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

https://doi.org/10.1007/s40735-019-0312-y

Mathematical Modeling and Electrochemical Behavior for Corrosion

Inhibition of Steel by Kiwi Juice Extract
Khalid H. Rashid1 · Anees A. Khadom2 

Received: 1 September 2019 / Revised: 10 October 2019 / Accepted: 20 November 2019

© Springer Nature Switzerland AG 2019

Abstract
The inhibition influence of kiwi juice extract (KJE) for corrosion of steel in 2.5 M hydrochloric acid has been studied by
polarization technique at various temperatures and inhibitor concentrations. The maximum inhibition efficiency was 87%
at 45 °C and 55 cm3/L concentration of inhibitor, while the minimum value was 81% at 45 °C and 5 cm3/L concentration of
inhibitor. Polarization curves showed that KJE is a mixed-type inhibitor but the cathode is more polarized than the anode.
The polarization curve curvature region near the potential of corrosion can be investigated depending on the overvoltage data
as a function of current densities. These data can be analyzed by suggesting a mathematical model to take into account the
influence of diffusion on the charge transfer process. The results obtained from electrochemical technique and mathematical
model are in good agreement.

Keywords  Low-carbon steel · Corrosion inhibition · Mass transfer · Green inhibitor

1 Introduction a comprehensive experimental work. Several methods are

Steel and its alloys are commonly utilized in the equipment
of petroleum refineries, pipelines, tank constructions, etc.
[1]. The principal issue of utilizing alloys of steel is the
aggressive reaction in acidic solution [2]. Acidic solutions
are generally used for clearing of rust, undesirable scale and
oil-well acidizing in numerous industrial cleaning processes
[3]. Corrosion can be controlled by different methods, such
as coating [4], cathodic protection [5], inhibitors [6], etc.
Inhibitors are added in small amount and widely used to
prevent or reduce the corrosion rates in acidic solutions
[7]. Corrosion inhibitors can be classified as inorganic [8]
and organic materials [9]. Consequently, organic corrosion
inhibitors can be subdivided to artificial synthesis [10] and
natural extracts [11]. Natural extracts have recently been
used as environmentally friendly, non-toxic, safely used
and economic anticorrosion materials [12–14]. Inhibi-
tion performance cannot be predicated without the use of
* Anees A. Khadom
aneesdr@gmail.com
1
Department of Chemical Engineering, University
of Technology, Baghdad, Iraq
2
Department of Chemical Engineering, College
of Engineering, University of Diyala, Baquba, Iraq
available for corrosion rate evaluation. Weight loss [15],
electrochemical polarization [16] and electrochemical
impedance spectroscopy [17] are the most common tech-
niques. An electrochemical polarization technique based
on Tafel extrapolation was widely used for the calculation
of corrosion parameters, such as corrosion current density,
corrosion potential and Tafel slopes [3]. Tafel extrapolation
technique assumed linear regions in the anodic and cathodic
curves. In other words, this technique neglects the effect of
mass transfer on the activation process.
It has been reported that plant extracts own significant
inhibitive performance and limited ecological hazards [18,
19]. Several previous studies are available about the suitabil-
ity of plant extracts as corrosion inhibitors of steel in hydro-
chloric acid, such as Ficus tikoua leaf extract with efficiency
of 95.8% for carbon steel [20], bitter kola leaf extract with
efficiency of 90% [21], Glycyrrhiza glabra leaf extract with
efficiency of 88% [22], Xanthium strumarium extract with
efficiency of 94.8% [23], peach juice with efficiency of 91%
[24], kiwi juice with efficiency of 96.1% [25], etc.
The aim of this study is to investigate the inhibition
influence of extracted kiwi juice as a cheap, raw and non-
toxic corrosion inhibitor on low-carbon steel corrosion in
2.5 M HCl at various temperatures. Mathematical modeling
was suggested to investigate the effect of mass transfer on

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activation polarization process. The mass transfer impact
on rates of corrosion was studied by the use of some funda-
mental hypothetical models. Electrochemical parameters and
kinetics were also calculated and compared.
2 Mathematical Approach
curve for the situation when the cathodic reaction is under
material transport dominance (ilim = icorr), mixed dominance
(ilim > icorr), or charge transfer dominance (ilim = ∞). On the
off chance that the exponential terms of Eq. 1 are extending
in the arrangement, at that point, the polarization equation
curve becomes an equation of polynomial [28] as:
i(𝜂) = Co + C1 𝜂 + C2 𝜂 2 + C3 𝜂 3 + … + Cn 𝜂 n (4)

The trendy used techniques for the calculation of rates of where Co, C1, C2, … Cn is constants. Equation 4 is a non-
corrosion from measurements of polarization are based linear equation of overpotential–current relationship. The
totally on the idea that the manner is managed via the coefficients of η can be acquired by a nonlinear estimation
cathodic and anodic rate partial reactions. The supply of technique. MATLAB v.12 (MATLAB Professional) software
reactants is limitless, and the mixed-predominant case, at program was used for estimation method. Experimental
the point when the process rate is together constrained by results of current (i) as a function of over potential (η) for
the reaction of surface, and the material transport from and low steel corrosion in 2.5 M HCl solution in the presence
to the surface has been substantially less explored, indeed, and absence of KJE as a corrosion inhibitor were used as
even idea this case may as often as possible reflect workable source data. Overpotential range was − 400 to 400  mV
circumstances. In this way, it is essential to think about the from corrosion potential. Equation 4 can be written as the
impact of disregarding the mass exchange on parameters of Maclaurin form as:
corrosion. From this point of view, it is valuable for circum- ( ) ( ) ( )
𝜕i 1 𝜕2 i 1 𝜕ni
stances when the transport impact of mass is insignificant; i(𝜂) = 𝜂+ 𝜂 2
+ … + 𝜂n
𝜕𝜂 𝜂=0 2! 𝜕𝜂 2 𝜂=0 n! 𝜕𝜂 n 𝜂=0
that is, the concentrations of the surface are equivalent to
the concentrations of the bulk and the observed overvoltage (5)
is equivalent to the transfer overvoltage of charge. If trans- By examination of Eq. 4 with Eq. 5, the coefficient of
port impact of mass is significant, the above assumptions polynomial can be composed as a set of following equations:
must be altered. Two alterations are required: the first one is C0 = 0
the observed overvoltage must be adjusted for the transport {( ) ( ) }
1 1
overvoltage of mass, and secondly, the density of exchange C1 = 2.303 icorr
ba
+
bc
(1 − 𝛽)
current has to be expressed as a function of bulk concentra- {( )
2 ( )2 }
1 1
tions. In the wake of considering these two presumptions,
2
( )
2C2 = 5.303 icorr − 1 − 3𝛽 + 2𝛽
ba bc
the following equation can be used [26]: {( )
3 ( )3 }
1 1
1 − 7𝛽 + 12𝛽 2 − 6𝛽 3
( )
6C3 = 12.214 icorr +
ba bc
[ ( ) ( )]
2.303 𝜂 2.303 𝜂
i = icorr exp − 𝜆 exp − (1) {( )
4 ( )4 }
ba bc 24C4 = 28.13 icorr
1
−
1 (
1 − 15𝛽 + 50𝛽 2 − 60𝛽 3 + 24𝛽 4
)
ba bc

1 (6)
𝜆=
icorr icorr
( )
(2) The dimensionless factor (β) or (icorr/ilim) has two con-
1− + exp − 2.303 𝜂
ilim ilim b c straining cases; the estimations of β have two constrain-
ing cases; β approaches zero, the kinetics of corrosion
where λ is the correction factor of mass transfer, which can
is subjected by the transportation of slow charge; and β
be written in the formula [27]:
approaches one, the restricting phase of the all-out procedure
1 is the depolarizer transport to the surface of the electrode.
𝜆=
(3) Korobove and Medvedeva [29] recommended that in the
( )
1 − 𝛽 + 𝛽 exp − 2.303 𝜂
b c scope of β > 0.95 and β < 0.05, it is conceivable to utilize
the simplified form of Eqs. 1 and 6 (for diffusion and activa-
β = icorr/ilim and ilim is the limiting diffusion current. Equa-
tion mechanism) without the accuracy of counts assessment.
tion 1 is totally general in that it portrays the polarization

13
Journal of Bio- and Tribo-Corrosion (2020) 6:13 Page 3 of 8  13
3 Experimental Work
The electrochemical conduct of low-carbon steel alloy was
studied using polarization technique with and without kiwi
juice extract (KJE) in 2.5 M HCl solution at various tem-
peratures (15, 25, 35, 45, 55 and 65 °C) and various con-
centrations of inhibitor (5, 15, 25, 35, 45 and 50 cm3/L).
Coupons of low-carbon steel alloy with dimensions of
3 cm length, 0.2 cm thickness and 2 cm width. The sam-
ples were first degreased by analar benzene and acetone,
then washed by the cleanser and rinsed by tap water pur-
sued by deionized water, then annealed in vacuum fur-
nace at 600 °C for 1 h and cooled under vacuum to 25 °C.
Annealing process was used for stresses removal. Prior
to each run, low-carbon steel samples were rubbed with
a series of silicon carbide abrasive paper (160, 220, 320,
400 and 600), then flushed by running tap water pursued
by deionized water, then dried with an immaculate cloth,
dipped in benzene, dried, dipped in analar ­C2H6O, dried
and lastly kept in a desiccator over silica gel until time of
use. The chemical compositions (wt%) of low-carbon steel
were 0.04% C, 0.309% Mn, 0.004% Si, 0.005% P, 0.007%
S, 0.021% Cr, 0.0009% Mo, 0.010% Ni, 0.004% Al, and
the remainder is Fe. The potentiostat measurements were
carried out in Wenking M-Lab device of Bank Electronic,
Germany, which contains the auxiliary electrode (Pt/Ti),
reference electrode (SCE) and the working electrode. The
polarization measurements were carried out in a cylindri-
cal glass beaker corrosion cell of 2 L. The cell contains
the working electrode (low-carbon-steel coupon), refer-
ence electrode (SCE), auxiliary electrode (Pt/Ti) and ther-
mometer. The saturated calomel reference electrode (SCE)
which was bridged by a Luggin–Haber capillary was set
near from the working electrode at a distance of not more
than the optimum value of 1.5 mm to minimize the experi-
mental error. Before each test, the cell and electrodes were
washed with running tap water, followed by deionized
water. The working electrode was placed in position and
immersed in the test solution at required temperature and
inhibitor concentration. After that, the corrosion cell parts
were joined to each other and then allowed to vary a volt-
age and recording current (i.e., ± 400 mV from Ecorr). The
investigation was carried out by using M-Lab software.
Potential against the current was recorded continuously
during the test; the results can be read directly on the dis-
play of the monitor.
4 Results and Discussion
4.1 Electrochemical Polarization Measurements
A polarization measurement at different temperatures
was evaluated. Then, at 45 °C, the polarization data were
evaluated at different inhibitor concentrations. Figure 1
demonstrates the polarization curves in the absence and
presence of KJE at different concentrations at 45 °C. Elec-
trochemical parameters of the corrosion process were
estimated by Tafel extrapolation method using polariza-
tion curve and listed in Table 1, while electrochemical
parameters evaluated using β-model (Eq. 6) are listed in
Table 1. Values of inhibition efficiency (% IE) [30] were
also calculated using Eq. 7 and listed in Tables 1 and 2.
(o
icorr − icorr
)
%IE = × 100 (7)
iocorr
The arrangements of Eq. 6 can be solved with the assis-
tance of MATLAB and Statistics Toolbox Release 2018
Substitution Method. Tables 1 and 2 show that the values
of corrosion current densities increase with an increase in
temperatures in the absence of inhibitor, while it decreases
with the increase in the inhibitor concentrations at 45 °C.
The potential of corrosion is affected by both temperature
and concentrations of inhibitor. In the inhibitor absence, the
potential of corrosion shifts to more active values as the tem-
perature increased from 15 to 65 °C. At a constant tempera-
ture, the potentials of corrosion in the presence of inhibitor
are shifted to more positive direction as the concentrations
of inhibitor increased. It is observed in Fig. 1 that the addi-
tion of KJE affects both the cathodic and anodic curve parts.
Therefore, KJE acts as mixed-type inhibitor, although the
small corrosion potential shifts in the positive sense as com-
pared to the uninhibited solution showing that the effect on
the anodic reaction is somewhat more pronounced than on
the cathodic reaction, and the further enhancement of the
corrosion inhibition with increasing concentration is almost
entirely due to the change in the anodic branch. Furthermore,
the inhibitor can be classified as the cathodic or anodic type
when the change in Ecorr value is larger than 85 mV [31]. The
largest displacement exhibited by KJE is 53 mV (Table 1).
Then this inhibitor molecule can be considered as mixed-
type inhibitors. Furthermore, the values of il > icorr, and β
ranged from 0.01 to 0.1 in the absence and presence of inhib-
itor at various temperatures. This indicates the mixed control
corrosion mechanism, with more effect for activation control
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Fig. 1  Anodic and cathodic 100

Tafel polarization curves for
LC-steel alloy in 2.5 M HCl 0
containing different concentra-
tions of KJE at 45 °C
-100

-200

Potential (mV) vs. SCE

-300

-400

Blank
-500 3
5 cm /L
-600 15 cm 3/L
25 cm 3/L
-700
35 cm 3/L
-800 45 cm 3/L
55 cm 3/L
-900
-4 -3 -2 -1 0 1 2 3 4 5 6 7

Log i ( µA/cm 2 )

Table 1  Corrosion parameters CEKJ ­(cm3/L) Temp. (°C) Ecorr (mV) Icorr (μA/cm2) + ba (mV) − bc (mV) % IE
Tafel extrapolation method
Blank 15 − 389.59 2040.8 143.2 141.2
25 − 396.46 2095.4 135.2 138.1
35 − 398.88 2123.2 134.8 139.7
45 − 398.91 2350.4 132.5 142.4
55 − 400.16 2454.3 126.5 141.3
65 − 409.56 3717.7 117.5 134.2
5 45 − 373.62 460.99 115.2 134.1 80.3
15 − 359.87 408.11 130.7 148.9 82.6
25 − 357.23 403.44 138.1 141.2 82.9
35 − 352.99 380.37 126.2 124.7 84.1
45 − 350.76 368.14 147.6 135.8 84.5
55 − 346.12 330.86 141.9 137.8 86.2

Table 2  Corrosion parameters CKJE ­(cm3/L) Temp. (°C) icorr (μA/cm2) iL (μA/cm2) β + ba (mV) − bc (mV) % IE
using β-model method
Blank 15 2229.2 34,500.5 0.065 139.2 139.2 –
25 2288.8 39,642.9 0.058 130.2 133.1 –
35 2319.2 43,475.6 0.053 130.8 136.7 –
45 2596.8 45,852.8 0.057 127.5 137.4 –
55 2680.8 47,839.4 0.056 122.5 147.3 –
65 4060.8 312,088.5 0.013 110.2 138.2 –
5 45 503.5 27,091.9 0.019 112.2 137.1 80.6
15 445.8 21,755.4 0.020 126.3 155.4 82.8
25 440.6 20,991.3 0.021 134.1 146.1 83.1
35 415.4 19,128.5 0.022 121.6 126.2 84.2
45 402.1 16,509.8 0.024 140.1 140.5 84.5
55 361.4 9897.2 0.037 146.9 144.4 86.1

13
Journal of Bio- and Tribo-Corrosion (2020) 6:13 Page 5 of 8  13
(because of β < 0.5). In the presence of inhibitor, the average
values of β were 0.02. Generally, the values of β are almost
stable as the inhibitor concentration increases. This stability
may indicate that the addition of KJE will make the charge
transfer process stable by adsorption on the metal surface,
i.e., the charge transport step will be fixed. This indicates the
adsorption of KJE on the metal surface, which adsorbed on
anodic and cathodic areas. However, it was concluded that
in the aerated system, KJE inhibits the anodic dissolution
of steel and the oxygen reduction reactions of steel in acidic
solution [32]. The effect of temperature at different inhibi-
tor concentrations on the values of β was approximately
negligible. The values of limiting diffusion current density
were increased with both temperature increasing and inhibi-
tor concentration decreasing. The values of icorr, ba, and bc
obtained from both methods were slightly deviated. This
deviation may be due to the influence of mass transport on
the activation process. Although the effect of mass transfer is
low in acidic solution, a mass transfer correction factor was
needed to take into account the deviations and nonlinearity
of the polarization curve near the corrosion potential. This
will be highly significant in a system of mixed control mech-
anism (activation + mass transfer) to get accurate results.
4.2 Mass Transfer Correction Factor
In acidic solution the step of charge transfer is dominated
due to the high concentration of hydrogen ions. In other
words, the mass transfer of ­H+ ions from bulk of the solution
Fig. 2  Mass transfer correc-
tion factor as a function of over
potential in the absence and
presence of KJE at 45 °C (cor-
relation coefficients (R2) of all
curve are 0.99)
to the metal surface is faster than charge transfer step. This
assumption leads to neglecting of mass transfer effect. How-
ever, the presence of corrosive species, such as hydrogen
and oxygen, leads to deviation from previous assumption.
Equation 3 can be utilized to determine the mass transfer
correction factor (λ) at various values of β and bc. The values
of λ as a function of overpotential are shown in Fig. 2. It
is known that both activation and concentration polariza-
tions usually occur at the electrode. At low rates of reac-
tion, the polarization of activation usually controls, while
at higher reaction rates concentration polarization becomes
the controlling factor. The total electrode polarization is
the sum of the contributions of activation and concentra-
tion polarizations (η = ηA + ηC) [33]. Therefore, as shown in
Fig. 2, the values of λ will approach unity at low overpoten-
tial and decrease as overpotential increases. Generally, the
values of λ increase with inhibitor concentrations, and these
values approach unity at low overpotential. This behavior
may be attributed to the adsorption of the inhibitor on the
metal surface; this adsorption will inhibit both the anodic
and cathodic reactions. The anodic reaction was assumed to
be always under charge transfer control, while the cathodic
reaction is a mixed control so that the inhibitor adsorption
will slow down the charge transfer step. This step will con-
trol the corrosion process more than the mass transport step
and the value of λ approaches unity (i.e., the correction fac-
tor becomes less important at low overpotential and as the
concentration of inhibitors increased).
13
 13   Page 6 of 8 Journal of Bio- and Tribo-Corrosion (2020) 6:13

4.3 Polarization Resistance polarization resistance is a measure of a metal to undergo

corrosion in a certain environment; it is a slope of the poten-
The approach that suggested here was to use the values of tial–current (η–i) curve at the corrosion potential, i.e.,
the second coefficient of β-model (C1) to evaluate the value
𝜕E 1
( )
of polarization resistance (Rp). It is clear that when β is equal RP = = (8)
𝜕i E=Ecorr C
to zero, the value of C1 is equal to 1/RP. This analysis may 1

take into account the nonlinearity of the polarization curve
near the corrosion potential. The polarization resistance
(Rp) of low-carbon steel in HCl solution in the absence and
presence of KJE at different conditions was studied using
the values of the second coefficient (C1) of β-model. The
The shape of this curve around the corrosion potential,
and hence, Rp is determined by the sum of the partial η–i
curves of both anodic and cathodic half-reactions. The
shape of both curves, in turn, depends on the respective

Fig. 3  a The effect of tempera- a

ture on polarization resistance 15
of LC-steel alloy in 2.5 M HCl
in the absence of KJE. b The 14
effect of inhibitor concentration
on polarization resistance of
LC-steel alloy in 2.5 M HCl in 13
the presence of KJE at 45 °C
12
R p (Ohm.cm 2)

11

10

6
10 20 30 40 50 60 70
o
Temperature ( C)
b 95

90

85

80
Rp (Ohm.cm 2)

75

70

65

60

55

50
0 10 20 30 40 50 60
3
Inhibitor Concentration (cm /L)

13
Journal of Bio- and Tribo-Corrosion (2020) 6:13 Page 7 of 8  13
kinetic parameters of their reaction. The term polariza-
tion resistance (Rp) must be not confused with resistance
polarization (R). Rp represents the charge transfer resist-
ance resulting from the separation of charges across the
solid interface to the outside edge of the double layer,
while R represents the resistance through the bulk solution
(Rs) and the resistance of any film present on the working
electrode surface (Rf) (i.e., R = Rp + Rf) [33]. Figure 3a and
b shows the effect of both the temperature and the inhibi-
tor concentration on the polarization resistance in the
absence and presence of KJE, respectively. It is clear that
the values of Rp in presence of KJE at different inhibitor
concentrations are higher than the values in the absence
of KJE at different temperatures. This indicates the high
efficiency of the protective film in presence of inhibitor.
KJE decreases the corrosion rate by acting as a diffusion
barrier and restricted the transport of reaction products of
both charge and mass transfer processes. Khadom et al.
[33] studied the inhibition effect of the formation of pro-
tective adsorption film on the steel surface in acidic solu-
tion. It was found that the values of Rp for the carbon steel
electrode increase with the decrease in the temperature
and increase in the inhibitor concentration.
5 Conclusion
KJE inhibits the corrosion of low-carbon steel in 2.5 M
HCl acid solution by influencing both cathodic and
anodic partial reaction with more impact on cathodic one.
With the increase in inhibitor concentration, corrosion
current density decreases, and Rp increases. β-model uti-
lized in the present work recommends that the mechanism
of low-carbon steel corrosion was a mixed control, i.e.,
both charge transfer and mass transfer will control the
corrosion process; however, the charge transfer step influ-
ence was more significant. The addition of KJE brings
down the β value, which shows the mixed control of this
inhibitor.
Acknowledgement  The authors would like to express their gratitude
to Department of Chemical Engineering, College of Engineering, Uni-
versity of Diyala, and Department of Chemical Engineering, University
of Technology, Iraq.
Compliance with Ethical Standards  trochemical and quantum chemical studies. Res Chem Intermed
Conflict of interest  There are no conflicts of interest arising from the
involvement of other parties either internal or external to the university.
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