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OPEN Highly efficient eco-friendly

corrosion inhibitor for mild steel in
5 M HCl at elevated temperatures:
Received: 19 July 2018
Accepted: 6 February 2019 experimental & molecular
dynamics study
Published: xx xx xxxx

Muhsen A. M. El-Haddad1, A. Bahgat Radwan2, Mostafa H. Sliem2, Walid M. I. Hassan3,4 &

Aboubakr M. Abdullah   2
Laurhydrazide N′-propan-3-one was used as an eco-friendly inhibitor for the corrosion of mild steel in
5 M HCl at elevated temperatures. Various electrochemical techniques and surface characterization
methods were utilized in this study. In addition, the kinetics and thermodynamic parameters were
calculated and discussed. Furthermore, a geometry optimization of LHP was performed and the time-
dependent density functional theory was utilized to calculate the electronic absorption spectra. Finally,
frequency calculations were, also, performed on the optimized geometry.

One of the important mineral acids that is widely used in many applications, including well acidizing, water treat-
ment, chemical cleaning, and acid pickling, is hydrochloric acid (HCl)1–8. The selection of cost-effective materials
to handle this acid requires extreme care and detailed engineering. The presence of certain impurities, such as
ferric salts, cupric salts, and chlorine, in the acid and/or a high level of aeration amplifies the oxidizing power of
the solution, leading to accelerated corrosion damage9. In the petroleum and gas industry, the exposure of mate-
rials to acidic environments is more common and frequent than to neutral or alkaline environments10–13. This
necessitates exploring options and efficient techniques to mitigate and control the corrosion of the different types
of steel as they constitute a large fraction of the metallic materials that are exposed to acidic media. Corrosion
inhibitors are widely utilized to mitigate corrosion risks. For example, Umoren14 investigated the corrosion inhi-
bition of polypropylene glycol for X60 pipeline steel in 15% HCl. The corrosion inhibition efficiency (IE%) was
found to be 90% at 55 °C using 1000 ppm of polypropylene glycol. Ituen et al.15 explored the corrosion inhibi-
tion of N-acetyl cysteine (NAC) as a base inhibitor compound with different additives of 5-hydroxytryptophan
(5-HTP), glutathione, potassium iodide (KI), and polyethylene glycol in 15% HCl solution for different grades
of steel (mild steel, J55, and X80) at elevated temperatures. The optimum composition showed a corrosion pro-
tection efficiency of 97% at 90 °C on X80 steel. Ansari et al.16 synthesized two pyrazolone derivatives (PZ-1 and
PZ-2) to study their corrosion inhibition in 15% HCl solution for N80 steel. They found that PZ-1, which contains
an additional methyl group, showed a better corrosion IE% of 93% at 35 °C in comparison to 85.5% for PZ-2.
Yadav et al.17, prepared two carbohydrate compounds namely BIHT and MIHT as green inhibitors for N80 steel
in the aforementioned HCl concentration. It was revealed that the chemisorbed inhibitor (BIHT) had the highest
IE% of 94.8% at 30 °C. Unfortunately, some of the effective corrosion inhibitors used to mitigate corrosion are
highly toxic. Increased environmental awareness and the development of regulations have imposed restrictions
on the use of such inhibitors. Additionally, the safe disposal of corrosion inhibitors after use or the treatment of
contaminated streams is critical and usually defined as a step in all chemical treatment programs, which adds to
the corrosion control cost. The environmental and safety concerns related to corrosion inhibition processes have
encouraged researchers to explore alternatives that are eco-friendly and offer acceptable inhibition efficiency,

1
Materials Science & Technology Program, College of Arts and Sciences, Qatar University, Doha, P.O. Box 2713,
Qatar. 2Center for Advanced Materials, Qatar University, Doha, P.O. Box 2713, Qatar. 3Chemistry Department,
Faculty of Science, Cairo University, Giza, 12613, Egypt. 4Chemistry Department, Faculty of Science, King Abdulaziz
University, B.O. 80203, Jeddah, 21589, Saudi Arabia. Correspondence and requests for materials should be addressed
to A.M.A. (email: [email protected])

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Element C Si Mn S P Cu Fe
Weight % 0.128 0.25 0.7 0.03 0.04 0.15 Bal.

Table 1.  Elemental composition analysis for MS.

Figure 1.  Laurhydrazide N′-propan-3-one chemical structure.

especially in acidizing treatment processes, which cost the state of Qatar, in addition to chemical treatment appli-
cations, a direct expenditure close to 8 billion USD per year18. Therefore, focus on natural and nature-based prod-
ucts is increased to produce so-called “green inhibitors”19–22. However, the harsh acidic and high-temperature
environments during drilling and stimulation processes in the oil and gas wells limit the full utilization of such
green corrosion inhibitors. The development of green corrosion inhibitors that withstand severe acidic corrosive
environments and cog the carbon steel corrosion, particularly in well acidizing, is highly desired, especially in the
carbonate formations found in the state of Qatar and many other countries.
In this work, laurhydrazide N′-propan-3-one (LHP) is tested as an inexpensive and highly efficient green
inhibitor for the corrosion of mild steel (MS) in 16% HCl solution (5 M) at various temperatures using the poten-
tiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) techniques. In addition, sev-
eral surface characterization methods are used, such as scanning electron microscopy (SEM) coupled with an
energy-dispersive X-ray spectroscopy (EDX) unit, atomic force microscopy (AFM), and X-ray photoelectron
spectroscopy (XPS). Furthermore, the kinetics and thermodynamic parameters are measured and/or calculated.
A geometry optimization of LHP is also performed and the time-dependent density functional theory was used
to calculate the electronic absorption spectra. Furthermore, frequency calculations are also performed on the
optimized geometry.

Experimental Work
Materials and Material Preparation.  The elemental analysis of the MS (MS) used in this work, shown in
Table 1, was performed using the ARL 3460 optical emission spectrometer (ThermoFisher Scientific, Waltham,
MA, USA).
Coupons of equal size (1.5 × 1.5 × 0.5 cm3) were cold-cut from a MS plate. They were polished using SiC
emery papers from 250 down to 4000 grit, washed with ethanol for 10 min in an ultrasonic bath, then degreased
with acetone for 1 min, followed by rinsing with ethanol and finally with deionized (DI) water. Finally, they
were dried using air. The corrosive acidic solution that was used in this work was prepared by diluting analytical
HCl from 36 to 16% (5 M) using DI water. The chemical structure of LHP (purchased from Shanghai Dejun
Technology Co., Ltd, Shanghai, China) is shown in Fig. 1.

Electrochemical Measurements.  A 250 ml double-jacketed three-electrode corrosion cell was used, in

which a graphite rod, MS coupon (only 0.5 cm2 is exposed to the corrosive solution), and saturated calomel elec-
trode were the counter, working and reference electrodes, respectively. SCE was used with a Luggin capillary to
minimize the IR drop. The temperature of the cell was controlled 20 and 80 °C using a thermostat water circulator
(Julabo F12, Seelbach, Germany). A thermometer was used to monitor the temperature of the electrolyte before
and during the experiments. A Reference 300 GAMRY (Warminster, PA, USA) was the potentiostat used to meas-
ure the EIS and PDP curves. The GAMRY measurement software packages include EIS300 for EIS and DC105
for corrosion analysis. The free corrosion potential (EOCP) was stabilized before any electrochemical testing by
placing it in the solution for 30 min. EIS was performed within a frequency range of 1 × 10−1 to 1 × 105 Hz, with a
5 mV AC peak-to-peak amplitude. PDP curves were measured between −250 and +250 mV with respect to EOCP
in the more noble direction. The sweep rate was always 0.3 mV s−1. Four concentrations of the corrosion inhibitor
were used: 92, 185, 277, and 370 μmol L−1.

Surface Analysis.  Surface analysis has a vital role in characterizing the surface morphology and studying
the effect of the inhibitor and its interaction with the substrate. Immersion tests were conducted to quantify the
effect of the corrosive acidic medium on the MS electrode and to study the surface topography before and after
the addition of the LHP inhibitor. Three steel coupons were ground and then polished to a mirror-like finish using
alumina suspensions of different particle size. The coupons were immersed in the LHP -free 5 M HCl solution for
24 h at 25 °C. The same procedure was repeated, but with the addition of 370 μmol L−1 of LHP. The morphology
of the two samples was examined and compared using SEM (FEI NOVA NANOSEM 450, Hillsporo, OR, USA),
typically operated with an acceleration voltage of 20 kV coupled with an EDX unit. The adsorbed inhibitors on the
MS were analyzed using XPS (AXIX Ultra DLD, Kratos, UK), employing a monochromatic Al Kα X-ray source.

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Figure 2.  PDP curves of MS in 5 M HCl before and after the addition of different concentrations of LHP at (a)
20, (b) 40, (c) 60, and (d) 80 °C.

AFM (MFP-3D, Asylum Research, Goleta, CA, USA) was used in the non-contact tapping mode in air for deter-
mining the surface roughness.

Computational.  The geometry optimization was performed using the wb97xd density functional method
and 6-311++ g(d, p) as a basis set23. The time-dependent density functional theory was utilized to calculate the
electronic absorption spectra (using 30 excited states) and the frequency calculations were also performed on
the optimized geometry. All these simulations were performed using the Gaussian 09 software package24. The
electronic absorption spectra were collected using a UV–Vis peak half-width of 0.15 eV. The visualizations were
created using the Chemcraft software package25. The molecular simulations were created using the adsorption
locator tool in Materials Studio26. Adsorption Locator identifies possible adsorption configurations by carrying
out Monte Carlo searches of the configurational space of the substrate-adsorbate system as the temperature is
slowly decreased using simulated annealing. In our calculation we implement the universal force field with fine
quality. The surfaces were constructed from pure iron metal followed by a 100, 110, or 111-orientation surface
cleavage with a thickness of two layers and a 30 Å vacuum slab. A super cell with dimensions of 10 × 10 was uti-
lized to measure the adsorption energy and the geometry of the adsorbed molecules. The GaussView 5.0 software
package was further applied in visualizing the graphical isosurfaces of the electron density.

Results and Discussion

Potentiodynamic Polarization Studies.  Figure 2 illustrates the PDP curves at different temperatures
for MS in 5 M HCl at various LHP concentrations. The values of Ecorr, cathodic (βc) and anodic (βa) Tafel slopes
besides the corrosion current density (icorr) are listed in Table 2. In addition, the IE% and surface coverage, θ in
Table 2 are calculated using Equations (1) and (2), respectively27.
 i − i2 
IE% =  1  × 100
 i  (1)
1

IE%
θ=
100 (2)
where i1 and i2 are the corrosion current densities in the absence and presence of LHP, respectively. Furthermore,
the Stern–Geary equation, Equation (3), is utilized to calculate the polarization resistance, Rp28:

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T (°C) Cinh µmol L−1 β a (V decade−1) − β c (V decade−1) Rp Ω cm2 Ecorr (mV) SCE icorr (mA cm−2) IE% θ
— 0.14 0.19 25.1 358 1.4 — —
92 0.1 0.162 51.6 376 0.52 62 0.62
20 185 0.08 0.153 76.1 349 0.3 78 0.78
277 0.06 0.146 97.2 380 0.19 86 0.86
370 0.03 0.131 117.7 354 0.08 94 0.94
— 0.21 0.261 9.7 399 5.2 — —
92 0.184 0.241 18.8 380 2.4 53 0.53
40 185 0.179 0.221 25.2 362 1.7 67 0.67
277 0.165 0.211 34.6 358 1.16 77 0.77
370 0.153 0.209 51.8 342 0.74 86 0.86
— 0.23 0.298 4.8 396 11.7 — —
92 0.188 0.285 6.9 360 7.1 39 0.39
60 185 0.18 0.281 8.2 364 5.8 50 0.5
277 0.171 0.276 10.7 354 4.3 63 0.63
370 0.165 0.269 14.3 347 3.1 73 0.73
— 0.242 0.302 3.4 398 17.2 — —
92 0.197 0.32 3.8 390 13.9 19 0.19
80 185 0.185 0.298 4.5 386 11.1 35 0.35
277 0.181 0.287 5.4 382 8.9 48 0.48
370 0.173 0.278 7.1 412 6.6 61 0.61

Table 2.  PDP parameters at various temperatures for MS in 5 M HCl at different concentrations of LHP.

Figure 3.  Equivalent circuit used to fit the measured impedance spectra for MS in 5 M HCl.

βc βa
Rp =
2.303 icorr(βc + βa ) (3)
Table 2 reveals the direct relation between the inhibitor concentration and the reduction in the rate of cor-
rosion. It can be noticed that by increasing the inhibitor concentration, the corrosion current density (icorr),
decreases. However, the corrosion current density (icorr), increases by increasing the temperature. A maximum
IE% of 94% is attained at 20 °C using 370 µmol L−1 of LHP. Elevating the temperature to 80 °C decreases the IE%
to 61%. The parallel anodic and cathodic Tafel lines and their slopes suggest that the cathodic reaction is primarily
activation-controlled, i.e. cathodic and anodic currents were moved to lower values at the same potential with
increasing the inhibitor concentration at elevated temperatures. This behavior indicates that both the anodic
dissolution and cathodic reactions were suppressed, i.e., LHP is a mixed-type inhibitor. Moreover, an 85 mV
shift in Ecorr, in the more or less noble directions after the addition of an inhibitor, the inhibitor is classified as an
anodic or cathodic inhibitor, respectively29. Otherwise, the inhibitor is considered as mixed type category, i.e., it
suppresses both reactions30–32. That is, the explored compound inhibit the anodic dissolution of the metal surface
in the 5 M HCl in addition to the cathodic reaction.
Figure 2 shows shoulders in the anodic curves at high inhibitor concentrations, at all temperatures except for
80 °C. This can be attributed to the alteration of the surface area covered with the corrosion inhibitor, because
of the rearrangement of the adsorbed inhibitor molecules on the electrode surface and/or the destabilization or
delamination of the thin protective layer formed over the substrate. Additionally, a change in the adsorption or
desorption rate of the inhibitor molecules or a local change in the inhibition mechanism for the anodic reaction33
could be reasons for the appearance of these shoulders.

EIS Studies.  EIS is widely employed to provide useful information about the kinetics and mechanisms of
electrochemical systems34–37. Figure 3 shows a typical one time constant equivalent electrical circuit that is used
to analyze all the measured EIS data in this study. The used one time constant equivalent circuit indicate that the
adsorbed inhibitor forms a monolayer on the MS surface38.

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Figure 4.  EIS: (a) Nyquist plots and (b) Bode plots for MS in a LHP – free 5 M HCl at various temperatures.

It consists of a charge transfer resistance (Rct), solution resistance (Rs), and constant phase element (CPE)
used to describe the non-ideal behavior of the double layer, which is mainly attributed to non-uniform surface
coverage and/or surface roughness.
The impedance of the CPE is analyzed using Equation 439:

ZQ = [Y0(jw )n ]−1 (4)

where ZQ represents the CPE impedance (Ω cm ), Y0 is the CPE constant, ω is the frequency in rad s , and the
−2 −1

values of n range between 0 and 1 and define the divergence from capacitance linearity. When n = 1, Y0 is equiv-
alent to that of an ideal capacitor. When n = 0, Y0 is equivalent to that of a resistor.
The measured (dotted lines) and fitted (solid lines) impedance spectra shown in Fig. 4 are for MS in a
LHP-free 5 M HCl solution at 20, 40, 60, and 80 °C. It is clear that the semicircles decrease in size as the temper-
ature increases.
Figures 5 and 6 show the Nyquist and Bode plots, respectively, of MS in a 5 M HCl solution with various con-
centrations of LHP at (b) 20, (c) 40, (d) 60, and (e) 80 °C. It can be noticed from the Nyquist plots that the diame-
ter of the semicircle increases as the corrosion inhibitor concentration increases at different temperatures. The low
impedance modulus (Z) increases in line with the increase in the LHP concentration due to the increased amount
adsorbed of LHP on the metallic substrate. It can be seen from the Bode plots, that the values of phase angle (θ),
for the inhibited samples are higher than that of the uninhibited MS at elevated temperature. The increased values
of the phase angle for the specimens in the inhibited solutions indicated that the metallic surface significantly
becomes smooth due to the formation of protective layer by the adsorbed inhibitors over the MS surface.
Table 3 shows the EIS parameters derived from Figs 4–6 using the equivalent circuit shown in Fig. 3. The IE%
is calculated using Equation (5)40:
 R − Rct1 
IE% =  ct2  × 100
 Rct1 
 (5)
where Rct2 and Rct1 represent the charge transfer resistances in the inhibited and uninhibited test solutions, respec-
tively. θ is calculated using Equation 2.
Rct, Y0, and n are used to calculate the metal solution interface double layer capacitance (Cdl) using Equation (6)41:

Cdl = (Y0Rct1 −n)1/n (6)

Table 3 reveals that Rct increases as LHP concentration is raised. This is attributed to the adsorbed molecules
of LHP on the MS forming a barrier film, which restricts the accessibility of Cl− ions to the metal surface. On
the contrary, the double layer capacitance (Cdl) gradually decreases as the inhibitor concentration increases. The
decrease in the Cdl is primarily caused by (i) the increase in the thickness of the double layer thickness (δ) because
of the adsorption of the LHP onto the MS surface and/or (ii) the decrease in the dielectric constant (ε) due to the
replacement of water molecules by the LHP ones as indicated by the Helmholtz equation42:
ε ε0 A
Cdl =
δ (7)
where A represents the cross-sectional area of the electrode, and ε0 and ε represent the dielectric constants of air
and water, respectively.
As the IE% is directly proportional to Rct2, it also increases as the LHP concentration increases and decreases
as the temperature is raised, as seen in Table 3.
It is worth noting that n has the highest values in LHP-free solution at any temperature, and decreases as the
LHP dosage increases at a given temperature. In addition, the higher the temperature is, the higher is the value of
n at any concentration of LHP. The values of n (approaching unity), indicate that the CPE is getting closer to the

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Figure 5.  EIS Nyquist plots MS in 5 M HCl with various concentrations of LHP at (A) 20, (B) 40, (C) 60, and
(D) 80 °C.

Figure 6.  EIS Bode for MS in 5 M HCl in the presence of 92, 185, 277, and 370 µmol L−1 of LHP at (a) 20,
(b) 40, (c) 60, and (d) 80 °C. The symbols are the measured data and the solid lines are the fittings using the
equivalent circuit shown in Fig. 3.

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CPE
Y0 × 10−6 sn Goodness
T (°C) Cinh, µmol L−1 Rct, Ω cm2 Ω −1 cm−2 n Cdl, µF IE% θ of fit (χ2)
0 15 751 0.810 258 — — 6.7 × 10−5
92 44 641 0.743 186 65.8 0.66 5.6 × 10−4
185 62 610 0.720 171 75.8 0.76 1.3 × 10−4
20
2.
277 100 550 0.697 162 84.9 0.85
2 × 10−5
370 210 524 0.625 140 92.8 0.93 3.2 × 10−4
0 11 772 0.826 280 — — 3.7 × 10−4
92 23 656 0.784 206 54.3 0.54 4.8 × 10−4
40 185 33 621 0.766 189 68.2 0.68 7.2 × 10−5
277 42 566 0.758 171 75 0.75 4.4 × 10−5
370 85 533 0.734 148 87.6 0.87 6.1 × 10−4
0 5 818 0.857 324 — — 8.4 × 10−5
92 9 781 0.827 273 43.5 0.44 5.3 × 10−4
60 185 11 761 0.801 230 55.6 0.56 7.5 × 10−4
277 15 732 0.789 219 68.4 0.68 9.3 × 10−5
370 20 714 0.761 186 75.4 0.75 2.8 × 10−4
0 3 885 0.894 444 — — 1.2 × 10−5
92 4 826 0.864 336 15 0.15 6.7 × 10−4
80 185 6 806 0.839 284 38.1 0.38 9.5 × 10−4
277 7 784 0.816 242 51.4 0.51 1.8 × 10−4
370 10 764 0.792 210 64.6 0.65 4.9 × 10−4

Table 3.  EIS parameters at various temperatures for MS in 5 M HCl with various concentrations of LHP.

Figure 7.  Langmuir adsorption plots at various temperatures for MS in 5 M HCl.

ideal capacitor behavior. It is noteworthy that the EIS parameters summarized in Table 3, are consistent with the
Tafel analyses shown in Table 2.

Adsorption Isotherm and Thermodynamic Calculations.  Adsorption isotherms are used extensively
to illustrate and characterize the interaction between the applied corrosion inhibitor and a metallic substrate.
Langmuir is found to be the best isotherm by far that fits the measured experimental data. The Langmuir
isotherm relates Cinh and θ as follows43:
Cinh 1
= + Cinh
θ Kads (8)
where Cinh is the LHP concentration and Kads is the adsorption equilibrium constant, which can be obtained from
the intercept of the plots shown in Fig. 7.
Figure 7 shows the relation between Cinh/θ and Cinh at various temperatures. The standard Gibbs free energy
o
change of adsorption (∆Gads ) can be readily obtained using Equation (9) after getting the constants of adsorption
(Kads) at different temperatures from the (Cinh/θ)-intercepts of the plots in Fig. 7.

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Figure 8. ln Kads vs. T−1 for the LHP at the MS surface in 5 M HCl.

0 0 0
Temperature, K Kads, L mole−1 ΔGads , kJ mol
−1
ΔHads , kJ mol−1 ΔSads , J mol K
−1 −1

293.15 14139 −33.1 −27.7 18.5

313.15 10337 −34.5 −27.7 21.8
333.15 5354 −34.8 −27.7 21.4
353.15 2211 −34.4 −27.7 19.1

Table 4.  Thermodynamic parameters derived from Figs 7 and 8.

o
1 − ∆Gads
Kads = e RT
55.5 (9)
where R equals 8.314 j mol K , T is the temperature, and the 55.5 is the number of moles of water in 1 liter .
−1 −1 20

By plotting ln Kads versus T−1, as shown in Fig. 8, a straight line is obtained, which follows the van’t Hoff
equation19:

−∆H 0ads ∆S 0ads

ln Kads = +
RT R (10)
0 0
where ∆Sads and ∆Hads are change in the entropy and standard enthalpy of adsorption, respectively.
0 0
By determining ∆Hads from Equation (10), ∆Sads is calculated utilizing either Equation (10)44 or Equation (11).
0 0 0
∆Gads = ∆Hads − T ∆Sads (11)
0 0 o
Table 4 lists the ∆Hads , ∆Sads , Kads, and ∆Gads values for the adsorption of LHP at the MS surface in 5 M HCl.
0
The positive values of ∆Sads indicate an increase in the entropy due to the adsorption of LHP on the MS sur-
face. This is attributed to the exothermic nature of the adsorption process, as seen from the negative values of
0
∆Hads . The high values for the constant of adsorption (Kads), particularly at 25 °C, for the studied LHP corrosion
inhibitor indicate strong adsorption on the MS substrate. Large Kads values suggest a strong adsorption tendency
and hence a better inhibition performance. This is explained by the presence of π-electrons in the inhibitor’s
inherent molecular structure.
0
The negative values of ∆Gads are aligned with the spontaneity of the LHP adsorption on the MS surface (as
0
-RT ln Kads has negative values too). The values of ∆Gads are usually interpreted in relation to the nature of the
0
adsorption process: whether it is physisorption or chemisorption. Generally, if the values of ∆Gads are more than
0
−20 kJ mol−1, then the physisorption mechanism is favored, whereas if the values of ∆Gads are −40 kJ mol−1 or
lower, then the adsorption process is chemisorption.
0
As seen in Table 4, the obtained ∆Gads ranges from −33.1 to −34.8 kJ mol−1, which is between −20 and
−40 kJ mol−1. Thus, the process cannot be classified as chemisorption or physisorption. Rather, it is a mix of
chemisorption and physisorption.

Effect of Activation Energy and Temperature on the Corrosion Rate.  The inhibition mechanism
and efficiency are directly influenced by the activation energy (E a). The rate of most chemical reactions tends
to increase as the temperature increases. The effect of temperature on the corrosion rate of MS can be evaluated
using the Arrhenius equation:

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Figure 9.  Arrhenius plots for MS in 5 M HCl with various concentrations of LHP.

Conc. of inhibitor
(µmol L−1) Ea (kJ mol−1) r2 ΔH* (kJ mol−1) ΔS* (J mol−1 K−1)
0 36.3 0.95 33.6 −126
92 47.1 0.97 44.4 −97
185 52.5 0.97 49.8 −84
277 55.7 0.97 53.1 −76
370 61.7 0.98 61.7 −6

Table 5.  Activation energy (Ea), regression coefficient (r2), ∆H*, and ∆S* for MS in 5 M HCl with various
concentrations of LHP.

Ea
log CR = log A −
2.303 RT (12)
where CR is the corrosion rate expressed in terms of icorr at a specific temperature (T), (Ea) is the activation
energy, R = 8.314 J mol−1 K−1, and A is the Arrhenius constant, which is affected by the metal type and electrolyte
composition.
The Arrhenius plots of the MS before and after the addition of the corrosion inhibitor are given in Fig. 9, with
a linear regression rate that is close to unity.
The calculated Ea are listed in Table 5. Ea increases as the inhibitor concentration is raised. The higher value of
Ea is referred to the formed barrier film of LHP molecules at the MS surface.
The entropy of activation (∆S*) and the enthalpy of activation (∆H*) due to the dissolution of MS in 5 M HCl
are calculated using the Arrhenius equation33:
RT ∆S ⁎ −∆H ⁎
CR = exp R exp RT
Nh (13)
where h is Planck’s constant and N is Avogadro’s number.
From Fig. 10, ∆H* and ∆S* are obtained from the slope of (∆H*/2.303R) and the intercept of [log
(R/Nh) + (∆S*/2.303R)] are used to calculate respectively. The average difference between Ea and ∆H* is approxi-
mately 2.6 kJ mol−1 for each test, which is almost the value of RT (2.63 kJ mol−1). This indicates that the dissolution
of MS in this environment is a unimolecular reaction.
The thermodynamic parameters of LHP inhibitor were compared with some other reported inhibitors in 5 M
HCl as shown in Table 6. It is worth to mention that the reported inhibitors herein, exhibited a mixed type of
adsorption.

Surface Topography and Characterization.  SEM analysis. Figure 11 depicts SEM micrographs that
show the morphology of the MS surface after immersion for 24 h in (a) a LHP -free 5 M HCl and (b) 5 M HCl with
370 µmol L−1 of LHP at 20 °C. Figure 11a shows that the examined surface is heavily corroded. However, for the
immersion in the presence of 370 µmol L−1 of LHP, the corrosion looks more uniform.
EDX is conducted to examine the presence of nitrogen on the corroded surfaces in HCl with 370 µmol L−1 of
the LHP at 20 °C. The presence of nitrogen on the metallic substrate is confirmed to be 1.9%, which demonstrates
the adsorption of LHP on the MS surface.

XPS analysis.  The XPS survey of the adsorbed inhibitor and the high-resolution XPS analysis of C, O, and
N are shown in Fig. 12 for MS after immersion in 5 M HCl with 370 µmol L−1 of LHP O at 20 °C. The C 1 s is

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Figure 10.  Transition-state plots for MS in 5 M HCl with various concentrations of LHP.

deconvoluted into three different peaks. A peak at 284.7 eV is related to the C-C of the adsorbed inhibitor45. In
addition, a second peak at 288.1 eV is credited to the existence of -C=O groups46,47 and a third one at 286.2 eV for
the C-N of the adsorbed LHP on the protected MS surface48. The deconvolution of the O 1 s spectrum yields three
peaks. The first at 529.6 eV is related to O2−, which is mainly is associated with oxygen atoms bonded to Fe2O349.
The second one at 531.5 eV is attributed to the OH− of FeOOH50. The third peak observed at 533.5 eV could be
ascribed to the existence of oxygen in the adsorbed water4. On the contrary, the deconvolution of the N 1 s spec-
trum peak results in two peaks around 399.8 and 402.3 eV, which are mainly referred to the N atoms bonded to
the MS surface (N-Fe) and to the protonated nitrogen atoms of the hydrazine group, respectively17. XPS confirms
the presence of the adsorbed LHP corrosion inhibitor on the metal surface.

Atomic force microscopy analysis.  AFM is a powerful technique that has been widely used to explore the effect
of inhibitor on the surface roughness and topography of the metal surface in aggressive media33,51–53. Figure 13
shows three-dimensional images of two MS samples that had been ground using SiC to 4000 grit and immersed
in 5 M HCl for 24 h with and without 370 µmol L−1 of LHP. The average roughness of a MS surface in the absence
and presence of LHP in 5 M HCl is approximately 43.4 and 16.4 nm, respectively. The appreciable decrease in the
surface roughness after the addition of LHP demonstrates the good inhibition performance of LHP in 5 M HCl.

Structural Geometrical Parameters of the Optimized Molecule.  The optimized geometry of the
studied LHP results in the structure shown in Fig. 14. The optimized geometry shows no imaginary frequencies,
which suggests the stability of the converged structure.
The asymmetric and symmetric vibrational bands of C=O are located at 1812 and 1827 cm−1, respectively. The
vibrational stretching bands of the two N-H groups are located at 3604 and 3658 cm−1, respectively. The aliphatic
straight chain with 10 C atoms has similar C-C bonds with an average value of 1.526 Å for the C-C bonds between
C1 and C10, whereas the C10-C11, C11-C12, C13-C14, and C13-C15 bond lengths are 1.536, 1.511, 1.532, and
1.514 Å, respectively. Both C15=O and C12=O have the same bond length of 1.21 Å. The C15-N2 bond length is
slightly shorter than the C12-N1 bond length, by approximately 0.015 Å, with values of 1.376 and 1.391 Å, respec-
tively. The N1-N2 bond length is 1.376 Å. The bond angles C11-C12-O1, O1-C12-N1, N1-C12-C11, C13-C15-O2,
O2-C15-N2, and N2-C15-C13 are 123.7°, 119.3°, 116.8°, 123.3°, 122.1°, and 114.6°, respectively, suggesting the
sp2 hybridizations whereby C=O bonds take up more space and consequently slightly decrease the N-C-C bond
angle. The dihedral angles O2-C15-N2-N1 and O1-C12-N1-N2 are −1.44° and −165.35°, suggesting more devi-
ation than planarity on the side of the longer aliphatic chain.
The natural bond order charge analysis showed that the most negative atoms are O1 and O2 with values of
−0.606 and −0.618, followed by N1 and N2 with values of −0.481 and −0.472, respectively. The most positive
atoms are C12 and C13, with charges of 0.712 and 0.686, respectively. All the other C atoms in CH2 have a partial
negative charge of approximately −0.4 that is neutralized by a positive charge of approximately 0.2 on each H
atom. The terminal C in CH3 carries a larger partial negative charge of approximately −0.577, because it is sur-
rounded by three H atoms each, which have a positive charge of approximately 0.19. The nonlocalized negative
charges suggest that more than one interaction site with the metal surface is involved, as opposed to the possibil-
ity of a single active site in the adsorption process. The total dipole moment is 5.7294 D, directed approximately
above the C9 atom and perpendicular to the C8-C9 bond, which further suggests the non-localized distribution
of atomic charges.

Molecular simulation.  The molecular simulation of LHP on different pure iron surfaces showed approximately
identical adsorbed molecular geometries to that shown in Fig. 15. The whole molecule is adsorbed on the surface,
with bond lengths of 4.9, 3.2, 2.9, and 3.1 Å for methyl, CH2, O, and N, respectively, as measured relative to the
nearest Fe atom on the surface. The molecular simulation suggested that adsorption sites are not localized on one
atom, and that the part with the heteroatoms are much more strongly adsorbed than aliphatic hydrocarbon. Upon
comparing the geometry of the isolated LHP with the adsorbed one, the main geometrical changes are localized
in C15-N2, C12-N1 and N1-N2 bond lengths with 1.359, 1.374, and 1.412 Å, respectively. Both C15-N2 and

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Type of
0
Inhibitor ΔH* (kJ mol−1) ΔS* (J mol−1 K−1) ΔGads , kJ mol
−1
adsorption Ref.
Polypropylene glycol 57.7 −120 −29.2 Mixed type 14

Propargyl alcohol 21.7 21.8 −25.7 Mixed type 54

5-(4-methoxyphenyl)-3-(4-methylphenyl)4,5-dihydro-1H-pyrazol-1-
−64.3 −88 −39.7 Mixed type 55
yl-(pyridin-4-yl)methanone
1-diphenylaminomethyl-3-(1-N-dithiooxamide) iminoisatin −58.7 49.4 −38.2 Mixed type 56

Xanthan gum-graft-poly(acrylamide) 98.8 92.3 −24.01 Mixed type 57

Table 6.  Comparison of the energetic parameters of the investigated inhibitor (LHP), and some other reported
inhibitors in 5 M HCl.

Figure 11.  SEM surface analysis micrograph for (a) MS immersed in 5 M HCl and (b) after the addition of
370 µmol L−1 of LHP at 20 °C for 24 h.

Figure 12. (a) XPS survey scan composition of the MS immersed in 5 M HCl with 370 µmol L−1 of LHP at
20 °C for 24 h and the profiles of (b) C 1 s, (c) O 1 s, and N 1 s.

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Figure 13.  AFM images for (a) the polished MS surface, (b) after immersion in 5 M HCl and (c) after the
addition of LHP for 24 h at 20 °C.

Figure 14.  Optimized geometry of LHP using the wb97xd/6-311++ g(d, p) level of the calculations.

Figure 15.  Adsorption of LHP on the 100 Fe surface; bond lengths are in Å.

C12-N1 have shortened by 0.017 Å, which results in elongation of N1-N2 by 0.035 Å. Furthermore, the calcula-
tion showed rigid adsorption energies of −2.914, −2.635, and −1.907 kcal mol−1 for iron surfaces with orienta-
tions of 100, 110, and 111, respectively. Although the values of the adsorption energy are not very different, the
adsorption energy values may lead to the conclusion that the 100-iron surface will have the best coverage of the
three surfaces, and that the 111 surface will have the weakest coverage.

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Summary and Conclusion

The LHP eco-friendly corrosion inhibitor has shown extraordinary performance at normal and elevated tempera-
tures in inhibiting the corrosion of MS in 5 M HCl. The efficiency was found to increase as the inhibitor concentra-
tion increased. When the testing temperature increased to 80 °C, a slight decline in efficiency was noted, due to the
increased rate of iron dissolution in the acidic brine and the expected desorption of the attached inhibitor from the
metallic substrate. An inhibition efficiency of more than 94% was successfully achieved upon the addition of the
candidate inhibitor to a concentration of 370 µmol L−1. The relationship between the surface coverage and inhibitor
concentration is consistent with Langmuir’s adsorption isotherm. LHP is found to be a mixed type inhibitor. The
adsorption of the inhibitor on the steel surface was proven to be chemi–physisorption, which is confirmed by the
0
calculated standard Gibbs free energy (∆Gads ). The optimized geometry shows no imaginary frequencies, which
suggests the stability of the converged structure. In addition, the molecular simulation of LHP proved that the
100-iron surface will have better coverage compared to the 110 surface, while the 111 surface will have the weakest
coverage. AFM analyses revealed a significant decrease in the surface roughness under an inhibited condition com-
pared to immersion with no inhibitor added. Additionally, EDS and XPS revealed the presence of nitrogen on the
MS, which validates the adsorption of LHP onto the surface. Applications of this inhibitor for the mitigation of acidic
corrosion in the petroleum and gas industry will add value in terms of enabling safer operations and contributing to
significant cost savings. Further qualification testing of the candidate inhibitor under dynamic conditions is recom-
mended to achieve greater assurance and gain more confidence in the inhibition capabilities.

Data Availability
The raw data required to reproduce these findings can be shared at any time based on direct requests to the au-
thors.

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Acknowledgements
This publication was supported by Qatar University Internal Grant No. GCC-2017-012. The findings achieved
herein are solely the responsibility of the authors. Additionally, the authors thank the Center for Advanced
Materials at Qatar University for their support.

Author Contributions
Mr. Muhsen El-Haddad and Mr. Ahmed Bahgat Radwan contributed equally to this manuscript. Both of them
contributed to the electrochemistry work and manuscript writing. Mr. Mostafa Sliem had significant contribution
in the surface characterization work and manuscript editing. Dr. Walid Hassan was responsible for all the
theoretical part in this manuscript. Dr. Aboubakr Abdullah is the team leader. He gathered everything, checked
the data, discussed it and digested it in one manuscript.

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