CHM578/674 2020

Experiment 4: Electrochemical Reactions and Corrosion Studies (20 marks)

Name: Nurul Husna binti Ibrahim ID: 2018226626 Group: AS2224M1

(Refer Lab manual Exp. 6 (CHM674) prior to answering the following Post-Lab
Questions)

Objectives:
To study electrochemical reactions of gold and iron in acidic solution.
To determine the corrosion rate of iron in different aqueous solution by Tafel Polarization method.

Billions of dollars are spent each year on the prevention of iron corrosion. Corrosion converts steel, an
extremely strong, cheap and versatile building material composed of iron and carbon (ie: steel), into
brittle iron oxides known as rust. The rust tends to scale off from the iron surface, exposing more iron
to the oxidizing environment. This is in contrast to some other metals, such as aluminium where an
oxide coating offers a degree of passivation, preventing further corrosion.

When iron is immersed into a deoxygenated acidic solution (or strong acid), the following reactions
are established.
Fe → Fe2+ + 2e
2H+ + 2e → H2
But, when it was exposed to neutral or alkaline solution, the following cathodic reaction will occur.
2H2O + 2e → H2 + 2OH-

But, for some noble metals such as Platinum (Pt), Gold (Au), Palladium (Pd),Silver (Ag), there are
inert and stable when exposed or immersed in strong acidic or strong alkaline solutions. They would
not dissolve to their ions but will oxidize to form metal oxide (eg: Au to AuO). Nevertheless, the inert
metals will oxidize to their ions if strong oxidizing agent present in the solution.

There are a few methods that can be used to measure corrosion rate of metals/alloys namely Weight
loss method, Tafel Plot/Polarization method, Linear Polarization Resistance (LPR) method and
Electrochemical Impedance Spectroscopy (EIS) method.

Measurement by Tafel Polarization method

A polarization curve or Tafel plot (I vs E) will be plotted and two linear portion of the cathodic and
anodic sections will be extrapolated to a point of intersection to obtain corrosion current density
(icorr) as well as corrosion potential (Ecorr).
Corrosion rate (CR) of metals in mm/yr can be calculated using the following equation:

CR = 0.00327 icorr. a
n. D

where a is the atomic mass of the metal (g/mol), n is the number of electrons involved in the corrosion
and D is the density of the metal (g/cm3). Other corrosion rate expressions are as follows:

mils per year (mpy) , CR = 0.129 icorr.a

n.D

micrometer per year (μm/yr), CR = 3.27 icorr.a

n. D

icorr must be in μA/cm2 to calculate corrosion rate using these three equations.

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Results
Part A (8 marks)

Table 1: Cyclic Voltammetric study of different electrodes in 0.5M HNO 3

Metal/Electrod Observations on Cyclic Voltammogram (CV)

e

Anodic Scan (0 V to +1.8V)

 Oxidation of gold to gold oxide (AuO) from +1.1 V to +1.4 V
Gold  Formation of O2 or Oxygen evolution reaction on gold surface >
+1.5 V
Reverse Scan (+1.8V to 0V)
 Reduction of AuO to Au from +1.0 to +0.7 V

Cathodic Scan (0V to -1.5V)

 Hydrogen evolution reaction (HER) starts to occur at -0.6 V
 Vigorous HER on gold surface as shown by current fluctuation at
>-1.0V
Anodic Scan (-0.5 V to +2.0 V)
 Oxidation/Dissolution of Fe metal to Fe (II) from -0.4V to +0.1V
Iron  Formation of passive film (Fe2O3) from +0.2 V to +1.5 V
 Oxygen evolution reaction (OER) on Ferum Oxide surface occurs
at >+1.6 V.
Reverse Scan (+1.5V to -0.5V)
 Oxidation of Fe to Fe(II) ions from +0.1V to -0.4V
HER: occurs at cathode ; OER: occurs at anode

Questions:

1. Identify the location of the oxidation and reduction reactions on the CV (as stated in Table 1)
occurred on gold and on iron by putting label (A – H).

CV of gold in 0.5M HNO3, scanned from 0V to +1.8V back to 0V at scan

Label : Reaction rate 100 mV/s.

A : Au → AuO

B : OER on gold

C : AuO → Au

CV of gold in 0.5M HNO3 scanned from 0 V to -1.5V back to 0V at

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100mV/s

D : HER on gold
(starting)

E : Vigorous HER
on gold

CV of iron in 0.5M HNO3 scanned from -0.5V to +2.0V and back to -0.5V
at 100 mV/s

F : Corrosion of
Fe → Fe2+ (Active
region)

G : Formation of
Fe2O3 (Passive
region)

H : OER on iron /
breakdown of
passive film
(Transpassive
region)

2. Comment on the cyclic voltammogram of gold electrode in 0.5M HNO 3 including the
oxidation/reduction of gold, the overpotential of H2 and O2 on gold surface (as
compared to standard electrode potential of HER and OER on platinum (ie: E oH+/H2 =
0.0 V and Eo H2O/O2 = +1.23 V, respectively).
- Gold is an inert metal which is not easily corrode or oxidize, but gold is slowly
oxidize when immersed in strong acid with 1.7V, forming a thin layer of protective
oxide and bubble gas is formed at anode surface. HER for gold starts to occur at
-0.6V and vigorous HER on gold surface showed bubble hydrogen gas of -0.1V.

3. Explain the oxidation behaviour of iron in 0.5M HNO3 as shown by CV.

- Iron is reactive and lower in series and easily to oxidize in HNO 3 solution forming
Fe2+ ions. Iron oxidize in active state at 0.1V and dropped before being constant
till 1.5V and oxidize again at transpassive region of 1.6V.

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Part B (12 marks)

Table 2 : Corrosion Rate measurement of Iron (Area: 0.5 cm2) in different solutions

Solution Ecorr (V) Icorr (A) CR Tafel Plot

(mm/yr)

0.5 M HNO3 -0.278 0.0060 139.7

0.5 M NaCl -0.270 5.7 x 10-6 0.1328

0.5 M -0.280 1.4 x 10-6 0.03262

NaOH

The addition of inhibitor in 0.5M HNO3 has

significantly changed the polarization curve
as follows:

Ecorr has shifted to more positive potential

0.5 M HNO3 +0.170 0.000003 0.06989 from -0.278V to +0.170V.
+
Inhibitor Icorr is reduced from 6000 μA to 3 μA

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1. Based on data in Table 2, calculate the corrosion rate of iron in different solutions.
(Atomic mass, Fe: 56 g/mol, Density of Fe = 7.86 g/cm3)

i) Corrosion rate (mm/yr) of iron in 0.5M HNO 3 = 0.00327 icorr. a

n. D

= 0.00327 (0.006 x 106 / 0.5) (56)

2 (7.86)

= 139.7 mm/yr

i) Corrosion rate (mm/yr) of iron in 0.5M NaCl =

icorr . a
0.00327
n.D
106 ( )
0.00327
( 5.7 × 10−6 ×
0.5) 56

2 ( 7.86 )
mm
0.1328
yr
ii) Corrosion rate (mm/yr) of iron in 0.5M NaOH =
icorr . a
0.00327
n.D
106 ( )
0.00327
( 1.4 × 10−6 ×
0.5 )56

2 (7.86 )
mm
0.03262
yr
iii) Corrosion rate (mm/yr) of iron in 0.5M HNO3 + Inhibitor =
icorr . a
0.00327
n.D
10 6 ( )
0.00327
( 0.000003 ×10−6 ×
0.5 ) 56

2 ( 7.86 )
mm
0.06989
yr

2. Calculate the corrosion protection efficiency of iron immersed in acidic solution (ie:
HNO3) containing inhibitor.

Corrosion protection efficiency (η%) =

( C Runprotected −CR protected )

×100 %
C Runprotected

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139.7−0.06989
×100 %
139.7

¿ 99.9 %

3. Identify the type of the inhibitor used in this study (either anodic, cathodic or mixed
type). Justify your answer.
- The inhibitor used in this experiment is anodic. Anodic inhibitors are chemical
substances that form a protective layer of oxide film on the surface of metal,
causing resistance to corrosion. These inhibitors particularly alter the anodic
reactions in a chemical cell, forcing the metallic surface into the passivation
region. Hence, Ecorr increase and icorr decrease on addition of anodic inhibitors.