Journal of Bio- and Tribo-Corrosion (2020) 6:9

https://doi.org/10.1007/s40735-019-0306-9

Synthesis, Characterization, and Anti‑corrosion Behavior of Novel

Mono Azo Dyes Derived from 4,5,6,7‑Tetrahydro‑1,3‑benzothiazole
for Mild Steel in Acid Solution
N. M. Mallikarjuna1 · J. Keshavayya1 · B. M. Prasanna2 · B. M. Praveen3 · H. C. Tandon4

Received: 27 September 2019 / Revised: 2 November 2019 / Accepted: 11 November 2019 / Published online: 22 November 2019
© Springer Nature Switzerland AG 2019

Abstract
The present study describes the use of 4,5,6,7-tetrahydro-1,3-benzothiazole incorporated azo dyes as anti-corrosive agents
and dissolution protection of mild steel from 1 M HCl solution. The inhibition efficiency of the azo dyes is determined by
potentiodynamic polarization technique and electrochemical impedance spectroscopic studies. Based on these experimental
results, it is noted that, the azo dye T1 is an effective inhibitor and the inhibition efficiency of the azo dyes is found to be
in the following order T1 > T2 > T3. From the polarization measurements, it is noted that, these azo dyes are mixed type of
inhibitors in 1 M HCl. The inhibition efficiency was increased as the concentration of the inhibitors increased and attains a
maximum value of 83.81% for T1 at 2.5 ppm concentration. The quantum chemical study was used to explain better about
the structural and electronic effects in relation to the inhibition efficiencies. Further, the surface morphology of the tested
mild steel samples was examined by scanning electron microscopy and energy-dispersive X-ray analysis with and without
inhibitors in 1 M HCl solution. The results of the analysis showed the effective corrosion inhibition properties after the
deposition of the inhibitors on to the metal surface.

Keywords Azo dye · Benzothiazole · Corrosion inhibition · Quantum studies

1 Introduction their structure exhibits a wide spectrum of colors and there-

fore they found to have applications in various fields such
Azo colorants are the important class of organic molecules as the textile industry, designing of optical storage devices,
having –N=N– chromophoric group in their structures and non-linear optical (NLO) materials, and also in many bio-
found to have a variety of applications in different fields [1, logical reactions [3–7]. Due to their high thermal stability
2]. Azo dyes were the largest used molecules among the and sensitivity, they are widely used in the design of photo
class of dyes and pigments due to their variations in the switches, electro-optic modulators [8–11], chemo sensors,
chemical structure and method of applications which are and photochemical molecular switches [12].
quite simple. The presence of heterocyclic ring systems in From the literature survey, it is observed that many
of the organic colorants were used as effective corrosion
* J. Keshavayya inhibitors to protect the metals from the aggressive media
[email protected] [13]. Particularly, the heterocyclic azo dyes were used to
be efficient inhibitors for metals to avoid corrosion from
1
Department of PG Studies and Research in Chemistry, acid solutions [14, 15]. It is an important and effective
School of Chemical Sciences, Kuvempu University, Jnana
Sahyadri, Shankaraghatta, Karnataka 577451, India protection technique and is widely used in chemical, petro-
2 leum, and other industries. There are a good number of
Department of Chemistry, Jain Institute of Technology,
Davanagere, Karnataka 577003, India organic inhibitors widely using throughout the world, but
3 some of the compounds fail to act effectively to protect the
Departement of Chemistry, College of Engineering
and Technology, Srinivas University, Mukka, Mangalore, surface of the metals and also they can cause severe envi-
Karnataka 574146, India ronmental problems due to toxicity, lack of inhibition effi-
4
Department of Chemistry, Sri Venkateswara College, Dhula ciency, high cost in the production. Therefore, researchers
Kuan, New Delhi 110021, India are trying to overcome these impeding challenges and to

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9 Page 2 of 17 Journal of Bio- and Tribo-Corrosion (2020) 6:9

improve the efficiency of the inhibitors [16, 17]. The pro- quantum chemical study and they were discussed in detail
tective coatings, cathodic protection, use of organic inhibi- at the end of the results and discussion section.
tors, etc. are the important corrosion control techniques to
avoid corrosion of the surface of the metals and also helps
in avoiding the metal dissolution [18, 19]. Among those, 2 Experimental
the use of heterocyclic compounds as corrosion inhibitors
is the most convenient and practical method to control All the solvents and chemicals used in the present study
the corrosion [20]. Normally the heterocyclic compounds were analytical grade (AR) and purchased from Sigma-
containing N, S, O, and P atoms and aromatic conjugated Aldrich Chemical Company and used without further puri-
systems permit the lone pair of electrons and π-electrons to fication. The completion of the reaction was monitored by
adsorb on to the metal surface, respectively [21]. Adsorp- thin-layer chromatography and performed on silica gel plates
tion is a physico-chemical phenomenon wherein the purchased from Merck. Melting points of the synthesized
loosely bound electrons on the heteroatoms of the inhibi- compounds were determined by using an electro-thermal
tor interact with the d-orbitals of the metal and forms a melting point apparatus and are uncorrected. UV–Vis spec-
protective film on to the metal surface thereby protect the tra were recorded on Elico-SL 164 double-beam spectro-
metal surface from corrosion [22–24]. The experimental photometer in the range 200–800 nm using ca. ­10−6 M solu-
techniques in the development of corrosion inhibitors are tion in four different solvents like ethanol, tetrahydrofuran,
more effective but their mechanism of inhibition to prevent N,N-dimethyl formamide, and dimethyl sulfoxide. FT-IR
the corrosion of metallic surfaces from the external fac- spectra of the compounds were recorded as KBr pellets on a
tors was not studied in detail [25]. Usually, the mechanism Perkin-Elmer-spectrum RX-IFTIR instrument in the region
of action was illustrated by the nature of the protecting 4000–400 cm−1. The 1H NMR spectra were recorded on the
layer developed on the metal surface and the inhibition FT-NMR spectrometer model Bruker Avance II, 400 MHz
efficiency of the adsorbed compounds. using DMSO-d6 as solvent. ESI–MS spectra of the com-
To achieve maximum inhibition efficiency of the applied pounds were recorded on a mass spectrometer equipped with
compounds and to develop effective corrosion inhibitors, electrospray ionization (ESI) source having a mass range of
chemists have tried to explain the mechanism through 4000 amu in quadruple and 20,000 amu in Tof. The quantum
molecular modeling (Quantum Chemical Calculations). chemical parameters of the azo dyes were obtained in the
Such theoretical methodologies are to provide a detailed gas phase from the parametric method 3 (PM3) by using
explanation from the experimental techniques to find out Hyperchem 7.5 package program.
the effective inhibition mechanism of the inhibitors [26].
Quantum chemical methods played a very significant role 2.1 Synthesis of 4,5,6,7‑Tetrahydro‑1,3‑benzothia‑
not only to develop effective corrosion inhibitors but also zol‑2‑amine (2)
used in the study of the inhibition mechanism. Some of the
parameters such as ­EHOMO, ­ELUMO, electronegativity, elec- The starting material 4,5,6,7-tetrahydro-1,3-benzothiazol-
tron affinity, global hardness, etc. signify the structural prop- 2-amine (2) was synthesized as per reported literature [29,
erties of the heterocyclic molecules, then the comparison 30]. To the hot solution of cyclohexanone (4.5 mL, 0.05 mol)
of these structural properties with the experimental results in 25 mL ethanol, thiourea (6 g, 0.1 mol) and iodine (12.7 g,
will have an influence on the mechanism of corrosion inhibi- 0.05 mol) were added and the reaction mixture was stirred
tion [27, 28]. Therefore, these theoretical studies will greatly for 5 h at reflux temperature. Then the reaction mixture was
help to design and develop efficient and eco-friendly corro- cooled to room temperature and 100 mL distilled water was
sion inhibitors for the protection of metals and alloys from added. The obtained solution was basified by the addition
aggressive media. of aqueous ammonia and extracted with ethyl acetate. The
From all these extensive observations, we have attempted organic layer (ethyl acetate layer) was washed several times
to synthesize novel azo dyes and their corrosion inhibitory with water and then finally filtered to remove insoluble sol-
effect over mild steel in 1 M HCl solution by electrochemi- ids. The ethyl acetate extract was concentrated to two-third
cal and quantum chemical methods. The chemical structures of its volume and we obtained pure red syrup as the final
of all the newly synthesized azo dyes were elucidated by compound.
various physico-chemical techniques. The electrochemical Red syrup, yield: 82%, m.p. 62–65 °C, IR (KBr, c­ m−1):
measurements include potentiodynamic polarization and 3364 (NH), 2963 (aliphatic C ­ H2), 1625 (C=N). 1H NMR
electrochemical impedance spectroscopy (EIS) and quan- (DMSO-d6, ppm): 6.63 (s, 2H, ­NH2), 2.51–2.36 (d, 4H,
tum chemical calculations were done by the PM3 method. ­CH2), 1.70 (s, 4H, C ­ H2). Anal. Calcd. For C­ 7H10N2S: C,
Further, the corrosion inhibition efficiency evaluated from 54.51; H, 6.54; N, 18.16. Found: C, 54.47; H, 6.12; N, 18.02.
the above experimental techniques was compared with the MS: 155 m/z (M+1)+.

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Journal of Bio- and Tribo-Corrosion (2020) 6:9 Page 3 of 17 9

2.2 General Procedure for the Synthesis of Azo Dyes Ar-H), 7.22–7.18 (t, 1H, Ar-H), 2.72–2.68 (d, 4H, C ­ H2),
(T1–T3) 2.33 (s, 3H, ­C H 3), 1.87 (s, 5H, ­C H 2). Anal. Calcd. For
­C 17H 17N 5OS: C, 60.16; H, 5.50; N, 20.63. Found: C,
A 2 mmol of the well-cooled solution of 4,5,6,7-tetrahydro- 59.96; H, 5.46; N, 20.25. MS: m/z 340 (M+1)+.
1,3-benzothiazol-2-amine (2) in 5 mL HCl was added drop
wise into the previously cooled solution of sodium nitrite
in 2 mL H ­ 2SO4 (nitrosyl sulphuric acid) and was kept on 2.2.2 Synthesis of 4‑Hydroxy‑3‑[4,5,6,7‑tetrahydro‑1,3‑ben‑
an ice-salt bath till the reaction mixture was attained the zothiazol‑2‑yldiazenyl]‑2H‑chromen‑2‑one (T2)
temperature 0–5 °C. After completion of the addition, the
reaction mixture was stirred continuously for 2 h to com- Brick red solid, yield: 78%, m.p. 196–8 °C, IR (KBr,
plete the diazotization. The resulting reaction mixture was ­c m −1 ): 3434 (OH), 3061, 1814 (C=N), 2932 (Ar-H),
then poured into the ice-cold solution of coupling compo- 1663 (C=O), 1465 (N=N), 1247 (C–O), 1180, 867
nents (2 mmol) (a–c) in acetic acid (8 mL). Furthermore, (C=S). 1H NMR (DMSO-d 6, ppm): 7.97–7.95 (d, 1H,
the reaction mixture was stirred for an additional 2 h in the Ar-H), 7.51–7.49 (t, 1H, Ar-H), 7.21–7.19 (t, 1H, Ar-H),
ice-salt bath. The pH of the reaction mixture was maintained 7.17–7.13 (d, 1H, Ar-H), 2.72–2.65 (d, 4H, ­CH2), 1.84 (s,
at 5–6 by adding the required volume of saturated sodium 4H, ­CH2). Anal. Calcd. For C
­ 16H13N3O3S3: C, 58.70; H,
bicarbonate solution. The obtained product was collected 4.00; N, 12.84. Found: C, 58.43; H, 5.62; N, 12.67. MS:
by filtration, washed with cold water and finally, the product m/z 328 (M+1)+.
was dried. The pure compounds (T1–T3) were obtained by
recrystallizing in ethanol [31]. The schematic representation
of the synthesis of azo dyes was depicted in Scheme 1. 2.2.3 Synthesis of 5‑[4,5,6,7‑Tetrahydro‑1,3‑benzothia‑
zol‑2‑yldiazenyl]‑2 thioxodihydropyrimidine 4,6(1H,
2.2.1 Synthesis of 4‑[3a, 4 5,6,7,7a‑hexahydro‑1,3‑benzo‑ 5H)‑dione (T3)
thiazol‑2‑yldiazenyl]‑5‑methyl‑2‑phenyl‑2, 4‑dihy‑
dro‑3H‑pyrazol‑3‑one (T1) Dark red solid, 75%, m.p. 192–4 °C, IR (KBr, ­cm−1): 3043
(NH), 2940 (Ar-H), 1683 (C=O), 1480 (N=N), 1149, 852
Orange-red solid, yield: 72%, m.p. 193–5 °C, IR (KBr, (C=S). 1H NMR (DMSO-d6, ppm): 12.59 (s, 2H, NH), 2.7
­c m −1): 3065, 1801 (C=N), 2938 (Ar-H), 1661 (C=O), (s, 2H, ­CH2), 2.60 (s, 2H, ­CH2), 1.79 (s, 5H, ­CH2). Anal.
1495 (N=N), 1158, 838 (C=S). 1 H NMR (DMSO- Calcd. For ­C 11H11N5O2S2: C, 42.71; H, 3.58; N, 22.64.
d 6, ppm): 7.92–7.91 (d, 2H, Ar-H), 7.43–7.39 (t, 2H, Found: C, 42.68; H, 3.43; N, 22.13. MS: m/z 310 (M+1)+.

Scheme 1  Synthesis of azo dyes (T1–T3)

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9 Page 4 of 17 Journal of Bio- and Tribo-Corrosion (2020) 6:9

2.3 Corrosion Inhibition Measurements phase using parametric method 3 (PM3) by the Hyper Chem
7.5 package program.
The inhibition effect of synthesized azo dyes (T1–T3) on
the corrosion of mild steel in 1 M HCl solution was studied 2.4 Investigation of surface morphology
by both experimental and theoretical methods. The work-
ing electrode (mild steel strip), the counter electrode (plat- The mild steel samples were used for the surface analysis
inum) and a reference electrode (SCE) were used for the and immersed in 1 M HCl solution in the absence and pres-
measurements. The mild steel strip (working electrode) was ence of inhibitors (T1–T3) for 4 h. After 4 h of immersion,
mechanically cut into 1 cm × 1 cm × 1 cm dimensions with the samples were washed with distilled water and dried.
an exposed area of 1 cm2 and the rest of the area was coated Then the samples were studied for their surface morphology
with Araldite resin. Before performing the electrochemical with the help of scanning electron microscopy (SEM). The
measurements, the mild steel strip was abraded by different elemental composition on the surface of the samples was
grade emery papers from 100 to 2000, finally washed with evaluated by energy-dispersive X-ray (EDX) spectroscopy
acetone and dried. The commercially available mild steel (GEMINI, Ultra 55).
strips (composition in %: C = 0.16, Mn = 0.35, Si = 0.016, The entire experimental program was shown in the form
P = 0.01, S = 0.029, Cr = 0.06, Cu = 0.1 and the remaining is of flowchart as depicted in Fig. 1.
Fe) were used for all the experimental methods [32–34]. The
various concentrations of inhibitor solutions were prepared
in 1 M HCl solution. 3 Results and Discussion
The experimental methods such as potentiodynamic
polarization and electrochemical impedance spectros- The present work mainly focuses on the design of novel
copy were carried out by an electrochemical work station heterocyclic azo dyes by conventional diazo-coupling reac-
CHI608D with the three-electrode system at 303 K. Before tion of 4,5,6,7-tetrahydro-1,3-benzothiazol-2-amine (2) with
the start of each electrochemical measurement, the working three coupling components such as 5-methyl-2-phenyl-2,
electrode was allowed to stand for about 30 min to establish 4-dihydro-3H-pyrazol-3-one (a), 4-hydroxy-2H-chromen-
the open circuit potential (OCP). In the potentiodynamic 2-one (b) and 2-thioxodihydropyrimidine-4,6(1H, 5H)-dione
polarization measurement, the potential/current curves were (c) at 0–5 °C and to measure the corrosion inhibition effi-
recorded at a scan rate of 0.001 Vs−1 with respect to OCP. ciency on mild steel in 1 M HCl solution by experimental
Impedance measurements were recorded with an AC signal and theoretical methods. All the newly synthesized azo dyes
at an amplitude of 5 mV at OCP in the given frequency were characterized by various analytical and spectroscopic
range from 100 kHz to 10 mHz. The quantum chemical techniques. The physical and analytical data of the azo
calculation of the inhibitors was performed in the gaseous dyes are presented in Table 1. The structures of the newly

Fig. 1  Flow chart for the syn-

Synthesis, Characterization and anticorrosion behavior of mono azo dyes derived from
thesis, structural characteriza-
4, 5, 6, 7-tetrahydro-1, 3-benzothiazole
tion and anti-corrosion behavior
of azo dyes (T1–T3)

Electrochemical Tafel’s
Polarization Measurement
Corrosion inhibition
experiments

Synthesis of mono azo dyes by the Electrochemical Impedance

simple diazo-coupling reaction in Spectroscopic (EIS) Measurement
the acid medium at 0-5 oC
Quantum Studies

Characterization Surface morphological studies

(SEM and EDX)

Electronic FT-IR NMR LC-MS

spectra spectra spectra spectra

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Table 1  Physical and analytical data of the synthesized azo dyes (T1–T3)
Compounds Mol. formula Mol. (wt) M. P. (oC) Color Elemental analysis (%) calc (found)
C H N

T1 C17H17N5OS 339.41 193–5 Orange-red 60.16 (59.96) 5.50 (5.46) 20.63 (20.25)
T2 C16H13N3O3S3 327.35 196–8 Brick red 58.70 (58.43) 4.00 (5.62) 12.84 (12.67)
T3 C11H11N5O2S2 309.36 192–4 Dark red 42.71 (42.68) 3.58 (3.43) 22.64 (22.13)

synthesized azo dyes were found to be in good agreement at m/z 340, 328 and 310 respectively. From the above spec-
with the spectral data. tral studies, it is noted that the obtained spectroscopic results
The presence of a typical carbonyl functional group in are in accordance with the proposed chemical structures of
all the synthesized azo dyes (T1–T3) was confirmed by the synthesized azo dyes.
the infrared spectra are displayed at the 1661–1683 cm−1
region. The spectra showed the existence of azo (–N=N–) 3.1 Electronic Absorption Spectra and Substituent
group at 1465–1495 cm−1 in all the dyes [35]. The aro- Effect
matic CH stretching vibrations and C=S groups in all the
compounds appeared in the region 2932–2940 cm −1 and Generally, the polarity of the solvent molecules and the elec-
1149–1180 cm−1, respectively. The absorption band of the tronic substituents present on the diazo components influ-
OH group in compound T2 appeared at 3434 cm−1 region. ence the values of the absorption maxima (λmax). Therefore,
In the 1H NMR spectra of dyes (T1–T3) recorded in in order to measure the effect of solvent polarity on the elec-
DMSO-d6 displayed signals of the respective protons based tronic spectra of the azo dyes, we recorded their absorption
on their chemical shifts and multiplicities. In the 1H NMR spectra (Figs. 2, 3, and 4) in four different solvents (Ethanol,
spectra of T1 and T2, the aromatic protons have resonated in tetrahydro furan, N,N-dimethyl formamide, and dimethyl
the region 7.92–7.18 and 7.97–7.13 ppm respectively. In the sulphoxide) in the range 200–800 nm at ~ 10−6 M concentra-
spectra of all azo dyes (T1–T3), the protons appeared in the tion and the results obtained are presented in Table 2. Form
region 2.70–1.79 ppm corresponds to the aliphatic protons the electronic spectral results it is evident that, the absorp-
of the tetrahydro benzothiazole moiety. Furthermore, the two tion spectra of the azo dyes (T1–T3) in different solvents
NH protons of the thiobarbitone ring in the compound T3 exhibited absorption maxima in the region 365–442 nm due
appeared as a singlet at 12.59 ppm. to π → π*or n → π* transition of the azo group. From Table 2,
The ESI-mass spectra of azo dyes (T1–T3) have been it is observed that, as the polarity of the solvent molecules
recorded for their mass spectral studies and their tentative increases (Ethanol > THF > DMF > DMSO), the value of
mass spectral fragmentation is given in Schemes 2, 3 and λmax also increases indicating a bathochromic shift in all the
4. The mass spectra of the azo dyes showed molecular ion studied azo compounds. For example, in the case of etha-
peaks equivalent to their molecular mass along with other nol, the observed values of λmax for the compounds (T1–T3)
fragment peaks. The mass spectra of synthesized azo dyes are in the range of 364–366 nm. In the case of THF, DMF,
T1, T2 and T3 exhibited their molecular ion peaks recorded and DMSO the wavelengths of absorptions of compounds

Scheme 2  Tentative mass spectral fragmentation of the azo dye T1

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Scheme 3  Tentative mass spectral fragmentation of the azo dye T2

Scheme 4  Tentative mass spectral fragmentation of the azo dye T3

(T1–T3) appeared in the range of 367–378, 384–394, and extended conjugation via increased polarity [36]. The dif-
439–442 nm, respectively. Therefore, from our studies, it ference in the value of λmax for the studied azo dyes can be
is inferred that the polarity of the solvents will play a cru- attributed to the electron releasing and withdrawing proper-
cial role in the interpretation of the electronic spectra of the ties of the substituents present on the conjugated system.
studied azo dyes. Particularly, in more polar solvents the By the close observation of Table 2, the introduction of
λmax significantly shifted towards longer wavelengths. This electron-donating –H, –CH3 and –C6H5 groups in the ben-
observed bathochromic shift of molecules can be attributed zene ring resulted in a bathochromic shift in all the solvents.
to the interaction of solvent molecules with the lone pair of Electron withdrawing substituents caused hypsochromic
electrons on the nitrogen atom of the azo group that causes shift when there is a change of polar to non-polar solvents

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Journal of Bio- and Tribo-Corrosion (2020) 6:9 Page 7 of 17 9

Fig. 2  Electronic spectrum of compound T1 Fig. 4  Electronic spectrum of the compound T3

i.e., shifts in the absorption maxima towards longer wave-

length was observed.

3.2 Corrosion Inhibition Studies

3.2.1 Polarization Measurement

The polarization curves for mild steel in 1 M HCl are given

in Fig. 5. Form polarization curves, the electrochemical
parameters such as corrosion potential (Ecorr) and corrosion
current density (icorr) values were calculated by the Tafel plot
analysis. Cathodic and anodic Tafel slopes (βc and βa) are
calculated by the extrapolation of the linear part of the Tafel
lines. Table 3 consists of computed corrosion parameters by
polarization measurement [38]. The inhibition efficiency of
the inhibitors was calculated by the following expression,

i0Corr − iCorr
𝜂P = × 100. (1)
Fig. 3  Electronic spectrum of compound T2 i0Corr

By the close observation of results obtained by the Tafel

[37]. In the present case, the presence of methyl and phenyl polarization method (Table 3), the corrosion current density
groups in the compound T1 showed a stronger bathochromic and rate of corrosion mild steel gradually decreases with
shift nearly in all solvents than T2 and T3. This is a result of the increasing of inhibitors concentration because of which
the effective interaction of the solvent molecules with the are gets adsorbed on the surface of mild steel. Therefore,
compounds demonstrate that different substituents on the the inhibition efficiency (ηp) increases with the increase of
benzene ring significantly change the extent of conjugation inhibitor concentrations.
in the molecules. From the above discussion, it is concluded The corrosion potential (E corr) of the inhibited solu-
that both the polarity of the solvent and electronic effects are tion with respect to the uninhibited solution is less than
the two major factors that will directly influence the posi- 80 mV. This result is an indication of the inhibitor acts
tion of the absorption maxima in the electronic spectra of as mixed type (both anodic and cathodic), because of the
the organic molecules. Therefore, an increase in the solvent displacement in Ecorr is less than ± 85 mV, the inhibitor is
polarity and enhancement of electron density on the diazo considered as mixed type. The cathodic Tafel slope (β c),
component will significantly produce a bathochromic effect changes with a minor extent with the increase of inhibitor

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Table 2  Electronic spectral Compounds λmax (nm) logε

data of the azo dyes T1-T3 in
different solvents Ethanol THF DMF DMSO Ethanol THF DMF DMSO

T1 366 378 389 442 5.91 5.79 5.95 5.53

T2 364 368 384 439 5.85 6.04 5.57 5.83
T3 365 367 394 441 5.92 5.79 5.97 5.55

Fig. 5  Tafel plots for the mild steel in the presence and absence of various concentrations of azo dyes (T1–T3) in 1 M HCl at 303 K

concentration is an indication of the hydrogen evolution strongly on mild steel surfaces than that of the adsorption
(reduction) was controlled by the surface coverage by the of the other two inhibitors (T1 and T2).
inhibitor. The corrosion rate of the inhibitor gradually
increases with the increasing concentrations of inhibi- 3.2.2 Electrochemical Impedance Spectroscopy (EIS)
tors due to the adsorption of inhibitor onto the surface of
mild steel. The change in anodic Tafel slope (βa) may be The corrosion behavior of mild steel in 1 M HCl media
reducing the reduction reaction due to the adsorption of in the absence and presence of the inhibitors (T1–T3) was
inhibitor on the mild steel surface. The inhibitor T1 shows studied by EIS after immersion for 30 min at 303 K. The
the maximum inhibition efficiency of 81.53% for 2.5 ppm typical Nyquist’s and Bode plots obtained for the uninhib-
of the inhibitor from the bulk of the solution than T2 and ited and inhibited acid solution containing synthesized azo
T3. This is attributed due to the inhibitor T1 get adsorbed dyes in various concentrations are presented in Figs. 6 and

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Table 3  Electrochemical Tafel polarization parameters for mild steel in the absence and presence of azo dyes (T1–T3) in 1 M HCl at 303 K
Compounds Inhibitor concn. Ecorr (V) icorr (µA ­cm−2) Corrosion rate βc (mV/dec) βa (mV/dec) Inhibition
(ppm) (mpy) efficiency
(ηp (%))

T1 Blank − 0.112 0.065 47.28 6.592 7.494 –

0.5 − 0.131 0.059 23.92 7.365 7.453 9.23
1.0 − 0.100 0.051 18.50 6.699 9.467 21.53
1.5 − 0.155 0.025 16.42 6.859 9.862 61.53
2.0 − 0.147 0.022 12.45 5.241 6.996 66.15
2.5 − 0.167 0.012 10.12 5.564 7.235 81.53
T2 Blank − 0.112 0.065 48.92 6.592 7.494 –
0.5 − 0.118 0.060 43.38 6.579 7.557 7.69
1.0 − 0.174 0.051 24.84 5.664 7.656 21.53
1.5 − 0.161 0.037 15.46 6.645 9.918 43.07
2.0 − 0.155 0.033 10.07 6.366 8.487 49.23
2.5 − 0.155 0.021 7.42 7.423 9.633 67.69
T3 Blank − 0.112 0.095 47.28 6.592 7.494 –
0.5 − 0.172 0.075 18.70 4.997 6.191 21.05
1.0 − 0.166 0.066 14.73 7.548 8.670 30.52
1.5 − 0.161 0.065 13.08 7.782 8.882 31.57
2.0 − 0.169 0.053 13.60 6.761 7.684 44.21
2.5 − 0.176 0.041 8.062 7.085 9.846 56.84

Fig. 6  Nyquist plots for the corrosion of mild steel in the absence and presence of different concentrations of azo dyes (T1–T3) in 1 M HCl at
303 K

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7, respectively. The electrical layer developed on the steel

surface can be shown by the electrical equivalent circuit
diagrams to model the metal/solution interface. The model
used for the fitting of the EIS results is shown in Fig. 8. EIS
parameters such as charge transfer resistance which is equal
to polarization resistance (RP), double-layer capacitance
(Cdl), surface coverage and inhibition efficiency are calcu-
lated and reported in Table 4. The Nyquist plots (Fig. 6) con-
sist of semicircles with their centers on the real axis. These
are described as polarization resistance (RP). The RP value Fig. 8  Equivalent circuit used to fit the EIS results
increases with the increase in the inhibitor concentrations.
These semicircles are not perfect, and there is a frequency
dispersion effect due to the roughness and inhomogeneity greatly with increasing the inhibitor concentration. It can
nature of the working electrode (mild steel). The increase be obtained from Bode phase plots that the corrosion pro-
in RP value is an indication of the corrosion inhibition of cess taking place at the electrode surface has two relaxa-
mild steel due to the formation of the protective layer by the tion time constants. One is related to the relaxation of an
adsorption of inhibitor molecules onto the surface of the electrical double layer capacitor, and the other is associated
mild steel. The decrease in the Cdl values (Table 3) with the with the relaxation process of the adsorbed inhibitor. It is
addition of inhibitor is attributed due to the increase in the also observed that increasing the concentration of inhibitor
electric double layer on the metal surface [39]. The inhibi- results in an increase in the maximum phase angle, which
tion efficiency of the compound T1 shows maximum due to indicates inhibition of the corrosion process [40]. The inhib-
the strong adsorption onto the mild steel surface. itor T1 shows the highest phase angle around 80° for 2.5 ppm
The Bode plots as depicted in Fig. 7 show that the imped- of the inhibitor from the bulk of the solution than T2 and
ance values over the whole frequency range increased T3. This is attributed due to the inhibitor T1 get adsorbed

Fig. 7  Bode plots for the corrosion of mild steel in the absence and presence of different concentrations of azo dyes (T1–T3) in 1 M HCl at
303 K

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Journal of Bio- and Tribo-Corrosion (2020) 6:9 Page 11 of 17 9

Table 4  Electrochemical Compounds Inhibitor concn. Polarization resistance Double-layer capacitance Inhibition
impedance spectroscopic (ppm) RP (Ω cm2) Cdl (µF cm−2) efficiency
parameters for the corrosion of (ηz (%))
mild steel in the absence and
presence of azo dyes (T1–T3) in T1 Blank 30.63 289.1 –
1 M HCl at 303 K
0.5 36.19 40.51 15.36
1.0 45.91 34.55 31.71
1.5 52.65 26.25 41.82
2.0 142.52 25.67 78.50
2.5 189.21 23.37 83.81
T2 Blank 30.63 249.1 –
0.5 76.60 244.2 60.01
1.0 81.46 134.4 62.40
1.5 122.56 66.27 75.00
2.0 147.72 51.98 79.26
2.5 154.78 50.42 80.21
T3 Blank 28.53 289.1 –
0.5 30.90 183.3 7.67
1.0 86.42 136.5 66.70
1.5 92.55 107.9 69.17
2.0 123.45 49.59 76.88
2.5 132.93 53.20 78.53

strongly on mild steel surfaces than that of the adsorption the molecule will be less reactive, kinetically stable and
of the other two inhibitors (T2 and T3). less polarization. This indicates that the molecule has less
electron density and become less reactive towards chemi-
3.2.3 Quantum Chemical Measurement cal reactions. Further, the HOMO and LUMO correspond
to ionization potential and electron affinity of a molecule.
Quantum chemical analysis is a powerful tool, which is Overall, the ability of a molecule that means potential-
used to design the structural study of the molecules as ity can be expressed in terms of some parameters such
corrosion inhibitors using the distribution of electron as chemical potential (α), hardness (η) and Electrophilic-
density for different molecular geometries. The highest ity index (ѡ) and these parameters were evaluated from
occupied molecular orbitals (HOMOs) and lowest unoccu- HOMO–LUMO energies obtained from PM3 method and
pied molecular orbitals (LUMOs) are the orbitals together their mathematical expressions were represented below,
referred as frontier molecular orbitals (FMOs) will play
an important role in determining the electronic density on
Energy gap (ΔE) = EHOMO − ELUMO , (2)
the molecule and to compare most of the physical proper-
ties with the energy difference between these HOMO and Electronegativity (𝜒) =
(I + A)
, (3)
LUMO. They are also referred to as electron donor and 2
acceptors respectively. The difference in energy between
the HOMO and LUMO will play an important role in (I + A)
Chemical potential (𝛼) = − , (4)
obtaining the various parameters like chemical reactivity, 2
kinetic stability, polarizability, dipole moment, and opti-
cal properties of the molecules. The energy gap between (I − A)
HOMO and LUMO is small indicating the energy required
Hardness (𝜂) = , (5)
2
to promote an electron from HOMO to LUMO is less, then
the molecule becomes more reactive, having low kinetic 𝛼2
stability and highly polarizable. Therefore, the electron Electrophilicity index (𝜔) = , (6)
2𝜂
density on the whole molecular system will be greatly
increased and thus more reactive towards any molecular where I and A are electron affinity and ionization potential
reactions. If the energy gap is high, the promotion of an and which are given by the expressions,
electron from HOMO to LUMO is difficult and therefore

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9 Page 12 of 17 Journal of Bio- and Tribo-Corrosion (2020) 6:9

Table 5  Calculated quantum chemical parameters for the azo dyes

Electron affinity (I) = −ELUMO , (7) (T1–T3) by PM3 method
Electronic parameters T1 T2 T3
Ionization potential (A) = −EHOMO . (8)
EHOMO (eV) − 8.78 − 9.07 − 9.33
The optimized molecular structures of the inhibitors ELUMO (eV) − 1.26 − 1.45 − 1.33
(T1–T3) are as shown in Fig. 9 and Table 5 is the computed EHOMO–ELUMO (eV) 7.53 7.62 8.00
quantum chemical parameters for the inhibitor molecules. Electronegativity (χ) 5.02 5.26 5.33
The structures of HOMO and LUMO are presented in Chemical potential (α) − 5.02 − 5.26 − 5.33
Figs. 10, 11 respectively. Hardness (η) 3.76 3.81 4.00
Inhibitor molecules are adsorbed on the metal surface by Electrophilicity index (ѡ) 3.35 3.63 3.55
the donor–acceptor interactions between inhibitor molecules Ionization potential (A) 8.78 9.07 9.33
and metal surface. EHOMO relates the electron-donating abil- Electron affinity (I) 1.26 1.45 1.33
ity of the inhibitor and higher values of EHOMO indicate high Dipole moment (µ) D 6.23 3.14 3.14
tendencies of inhibitor molecules to donate electrons to the
acceptor molecules. ELUMO relates the ability of a metal/mol-
ecule to accept electrons and the lower value of ELUMO indi-
cates the easier acceptance of electrons from the metal sur- decreased with an increase in ΔE values. The inhibitor T1
face [41]. The molecules with lower ΔE values give higher shows maximum inhibition efficiency due to a higher ΔE
inhibition efficiencies because the excitation energy gap is value of 8.0 eV. Dipole moment (μ) is another important
more polarizable and is generally associated with chemical parameter to decide the adsorption inhibitor molecule on
reactivity [42]. Lower ΔE values aid an electron transfer the mild steel surface. Higher dipole moment increases
process between inhibitor molecules and mild steel surface. the adsorption of inhibitors on the mild steel surface and
The calculated ΔE values for the inhibitors are justify- increases the inhibition efficiency. The calculated dipole
ing the results. The inhibition efficiency of these inhibitors moment (μ) of T1 is 6.23 D. The quantum studies concluded
decreased with an increase in ΔE values. Zhang et al. studied that comparatively T1 is the better corrosion inhibitor than
the corrosion inhibition performance of imidazoline phos- T2 and T3.
phate and they found ΔE value of 8.838 eV with inhibition
efficiency of 95% [43]. Nataraj et al. studied few organic 3.2.4 SEM and EDX Analysis
compounds and they found ΔE values of 8.13 eV 6.56 eV,
5.47 eV for HYD, TAD, TRD respectively [44]. Gener- To understand the type of interaction between the metal
ally, in the previous studies, corrosion inhibition efficiency surface and the deposited organic inhibitor, the tested steel
samples were examined by SEM and EDX techniques and

Fig. 9  Optimized molecular structures of azo dyes (T1–T3)

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Journal of Bio- and Tribo-Corrosion (2020) 6:9 Page 13 of 17 9

Fig. 10  Structures of HOMO energy states of azo dyes (T1–T3)

Fig. 11  Structures of LUMO energy states of azo dyes (T1–T3)

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9 Page 14 of 17 Journal of Bio- and Tribo-Corrosion (2020) 6:9

the surface morphology was analyzed in the absence and without inhibitors in 1 M HCl solution. The results of the
presence of inhibitors (T1–T3) at ambient temperature. The EDX analysis were obtained in terms of Weight (wt%)
SEM images of the mild steel with and without the presence and Atomic (at.%) percentages of elements obtained from
of inhibitors were recorded and are depicted in Fig. 12. From steel samples in the absence and presence of inhibitors
the analysis of SEM images of the steel sample in 1 M HCl (T 1–T 3) are shown in Table 6. The analysis of Table 6
solution (as shown in Fig. 12 Blank) in the absence of inhibi- indicated that, the peak corresponding to the oxygen atom
tors exhibited rough surface and damaged due to the corro- in the presence of inhibitors was gradually decreased as
sion by aggressive media. In the same Fig. 12 the images T1, compared to the steel samples without inhibitors. This sug-
T2 and T3 are showing smooth surface due to the deposition gests that, the inhibitors on the steel samples will not allow
of the inhibitors on to the steel surface and protect it by cor- forming the iron oxide on the metal surface while the per-
rosion. This effective deposition of the inhibitors on to the centage of O on the steel without inhibitors (Blank) is
metal surface often explained by the interaction between more. So, the EDX analysis will reveal the effective coat-
the iron and the electron-rich species in the azo molecules. ings on the metal surface in turn suggesting the enhanced
These groups block the metal sites against corrosion and inhibition efficiency as the azo dye molecule adsorb on to
helpful in protecting the surface of the metal by metal dis- the metal surface. Finally, it is the presence of inhibitors
solution caused by the acid solution [45]. that protects the surface from the aggressive or acid solu-
The energy-dispersive X-ray analysis (EDX) was car- tions, as also indicated by the SEM images. These two
ried out to evaluate the elemental composition of the morphological evaluations signify the effective adsorp-
coated inhibitors on to the metal surface. The spectra were tion of inhibitor molecules on the steel surface forming a
recorded after 2 h immersion of the steel samples with and protective film [46–48].

Fig. 12  The SEM images of the steel samples recorded in 1 M HCl with and without inhibitors (T1–T3) at room temperature

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Journal of Bio- and Tribo-Corrosion (2020) 6:9 Page 15 of 17 9

Table 6  The results of the EDX Element Blank T1 T2 T3

spectral analysis in terms of
weight (wt) and atomic (at.) wt% at.% wt% at.% wt% at.% wt% at.%
percentages of elements of steel
samples in 1 M HCl with and Fe 53.26 23.71 57.45 27.19 60.92 30.17 61.60 30.96
without inhibitors (T1–T3) at C 6.52 13.50 4.05 8.92 3.55 8.18 2.45 5.72
room temperature O 38.01 59.07 36.16 59.75 33.76 58.37 33.81 59.32
N 2.01 3.56 2.08 3.93 1.58 3.12 1.88 3.78
S 0.20 0.16 0.26 0.21 0.19 0.17 0.25 0.22

4 Conclusion at room temperature. The recent developments showed that

some of the organic compounds can also be more effective
The present work describes the synthesis of four novel dis- in controlling the corrosion at elevated temperatures. So that
perse azo dyes derived from 4,5,6,7-tetrahydro-1,3-benzo- our future aim is to design the compounds to act as efficient,
thiazole and their corrosion inhibition behavior over the mild eco-friendly corrosion inhibitors for metals and alloys to
steel in 1 M HCl solution. From overall observations, the protect form the aggressive media at higher temperatures.
following conclusions were made.
Acknowledgement Authors are thankful to the Department of chemis-
try, Kuvempu University, Shimoga and Srinivas School of Engineering,
• The chemical structures of the newly synthesized azo Mukka, Mangalore for providing laboratory and instrumental facility,
dyes (T1–T3) derived from 4,5,6,7-tetrahydro-1,3-ben- respectively. Authors are also grateful to SAIF and CIL Panjab Uni-
zothiazole were elucidated by various physico-chemical versity, Chandigarh for providing spectral data.
techniques.
• All the studied azo compounds showed efficient cor- Compliance with Ethical Standards
rosion inhibition properties in 1 M HCl solution. The
inhibition efficiency was increased with the increase of Conflict of interest On behalf of all authors, the corresponding author
states that there is no conflict of interest.
inhibitor concentration.
• From the polarization measurements, it is concluded that
the azo dyes are behaving as a mixed type of inhibitors
affecting both anodic and cathodic corrosion processes. References
• EIS study revealed that polarization resistance increases
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