used to protect iron and
steel objects.

Galvanization: It is a process of Coating a base metal with zinc metal. It is carried out by hot
dipping method.

11 | P a g e
 Module-4 1BCHES102/202

Hot dipping method: It involves the dipping of base metal in molten anodic metal (Zn). The
coating metal should melt at a relatively low temperature and the base metal must withstand this
temperature without undergoing any changes in its properties. The galvanization process
involves the following steps.
(a) The metal surface is washed with organic solvent to remove oil or grease present on the
surface.
(b) Rust and other deposits are removed by washing with dilute H2SO4.
(c) The clean and dry sheet is passed through aqueous solution of zinc chloride and
ammonium chloride flux and dried. The flux helps the molten metal to adhere (adsorb) on the
metal surface.
(d) The article is then dipped in a bath of molten Zinc maintained at 425-430oC.
(e) The excess Zn on the surface is removed by passing through a pair of hot rollers
which wipes out excess coating and produces a thin coating.

Galvanization is used extensively to protect iron from corrosion in the form of roofing sheets,
fencing wire, buckets, bolts, nuts, nails, screws, pipes, tubes etc. Galvanized steels are used in
construction where a high degree of corrosion resistance is required. Galvanized articles are not
used for preparing and storing food stuffs since zinc dissolves in dilute acids producing toxic Zinc
compound.

2. Surface conversion Coating

Inorganic coatings, primarily chemical conversion coatings, form a protective barrier by chemically
or electrochemically converting a metal’s surface layer into a compound. Unlike other coatings,
they integrate with the metal itself. Applied electrolytically, they enhance corrosion resistance,
electrical insulation, and adhesion for paints and organic coatings.

Anodization
Anodization is the process of oxidation of the outer layer of metal to its metal oxide by
electrolysis. Oxide layer formed over the metal itself acts as protective layer. A protective oxide
film generally produced on nonferrous metals like Al, Mg, Cr, Zn, Ni, and their alloys by anodic
oxidation process, in which the base metal is made as anode in electrolytic bath of suitable
composition (Chromic acid, H2SO4, H3PO4, H2CrO4) and by-passing direct current. Lead is
generally used as cathode.

12 | P a g e
 Module-4 1BCHES102/202

The anodic oxide film formed on Al in the electrolyte bath tends to be porous and provides good
adherence for paints and dyes. The strength and corrosion resistance of the anodized film can be
increased by the so-called sealing, which involves heating in boiling water or steam or metal salt
solution. The treatment changes porous alumina at the surface of coating into its mono hydrate
(Al2O3.H2O), which occupies more volume, thereby pores are sealed.
Anode : Aluminium article
Cathode : Steel or Copper
Temperature : 35OC
Electrolyte : 10% sulfuric acid or 5-10% chromic acid or oxalic acid
Current density: 10-20 mA/cm2

Anodized articles are used as exterior for roofs, walls and window frames, soap boxes and Tiffin
carriers etc.
Corrosion Penetration Rate (CPR)

The corrosion penetration rate (CPR) is defined as “the speed at which any metal in a specific
environment deteriorates due to a chemical reaction in the metal when it is exposed to a corrosive
environment” or the amount of corrosion loss per unit time in thickness or the speed at which
corrosion spreads to the inner portions of a material. Corrosion rate depends on the metal and the
environmental condition.

Importance of CPR:
 1. Predicts material lifespan: Helps estimate how long a metal component will last in a
specific environment.
 2. Aids material selection: Guides engineers in choosing corrosion-resistant materials.
 3. Evaluates protective coatings: Measures the effectiveness of paints, inhibitors, or
plating.
 4. Ensures safety and reliability: Prevents failures in pipelines, structures, and industrial
equipment.
 5. Economic assessment: Reduces maintenance costs and improves operational
efficiency.

Weight loss method

13 | P a g e
Module-4 1BCHES102/202

It is a commonly used method for the measurement of uniform corrosion. It involves the
exposure of a weighed piece of test metal or alloy to a specific environment for a precise time.
This is accompanied by thorough cleaning to remove the corrosion products and then
determining the weight of the lost metal as a result of corrosion.
The corrosion rate is best described in terms of the thickness or weight loss where the
surface of the metal disintegrates uniformly across the area that has been exposed.

The Corrosion Penetration Rate (CPR) is calculated by using the following mathematical relation,

k xW
CPR=
Dx A xT
where k = a constant
W = total weight lost
T = time taken for the loss of metal
A = the surface area of the exposed metal
D = the metal density in g/cm³

The corrosion penetration rate is expressed in terms of thickness or weight loss when the surface
of the metal corrodes uniformly across an area. This method involves the exposure of a weighed
piece of test metal or alloy to a specific environment for a specific time. This is followed by a
thorough cleaning to remove the corrosion products and then determining the weight of the metal
after corrosion.

The rate may vary if the rate expressed by the formula above is used to compare corrosion rates
for a period longer than one year with rates calculated over short periods. This is because the short
time periods are prone to fluctuating environmental changes from season to season and from day
to day.

Unit of CPR is mils per year if W is in mg, A in Inch 2, D in g/cm3, t in hrs and k value will be 534.
(1mil = 0.001 inch)
Unit of CPR is mm per year if W is in mg, A in cm 2, D in g/cm3, t in hrs and k value will be 87.6.
(1inch = 2.54 cm)
If CRP is less than 20m/year or 0.5 mm/year, it is acceptable for most of the applications.
Sample problem on CPR
1. A steel of area 100 in2 is exposed to air near the seashore. After 1 year it was found that the
steel sheet has lost 485g due to corrosion. What is the value of CPR in mils/year and in mm/year?
Can such steel sheet be applicable for the construction purpose where the steel sheet is exposed?

Given - Area (A) =100 inch 2, total weight lost (W) =485g = 485 x10 3 mg, T = 1 year =1 x 365 x
24hrs, D = 7.9g/cm3 and k=534.
k xW
CPR=
Dx A xT

534 x 485000
CPR=
7.9 x 100 x 365 x 24

CPR = 37.42 mils/year

14 | P a g e
Module-4 1BCHES102/202

Area =100 inch2 = 100 x 2.54×2.54 cm2 (1 inch = 2.54 cm) and k =87.6
k xW
CPR=
Dx A xT
87.6 x 485000
CPR=
7.9 x 100 x 2.54 x 2.54 x 365 x 24
CPR = 0.9516mm/year
Since CPR is not less than 20m/year or 0.5 mm/year, it is not applicable for construction purposes.

Vapour Corrosion Inhibitors (VCIs) for Protecting Computer Circuit Boards

Definition:
Vapour Corrosion Inhibitors (VCIs) are volatile chemical compounds that evaporate and form a
protective molecular layer on metal surfaces. This invisible film prevents moisture, oxygen, and
contaminants from causing corrosion, even in enclosed or hard-to-reach areas.

Organic VCIs: Form a protective film on metals; ideal for electronics.

Examples: Benzotriazole (BTA), Dicyclohexylamine nitrite (DICHAN).
Inorganic VCIs: Create passive oxide layers; used in industrial systems.
Examples: Sodium nitrite (NaNO₂), Ammonium benzoate.
Eco-friendly VCIs: Biodegradable, non-toxic alternatives for clean environments.
Examples: Amine carboxylate salts, Imidazole derivatives.

Working Principle:
 VCIs sublimate or vaporize at room temperature and fill the enclosed space to protect
printed circuit boards (PCBs), connectors, and electronic components during storage,
shipping, and operation in humid or corrosive environments. The vapor molecules
adsorb onto metal surfaces, forming a thin, corrosion-resistant barrier.
 This layer interrupts the electrochemical corrosion process by blocking the anodic and
cathodic reactions.
 When the enclosure is opened, the vapor layer dissipates without leaving harmful residues.

Self-Study component: Electrochemical gas sensor for the detection of SOx and NOx

Toxic gases compounds like NO2, NO and SO2 which can undergo redox reaction on the surface
of electrode can be measured with an electrochemical gas sensor. Basic construction of a gas
sensor is similar for all gases but the receptor coated on surface of sensing electrode (working
electrode) is different for each gas. Reaction that occurs on surface of the electrode is also
different for each case.
Detection of NO2 in an amperometric gas sensor in aqueous electrolyte is based on the following
electrochemical reduction reaction on the surface of sensing electrode. Au, Pt/Nafion is used as
sensing electrode with 10 M H2SO4 as an electrolyte.

NO2 + 2H+ + 2e- NO + H2O

15 | P a g e
Module-4 1BCHES102/202

Detection of NO in an amperometric gas sensor in aqueous electrolyte is based on the following

electrochemical oxidation reaction on the surface of sensing electrode. Au/[Link] 2 is
used as sensing electrode and electrolyte.
NO + 2H2O NO32- + 4H+ + 3e-
Detection of SO2 in an amperometric gas sensor in aqueous electrolyte is based on the following
electrochemical oxidation reaction on the surface of sensing electrode. Au/Nafion sensing
electrode with 0.5 M H2SO4 is used as electrolyte.
SO2 + 2H2O SO42- + 4H+ + 2e-

16 | P a g e