International Journal of Electrochemical Science 18 (2023) 100040

Contents lists available at ScienceDirect

International Journal of Electrochemical Science

journal homepage: www.journals.elsevier.com/ijoes

Estimation of the performances of creatine and creatinine as eco-friendly

corrosion inhibitors for copper in sodium hydroxide solution ]]
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Areej Al Bahir
Chemistry Department, Faculty of Science, King Khalid University, Abha 64734, Saudi Arabia

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

Keywords: The performances of two naturally occurring compounds, namely creatine and creatinine as ecologically friendly
Copper corrosion inhibitors versus the corrosion of copper in 0.5 M NaOH solution were inspected using chemical, electrochemical
Creatine and Creatinine and microscopic techniques. The acquired outcomes designated that the inhibition efficiencies (% IEs) of the
Inhibitors investigated compounds were increased with increasing their concentrations and decreased with rising tem-
Thermodynamic and kinetics
perature. The investigated compounds were served as mixed inhibitors with cathodic seniority. The inhibition
performances were interpreted on the basis of their strong adsorption on the copper surface and the adsorption
process obeyed Langmuir adsorption isotherm. Thermodynamic and kinetic parameters were evaluated and
debated that prove the physical adsorption nature of the investigated compounds. The kinetics of copper cor-
rosion and its inhibition by creatine and creatinine were studied. Throughout all applied techniques, the ob-
tained outcomes were in well agreement with each others which confirmed that the examined compounds acted
as excellent inhibitors for copper corrosion in 0.5 M NaOH solution and the values of % IEs of creatine were
slightly higher than those acquired for creatinine at all the studied concentrations.

1. Introduction arginine. Creatinine is a biological waste formed by the metabolism of

Corrosion of metals, a natural phenomenon, is the gradual destruction of
metals and alloys by chemical and/or electrochemical reactions with their
environments that costs the world’s economic much money each year and
causes dangerous ecological impacts. Copper is a strategic metal in various
industrial fields in heating and in cooling systems [1,2]. In addition, copper
alloys are regarded as the chief ingredients in technological device utiliza-
tions, like in manufacture of wire and sheets in electronics, etc [3]. Although
copper imparts a good corrosion resistance in air and in various media [4,5],
copper is subjected to corrosion phenomenon in aggressive media [6,7]. The
corrosion of copper has an adverse effect on the performances of systems
prepared from copper [8]. Therefore, the subject of copper corrosion and its
protection became very significant [9–13].
Corrosion inhibitors are compounds utilized to reduce or hinder
metallic corrosion [14–22]. The performances of such inhibitors depend
on their abilities for adsorption on the metallic surfaces [23–32]. Re-
cently, the improvement of ecological corrosion inhibitors became a
significant topic [33–40]. Creatine and creatinine (their structures
shown below) are naturally occurring nitrogenous organic compounds
[41]. Creatine occurs in vertebrates which helps to supply energy to all
cells in the body. Creatine is produced from the amino acids glycine and
creatine phosphate in muscle, and is usually produced by the body [42].
In this investigation, two naturally occurring compounds: creatine
and creatinine were tested as inhibitors for the corrosion of copper in a
0.5 M NaOH solution. These compounds were selected as inhibitors
because they are eco-friendly, have high water solubility, have good
abilities for adsorption on the metallic surfaces and inexpensive. This
research work was performed using different techniques, namely po-
tentiodynamic polarization (PDP), electrochemical impedance spec-
troscopy (EIS), weight loss (WL) and scanning electron miscroscopy
(SEM). The thermodynamic and kinetic parameters of the corrosion
process were evaluated. The kinetics of copper corrosion and its in-
hibition by the examined compound were also investigated.
.
Structures of creatine and creatinine.

E-mail address: areeej@kku.edu.sa.

https://doi.org/10.1016/j.ijoes.2023.100040
Received 1 October 2022; Accepted 11 November 2022
Available online 22 February 2023
1452-3981/© 2023 The Author(s). Published by Elsevier B.V. on behalf of ESG. This is an open access article under the CC BY-NC-ND license (http://creative-
commons.org/licenses/by-nc-nd/4.0/).
A.A. Bahir International Journal of Electrochemical Science 18 (2023) 100040

2. Experimental

2.1. Materials

A 0.5 M NaOH solution was the corrosive medium used in this paper
which prepared using double distilled water. The examined inhibitors
were creatine and creatinine where their solutions were made in double
distilled water. Experiments were carried out on copper specimens
(Merck 99.9 %). Prior to any experiment, the specimens were polished
with a sequence of emery papers of various sizes up to 1500, washed
with distilled water and dried before use. Each experiment was re-
peated about 3 times for reproducibility. All used chemicals in this
paper were analytical grade chemicals.

2.2. Techniques

Four techniques were applied in this paper, namely potentiody-

namic polarization (PDP), electrochemical impedance spectroscopy
(EIS), weight-loss (WL) and scanning electron microscopy (SEM). For
both electrochemical measurements (PDP and EIS), a thermostated
Potentiostat/Galvanostat (Gamry Reference 600+) was used. A three-
compartment cell was used which composed of a copper sheet with an
area of 1.0 cm2 as the working electrode, a saturated calomel electrode
(SCE) as a reference electrode, and a platinum sheet as a counter
electrode. Before starting any electrochemical measurement, the po-
tential of the working electrode (copper) was measured against SCE and
it was allowed to stabilize for about 20 min. PDP measurements were
conveyed out at scan rate of 2.0 mV/s and the potential was altered in
the range of: −300 to +300 mV vs. OCP (open circuit potential). EIS
experiments were carried out at a frequency range of 100 kHz to 0.1 Hz
with an amplitude of 5.0 mV peak-to-peak. Before each electrochemical
measurement, copper electrode was prepared as reported elsewhere
[37] and was directly inserted into the 0.5 M NaOH solution (corrosive
medium) and in the presence of definite concentrations of the examined
inhibitors at OCP. The WL method was applied to copper sheets with a
mean area for each sheet of about 12 cm2 in glass vessels at fixed
temperatures. These sheets were also prepared for such tests as stated Fig. 1. Potentiodynamic polarization curves of copper in 0.5 M NaOH solution
before [37]. Then, the sheets were immersed in a 100 ml of the tested at 298 K in the presence of: (A) creatine, and (B) creatinine.
solutions for 6 h immersion period. After this period, the copper sheets
were taken out from solution, washed with distilled water, dried and
weighted. A scanning electron microscope (SEM) model T-200 was cathodic hydrogen evolution reaction. The value of Ecorr for copper in
employed to examine the morphologies of the surfaces of copper spe- 0.5 M NaOH solution was slightly moved to negative or cathodic di-
cimens before and after the experiments. All microscopic micrographs rection after addition of the examined compounds indicating that such
of the copper specimens were taken with magnification of × 2500. compounds are mixed inhibitors with cathodic majority [43]. The value
Prior to SEM imaging, the examined specimens were immersed in the of icorr of copper was decreased whereas that of Rp was enhanced with
tested solutions for 24 h. increasing the concentrations of the tested compounds signifying cor-
rosion inhibition.
3. Results and discussion The values of % IEs and the surface coverage (θ) of the tested
compounds were calculated via the following equation [44]:
3.1. PDP Measurements
icorr (inh)
% IE = x 100 = 1 x 100
3.1.1. Effect of Inhibitors’ concentrations icorr (1)
Fig. 1 (A & B) manifests the potentiodynamic polarization (PDP)
curves of copper in the inhibitor-free 0.5 M NaOH solution and in the where, icorr and icorr(inh) are the corrosion current densities without and
existence of several concentrations (100 – 500 mg/L) of the examined with the inhibitors, correspondingly.
inhibitors (creatine and creatinine) at fixed temperature of 298 K. The The results indicated that the values of % IEs were increased with
values of PDP parameters, viz. corrosion potential (Ecorr), anodic (βa) rising the inhibitors’ concentrations. At the same concentrations of the
and cathodic (βc) Tafel slopes, corrosion current density (icorr) and examined compounds, the % IE values of creatine are slightly greater
polarization resistance (Rp) were evaluated and are inserted in Table 1. than those of creatinine. The acquired % IE values at a concentration of
From Fig. 1, it can be observe that, addition of the examined com- 500 mg/L of creatine and creatinine were found to be 89.7 and 86.4,
pounds to NaOH solution shifted the PDP curves towards lower current correspondingly. This confirm that such compounds act as excellent
densities signifying a decrease of the rate of copper corrosion. The inhibitors for copper corrosion in 0.5 M NaOH solution. The acquired
evaluated parameters inserted in Table 1 revealed that the values of greater % IE values were interpreted on the basis of potent adsorption
both βa and βc were decreased with increasing the concentrations of the of the molecules of the examined compounds on the copper surface
examined inhibitors signifying that such compounds are mixed in- leading to a delay of both metal dissolution and hydrogen evolution,
hibitors. i.e. hinder the anodic dissolution of copper and retard the thus lowers the corrosion rate.

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A.A. Bahir International Journal of Electrochemical Science 18 (2023) 100040

Table 1
Potentiodynamic polarization parameters for copper in 0.5 M NaOH solution at 298 K in the presence of creatine and creatinine.

Inhibitor Inh. conc. (mg/L) Ecorr (mV(SCE)) βa (mV/dec.) βc (mV/dec.) icorr (µA/cm2) 10−2 Rp (ohm cm2) % IE θ

0 -278 38 -119 39.1 3.20 – –

Creatine 100 -280 36 -108 15.1 7.77 61.4 0.614
200 -297 35 -102 10.7 10.59 72.6 0.726
300 -293 33 -98 7.9 13.59 79.8 0.798
400 -306 34 -93 5.4 20.05 86.3 0.863
500 -302 31 -88 4.0 24.92 89.7 0.897
Creatinine 100 -282 37 -116 15.3 7.97 60.8 0.608
200 -294 39 -109 11.9 10.78 69.5 0.695
300 -299 36 -104 8.6 13.52 78.0 0.780
400 -296 36 -97 6.2 18.41 84.1 0.841
500 -298 34 -94 5.3 20.48 86.4 0.864

Fig. 2. Effect of concentration of NaOH solution at 298 K on the values of % IEs

of: (A) creatine, and (B) creatinine.

3.1.2. Effect of NaOH concentration on % IEs

The values of % IEs of the investigated compounds were evaluated
by potentiodynamic polarization technique in a variety of concentra-
tions of NaOH solution, i.e. from 0.1 to 1.0 M NaOH in the existence of a
500 mg/L of the compounds at 298 K and are exemplified in Fig. 2. As
presented in Fig. 2, with rising the concentration of NaOH solution, the
values of % IEs were considerably reduced. This behavior can be as-
cribed to the enlarged ferociousness of the corrosive solution with its
concentration.

3.2. EIS Measurements and the effect of inhibitors’ concentrations

The accumulation of species present in solution throughout corro-

sion process at the metal/electrolyte interface leads to the construction
of an electric double layer with capacitance and resistance character-
istic to charge transfer. The constructed double layer can affect both the
mechanism and the rate of electron transfer amongst cathodic and
anodic sites on the metal surface [45]. EIS measurements are beneficial
technique to explain the interfacial property and adsorption behavior of
the inhibitors’ molecules. Fig. 3 (A & B) shows the Nyquist plots of
copper in 0.5 M NaOH solution and in the presence of variety of con-
centrations of creatine and creatinine at 298 K. The acquired Nyquist
plots were found to consist of only depressed capacitive loops signifying
that the adsorption of the examined compounds arises via coverage of
the metal surface [46]. Similar Nyquist plots were recorded in both the
absence and presence of the examined compounds indicating that ad-
dition of such compounds does not alter the mecha*nism of the cor-
rosion process [47]. It was recognized from Nyquist plots that the size
of the capacitive semicircle was set to increase with rising inhibitors’
concentrations indicating a decrease in the corrosion rate of copper.
Fig. 3. Nyquist plots for copper in 0.5 M NaOH solution at 298 K in the pre-
sence of: (A) creatine, and (B) creatinine.
The impedance spectra were analyzed by using a suitable equivalent
circuit including solution resistance (Rs), charge transfer resistance (Rct)
and constant phase element (CPE) which were calculated and are listed
in Table 2. The gained outcomes manifested that rising the concentra-
tion of the added compounds increased the value of Rct. This can be
ascribed to adsorption of the examined compounds on the copper/so-
lution interface leading to the protection of the metal surface [48]. The
values of % IE were calculated via the following equation [49]:
Rct
% IE = 1 x 100
R ct (inh) (2)
where Rct and Rct(inh) are the charge transfer resistance values without
and with the inhibitor, correspondingly.

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A.A. Bahir International Journal of Electrochemical Science 18 (2023) 100040

Table 2
EIS parameters for copper in 0.5 M NaOH solution at 298 K in the presence of creatine and creatinine.

Inhibitor Inh. conc. (mg/L) Rs (ohm cm2) Rct (ohm cm2) CPE (µF/cm2) % IE θ

0 6.82 255 83.72 – –

Creatine 100 11.95 605 42.08 57.8 0.578
200 13.24 846 31.07 69.9 0.699
300 5.81 1190 22.14 78.6 0.786
400 3.71 1722 17.80 85.2 0.852
500 7.12 2256 13.11 88.7 0.887
Creatinine 100 11.57 615 41.11 58.5 0.585
200 14.51 796 31.78 68.0 0.680
300 11.43 1055 23.58 75.8 0.758
400 3.50 1492 18.67 82.9 0.829
500 2.82 1875 14.15 86.4 0.864

The values of % IEs were improved with rising the concentration of manifests that the weight loss of copper was reduced with increasing
the examined compounds demonstrating that such compounds are ex- the concentrations of the tested compounds confirming that these
cellent inhibitors for the corrosion of copper in sodium hydroxide so- compounds played as inhibitors for copper corrosion. The corrosion
lution. As obtained from PDP measurements, the % IE values of creatine rate (CR) of copper was evaluated from the equation [50]:
were greater than those of creatinine.
KW
CR (mpy ) =
Atd (3)
3.3. WL measurements
6
where, mpy is mils penetration per year, K is a constant (3.45 ×10 ), W
3.3.1. Effect of inhibitors’ concentrations is the weight loss in grams, A is the area of copper sheet in cm2, t is the
WL experiments of copper in 0.5 M NaOH solution and in the pre- time in hour and d is the copper density. The values of % IEs were
sence of several concentrations of creatine and creatinine were per- calculated from the equation [44]:
formed at four temperatures from 288 to 318 K. Fig. 4 (A & B) illustrates CRinh
only the WL versus immersion time plots gained at 298 K. The figure % IE = x 100 = 1 x 100
CR (4)

where CR and CRinh are the corrosion rates without and with the in-
hibitor, respectively.
Values of CR, % IE and θ of the examined compounds are listed in
Table 3 which indicate that the value of CR of copper in NaOH solution
was decreased and the values of % IEs of the examined compounds
were enhanced with augmenting their concentrations. These outcomes
resulted in the conclusion that these compounds were acted as excellent
inhibitors for the corrosion of copper in 0.5 M NaOH solution. In
agreement with the applied PDP and EIS techniques, the values of % IEs
of creatine were slightly higher than those of creatinine confirming the
consistency and validity of obtained results.

3.3.2. Effect of immersion time on % IEs

The effect of immersion time on the values of % IEs of the ex-
amined compounds with a concentration of 500 mg/L in 0.5 M NaOH
solution was tested for periods of time from 6 to 30 h at fixed tem-
perature of 298 K and is illustrated in Fig. 5. The figure manifests that
the values % IEs increase significantly with enlarging the immersion
time up to approximately 16 h, then increased slightly and finally
reach constant values. This behavior can be interpreted as follows: at
first periods, increasing the values of % IEs with time was attributed
to adsorption of multilayers of the molecules of the tested inhibitors
on the copper surface leading to enhancement of % IEs. After ap-
proximately 16 h, the adsorbed layers became more compacted and
stable on the copper surface. This indicates that the examined com-
pounds are excellent inhibitors for the corrosion of copper in 0.5 M
NaOH solution.

3.3.3. Effect of temperature

Fig. 4. WL against immersion time plots for copper in 0.5 M NaOH solution at
298 K in the presence of: (A) creatine, (B) and creatinine.
The impact of increasing temperature on copper corrosion in 0.5 M
NaOH solution and in the presence of the applied concentrations of the
examined compounds was inspected. The values of the corrosion
parameters gained from the WL results are inserted in Table 3. Also,
Fig. 6 (A & B) illustrates the variation of % IE values with temperature.
The data inserted in Table 3 and Fig. 6 indicated that as the temperature
rises, the values of CR increase whereas the values of both % IEs and θ
diminish. This shows that the inhibition was decreased at higher

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A.A. Bahir International Journal of Electrochemical Science 18 (2023) 100040

Table 3
Mean values of corrosion rates (CRs) of copper in 0.5 M NaOH solution and in the presence of creatine and creatinine at diverse temperatures.

Inhibitor Conc. (mg/L) 288 K 298 K 308 K 318 K

CR % IE θ CR % IE θ CR % IE θ CR % IE θ
0 23.40 – – 28.61 – – 32.11 – – 35.30 – –

Creatine 100 8.30 64.5 0.645 10.53 63.2 0.632 13.29 58.6 0.586 16.31 53.8 0.538
200 5.66 75.8 0.758 7.58 73.5 0.735 10.05 68.7 0.687 12.36 65.0 0.650
300 3.74 84.0 0.840 5.32 81.4 0.814 6.90 78.5 0.785 8.79 75.1 0.751
400 2.64 88.7 0.887 3.81 86.7 0.867 4.82 85.0 0.850 6.71 81.0 0.810
500 2.11 91.0 0.910 2.80 90.2 0.902 3.98 87.6 0.876 5.51 84.4 0.844
Creatinine 100 8.98 62.0 0.620 11.53 59.7 0.597 14.13 56.0 0.560 16.13 54.3 0.543
200 6.04 74.2 0.742 8.55 70.1 0.701 10.15 68.4 0.684 12.21 65.4 0.654
300 4.49 80.8 0.808 6.04 78.9 0.789 8.48 73.6 0.736 9.88 72.0 0.720
400 3.30 85.9 0.859 4.43 84.5 0.845 6.36 80.2 0.802 8.51 75.9 0.759
500 2.78 88.1 0.881 3.95 86.2 0.862 5.65 82.4 0.824 7.31 79.3 0.793

Fig. 5. Effect of immersion time on the values of % IEs of: (A) creatine, and (B)
creatinine for the corrosion of copper in 0.5 M NaOH solution at 298 K.

temperatures indicating that the nature of adsorption of inhibitors’

molecules on the metal surface was physical [51].

3.3.4. Adsorption isotherms

The results of the three applied techniques (PDP, EIS and WL)
confirmed that the examined compounds are excellent inhibitors for the
corrosion of copper in 0.5 M NaOH solution. This action was interpreted
by potent adsorption of the inhibitors’ molecules on the copper surface
and constructing protective layer(s). It was reported [52] that two kinds
of adsorption process were suggested: physical and chemical. For ex-
amining the best adsorption kind, the experimental outcomes acquired
at different temperatures were applied on variety of adsorption iso-
therms such as Langmuir, Temkin, Freundlich, Frumkin, Flor-
y–Huggins, etc. It was found that Langmuir isotherm was the most
appropriate adsorption isotherm corresponding to the equation [53]:

Cinh 1 Fig. 6. Effect of rising temperature on the values of % IE values of: (A) creatine,
= + Cinh and (B) creatinine for the corrosion of copper in 0.5 M NaOH solution.
K ads (5)

where Kads is the adsorption constant.

Fig. 7 illustrates Langmuir isotherm for the adsorption of the ex-
amined compounds on the surface of copper in 0.5 M NaOH solution at
several temperatures. Straight lines were acquired with gradients of
about unity. The values of Kads were calculated from the intercept of
Langmuir isotherms at different temperatures and are recorded in
Table 4. Values of Kads were found to decrease with rising temperature
suggesting promotion of the adsorption process of the inhibitors’ mo-
lecules on the metal surface at lower temperatures and desorption of
the adsorbed molecules at higher ones.
3.3.5. Thermodynamic parameters
In order to give significant information about the mechanisms of
corrosion process and its inhibition, thermodynamic parameters of the
adsorption process like standard free energy (ΔG°ads), standard heat
(ΔH°ads) and standard entropy (∆S°ads) were evaluated and are listed in
Table 4. The values of ΔG°ads were computed at various temperatures by
the following equation [54]:
ΔG°ads = ‐RT ln(55·5 Kads) (6)

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A.A. Bahir International Journal of Electrochemical Science 18 (2023) 100040

Fig. 8. Van’t Hoff plots for: (A) creatine, and (B) creatinine, adsorbed on
copper in 0.5 M NaOH solution.

Fig. 8 shows the relationship between ln Kads and 1/T. The values of
ΔH°ads were gained from the slopes of the straight lines and are listed
also in Table 4. The acquired negative values of ΔH°ads signified that the
adsorption of examined inhibitors was exothermic with a physical
nature [55,56].
Also, via Gibbs–Helmholtz equation the values of ∆S°ads were cal-
culated:

∆G°ads = ∆H°ads - T∆S°ads (8)

The acquired positive values of ΔS°ads signified rising in the ran-

domness of the adsorbed inhibitors’ molecules at the copper/solution
interface. This may be as a result of more and more H2O molecules were
desorbed from the copper surface by inhibitors’ molecules [57].

3.3.6. Kinetic parameters

Fig. 7. Langmuir adsorption isotherms for: (A) creatine, and (B) creatinine,
adsorbed on copper in 0.5 M NaOH solution at variety of temperatures.
The obtained negative ΔG°ads values suggest that the adsorption of
inhibitors’ molecules was spontaneous and the absorbed protective
layer on the copper surface was stable. This is in a good agreement with
% IEs of the examined compounds obtained from all applied techni-
ques. Also, the obtained values of ΔG°ads illuminated that the adsorption
mechanism of the examined inhibitors in 0.5 M NaOH solution could be
a mixed in its nature, i.e. physical and chemical [55].
Using the van’t Hoff equation, the values of ΔH°ads were calculated
as follows [50]:
H o ads
lnK ads = + Constant
RT
The effect of temperature on the value of CR is inspected by
Arrhenius equation which gives the values of the activation energy
(Ea*) [58]:
Ea*
ln CR = ln A
(9)
RT
Fig. 9 shows the relationship between ln CR and 1/T for copper in
0.5 M NaOH solution at several concentrations of the tested com-
pounds. The values of Ea* obtained from the gradient of the straight
lines are listed in Table 5. The values of Ea* obtained in the presence of
the tested compounds were higher than that in the free corrosive so-
lution illuminating that the molecules of the examined compounds are
adsorbed on the copper surface constructing a barrier between the
surface and the corrosive solution [59,60]. The gained Ea* values were
(7)
in the range of 14.27–24.86 kJ/mol which are lesser than 80 kJ/mol,

Table 4
Values of Kads and thermodynamic parameters for the corrosion of copper in 0.5 M NaOH solution with various concentrations of creatine and creatinine at various
temperatures.

Inhibitor Temperature (K) 10−3 Kads L/mol ∆Goads kJ/mol ∆Hoads kJ/mol ∆Soads J/mol K

Creatine 288 2.08 -27.91 -11.22 57.95

298 1.89 -28.65 58.49
308 1.57 -29.12 58.12
318 1.35 -29.68 57.96
Creatinine 288 2.02 -27.84 -6.64 73.61
298 1.77 -28.48 73.29
308 1.67 -29.28 73.51
318 1.54 -30.02 73.52

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A.A. Bahir International Journal of Electrochemical Science 18 (2023) 100040

Fig. 10. Transition state plots for copper corrosion in 0.5 M NaOH solution and
Fig. 9. Arrhenius plots for copper corrosion in 0.5 M NaOH solution and in the in the presence of a variety of concentrations of: (A) creatine, and (B) creati-
presence of variety of concentrations of: (A) creatine, and (B) creatinine. nine.

Table 5
Activation parameters for copper corrosion in 0.5 M NaOH solution and in the where, N is Avogadro’s number and h is Planck’s constant.When the
presence of various concentrations of creatine and creatinine. values of ln(CR/T) were plotted against those of 1/T, straight lines were
Inhibitor Inh. conc. Ea* ∆H* ∆S* obtained as illustrated in Fig. 10 (A & B). The calculated ΔH* and ΔS*
(mg/L) kJ/mol kJ/mol J/mol K values are presented in Table 5. The acquired positive sign of ΔH* il-
luminated that the corrosion process was endothermic. Additionally,
0 10.31 7.82 -64.02
the acquired great negatively values of ΔS* signify a great reduce in the
Creatine 100 17.21 14.72 -78.98
200 20.01 17.46 -85.63 disorder as a result of construction of activated complexes [64,65].
300 21.53 19.08 -87.71 On comparing the variation of the values of % IEs of the tested
400 23.11 20.62 -90.04 compounds obtained from all applied tools, PDP, EIS and WL as a
500 24.57 22.03 -99.60 function of their concentrations in the copper corrosion in 0.5 M NaOH
Creatinine 100 14.97 12.46 -72.08
solution at 298 K, a great consistence between the results was attained
200 17.46 14.97 -77.57
300 20.62 18.12 -86.05 as manifested in Fig. 11. This confirms the rationality of the gained
400 24.36 21.87 -96.11 outcomes.
500 24.86 22.36 -96.44
3.3.7. Kinetics of copper corrosion and its inhibition
To investigate the kinetics of copper corrosion in 0.5 M NaOH so-
required for chemical adsorption, signifying that the mechanism of lution and its inhibition by the examined compounds, the values of –ln
adsorption was physical [61,62]. These findings are in a good agree- WL were plotted against dipping time at 298 K. Straight lines were
ment with those based on the values of both ΔGoads and ΔHoads proving obtained as illustrated in Fig. 12 (A & B). This behavior confirms that
the rationality of the obtained results. the kinetics of copper corrosion in the tested solution and its inhibition
The transition state equation [63,64] give the values of the enthalpy by the tested compounds were negatively first order reactions. The first
of activation (ΔH*) and entropy of activation (ΔS*) of corrosion, order rate constant values, k1 (in h−1), gradients of these plots, were
evaluated and are inserted in Table 6. The values of half-life times (t1/2,
CR R S* H* 1 h) were calculated from the values of k1 (t1/2 = 0.693/k1) and are also
ln = ln +
T Nh R R T (10) inserted in Table 6.

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A.A. Bahir International Journal of Electrochemical Science 18 (2023) 100040

Fig. 11. Comparison between the values of % IEs of: (A) creatine, and (B) creatinine, gained from PDP, EIS and WL techniques in the copper corrosion in 0.5 M NaOH
solution at 298 K.

Table 6
Values of first-order rate constant (k1) and half-life times (t1/2) for copper
corrosion in 0.5 M NaOH solution and in the presence of a variety of con-
centrations of creatine and creatinine at 298 K.

Inhibitor conc. Creatine Creatinine

(mg/L)
103 k1, h−1 t1/2, h 103 k1, h−1 t1/2, h

Blank 77 9.01 77 9.01

100 84 8.25 82 8.45
200 83 8.35 83 8.35
300 88 7.88 84 8.25
400 86 8.06 89 7.79
500 87 7.97 90 7.70

Fig. 13. log CR vs. log Cinh for the inhibition of copper corrosion in 0.5 M
NaOH solution using: (A) creatine, and (B) creatinine at 298 K.

Fig. 12. First-order rate constant plots in the copper corrosion in 0.5 M NaOH
solution and in the presence of various concentrations of: (A) creatine, and (B)
creatinine at 298 K.
Moreover, the order (n) of corrosion inhibition of copper with re-
spect to the concentrations of the examined compounds (Cinh) were
calculated using Eq. (10) [66–68]:
log CR = log k + n log Cinh (10)
2
where, k refers to the specific rate constant (mg/cm h).
The plots of log CR versus log Cinh at 298 K were linear as shown in
Fig. 13. Values of n were set to be − 0.85 and − 0.79 for creatine and
creatinine, correspondingly. The acquired values of n suggest that the
corrosion inhibition was negative fractional-first order reactions re-
garding to the inhibitors concentration. The negative sign of n values
and the opposite dependence of the CRs with the inhibitors’ con-
centrations (as shown in Fig. 13) illuminated good % IEs of the ex-
amined compounds [69,70].

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A.A. Bahir
Fig. 14. SEM micrographs (x 2500) of the surfaces of copper specimens; (A) before, and (B) after immersion in 0.5 M NaOH solution for 24 h, (C & D) after 24 h
immersion in 0.5 M NaOH with a 500 mg/L of creatine and creatinine, respectively.
3.4. Surface investigation
The morphologies of the surfaces of copper samples before and after
immersion (for 24 h) in 0.5 M NaOH in the absence and presence of a
500 mg/L of the tested compounds were investigated by SEM technique
and are presented in Fig. 14 (A – D). Fig. 12 manifests a polished copper
surfaces: (A) before, and (B) after immersion in NaOH solution where
the later shows a scratched and corroded copper surface. Fig. 14 (C) and
(D) show micrographs of the copper surfaces after addition of a
500 mg/L of creatine and creatinine, respectively, to the tested solution.
Such micrographs show vanishing of the damage which was observed in
the copper surface immersed in NaOH solution, and the surfaces of
copper specimens were mainly covered with the molecules of the ex-
amined inhibitors. This is due to potent adsorption of such compounds
on the metal surfaces leading to protection of the copper surfaces, thus
demonstrating excellent inhibitive properties.
4. Conclusions
• The performances of creatine and creatinine as ecologically friendly
inhibitors versus copper corrosion in 0.5 M NaOH solution were
inspected using several techniques.
• The examined compounds were discovered to be excellent inhibitors
for copper corrosion in 0.5 M NaOH solution.
• The inhibition efficiencies (% IEs) of the tested compounds were
increased with increasing their concentrations and decreased with
rising temperature.
• The tested compounds behave as mixed inhibitors with cathodic
priority.
•
The % IEs were interpreted on the basis of their strong adsorption on
the copper surface and the adsorption process obeyed Langmuir
adsorption isotherm.
• Thermodynamic and kinetic parameters were evaluated and dis-
cussed that prove the physical adsorption nature of the examined
compounds.
• The kinetics of copper corrosion and its inhibition by creatine and
creatinine were investigated.
• Through all applied techniques, the obtained results were in well
agreement with each others.
9
International Journal of Electrochemical Science 18 (2023) 100040
• The values of % IEs of creatine were slightly higher than those ac-
quired for creatinine.
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