Inorganic Chemistry Communications 160 (2024) 111911

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Inorganic Chemistry Communications

journal homepage: www.elsevier.com/locate/inoche

Short communication

Optimization of the corrosion inhibition performance of novel oxadiazole

thione-based Schiff base for mild steel in HCl media using Doehlert
experimental design
Zenaa Ibraheem Jasim a, Khalid H. Rashid a, Khalida F. AL-Azawi b, Anees A. Khadom c, *
a
Department of Chemical Engineering, University of Technology, Iraq, Baghdad, Iraq
b
Applied Chemistry Branch, Applied Science Department, University of Technology-Iraq, Baghdad, Iraq
c
Department of Chemical Engineering, College of Engineering, University of Diyala, Daiyla Governorate, Iraq

A R T I C L E I N F O A B S T R A C T

Keywords: This study aimed to evaluate the effectiveness of 3-((dicyclohexylamino) methyl)-5-(4-((3, 4-dimethoxybenzyli­
Mild-steel dene) amino) phenyl)-1, 3, 4-oxadiazole-2(3H)-thione (DMOT) in inhibiting the deterioration of mild steel in a 1
Corrosion M HCl solution. Weight loss and electrochemical measurements were used to assess the inhibition performance
Inhibitor
and synthesis of DMOT. The characterization of DMOT was conducted through NMR and FTIR measurements,
Synthesis
while SEM and AFM were used in the surface analysis. DFT calculations were used to investigate the chemical
and theoretical properties of DMOT. The results of electrochemical measurements showed that the inhibition
efficiency increased as the concentration of the inhibitor increased, with an optimal concentration reaching an
inhibition efficiency of 99.17%. Polarization curves revealed that DMOT molecules behaved as a mixed-type
inhibitor, with adsorption following the isotherm of Langmuir. The adsorption of DMOT on the corroded
metal’s surface was verified by SEM and AFM investigations. Using quantum chemical calculations, the quantum
chemical properties of the DMOT were evaluated.

1. Introduction creates a protective layer that effectively prevents corrosion from

occurring [7,8]. Electrostatic attraction facilitates the adsorption of ar­
One of the most important problems now facing industrial companies omatic rings and polar groups (including but not limited to C=O, –NH2,
is metal corrosion. Although one of the most often used building mate­ and –OH) onto metal surfaces [9–14].
rials, mild steel (MS), offers several advantages, including tremendous Nitrogen-containing derivatives have received a lot of attention in
mechanical capabilities and affordability, it is extremely vulnerable to the field of pharmaceutical activity [15–19]. Recently, a new classifi­
corrosive ions [1–3]. Mild and low-carbon steel alloys have a proclivity cation of metal corrosion inhibitors has been discovered by various
to react violently with acids that are among the most corrosive media, studies due to the availability of p-electrons in –C=N double bonds.
transitioning from a metallic to an ionic state and causing economic Heteroatoms such as O and S have been found to offer superior inhibi­
drops. There have been numerous proposed methods for preventing tion performance. These compounds have been extensively studied as a
corrosion, including but not limited to anodic and cathodic protection, means of preventing carbon steel corrosion in acidic conditions. By
anti-corrosion coatings, and corrosion inhibitors. In particular, corro­ incorporating these heteroatoms into organic structures, it is possible to
sion inhibitors have been identified as a promising technique among the design and synthesize new corrosion inhibitors. The use of synthesized
various methods available. The selection of the ideal corrosion inhibitor organic inhibitors is regarded as one of the most effective methods, as
involves taking into account vital factors like adsorption capacity, they exhibit high efficiency even at low concentrations. In general,
environmental impact, and cost-effectiveness [4–6]. particles containing one active heteroatom at least, can adhere to the
Typically, corrosion inhibitors that contain heteroatoms (such as metallic surface [20,21].
oxygen, nitrogen, sulfur, and phosphorus) form bonds with the vacant The research conducted here focuses on the continued exploration of
d orbital of iron using their non-bonding electron pairs. This process high-performance hetero-compounds as effective corrosion inhibitors.

* Corresponding author.
E-mail addresses: draneesabdullah@uodiyala.edu.iq, aneesdr@gmail.com (A.A. Khadom).

https://doi.org/10.1016/j.inoche.2023.111911
Received 20 October 2023; Received in revised form 2 December 2023; Accepted 10 December 2023
Available online 12 December 2023
1387-7003/© 2023 Elsevier B.V. All rights reserved.
Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 1. Schematic forming of intermediate compounds and DMOT.

To achieve this goal, we examined the inhibitive mechanisms of syn­ 2. Experimental work
thesized inhibitors and their potential for novel applications. Specif­
ically, our work aimed to synthesize, characterize, and test the corrosion 2.1. Materials and chemicals
inhibitory effect of DMOT, a newly developed compound, against low-
carbon steel corrosion in 1 M HCl. The research conducted here fo­ To conduct corrosion experiments on mild steel samples, rectangular
cuses on the further exploration of powerful heterogeneous compounds steel pieces measuring 3 cm × 1 cm × 0.1 cm were used. The mild steel
as effective corrosion inhibitors. To achieve this goal, we investigated compositions were comprised of Fe as the main component, with C 0.08
the inhibitory mechanisms of synthetic inhibitors and their potential for %, Mn 0.2 %, Si 0.03%, P 0.01%, Al 0.02%, and Cr 0.05% (weight
new applications. The characterization of this corrosion inhibitor was percent). Prior to submersion in the corrosive solution, the metal sam­
performed using both FTIR and NMR techniques. The experiments ples were thoroughly cleaned using sandpaper ranging from 800 to 1500
concerning weight decrease were carried out and refined using the grit and rinsed with distilled water after each cleaning. Our previous
Doehlert experimental design, which took into account both tempera­ works [4–6] have documented the comprehensive experimental process,
ture and DMOT concentration. Subsequently, in ideal conditions, several including the cleaning stages. A 1 M HCl solution was prepared using
significant tests were conducted including electrochemical and diluted hydrochloric acid (37% wt). To ensure consistency, all mea­
morphological analyses. surements were taken twice.

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 2. FTIR and 1H NMR configuration of DMOT.

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Table 1
Experimental Doehlert design in coded and real factors with absolute percentage error and the response corrosion rates for A285/C mild steel in 1 M HCl in presence
and absence DMOT.
⃒
Trial X1 X2 T ◦C CDMOT ppm Exp. C.R. gmd Predicted C.R. gmd ⃒ P − E⃒
Exp. Error |ε i|[%]=⃒ ⃒
E ⃒
Coded Real

1 0 0 50 75 83.72 83.72 0.00

2 1 0 70 75 92.65 191.09 1.06
3 0.5 0.866 60 150 45.29 53.15 0.17
4 − 0.5 0.866 40 150 28.37 126.81 3.46
5 − 1 0 30 75 12.70 85.75 5.75
6 − 0.5 − 0.866 40 Blank 326.52 424.96 0.30
7 0.5 − 0.866 60 Blank 980.25 881.80 0.10
8 0 0 50 75 83.72 83.72 0.00
9 0 0 50 75 83.72 83.72 0.00

The percentage of average absolute error |ε i | = 1.20 %.

2.2. FTIR, 1HNMR, and UV–vis considerations electrode constructed with mild steel. The working electrode samples
had an exposed area of 1 cm2 and were subjected to corrosive solutions
Spectra were collected using a SPEACTUM-65 (PerkinElmer® FT-IR under specific conditions. To determine the open circuit potential (OCP)
spectrometers) for FTIR analysis of KBr Discs. At ideal circumstances, value, the working electrode was immersed in a 1 M HCl solution for
the FTIR of the synthesised DMOT and the corrosion products resulting approximately 120 min. Polarisation measurements were obtained
from metal surfaces in the presence of DMOT were investigated. UV–vis under ideal circumstances, both with and without DMOT. In this
readings were taken with a UV-spectrophotometer (Shimadzu, Japan, experiment, the scan rate is 1.00 millivolts per second. The cathodic
UV-1800) before and after the samples were immersed for 3 h at the potential range spans from − 250 millivolts to the anodic potential range
ideal heat and concentration of DMOT in 1.0 M HCl. Furthermore, of +250 millivolts in reference to OCP. The electrochemical impedance
DMOT was studied using 1HNMR spectroscopy with BRUKER in­ spectroscopy (EIS) experiments were performed in the frequency range
struments (USA). 100 kHz to 10 mHz using OCP with a sinusoidal alternating potential of
±10 mV. The Vertex-One equipment potentiostat from the Netherlands
2.3. Synthesis of DMOT was utilized to conduct all electrochemical inquiries.

The synthesis process for DMOT involves the creation of four inter­ 2.6. Design of experiment
mediary compounds, which are designated as z1-z3, before the final
product is achieved. DMOT is synthesized using a standard Mannich To build up the most effective conditions for achieving a corrosion
reaction. A schematic path was shown in Fig. 1. The full details of z1 to rate that results in weight loss, a Doehlert experimental design was
z3 synthesis were given in our previous work [22]. However, the syn­ employed, utilizing both DMOT concentration and temperature. The
thesis of novel DMOT was as follow. Begin by dissolving 0.003 mol of Doehlert design focuses on achieving spatial homogeneity throughout
Schiff bases (z3) in 15 mL of absolute ethanol. Gradually add 0.003 mol the experiment, and defines the experimental domain as spherical.
of formaldehyde, followed by 0.003 mol of amines for each type of While the matrix is not rotatable or orthogonal, it maintains the
amine used, while continuously stirring the reaction mixture in an ice necessary characteristics for practical use. The experiment consisted of
bath for one hour. The precipitate is then left in the refrigerator for 24 h five levels of temperature (30, 40, 50, 60, and 70 ◦ C) and three con­
before undergoing filtration and recrystallization using absolute centrations of DMOT (0.0, 75.0, and 150.0 ppm). Although the matrix is
ethanol. To prepare DMOT, combine an equal number of moles of not rotatable or orthonormal, it retains properties needed for practical
Dicyclohexyl amine and Schiff bases (z3). The resulting outcome, use. The conversion of real variables to code variables was accomplished
melting point, color, recovery solvent, and molecular formula of DMOT using the next equations:
were 88%, 129–131 ◦ C, yellow, ethanol, and C30H38N4O3S,
Zj − Zj (0)
respectively. Xj = (1)
ΔZj

2.4. Gravimetrical measurements where Xj means here the coded variable, Zj stands for the real variable,
there for Zj(0) means the center value (50 ◦ C and 75 ppm), and in the
The using of conventional method of weight loss is to calculate same way ΔZj represents the step variation (20 ◦ C and 75 ppm). The
corrosion rates were measured. By losing weight, as is customary, temperature levels were computed as follows: − 1, − 0.866, − 0.5, 0, 0.5,
corrosion rates were calculated. We used the procedures we previously 00.866, and 1. As for the concentration of DMOT, the levels were
outlined [4–6] to clean the samples. After being subjected to the cor­ − 00.866, 0, and 00.866. A second order polynomial model (Eq. (2)) was
rosive solution (composed of 1 M HCl) at the designated conditions, the proposed to express the corrosion rate in relation to both temperature
metal samples were exposed for three hours before being washed and and inhibitor concentration.
dried. The rate of corrosion was measured in grams per square meter per
day (gmd). Assessments of corrosion rate were conducted with and Y = h0 + h1 X1 + h2 X2 + h3 X21 + h4 X22 + h5 X1 X2 (2)
without DMOT. Mild steel corrosion rates were estimated under a Y stands for the corrosion rate and h1, h2, …, h5 are the coefficients of
multitude of conditions as outlined in the practical design. the model.

2.5. Electrochemical measurements 3. Results and discussion

To conduct an electrochemical study, a standard three-electrode cell 3.1. FTIR and 1H NMR studies
was utilized. The cell featured a reference electrode composed of
calomel, a counter electrode made of platinum wire, and a working IR taken in KBr, vmax cm− 1; 3421.83 (NH), 2935.76 (CH2), 3100.91

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

(Aromatic stretching), 1269.2 and 1060.88 (Amines) [23-26]. The 3.2. Weight loss outcomes
1
HNMR (δ ppm) spectrum of a DMOT δ equals to 8.9058 ppm (s,1H,
–CH=N) belongs to a proton azomethine, δ = 6.62–7.81 ppm (m, 7H, Ar) The measurement of weight loss is widely employed as the primary
returns to the protons of the Aromaticity ring, δ = 3.85 ppm means of evaluating the effectiveness of corrosion inhibition. This
(s,6H,2CH3O–) it corresponds to protons of the dimethoxy groups, δ method is valued for its straightforwardness and reliability in deter­
equals to 3.45 ppm (s, 2H, CH2-N) it corresponds to protons of the CH2, δ mining both corrosion rate and the efficiency of corrosion inhibition.
= 1.07–1.99 ppm (m,22H, cyclohexyl) it corresponds to protons of the Measurement of weight loss is often used as the primary means of
cyclohexyl [27]. Fig. 2 exposes FTIR and 1H NMR for DMOT. assessing corrosion control effectiveness. The method is valued for its
simplicity and reliability in determining corrosion rates and corrosion

Fig. 3. Statistical analysis of experimental and predicated corrosion rate as a function of temperature and inhibitor concentration. (a) Experimental corrosion rate
versus predicted corrosion rate for DMOT. (b) Horizontal multiple bar column diagram for DMOT inhibitor. (c) Surface plot temperature and DMOT concentration
versus corrosion rate (d) Contour plot temperature and DMOT concentration versus corrosion rate.

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 3. (continued).

control effectiveness. By analyzing the data obtained from weight loss rate was determined to be 1.7150 gmd at a heat of 46.6470 ◦ C and an
measurements, the corrosion rate can be determined using Eq. (3) [28]: inhibitor concentration of 110.03 ppm (− 00.175 and 00.406 for coded
values of temperature and inhibitor concentration, respectively). The
ΔW
CR = (3) statistical outcomes of the model are presented in Fig. 3. Fig. 3A pro­
A.t
vides a visual comparison between the experimental and predicted
ΔW states the weight difference measured in grams (g), A stands for corrosion rates. The impact of the model coefficients is depicted in
the sample surface area in square meters (m2), and t stands for the time Fig. 3B. Notably, effects of inhibitor concentration and the interaction
measured in (days). The matrix of Doehlert design and corrosion rate between temperature and inhibitor concentration had a more influence
data were gathered in Table 1. than the individual effect of heat. In other words, Fig. 3A, there is a
To formulate the polynomial model of second-order, the real vari­ visual representation of the corrosion rates, comparing the experimental
ables (Eq. (4)) and the coded variables (Eq. (5)) were employed. The and predicted values. While Fig. 3B illustrates the impact of the model
regression process, utilizing STATISTICA 10 software, relied on the coefficients, highlighting the significant influence of inhibitor concen­
Quasi-Newton and Rosenbrock approximation methods. The resulting tration and the interaction between temperature and inhibitor concen­
correlation coefficient (R2) values were 0.98 for Eq. (4) and 0.97 for Eq. tration, which outweighed the individual effect of heat. Fig. 3C and 3D
(5), respectively. show the three-dimensional surface and contour plots, respectively,
which illustrate the variation in corrosion rate across different temper­
PC.R.(W.L) = − 674.99 + 30.604 T − 0.674 CDMOT − 0.078 T2 + 0.048 C2DMOT
ature and inhibitor concentration ranges. These plots represent the
− 0.212 TCDMOT
upper, middle, and lower portions of the corrosion rate.
(4)

Y = 83.72 + 138.43 X1 − 355.98 X2 − 31.05 X21 + 358.89 X22 − 367.67 X1 X2 3.3. Reaction kinetics and adsorption isotherms
(5)
As mentioned above, Eq. (4) with 1.2% absolute error and 0.98
where T represents temperature measured using (◦ C), CDMOT stands for correlation coefficient can be used as a powerful tool for forecasting the
the inhibitor concentration of 3-((dicyclohexylamino) methyl)-5-(4-((3, corrosion rate values as a function of temperatures (30, 40, 50, 60, and
4-dimethoxybenzylidene) imino) phenyl)-1, 3, 4-oxadiazole-2(3H)-thi­ 70 ◦ C) and DMOT concentrations (0, 25, 50, 75, 100, 125, and 150
one (ppm), and PC.R.(W.L) represents the predicted decrease in weight ppm). The data presented in Fig. 4A illustrates the relationship between
corrosion rate measured in (g/m2. day). The predicted rates of corrosion corrosion rate and temperature, as well as inhibitor concentration, as
closely aligned with the experimental results, with an average absolute predicted by Eq. (4). The findings appear to be logical, as the corrosion
error of 1.2%. By optimizing Eqs. (4) and (5), the minimum corrosion rate increased with higher temperatures, but decreased with an increase

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 4. Corrosion rate changes depending on temperature and inhibitor concentration.

in DMOT concentration. Additionally, as depicted in Fig. 4B, the effi­ elevated temperatures. Understanding the inhibition mechanism re­
ciency of inhibition increased with higher concentrations of the inhibi­ quires a thorough examination of reaction kinetics and adsorption
tor. According to the information provided in Fig. 4A, there seems to be isotherms.
a correlation between corrosion rate and temperature, as well as the Table 1 shows the starting and thermodynamic parameters for DMOT
concentration of the inhibitor, as projected by Eq. (4). The results of this adsorption on the steel surface. The estimation of these parameters was
analysis appear to align with expectations, as the corrosion rate carried out through the utilization of the equations outlined below.
demonstrated an upward trend with rising temperatures, but showed a ( )
Ea
decline with an increase in DMOT concentration. However, it was CR = Aexp − (6)
RT
observed that the inhibition efficiency reached its maximum value of
95.96% when we have 150 ppm DMOT concentration and 50 ◦ C, after ( ) ( ) ( )
RT ΔSa ΔHa
which it started to decline. This could be in relation to the chemisorption CR = exp exp − (7)
Nh R RT
of the inhibitor on the metal surface. Moreover, when the temperature
was further increased to 60 and 70 ◦ C, a decrease in inhibitor efficiency In Arrhenius equation (Eq. (6)), A represents frequency factor and Ea
was observed, potentially due to the desorption of inhibitor molecules at stands for the activation energy, on another side in the transition state

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

enthalpy values. The measurements of A (frequency factor) in the con­

dition of DMOT were less than in the absence of DMOT, which is ad­
vantageous for the steel corrosion processes. The DMOT-acid solution
has a high negative ΔSa value, indicating that the activated complex is
more likely to be in an associative phase rather than a dissociative phase
when transitioning from the reactant to the activated complex [30].
In order to gain a deeper understanding of the adsorption of DMOT
on the surface of steel, the first stage data was analyzed using Langmuir
adsorption isotherms (Eq. (8)). This approach was taken to identify the
most suitable isotherms that accurately depict the behavior of the
corrosion inhibition process.
C 1
= +C (8)
θ K
C stands for the inhibitor concentration, K represents the adsorption
constant, and θ means the surface coverage. Fig. 6 illustrates the plot for
Eq. (8), while the corresponding results are recorded in Table3. The
exceptional linearity and successful fitting of the data confirm the
adherence to the Langmuir adsorption isotherm. This is further evident
in the near unity of both the slope and correlation coefficients, as indi­
cated in Table 3.
The measurement of the strength of the bonding forces between in­
hibitor molecules and the surface of the metal can be carried out by
utilizing K values [31]. According to Eq. (9), the value of K is directly
connected to the adsorption free energy standard (ΔGads). [32]:
( )
1 ΔGads
K= − exp − (9)
55.5 RT

R is the universal gas constant, T is the thermodynamic temperature and

the value of 55.55 is the concentration of water in the solution in mol/l.
The stability and spontaneity of the adsorption process are indicated
by the average value of ΔGads, which was found to be − 31.6192 kJ/mol.
Negative values were observed, suggesting a chemical adsorption pro­
cess. This was supported by the fact that the ΔGads values were greater
than − 20 kJ.mol− 1 [28]. To estimate the enthalpy of adsorption (ΔHads)
and entropy of adsorption (ΔSads), the Van’t Hoff equation (Eq. (10) and
Eq. (11)) were employed [33]. These equations are depicted in Fig. 7.
Fig. 5. Activation representation of corrosion rate of low-carbon steel in 1 M
HCl in absence and presence of DMOT (A) Arrhenius plots (B) Transition ΔHads
lnK = − + const (10)
state plots. RT

ΔGads = ΔHads − TΔSads (11)

Table 2 According to Table 3 the results of this study challenge the conven­
Corrosion kinetic parameters for mild steel in 1 M HCl solution at DMOT
tional ideas regarding adsorption phenomena. It has been widely
different concentrations.
accepted that adsorption is a process that releases heat, with a negative
CDMOT (ppm) A (gmd) Eact (J/mol) ΔHact (J/mol) ΔSact (J/mol. K) value for adsorption heat and a reduction in the entropy of adsorption
Blank 1.5 × 103 52.129 37.295 − 195.61 [34]. In aqueous solutions, the adsorption of organic molecules results in
25 2.9 × 102 50.981 33.221 − 208.99 the desorption of water molecules. During the replenishment process of
50 1.7 × 102 43.756 25.731 213.81
−
adsorption of organic molecules at the metal-solution interface, each
75 1.1× 102 38.268 19.870 − 217.64
100 6.2 × 101 33.584 13.331 –222.55
DMOT molecule repels a water molecule. The adsorption of DMOT
125 3.7 × 101 28.762 7.659 − 226.74 molecules and the desorption of water molecules together led to the
150 2.2 × 101 23.238 5.158 − 229.51 production of Sads. The increase in solvent entropy can be used to explain
the increase in entropy observed [35].

equation (Eq. (7)), ΔHa states the enthalpy of activation, ΔSa represents
3.4. Electrochemical investigations
the entropy of activation, Plank’s constant is h, and Avogadro’s number
is N. Fig. 5 shows the linearization of these equations. The information in
Electrochemical experiments were carried out to verify the results of
Table 2 was derived using the slopes and intercepts of Eqs. (6) and (7).
the gravimetrical studies. As shown in Fig. 8, optimal circumstances
Enthalpy and activation energy oscillate similarly, as is easily seen. The
were used to assess a potentiodynamic polarisation (PDP) and an open
variance between the activation energy and the enthalpy in the acidic
circuit potential (OCP). When DMOT had been added to the inhibitor ’s
solution, both in the presence and absence of the inhibitor, appears
OCP in Fig. 8A changed toward positive potential, indicating a diversion
illogical. This unusual outcome could be attributed to the inhibitor
into the noble area. In contrast to the absence of the inhibitor, the OCP
particles covering more metal surfaces at elevated temperatures. Alter­
shifting was within the range of 85 mV vs. OCP value. This implies that
natively, it could be explained by the chemisorbed layer’s formation
the inhibitor under study is a mixed-type compound [36]. The impact of
occurring more rapidly than its dissolution [29]. The endothermic
DMOT on the reactions occurring at the cathode and anode was exam­
character of the process of dissolving steel is reflected in the positive
ined through the use of Potentiodynamic Polarization (PDP) testing.

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 6. Langmuir adsorption isotherm on mild steel surface in 1 M HCl solution at different DMOT concentrations.

Table 3
Thermodynamic parameters for the DMOT adsorption on steel surface in 1 M HCl solution at different temperature.
T (K) Slope Kads (l/mol) ΔGads (kJ/mol) R2 ΔSads (kJ/mol. K) ΔHads (kJ/mol) R2

303 1.051 1666 − 28.8053 0.9982 0.102 1.2744 0.998

313 1.032 2500 − 30.8121 0.9979
323 1.001 3333 − 32.5688 0.9982
333 1.020 2500 − 32.7809 0.9982
343 1.031 2000 − 33.1290 0.9986
Average value 1.027 2399.8 − 31.6192 0.9982

This testing involved immersing the specimens in hydrochloric acid significant changes following the addition of DMOT, indicating that the
(HCl) for a duration of 3 h, both with and without the presence of DMOT corrosion mechanism of mild steel remains unaffected.
under ideal conditions (as depicted in Fig. 8B). The resulting data, In order to delve deeper into the subject, additional electrochemical
including the corrosion current density (icorr), corrosion potential (Ecorr), investigations were carried out. The focus of these investigations was to
polarization resistance (Rp), and the slopes of the anodic and cathodic examine the effects of DMOT on the corrosion properties of mild steel in
branches (βa and βc), have been compiled in Table 4. Furthermore, the 1 M HCl, both with and without the presence of the compound. To
efficiency of corrosion inhibition was determined using Eq. (12) [37]. In achieve this, the electrochemical impedance spectroscopy (EIS) tech­
this equation, iocorr represents the corrosion current density in the nique was employed under optimal conditions. Observations made
absence of DMOT, while icorr represents the corrosion flow with the during these experiments are displayed in Fig. 9, which includes the
optimal concentration of DMOT. Based on the data presented in Fig. 8B, equivalent circuit, Nyquist diagrams, and Bode diagrams. Additionally,
it is evident that the presence of DMOT has resulted in a reduction in the inhibition efficiency can be determined through the application of
current density for both the anodic and cathodic branches when EIS calculations, as outlined in Eq. (13).
compared to the control.
Roct − Rct
%IEEIS = × 100 (13)
io − icorr Roct
%IEPDP = corr o × 100 (12)
icorr
where Rct and Roct are the charge transfer resistance of steel in the
The presence of DMOT resulted in a significant decrease in the Ecorr absence and presence of DMOT, respectively.
shift, which was observed to be less than ±85 mV. Specifically, the shift The behavior of the impedance is generally fitted to Randle equiv­
was measured to be 40.65 mV towards the anodic branch. This indicates alent circuit (Fig. 9), including the solution resistance (Rs), charge
that DMOT functions as a mixed-type inhibitor, with a greater impact on transfer resistance (Rct), and double-layer capacitance (Cdl). All these
the anodic process. Under optimal conditions, the inhibitor efficiency parameters with the percentage of the impedance efficiency (%IEEIS),
reached 99.17%. The reduction in corrosion flow density with DMOT can be found in Table 5. The Nyquist graphical depiction shows that the
suggests the formation of a protective layer on the metal surface. size of the capacitive loop increases when the inhibitor is injected,
Interestingly, the values of Tafel slopes (βa and βc) did not exhibit demonstrating the creation of an inhibitory layer on the metal’s surface

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 7. (A) Adsorption constant against temperature (B) Standard adsorption free energy against temperature for DMOT adsorption on low-carbon steel.

[38]. The increased values of modulus and phase angle in the inhibited the surface area of the electrode. It is evident that the introduction of an
Bode plots indicate that the surface s become smoother as a result of the optimal concentration of DMOT leads to a decrease in the value of Cdl.
adsorption of DMOT molecules on the steel surface. This decrease can be attributed to the replacement of water molecules by
Mathematically, Cdl can be given by Eq. (14) [39]. DMOT molecules on the surface of the metal. Furthermore, the decrease
in Cdl values with the addition of DMOT can be explained by the
εo εA
Cdl = (14) behavior of the inhibitor molecules as adsorbents on the metal surface,
d
as a consequence of which the local dielectric value decreases and/or the
The equation provided above includes several variables: ε0 repre­ dimension of the double layer of electricity increases [40].
sents the permittivity, ε denotes the dielectric constant of the protective
layer, d signifies the thickness of the protective layer, and A represents

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 8. Electrochemical illustrations for corrosion of low-carbon steel in 1 M HCl solution with and without DMOT at optimum conditions (A) Open Circuit Potential
(OCP) (B) Tafel polarization.

Table 4
Corrosion parameters obtained for mild steel in 1 M HCl solution at optimum condition in absence and presence of DMOT.
Condition βa (mV) βc (mV) Icorr (µA/cm2) Rp (Ω⋅cm2) Ecorr (mV) SCE OCP (mV) SCE IEPDP

Blank 80.16 − 110.1 2331.46 8.64 − 344.32 − 348.13 99.17 %

DMOT 87.02 − 117.6 6.86 3165.6 − 303.67 − 303.17

3.5. Surface morphology investigations (SEM) and optical microscopy tomography (OMT) images were shown
in Fig. 10. For SEM (upper images), mild steel surface before immersion
Under optimum conditions, the surface morphology of low-carbon (Fig. 10 A) seems smooth and undamaged. After being submerged in the
metals was investigated in both the absence and presence of DMOT corrosive acidic solution, the damage was depicted (Fig. 10B). However,
following a 3 h immersion in 1 M HCl. Scanning electron microscopy by adding the right amount of DMOT to the acidic solution, corrosion

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 9. Equivalent circuit, Nyquist diagrams, and Bode diagrams of mild steel in 1 M HCl in the absence and presence of optimum DMOT concentration.

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 9. (continued).

products were limited, leaving a comparatively homogeneous and

Table 5 smooth surface (Fig. 10B). Optical Microscope Tomography (OMT)
EIS parameters obtained for mild steel in 1 M HCl solution at optimum condition pictures (Fig. 10A, B, and C, lower images) showed a similar pattern of
in absence and presence of (DMOT). activity.
Condition Rs (Ω⋅cm2) Rct (Ω⋅cm2) Cdl (F) IEEIS The impacts of DMOT on the surface hardness and microstructure of
Blank 5.721 05.84 1.06 × 10 − 84
94.71 %
low-carbon metals were studied. through Atomic Force Microscopy
DMOT 7.718 110.54 1.81 × 10− 85 (AFM) analysis, as depicted in Fig. 11. The analysis yielded measure­
ments that demonstrated the impact of DMOT on the mild-steel samples.
Prior to immersion, the average roughness (Ra) of the samples was
55.07 nm. However, when placed in a blank acidic solution, the
roughness increased to 162.4 nm. In the presence of inhibited acidic

Fig. 10. The mild steel A285/C sample’s SEM (upper) and OMT (lower) pictures for the polished sample (A) before the corrosion test, (B) the sample submerged in 1
M HCl in the absence and (C) presence of DMOT, at optimum conditions.

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Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 11. AFM surface images, with corresponding roughness parameters, after 3 h corrosion of A285/C mild steel in 1 M HCl solution at optimum conditions (A)
Polished sample before corrosion test (B) without inhibitor, and (C) in the presence of DMOT.

14
Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

3.6. FTIR investigations

In an ideal scenario, the FTIR spectra of corrosion products on the

surface of mild steel were obtained when submerged in an acidic solu­
tion both with and without DMOT. The appearance of peaks in the range
of 1500–2000, as shown in Fig. 13, can be attributed to the stretching of
the C=C bond in the aromatic ring. Furthermore, the stretching of the
C=O bond is observed at 1605 cm− 1 and 1715 cm− 1, respectively
[42,43]. The range of frequencies between 400 cm− 1 and 1000 cm− 1
may be attributed to the bending of aliphatic and aromatic C–H bonds.
When the DMOT is not present, the corrosion products exhibit multiple
similar peaks, suggesting that DMOT molecules have bonded to the
surface of the mild-steel. Additionally, the building of a complex be­
tween DMOT and iron ions may be to blame for the displacement of the
peaks in the range of 1700 cm− 1–1750 cm− 1 and from 1600 cm− 1 to
1630 cm− 1, which may be attributed to C=O stretching and C=C
stretching, respectively [44]. In summary, the findings indicated that
the connection between inhibitor molecules and the metal surface could
be ascribed to various factors such as functional chains, rings of aro­
matics, nitrogen- and groups that contain oxygen, and functional groups
Fig. 12. XRD surface images after 3 h corrosion of A285/C mild steel in 1 M within the DMOT structure.
HCl solution at optimum conditions for polished sample before corrosion test,
without inhibitor, and in the presence of DMOT.
3.7. UV–Vis investigations

Using the UV–Vis examination, the likelihood of complex formation

between the DMOT molecule and iron ions was taken into account.
Fig. 14 compares the UV–Vis spectra of mild steel before and after im­
mersion in an acidic solution containing DMOT under ideal circum­
stances. Before immersion, the solution’s UV–Vis spectra showed a
number of peaks. O–H bonds may be responsible for the greatest signal,
which was centered at 340 nm. -* transitions of C=C bonds in aromatic
rings and C=O bonds are responsible for additional peaks in the
200–300 nm range [45,46]. After immersing mild steel in a corrosive
solution with DMOT for a duration of three hours, it was observed that
the absorption peaks linked to -* and n-* transitions had diminished in
intensity. Additionally, the UV–Vis spectrum had undergone a shift.
These findings suggest that there may have been adsorption of DMOT
molecules on the surface of the metal, leading to the creation of an
organic–inorganic complex as a result of the interaction between the
electron pairs of the DMOT molecule and the vacant orbital of Fe2+/Fe3+
[47].

3.8. Quantum chemical and theoretical investigations

Computational methods have been identified as having prospective

uses in the design and development of organic corrosion inhibitors in the
Fig. 13. FT-IR spectrum of sample corrosion products for blank, with DMOT in corrosion field [47,48]. Quantum chemical calculations were carried out
1 M HCl at optimum conditions. using the PM3-SCF technique in the ArgusLab 4.0.1 package to look at
the allocation of charges of the DMOT molecule. The highest occupied
solutions, the roughness decreased to 154.4 nm. This reduction in molecular orbital (HOMO), lowest unoccupied molecular orbital
roughness can be attributed to the decrease in metal corrosion caused by (LUMO), and Mulliken charge distributions were computed and shown
the inhibitor. in Figs. 15 and 16. It has been discovered that the simpler an atom is
In order to examine the chemical makeup of the steel, an XRD attracted to a steel surface, the harsher the adsorbed center’s atomic
analysis was performed as shown in Fig. 12. This analysis was conducted partial charges are. It is obvious that S, O, N, and certain C atoms have a
before the steel was submerged in an acidic solution, after it was sub­ higher concentration of negative charges. Some of the important
merged in the acidic solution without the presence of DMOT, and when quantum chemistry characteristics are shown in Table 6. The majority of
DMOT was present under ideal circumstances. The presence of corrosion them are the energy gap (Egap), heat of formation (ΔHf), proportion of
products on the steel surface is indicated by the peaks at 2θ around 36◦ , electron transfer (ΔN), maximum occupied (EHOMO), and lowest unoc­
which can be attributed to Fe2O3/FeCl3. Additionally, peaks at 2θ = 45◦ cupied (ELUMO). According to researches, the best corrosion inhibitors
and 65◦ are associated with Fe [41]. Upon comparison of the XRD pat­ are organic compounds that not only offer electrons to unoccupied metal
terns, it is evident that the peaks corresponding to corrosion products orbitals, but also accept free electrons from the metal [45]. In other
vanish after the addition of DMOT. Moreover, the intensification of the words, the higher the inhibitor ’s HOMO energy, the greater the ten­
peak at 45◦ and the emergence of a peak at 65◦ (both associated with Fe dency of offering electrons to the metal’s unoccupied d orbital, and thus
metal) provide evidence of the interaction between DMOT and the steel the higher the corrosion inhibition efficiency. In addition, as the energy
surface, supporting the notion of reduced corrosion product formation. difference diminishes and the effectiveness of inhibitors increases, it
becomes simpler for electrons to be accepted from the surface of the

15
Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 14. UV–Vis spectra of 1 M HCl solution containing optimum concentration of DMOT before and after immersion.

Fig. 15. Mulliken atomic charges distribution of DMOT molecule.

metal when the energy of the Lowest Unoccupied Molecular Orbital I − A − (EHOMO − ELUMO )
(LUMO) decreases. η= = (17)
2 2
The portion of transferred electrons (ΔN) was also measured as in the
following equation: Based on previous research, it has been determined that XFe has a
theoretical value of 7, while η Fe has a value of 0 eV/mol [49,50]. The
ΔN =
XFe − XDMOT
(15) value of ΔN, which indicates the degree of inhibition caused by electron
2(ηFe + ηDMOT ) donation, has been found to have a significant impact. According to
Knowing that XDMOT and XFe states the DMOT and steel electrostatic Lukovits’s findings [51–54], when ΔN is below 3.6, the efficiency of
attraction, correspondingly. ηFe and ηDMOT refers to steel hardness and inhibition increases with the metal surface ’s ability to donate electrons.
DMOT, correspondingly. These variables are connected to the ionization In our current study, the fraction of electron transfer was determined to
potential (I) and the affinity of electrons (A), which are linked to the be 0.355, with DMOT serving as the electron donor and the mild steel
EHOMO and ELUMO: surface acting as the electron acceptor. The formation of a corrosion-
inhibiting adsorption layer occurred as a result of the connection be­
x=
I + A − (EHOMO + ELUMO )
= (16) tween DMOT and the mild-steel surface.
2 2

16
Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 16. (A) Optimazed DMOT structure (B) HOMO, (C) LUMO distribution, and (D) mapped-density surface.

17
Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Fig. 16. (continued).

3.9. Mechanism of inhibition

Table 6
Quantum chemical parameters of DMOT. The interaction between DMOT molecules and metal surface greatly
EHOMO (eV) ELUMO (eV) E gap (eV) ΔN ΔHf (kcal/mol) µ (dybe) affects the adsorption behavior. Fig. 17 illustrates the suggested
adsorption mechanism for DMOT on iron surface which was developed
− 8.024 − 0.935 7.089 0.355 128.419 4.657
through both theoretical and experimental calculations. In hydrochloric
acid solution, the surface of mild steel carries a positive charge.
Furthermore, in acidic environments, organic compounds can

Fig. 17. Mechanism of inhibition DMOT on mild steel surface.

18
Z.I. Jasim et al. Inorganic Chemistry Communications 160 (2024) 111911

Table 7 of DMOT on metal surface s follows the Langmuir adsorption isotherm.

Comparison of DMOT performance with other inhibitors from literature for The formation of a protective layer on the metal surface by the inhibitor
protection of mild steel in 1 M HCl. was confirmed by SEM, AFM, and optical evaluations. The experimental
Inhibitor Inhibitor Inhibitor Reference results achieved with DMOT agreed with the theoretical outcomes
concentration efficiency generated from the study of quantum chemistry.
2-benzyl-5-(4nitrophenyl)-1,3,4- 300 ppm 96.54% 59
oxadiazole (2B54NPO) CRediT authorship contribution statement
2-(4-methoxyphenyl)-5- 300 ppm 92.19% 59
(phenoxymethyl)-1,3,4-
oxadiazole (24MO5POO) Zenaa Ibraheem Jasim: Data curation. Khalid H. Rashid: Meth­
2-N-phenylamino-5-(3-phenyl-3- 500 ppm 95.1% 60 odology, Software, Supervision. Khalida F. AL-Azawi: Investigation,
oxo-1-propyl)-1,3,4-oxadiazole Methodology, Supervision. Anees A. Khadom: Investigation, Method­
(NPOPO)
ology, Software, Supervision.
5-(phenoxy methyl)-1,3,4- 300 ppm 88.93 % 61
oxadiazole-2(3H)-thione (PMOT)
5-benzyl-1,3,4-oxadiazole-2(3H)- 300 ppm 85.99 % 61
thione (BOT) Declaration of Competing Interest
1,3,4-oxadiazole derivatives, 500 ppm 97.83% 62
namely, 2-phenyl-5-(pyridin-3-
The authors declare that they have no known competing financial
yl)-1,3,4-oxadiazole (POX)
2-(4-methoxyphenyl)-5-(pyridin-3- 500 ppm 98% 62 interests or personal relationships that could have appeared to influence
yl)-1,3,4-oxadiazole (4-PMOX) the work reported in this paper.
2,5-bis(4-dimethylaminophenyl)- 1 mM 93% 63
1,3,4-oxadiazole (DAPO) Data availability
DMOT 110.03 ppm 99.17% Present
work
Data will be made available on request.

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