Send Orders for Reprints to reprints@benthamscience.

ae
60
Innovations in Corrosion and Materials Science, 2018, 8, 60-66
RESEARCH ARTICLE
ISSN: 2352-0949
eISSN: 2352-0957

Corrosion Inhibition of Copper in Sea Water Using Derivatives of

Tetrazoles and Thiosemicarbazide

Abdul-Khalek Younes1, Ibrahim Ghayad2,*, Emel B. Ömer3 and Fatma Kandemirli1

Innovations in Corrosion and Materials Science

1
Department of Material Science, Kastamonu University, Kastamonu, Turkey; 2Central Metallurgical Research &
Development Institute, Helwan, Egypt and 3Department of Chemistry, Halisdmir University, Nigde, Turkey

ARTICLE HISTORY
Received: April 27, 2018
Revised: August 08, 2018
Accepted: August 29, 2018
DOI:
10.2174/2352094908666180830123952
Keywords: Corrosion inhibition, copper, sea water, thiosemicarbazides, tetrazoles, inhibition efficiency.
Abstract: Background: The present paper investigates the corrosion inhibition of copper using six cor-
rosion inhibitors namely: 4-phenyl thiosemicarbazide (PTSC), Salicylaldehydethiosemicarbazone
(STSC). 5-Mercapto-1-methyle tetrazole (MMT), 5-(3-Pyridyl)-1H-tetrazole (PyTA), 5-phenyl-1-H-
tetrazole (PTA) and 5-Amino-tetrazole monohydrate (ATA).
Method: Copper samples were tested using potentiodynamic polarization technique in the absence and
in the presence of corrosion inhibitors.
Results: Results show that tetrazole derivatives show high inhibition efficiencies (90%) in comparison
to thiosemicarbazide derivatives (<80%). The highest inhibition efficiency of 92.9% was shown by
ATAH at 2000 ppm. The order of inhibition efficiencies of the tested compounds was as follows:
PTAATA >PyTA> MMT > STC > PTSC.

1. INTRODUCTION The corrosion inhibition of Cu using1-phenyl-5-

Copper and its alloys possess excellent thermal, electrical
and mechanical properties [1, 2]. These properties make them
suitable choices for construction materials including tubes,
pumps, valves, fittings, interconnects, circuit boards,…etc.
However, copper alloys suffer from some forms of corrosion
which limit their performance [3-6].
Tetrazoles are a family of organic heterocyclic com-
pounds composed of a 5-member ring having four nitrogen
and one carbon atoms in addition to hydrogen atoms [7].
Substitution of H atom attached to the carbon or the nitrogen
atoms of the tetrazole ring with other function groups like
NH2, CH3, SH, phenyl result in the synthesis of a huge num-
ber of tetrazoles. Tetrazoles possess a high tendency to ad-
sorb on copper due to lone pairs of electrons on the nitrogen
atoms of the tetrazole ring. The coordination of these lone
pairs of electrons with the Cu(I) ions, produced from copper
oxidation, results in the formation of a protective complex.
The effect of 2-mercaptobenzothiazole (MBT) and te-
trazole (TTA) on the corrosion inhibition of copper in the
ethanol solution and 0.1 M NaOH was investigated [8, 9].
0.001 M of MBT lead to reduction of current density 4
times. The inhibition efficiency is strongly dependent on the
structure and chemical properties of the species formed un-
der the specific experimental conditions.
*
Address correspondence to this author at the Central Metallurgical
Research & Development Institute, Helwan, Egypt;
Tel: 955884842; E-mail: ighayad@yahoo.com
mercapto-1,2,3,4-tetrazole (PMT) in 0.1M HNO3 has been
investigated [10]. PMT behaves as a mixed type inhibitor
and is chemisorbed on the copper surface and follows Lang-
muir isotherm. Other papers [11-13] investigated 5-(3-
Aminophenyl) tetrazole 5-Substituted,(E)-3-phenyl-2-(1H-
tetrazole-5-yl)acrylonitrile (PTA), (E)-3-(4-nitrophenyl)-2-
(1Htetrazole-5-yl)acrylonitrile (NTA), and (E)-3-(4-
hydroxyphenyl)-2-(1H-tetrazole-5-yl)acrylonitrile (HTA) for
the corrosion inhibition of copper and steel in seawater, hy-
drochloric and sulfuric acid environments. The relation be-
tween the adsorption bonding and corrosion inhibition of
copper was also addressed [11-13].
Semicarbazide, known as carbohydrazide, is the chemical
compound with the formula OC(NH2)(N2H3). It is a water-
soluble white solid. It is a derivative of urea prepared by
treating urea with hydrazine [14]:
OC(NH2)2 + N2 H4  OC (NH2)(N2 H3) + NH3 (1)
A thiosemicarbazide is an analog to semicarbazide with
the sulfur atom in place of oxygen atom. Semicarbazones are
derived by the condensation reaction between a ketone (or
aldehyde) and a semicarbazide. Thiosemicarbazide and its
derivatives are used as corrosion inhibitors for different me-
tallic substrates [15-27]. Thiosemicarbazide and thiocarbo-
hydrazide functionalized chitosan were evaluated as eco-
friendly corrosion inhibitors for carbon steel in hydrochloric
acid solution [15]. Al-Bonayan [16] used thiosemicarbazide
and 4-phenyl thiosemicarbazide as corrosion inhibitors of

2352-0957/18 $58.00+.00 © 2018 Bentham Science Publishers

Corrosion Inhibition of Copper in Sea Water Using Derivatives
carbon steel in 2 N H3PO4 solutions. The inhibition efficien-
cy increases with increase in inhibitors concentrations and
decreases with rising temperature. The influence of thio-
semicarbazide, phenylthiosemicarbazide on the corrosion
rate of steel in 2MHCl was investigated [17]. Results showed
that all the compounds investigated acted as cathodic-type
inhibitors. The corrosion inhibition efficiency of synthesized
2-(1-methyl-4-((E)-(2-methylbenzylidene)amino)-2-phenyl-
1H-pyrazol-3(2H)-ylidene)-hydrazineecarbothioamide (HCB)
on mild steel in 1.0 M HCl was investigated [18]. The results
showed that HCB inhibited mild steel corrosion in acidic
solution and inhibition efficiency increased with an increase
in the concentration of the inhibitor. The inhibition efficien-
cy of 1,4-bis (2-nitrobenzylidene) thiosemicarbazide (BBTS)
on the corrosion of mild steel in 1 mol/L HCl was investigat-
ed [19]. The results showed that this compound had good
inhibiting properties for mild steel corrosion in hydrochloric
acid and BBTS was a mixed-type inhibitor. In the study of
Wazzan [20], thiosemicarbazide, aryl isothiocyanates, and 1-
aryl-2,5-dithiohydrazodicarbonamides were investigated as
corrosion inhibitors of copper in an aqueous chloride
solution.
It is obvious that literature mostly investigated the use of
thiosemicarbazides as corrosion inhibitors for mild steel with
little work on copper. Mean whiletetrazoles were tested as
corrosion inhibitors of copper in acid media but not salt wa-
ter. The present paper investigates and compares the corro-
sion inhibition of copper in sea water environment using
some tetrazoles and thiosmicarbazide derivative.
2. OBJECTIVES
• Comparing the corrosion inhibition efficiencies of some
tetrazoles and thiosmicarbazide derivative.
• Corelating the inhibition efficieny to the inhibitor molec-
ular structure and its functionality.
3. METHOD
Disc specimens were prepared from electrolytic copper
(99.9%) having a diameter of 1.5 cm2. Disc specimens were
Table 1. Names and structural formula of tested inhibitors.
salicylaldehydethiosemicarbazone (MW =195.24)
4-phenylthiosemicarbazide (MW = 167.23)
S
NH2
N N
H H
5-Mercapto-1-methyltetrazole (Mwt =116.14)
Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 61
fixed in the corrosion cell so that an area of 0.785 cm2 was
exposed to the testing solution. Specimens were polished
using SiC papers successively up to 2400 grits to acquire a
mirror-like finish. After polishing, specimens were thorough-
ly washed with distilled water and dried in air.
Potentiodynamic polarization curves were measured on
the Cu electrodes using a conventional three-electrode cell
with an Ag/AgCl reference electrode and a Pt sheet counter
electrode. The potential was controlled using a computerized
potentiostat (AutoLab PG STAT 30). The potential was
scanned from -0.3 V below the Ecorr towards 1 V above the
Ecorr at a scan rate of 1 mVs-1. Experiments were carried out
in 0.6 mol L-1NaCl solution simulating sea water environ-
ment. Corrosion parameters: corrosion current (Icorr), corro-
sion potential (Ecorr) and corrosion rate (CR) were deduced
from the analysis of polarization curves using the AutoLab
software.
Six corrosion inhibitors namely: 4-phenyl thiosemicarba-
zide, Salicylaldehydethiosemicarbazone. 5-Mercapto-1-methyle
tetrazole, 5-(3-Pyridyl)-1H-tetrazole,5-phenyl-1-H-tetrazole
(PTAH) and 5-Amino-tetrazole monohydrate (ATAH) from
Aldrich were investigated. The inhibitor solutions were dis-
solved in the least amount of dimethylformamide (DMF) or
sodium hydroxide. Measurements were performed at 20 ± 1oC
while the testing solution was open to air. The structural formu-
la and their molecular weight are shown in Table 1
4. RESULTS AND DISCUSSION
Potentiodynamic polarization curves are used to illustrate
the corrosion behavior of the alloy under test and to show the
effect of the corrosion inhibitor, i.e. if the corrosion inhibitor
leads to the appearance of a passive region or not. Poten-
tiodynamic polarization curves are used also to deduce cor-
rosion parameters: corrosion potential (Ecorr), corrosion cur-
rent (icorr) and corrosion rate (CR) in the presence of the cor-
rosion inhibitors compared to those obtained in the absence
of corrosion inhibitor and thus, determining the corrosion
inhibition efficiency. The corrosion inhibition efficiency of
the corrosion inhibitor can be calculated using the following
equation:
5-(3-Pyridyl)-1H-tetrazole (MW =147.14)
5-phenyl-1-H-tetrazole (PTAH) (MW=146.15)
5-Amino-tetrazole.H2O (ATAH) (MW=103.08)
62 Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 Younes et al.

icorr(b) - icorr(inh) Figs. (2-6) present the Potentiodynamic polarization

Efficiency = ------------------------------ X 100 (2) curves of cu in 3.5% NaCl solution at 1mvs-1 and 20°C and
icorr(b) in presence of the investigated corrosion inhibitors: 4-
phenylthiosemicarbazide, 5-mercapto-1-methyltetrazole, 5-
where icorr(b), icorr(inh)represent corrosion current densities in (3-pyridyl)-1H-tetrazole, 5-amminotetrazolemonohydrate &
the absence and in the presence of the inhibitor, respectively. 5-phenyl-1H-tetrazole, respectively. The blank curve (in
absence of corrosion inhibitor) is included for comparison.
Table 2 presents the electrochemical parameters deduced
0.8 500 ppm (a) from these Potentiodynamic polarization curves.
1000 ppm
2000 ppm
4-phenylthiosemicarbazid inhibitor shows better behavior
0.6
Blank compared to the blank (Fig. 2) but the reduction in the cur-
0.4 rent density is not satisfactory. No inhibition is shown by the
Potential / V

inhibitor at all concentrations (Table 2). The corrosion poten-

0.2 tials were shifted markedly in the active direction in the
presence of the inhibitor compared to the blank. The shift in
0.0 Ecorr mostly related to the adsorbed species on the copper
surface.
-0.2
5-Mercapto-1-methyltetrazolecorrosion inhibitor reveals
-0.4 an appreciable reduction in the current density compared to
the current density obtained in the solution without the inhib-
10-8 10-7 10-6 10-5 10-4 10-3 10-2 itor (Fig. 3). Increasing the inhibitor concentration brings a
-2 mild decrease in the current density. Corrosion rate obtained
Current /Acm
is decreased from 0.097 to 0.05 mm/y upon increase of in-
0.8
hibitor concentration from 0.0043 to 0.0086 M. Further in-
1000 ppm-0.1 M NaCl (b) crease of inhibitor concentration up to 0.0172 M led to an
1000 ppm-0.4 M NaCl
0.6 1000 ppm-0.6 M NaCl
increase of the corrosion rate up to 0.066 mm/y. The corro-
sion inhibition efficiency reaches as high as 70% at 0.0086
0.4 M of the inhibitor. Corrosion potentials are more or less the
Potential / V

same as the blank.

0.2
Table 2. Corrosion parameters including corrosion current
0.0 (Icorr), corrosion potential (Ecorr) and corrosion rate
(CR) derived from potentiodynamic curves of copper
-0.2
in 0.6 M NaCl in the absence (blank) and in the
-0.4 presence of corrosion inhibitors.

-0.6 Inhibition
Inhibitor/
icorr ( A/cm2) Ecorr (V) CR (mm/y) Efficiency
10 -9
10 -8
10 -7
10 -6
10 -5
10
-4
10 -3
10-2
M
(%)
-2
Current /Acm
Blank 1.479E-5 -0.236 0.1716

Fig. (1). (a) Potentiodynamic polarization curves of Salicylaldehydethiosemicarbazone

salicylaldehydethiosemicarbazonecorrosion inhibitor in 3.5% NaCl
at 1 mVs-1 scan rate and 20oC. (b) represents the effect of NaCl 0.0026 6.46 x10-6 -0.196 0.075 56.32
concentration on the efficiency of the inhibitor. 0.0051 4.27x10-6 -0.236 0.050 71.13
Fig. (1a) shows potentiodynamic polarization curves of
0.0102 2.79x10-6 -0.188 0.032 81.14
Cu in presence of Salicylaldehydethiosemicarbazone inhibi-
tor. The inhibitor shows better behavior compared to the 4-phenyl thiosemicarbazide
blank as shown by the lower current density, however, the
reduction in the current density is not significant. On the 0.0030 1.85x10-5 -0.412 0.21 --
other hand, with increasing inhibitor concentration, current 0.0060 2.14x10 -5
-0.438 0.25 --
density slightly decreases. Fig. (1b) shows the effect of sodi-
-5
um chloride concentration on the potentiodynamic polariza- 0.0120 1.711x10 -0.446 0.198 --
tion curves of the copper electrode in the presence of 0.0051
5-Mercapto-1-methyltetrazole
ppm inhibitor. An obviously low current density is obtained
in 0.1 M NaCl indicating high corrosion resistance of copper. 0.0043 8.33x10-6 -0.272 0.097 43.68
The current density is also increased upon increasing of
NaCl concentration from 0.1 to 0.4 then 0.6 M NaCl. The 0.0086 4.36x10-6 -0.226 0.050 70.52
tested inhibitors show Ecorrvalues comparable to that shown 0.0172 5.71x10-6 -0.262 0.066 61.39
by the blank.
Table (2) contd….
Corrosion Inhibition of Copper in Sea Water Using Derivatives Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 63

5-(3-Pyridyl-1H-tetrazole
5-(3-Pyridyl)-1H-tetrazole corrosion inhibitor shows bet-
ter behavior compared to the blank (Fig. 4), however, the
0.0034 1.28x10-6 -0.233 0.015 91.34 reduction in the current density is not much appreciable.
Concentrations of 0.0068&0.0136M show higher current
0.0068 2.99x10-6 -0.191 0.035 79.78
densities compared to 0.0034 M. Corrosion inhibition effi-
0.0136 1.63x10 -6
-0.203 0.019 88.79 ciency is as high as 91% at 0.0192 ppm inhibitor.
5-phenyl-1-H-tetrazole(PTA)
0.8
0.0034 2.36x10-6 -0.204 0.027 84.04 500 ppm
1000 ppm
0.6 2000 ppm
0.0068 2.22x10-6 -0.35 0.026 84.98 Blank

0.4
0.0137 1.19x10-6 -0.239 0.014 91.95

Potential / V
5-Amino-tetrazole mono hydrate (ATA) 0.2

0.0048 6.96x10-6 -0.191 0.081 52.94 0.0

0.0096 4.63x10-6 -0.208 0.054 68.69 -0.2

-6
0.0192 1.05x10 -0.234 0.012 92.90 -0.4

-0.6
10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2
0.6 Current /Acm
-2

500 ppm
0.4 1000 ppm Fig. (4). (a) Potentiodynamic polarization curves of 5-(3-Pyridyl)-
2000 ppm
1H-tetrazole corrosion inhibitor in 3.5% NaCl at 1 mVs-1 scan rate
Blank
0.2 and 20oC.
Potential / V

In the case of 5-Aminotetrazole monohydrate (ATAH)

0.0 corrosion inhibitor (Fig. 5), anodic current density is consid-
erably reduced compared to the blank. The extent of reduc-
-0.2 tion of the current density is increased with the increase of
the inhibitor concentration. The inhibition efficiency reaches
-0.4 as high as 92% at 0.0192 ppm inhibitor concentration.

0.8
-0.6 Blank
500 ppm
0.6 1000 ppm
-0.8 2000 ppm
Potential / V

0.4
Fig. (2). Potentiodynamic polarization curves of 4- 0.2
phenylthiosemicarbazide corrosioninhibitor in 3.5%.
0.0
0.8 500 ppm
-0.2
1000 ppm
0.6 2000 ppm
Blank vs Col 8 -0.4
0.4
-0.6
Potential / V

0.2 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2

0.0 Current / A cm-2

-0.2 Fig. (5). Potentiodynamic polarization curves of copper in the pres-

ence of 5-Aminotetrazole monohydrate (ATAH)corrosion inhibitor
-0.4 in 3.5% NaCl at 1 mVs-1 scan rate and 20oC.

-0.6 The enhancement in corrosion resistance of copper in the

10-8 10-7 10-6 10-5 10-4 10-3 10-2 presence of ATAH can be attributed to the formation of a protec-
-2 tive layer on copper surface. In the pH range 6-8, the inhibitor
Current /Acm
form a protective film of Cu(I) ATA complex [27-29] on the
copper surface according to the following equation:
Fig. (3). Potentiodynamic polarization curves of 5-Mercapto-1-
methyltetrazole corrosioninhibitor in 3.5% NaCl 1 mVs-1 scan rate Cu + ATAH = Cu(1)ATA + e- (3)
and 20oC.
64 Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 Younes et al.

The degree of surface coverage at different concentra- It is obvious to note that 5-phenyl-1H-tetrazole (PTAH)
tions of ATAH can be obtained from the following expres- corrosion inhibitor behaves more or less in the same trend as
sion: ATA (Fig. 7). Moreover, a clear passive region was obtained
at concentrations  0.0068 ppm inhibitor. No passivation
Icorr(b) - Icorr(inh)
was shown at higher potentials due to the degradation of the
 = ------------------------------ X 100 (4)
protective film formed on copper surface. The corrosion in-
Icorr(b) hibition efficiency reaches as high as 92% at 0.0137 ppm.
Where icorr(b), icorr(inh) represent corrosion current densities 0.8
in the absence and in the presence of the inhibitor, respec- Blank
500 ppm
tively. The adsorption of ATAH on the surface of Cu was 0.6 1000 ppm
best illustrated using the Langmuir isotherm [30, 31]: 2000 ppm
0.4 4000 ppm

Potential / V
/1- = AC exp [–E#/RT] = KC (5)
0.2
where  is the surface coverage, E# is the activation energy,
0.0
C is the concentration in mol L-1 and K is the constant of the
adsorption process. Rearranging equation 5 gives: -0.2
C/  = 1/K + C (6)
-0.4

Table 3. The degree of surface coverage against -0.6

concentration of the inhibitor. 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2

ATAH Concentration, ppm 0.0048 0.0096
Surface Coverage / 52.94 68.69
Table 2 shows the surface coverage at different ATAH
inhibitor concentrations. A plot of C/ versus C (Fig. 6)
yields a straight line with intercept 1/K. Linear regression of
the obtained straight line was used to obtain 1/K and conse-
quently, K the standard free energy of adsorption (Go) can
be calculated after determining the adsorption constant (K)
using the following expression [31]: K=1/55.55exp[- Go
/RT] [7] Where R is the universal gas constant and T is the
absolute temperature. The standard free energy of adsorption
(Go) of -35.14 kJ mol-1 was obtained at 20oC. The negative
value of Go indicates that ATAH is spontaneously chemi-
sorbed on the surface of copper. A co-ordinate bond was
formed through charge sharing or transfer from the ATAH
molecules to the copper surface.
240x10-6 b[0] 2.96742066e-5
b[1] 0.010767442
r ² 0.9978453165
200x10-6
C/
Current / A cm-2
0.0192
Fig. (7). Potentiodynamic polarization curves of copper in the pres-
92.90
ence of 5-phenyl-1-H-tetrazole(PTA) corrosion inhibitorin 3.5%
NaClat 1 mVs-1 scan rate and 20oC.
Ɵ values for various PTA concentrations can be shown
on Table 3. (Go) of -36.582 kJ mol-1 was observed at 20oC.
Table 4. The degree of surface coverage versus concentration
of the inhibitor.
PTAH Concentration, ppm 0.0034 0.0068 0.0137
Surface Coverage / 84.04 84.98 91.95
Thiosemicarbazide and tetrazole derivatives inhibit the
corrosion of copper by adsorption at the metal/solution inter-
face. Corrosion inhibition results from the presence of free
electron pairs in the S and the N atoms, p -electrons on the
aromatic rings, inhibitor molecular size and the formation of
copper complexes. The free and p-electrons interact with d-
orbital of Cu to provide a protective film. The corrosion in-
hibition of thiosemicarbazide and tetrazole derivatives in-
creases with the increase of the electron densities around the

active center [11, 32].

160x10-6

5. SURFACE INVESTIGATION
120x10-6 The effect of inhibitors on the surface morphology of the
copper electrode was investigated. An illustrative example is
80x10-6
shown in Fig. (8). The figure shows the SEM micrograph of
copper treated in 0.6 M NaCl in the absence (Fig. 9a) and in
0.004 0.008 0.012 0.016 0.020 the presence of 0.0137mol L-1PTA (Fig. 8b). The copper
C/ mol L-1 surface shows very good appearance with no corrosion at-
tack in the presence of PTA whereas a high degree of surface
Fig. (6). Langmuir adsorption isotherms of copper in 0.6 mol L- roughness is shown in the absence of the inhibitor. The high
1
NaCl in the presence of ATA at 20ºC. surface roughness indicates general corrosion attack.
Corrosion Inhibition of Copper in Sea Water Using Derivatives
(a)
(b)
-1
Fig. (8). SEM micrographs of copper treated in 0.6 mol L NaCl
under the following conditions: a) 0.6 M NaCl only (b) In the pres-
ence of 10-2 mol L-1 PTAH.
The present work reveals that tetrazoles derivatives ex-
hibit high corrosion inhibition efficiency than thiosemicarba-
zide derivatives. Tetrazole derivatives are able to interact
with copper surfaces giving rise to a film having protective
properties. The presence of hydrogen atom in the
heterocyclic ring favors the formation of organic anion at
neutral and alkaline medium. The interaction of the anion
with the copper surface or with the copper ions results in the
formation of a stable complex. The decrease in inhibition
efficiency of mercapto methyl tetrazole can be assigned to
the fact that sulfur-containing heterocyclic compound) acted
more efficiently as inhibitors in sulfate medium while
nitrogen-containing compounds show better inhibitive be-
havior in chloride solutions. The high inhibition efficiencies
of PTA and PyTA compounds can be related to the introduc-
tion of a phenyl group in the tetrazole ring which led to an
increase in the surface area and/or to the higher hydrophobi-
city of substituted molecule. The introduction of a –NH2
group in the heterocyclic ring of the TAT compound increas-
es the inhibition efficiency due to its electron-donor proper-
ties and/or to the possibility of an internal salt formation.
Thiosemicarbazides as sulfur-containing organic molecules
do not act well in chloride solutions, the lone pair of elec-
trons are likely more difficult to coordinate with copper to
form the copper inhibitor complex [11, 29, 33].
Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 65
CONCLUSION
Tetrazole derivatives show higher corrosion inhibition ef-
ficiency (>90%) than thiosemicarbazide derivatives (<80%).
The order of inhibition efficiencies of the tested compounds
is as follows: PTA
ATA >PyTA> MMT > STC > PTSC.
The high inhibition efficiency of tetrazoles can denote the
formation of a protective film of Cu(I)Tetrazole complex on
the copper surface. The inhibition efficiency of Tetrazole
derivatives obeys Langmuir adsorption isotherms while the
calculated free energy of adsorption indicates chemisorptions
of the inhibitor on the copper surface.
ETHICS APPROVAL AND CONSENT TO PARTICI-
PATE
Not applicable.
HUMAN AND ANIMAL RIGHTS
No Animals/Humans were used for studies that are the
basis of this research.
CONSENT FOR PUBLICATION
Not applicable.
CONFLICT OF INTEREST
The authors declare no conflict of interest, financial or
otherwise.
ACKNOWLEDGEMENTS
The authors of the present work acknowledge the revi-
sion of the manuscript by Prof. Dr. Nabil Nassif, emeritus
Prof. of Corrosion, CMRDI. The authors also acknowledge
that there is no conflict of interest regarding the performed
research work.
REFERENCES
[1] R.B. Ross, Metallic materials specifications handbook. London:
Chapman and Hall, 1992.
[2] L. La Que, Marine corrosion. New York: John Wiley & Sons, Inc,
1975.
[3] D. Tromans and J.C. Silvia, "Anodic Behavior of Copper in Chlo-
ride/Tolytriazole and Chloride/Benzotriazole Solutions", Corro-
sion, vol. 53, pp. 16-25, 1997.
[4] G, Kear, B.D, Barker and F.C. Walsh, "Electrochemical corrosion
of unalloyed copper in chloride media: A critical review“, Corros.
Sci., vol. 46, pp. 109-135, 2004.
[5] F.J. Satchell and J.B. Smith, "Calculation of aqueous dissociation
constants of 1,2,4-triazole and tetrazole: A comparison of solvation mod-
els“ Phys. Chem. Chem. Phys., vol. 4, pp. 4314-4318, 2002.
[6] J.C. Marconato, L.O. Bulhões and M.L. Temperini, “A spectroelec-
trochemical study of the inhibition of the electrode process on cop-
per by 2-mercaptobenzothiazole in ethanolic solutions”, Electro-
chem. Acta, vol. 43, pp. 771-780, 1998.
[7] F.R. Benson, “The Chemistry of the Tetrazoles”, Chem. Rev., vol.
41, pp. 1-61, 1947.
[8] E. Szocs, G. Vastag, A. Shaban and E. Kalman, “Electrochemical
behaviour of an inhibitor film formed on copper surface”, Corros.
Sci., vol. 47, pp. 893-908, 2005.
[9] B.V.A. Rao, and K.C. Kumar, “5-(3-Aminophenyl)tetrazole–A
new corrosion inhibitor for Cu–Ni (90/10) alloy in seawater and
sulphide containing seawater”, Arabian J. Chem., Vol.10, pp.
s2245-s2259. May 2017.
66 Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1
[10] N. Kovaevi, I. Miloev, and A. Kokalj, “How relevant is the
adsorption bonding of imidazoles and triazoles for their corrosion
inhibition of copper?”, Corros. Sci., vol. 124, pp. 25-34. 2017
[11] C. Verma, M.A. Quraishi, and A. Singh, "5-Substituted 1H-
tetrazoles as effective corrosion inhibitors for mild steel in 1 M hy-
drochloric acid”, J. Taibah Uni. Sci., vol. 10, pp. 718-733, 2016.
[12] El-Sayed and M. Sherif, “Corrosion inhibition in 2.0 M sulfuric
acid solutions of high strength maraging steel by aminophenylte-
trazole as a corrosion inhibitor”, Appl. Surf. Sci., vol. 292, pp. 190-
196, 2014.
[13] N. Kovaevi, and A. Kokalj, “The relation between adsorption
bonding and corrosion inhibition of azole molecules on copper”,
Corros. Sci., vol. 73, pp. 7-17, 2013.
[14] J. McMurry, “The inductive effect: Theory and quantitative as-
sessment”, Organic Chem., 1984. [Epub ahead of print]
[15] D.S. Chauhan, K.R. Ansari , A.A. Sorour, M.A. Quraishi, H. Lgaz,
and R. Salghi, “Thiosemicarbazide and thiocarbohydrazide func-
tionalized chitosan as ecofriendly corrosion inhibitors for carbon
steel in hydrochloric acid solution", Int. J. Biol. Macromol., vol.
107, pp. 1747-1757, 2018.
[16] A.M. Al-Bonayan, "inhibiting effect of thiosemicarbazide and 4-
phenyl thiosemicarbazide towards the corrosion of carbon steel in
H3PO4 solutions", Int. J. Electrochem. Sci., vol. 10, pp. 589-601,
2015.
[17] A.A. El-Shafei, M.N.H. Moussa, and A.A. El-Far, "The corrosion
inhibition character of thiosemicarbazide and its derivatives for C-
steel in hydrochloric acid solution", Mater. Chem. Phys., vol. 70,
2001, pp. 175–180.
[18] A.A. Al-Amiery, A.H. Kadhum, A. Mohamad and S. Junaedi, "A
novel hydrazine carbothioamide as a potential corrosion inhibitor
for mild steel in HCl", Materials, vol. 6, pp. 1420-1431, 2013.
[19] P. Mohan, G. P. Kalaignan, "1, 4-Bis (2-nitrobenzylidene) thio-
semicarbazide as effective corrosion inhibitor for mild steel”, J.
Mater. Sci. Techn., vol. 29, pp. 1096-1100, 2013.
[20] N. A. Wazzan, " DFT calculations of thiosemicarbazide, arylisothi-
ocynates, and 1-aryl-2,5-dithiohydrazodicarbonamides as corrosion
inhibitors of copper in an aqueous chloride solution” J. Ind. Eng.
Chem., vol. 26, pp. 291-308, 2015.
[21] K. Ramya, R. Mohan, K.K. Anupama, A. Joseph, D. S. Chauhan,
K.R. Ansari, A.A. Sorour, M.A. Quraishi, and R. Salghi, “Electro-
chemical and theoretical studies on the synergistic interaction and
corrosion inhibition of alkyl benzimidazoles and thiosemicarbazide
pair on mild steel in hydrochloric acid”, Mater. Chem. Phys., vol.
149-150, pp. 632-647, 2015.
Younes et al.
[22] Bin Xu, Wenzhong Yang, Ying Liu, Xiaoshuang Yin, Weinan
Gong, Yizhong Chen, “Experimental and theoretical evaluation of
two pyridinecarboxaldehydethiosemicarbazone compounds as cor-
rosion inhibitors for mild steel in hydrochloric acid solution”, Cor-
ros. Sci., vol. 78, pp. 260-268, 2014.
[23] FatmaKandemirli, SedaSagdinc, “Theoretical study of corrosion
inhibition of amides and thiosemicarbazones”, Corros. Sci., vol. 49,
pp. 2118-2130, 2007.
[24] K. S. Jacob, G. Parameswaran, “Corrosion inhibition of mild steel
in hydrochloric acid solution by Schiff base furointhiosemicarba-
zone”, Corros. Sci., vol. 52, pp. 224-228, 2010.
[25] T. Poornima, J. Nayak, A.N. Shetty, “Effect of 4-(N,N-
diethylamino)benzaldehydethiosemicarbazone on the corrosion of
aged 18 Ni 250 grade maraging steel in phosphoric acid solution”,
Corros. Sci., vol. 53, pp. 3688-3696, 2011.
[26] A. Xu, Y Liu, X Yin, W Yang and Y Chen, "Experimental and
theoretical study of corrosion inhibition of 3-pyridinecarbozalde
thiosemicarbazone for mild steel in hydrochloric acid", Corros.
Sci., vol. 74, pp. 206-213, 2013.
[27] N.K. Allam, A. Abdel Nazeer, and E.A. Ashour, “Electrochemical
characterization and stress corrosion cracking behavior of -brass
in molybdate-containing electrolytes”, J. Appl. Electrochem., vol.
16, pp. 39, 2009.
[28] S.S. El-Egamy, “Corrosion and corrosion inhibition of Cu–20%Fe
alloy in sodium chloride solution”, Corros. Sci., vol. 50, pp. 928-
937, 2008.
[29] S.M. Milic, M. Antonijevic, "Some aspects of copper corrosion in
presence of benzotriazole and chloride ions", Corros. Sci., vol. 51,
pp. 28-34, 2009.
[30] M. Ehteshamzade, T. Shahrabi and M.G. Hosseini, “Inhibition of
copper corrosion by self-assembled films of new Schiff bases and
their modification with alkanethiols in aqueous medium”, Appl.
Surf. Sci., vol. 252, pp. 2949-2959, 2006.
[31] M. Scendo, “Corrosion inhibition of copper by purine or adenine in
sulphate solutions”, Corros. Sci., vol., 49, pp. 3953-3963, 2007.
[32] G.E. Bad, “The role of some thiosemicarbazide derivatives as cor-
rosion inhibitors for C-steel in acidic media”, Corros. Sci., vol. 51,
pp. 2529–2536, 2009.
[33] C. Verma, L.O. Olasunkanmi, E. E. Ebenso and M.A. Quraishi,
"Substituents effect on corrosion inhibition performance of organic
compounds in aggressive ionic solutions: A review”, J. Molecu.
Liq., vol. 251, pp. 100-118, 2018.