Journal of Mechanical Engineering Research and Developments

ISSN: 1024-1752
CODEN: JERDFO
Vol. 44, No. 6, pp. 387-397
Published Year 2021

Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel

in Hydrochloric Acid Medium
Narjes Ibrahem Khaled†, Nawras Jameel Jassim‡ and Khitam Zanad Abdul Sada†
†
Department of Chemical and Petrochemical Techniques Engineering Southern Technical University.
Basra, Iraq
‡
Department of Chemical Industries, Southern Technical University, Basra, Iraq

*Corresponding author email: [email protected]

ABSTRACT: With the utilizations of the approaches of weight-loss, the inhibitive actions related to the
leaves extract of Sonchus Asper on a mild steel corrosion in HCl solution of 1M have been investigated.
The results specified that the extract functions as an excellent inhibitor enhancing the effectiveness of
inhibition with the extract’s concentration. The increase of the temperature will results in a decrease in
the inhibition effectiveness of the extract and that was indicated via temperature studies between (25
and 65) Celsius. At 25 Celsius, inhibition effectiveness of 2g/L (EESA) achieves 94.07%. With regard
to inhibition conduct, an approach of chemical adsorption regarding the elements of the extract on the
surface of metal was presented. The adsorption properties of inhibitor have been in consistency with
isotherm Langmuir adsorption. Furthermore, the activation and dissolution energy thermo-dynamic
functions are evaluated and examined.

KEYWORDS: Adsorption mechanism, Corrosion inhibition, Free energy of adsorption and Mild steel.

INTRODUCTION

Corrosion can be defined as one of the feasible thermodynamic processes due to the fact that it was
associated with the decrease in the free energy from Gibbs. Commonly, mild steel is utilized as one of
the building materials in the majority of sectors, particularly in the electrochemical, oil, energy food
and chemical industries, particularly, because of its low-costs and significant mechanical properties [1–
3]. Often, in the sector, the acid solution was utilized to clean, descale, pickle the metallic surfaces,
processes which were typically succeeded via a considerable dissolution on the mild steel [4,5]. Using
the corrosion inhibitors is economical and effective method in this aggressive media for the purpose of
safeguarding metal surfaces from corrosion. [6,7]. The majority of recognized corrosion inhibitors
related to the acidic mild steel were specified as organic compounds containing oxygen atoms, sulfur,
nitrogen, or N–hetero-cyclic complexes with the polar groups. Almost all business inhibitors considered
to be toxic; thus, it’s highly important that they must be replaced by inhibitors beginning from the
environment.

In this work, the major aim is examining the inhibition effects of Ethanol Extract (EESA) from
Sonchus Asper as naturally-occurring, environmentally friendly and inexpensive substance on corrosion
behavior that is related to mild steel in the HCl of 1 M through evaluating the weight loss. Also, the
inhibitor’s adsorption has been examined, whereas the thermodynamic adsorption parameters are
indicated in presence and absence of an inhibitor [8 – 10].

METHODS

Materials and Solutions

In this work, the utilized materials are mild rectangular steel form coupons (5.5x1.81x0.3cm) with 0.04
% Mn, 0.07 % p, 0.02 % Al, 0.22 % C, 0.04 % S, and 0.36 % Si structure, while the rest of the Fe
comprises a hole with a diameter of approximately (4mm) near the bottom edge being utilized for
examining the inhibitors of the corrosion. Also, aggressive solutions of (HCl of 1 M) have been
prepared via a dilution regarding analytical grades (37% HCl) with doubly distilled water.

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

Inhibitor

The leaves have been gathered at the city of Abu Al-Khaseeb, Basra / Iraq plant at Sonchus Asper, then
washed at R.T. and after that powdered. There are 2 extraction techniques are screened. These processes
of ethanol extraction and distilled water were conducted at RT Preliminary measurement of the weight-
loss corrosion studies have been used for finding the optimal process of extraction. Those initial
corrosion checks specified that ethanol extraction process has been more effective or the same as other
procedures. In the presented study, this method of extraction was applied (2g) of the powdered plant has
been soaked in ethanol of (60ml) at R.T, then filtered for 24hrs. For making stock solutions of (1.0 Liter)
in HCl of (1M), the filtrate was added to an aqueous solution of the HCl. After that, a set of the diluted
solutions in the HCl of (1M) with levels between (0.50g / L and 2g / L) have been produced from the
stock solutions.

Approaches of Weight Loss

Emery paper of up to (1000 grades) was used for grounding and polishing the mild steel specimens,
after that, distilled water was used for rinsing such specimens, then a smooth tissue paper is used for
drying them, degraded for 5 secs via acetone and dried through air at R.T. Following adequate
weighing, the specimens have been vertically suspended in a breaker of (100.0ml) that contains (1M
HCl) without and with the additives of various inhibitor levels. Following immersion time of 3 hours,
the samples are removed, then with distilled water, subjected to washing, drying and after that weighed
with ethanol, such experiments are repeated at various temperatures with magnetic stirrer hot plates.

RESULTS AND DISCUSSIONS

Concentration of the Inhibitor

Table1, is setting out corrosion rate (CR) (mg/cm2/h), inhibition efficiency (%IE) and surface coverage
(Ɵ) acquired from approaches of the weight loss and utilizing the equations that have been indicated
below at various EECD concentration levels in the HCl of (1M) at a temperature of 25 Celsius for a
period of 3hrs.

Ө= (1)
%IE = Ɵx100 (2)

In which; CRi and CRo were the rates of the corrosion that are related to the mild steel in the existence
and absence of inhibitors.

With an increase in inhibitor’s concentration there will be a reduction in inhibitor containing corrosion
rate related to the mild steel in HCl of (1M), the corrosion inhibition will be increased with an increase
in the inhibitor as may be observed in the Figure1, such behavior is caused by the increment in
surface coverage and adsorption quantity regarding the mild steel inhibitors at inhibitor’s concentration
[11]. The (% IE) increase for the inhibitor with an increase in inhibitor’s concentration from (0.50-2.0g /
L). Furthermore, the maximal (% IE) (94.07%) has been reached at 25 Celsius and (2g / L) as can be
seen in the Figure.2.

Table 1. Mild steel corrosion factors with various concentration levels of (EESA) in 1M HCl at 25oC.

Additivee Inhibitor Conc. CR %IE Ɵ

Blank (g/L) (mpy) -
(EESA) 0.0 1023.409 - 0.8012
0.5 203.38 80.12 0.9242
1 77.570 92.42 0.9312
1.5 70.400 93.12 0.9407
2 60.622 94.07

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

Figure 1. Variations of rates of corrosion with the concentration levels of inhibitor at HCl of (1M) on
mild steel at a temperature of 25 Celsius.

Figure 2. Inhibition efficiency variation with inhibitor’s concentration levels in HCl of (1 M) on mild steel at a
temperature of 25 Celsius.

Adsorption Isotherm

The isothermic adsorption is one of the major evidences of interactions between the inhibitor as well as
the material’s surface. Many efforts were made for fitting various isotherms such as (Temkin, Frumkin,
Bockriss, Frendlich, Flory-Huggins and isotherms from Langmuir) [12]. In this study, the results have
been excellently equipped with Langmuir isotherm adsorption. Based on this isotherm is associated
with the coverage of the surface (Ө) [ 13, 14]

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

=K ads. C (3)
Re-ordering equation (3) provides:
= (4)
A fitted straight line with slopes that are near 1, as can be seen in the Figure3, also the variables that
have been indicated in the Table2 was acquired from plots of C / Ө vs. C. In addition, the powerful
relation (R 2 > 0.99) suggesting that Langmuir adsorption isotherm is succeeded via inhibitor’s
adsorption on the surface of mild steel. Also, table 2 is showing that there is a decrease in the value of
the constant of adsorption equilibrium (K ads) in (L / g) with the increase in temperature, specifying that
the inhibitor has been strongly and readily adsorbed on surface of mild steel at fairly low temperatures.
However, in the case where the temperature is high, the adsorbed inhibitors will be desorbed from
surface of the mild steel [15,16].

Figure 3. Langmuir model (EESA) in 1 M HCl at various temperature values on a mild steel surface
Table 2. Adsorption parameters for (EESA) acquired at different temperatures from Langmuir isotherm.

Temperature Adsorption parameter

Additives
C R2 Slope Intercept Kads (L/g)
25 0.9937 1.0877 0.0347 28.818
35 0.9973 1.0205 0.1707 5.858
(EESA) 45 0.9941 1.0794 0.1967 5.083
55 0.9996 0.9936 0.3898 2.565
65 0.9999 0.9228 0.5678 1.761

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

Temperature influence on mild steel corrosion inhibition

It has been identified from corrosion researches that are related to mild steel at HCl of (1 M) in the
inhibitors’ absence at temperature between (25 and 65) Celsius for immersion of 3hrs that there has been
an increase in corrosion rate with the increase of temperature, as can be seen in the Fig.4. In addition,
Table 3 is listing the results regarding the studies of temperature of the mild steel corrosion in HCl of
(1M) in a presence and absence of (EESA) at a value of the temperature between (25oC and 65oC) for
immersion of 3hrs, showed that the increase of the temperature causes a reduction in inhibition
performance and an elevation in the corrosion rates at all the studied levels. This is due to the fact that the
increase in temperature helped via desorption [17-19]. Therefore, the action is showing that the physical
adsorption leads to (EESA) adsorption on mild steel layer. The inhibition’s effectiveness was reduced
from (94.070% to 83.082%) with regard to optimal concentration (2g / L), whereas there is an increase
in the degree of the temperature from (25oC –65oC) as can be seen from Figure5.

Table 3. Impact of temperature on factors of the mild steel corrosion in 1.0M HCl at a variety of the
concentrations of 3 hours (EESA).

Additive Concentrations Temperature Corrosion rate %IE Ɵ

(g/L) (oC) (mpy)
Blank 1.0M HCl 25 1023.409 - -
35 1971.856 - -
45 2027.264 - -
55 2734.525 - -
65 3544.779 - -
0. 50 25 203.378 80.12 0.80120
35 460.208 76.66 0.76660
45 556.031 72.57 0.72570
55 1207.884 55.82 0.55820
65 1812.804 48.85 0.48850
1.0 25 77.570 92.42 092420
35 381.986 80.62 0.80620
45 497.364 75.46 0.75460
(EESA) 55 731.379 73.25 0.73250
65 1174.64 66.86 0.66860
1.50 25 70.400 93.12 0.93120
35 220.978 88.79 0.88790
45 392.415 80.64 0.80640
55 563.853 79.38 0.79380
65 829.809 76.59 0.76590
2.0 25 60.622 94.07 0.94070
35 181.867 90.77 0.90770
45 271.822 86.59 0.86590
55 433.482 84.14 0.84140
65 599.705 83.08 0.83080

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

Figure 4. Variations of mild steel corrosion rate in HCl of (1 M) with a degree of temperature between
(25oC and 65oC) for immersion of 3 hrs (2g / l).

Figure 5. Variations of the efficiency of inhibition with increased temperature on mild steel at 1 M HCl at
immersion (2 g / L) for 3 h.

Thermo-dynamic Function

The adsorption constant (K ads), has been associated with the adsorption’s standard free energy value (∆ Go
ads) in (kJ/mol) with the formula below [20, 21].

∆ Goads = - RT Ln (C H2O. K ads) (5)

The heat of the adsorption (∆Hoads) and the entropy (∆So ads) may be resulted from thermos-dynamic
basic formula [22, 23].
∆ Goads = ∆ Hoads – T ∆ So ads (6)

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

Fig6 exhibits the differences between T ad the (∆ Go). It's purchased in straight line. The path presents
various ubiquitous (∆ So) and intercept results various highlights. Table4 lists all the

thermos-dynamic adsorption variable (EESA) values, providing the data on mechanisms for the
inhibition of the corrosion. The (∆ Goads) negative value is an indication of the fact that the inhibitor
molecules’ adsorption on mild steel is one of the spontaneous processes. In general, values that are upads
to (-
20kJ/mol) are in consistency with electro-static interactions between the charged metal (i.e. the physical
adsorption) and charged molecules, whereas the ones which are more negative than -40kJ/mol include the
transfer
Ho or sharing of the charges for the purpose of forming a coordinate bonding (i.e. chemi-sorptions)
[24,25]. Which is why, in the present analysis, the inhibitor values are about (-20kJ/mol); physi-
sorption has been typical of inhibitor adsorption mechanism on mild steel in 1.0M of the solution of HCl.
Whereas a method of the endothermic adsorption (Hoads higher than 0) for the chemisorption is
recognized in an unambiguous manner, an exothermic approach of adsorption (Ho less than 0) could be
involving either the chemi-sorptions the physisorption or a combination of the two [26, 27]. In the
present research, the adverse value that has been obtained could result in the introduction of the
physisorption as well as the chemisorptions processes. In addition to that, the (∆ ads) negative value has
shown that adsorption becomes exothermic with the ordered phenomenon that results from the negative
values (∆ Soads). The likelihood to form a complex of iron on the surface of the metal could be explaining
that order [28].
Table 4. Factors of hermo-dynamic adsorption (EESA) for the mild steel at various temperatures in 1 M HCl

Temperature K ads ∆ Goads ∆ Hoads ∆ Soads

Additive (kJ/mol) (kJ/mol) (kJ/mol.K)
C (L/g)
25o 28.8180 -25.4410 -0.09350
35o 5.8580 -22.2610 -0.1010
(EESA)
45o 5.0830 -22.5630 -53.3240 -0.09670
55o 2.5650 -21.4070 -0.09730
65o 1.7610 -21.0330 -0.09560

Figure 6: Variations of the value of ∆ Goads vs. Temperature

Thermo-dynamic Activation Functions

The thermos-dynamic factor sufficiently described the phenomenon of the adsorption, additionally
explaining the inhibitor’s inhibition properties, kinetic model has been considered as an additional

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

helpful tool for explaining the corrosion inhibition of the mechanism of inhibitor. In Arrhenius
equation, the variables of the activation for the approach of the corrosion method have been computed
[29, 30]:

CR= Aexp ( ) (7)

(R) represents the gas constant, (Ea) denotes apparent activation energy, A denotes pre-exponential factor
and (CR) represents the rate of the corrosion, resulted from the method of weight loss.

Fig.7 shows the values of Ea for the mild steel in 1.0M of the HCl with (EESA) at a vaiety of the
concentration levels, corrosion rate Arrhenius plots for the mild steel have been computed from the linear
regression between (Ln CR & 1/T). results have been listed in Table5.

A substitute formulation of Arrhenius eq. is [31, 32]: CR= ( ) ( ) exp( ) (8)

(N) represents Avogadro s number, ( h) represents the constant of Plank s, (Δ H˚a) denotes activation
enthalpy, (R) represents universal gas constant, and (∆ S°a) denotes the activation entropy.

Fig8 represents the plot of Ln (CR/T) versus 1/T. straight lines have been created with a (-∆ H°a / R)
slope and ( ) + Ln( ) intercept from which the (Δ H˚a & ∆ S°a ) values have been computed
and given in Table5.

Table5 showed that (∆Ho a) and Ea were varying in an identical mode. For the inhibited solutions, the
values of Ea have been higher (23500 kJ/mol) for uninhibited types of solutions, and Ea values have
been increased with increasing the concentration of the inhibitor from (0.50 to 2.0g / L) for the inhibitor
(the increase in the Ea has resulted in the deceleration of the mild steel’s corrosion rate [33]. The
positive ( ∆ Ho a ) values have shown that the approach of mild steel dissolution is endothermic.
(∆ S°a) values have been higher for the inhibited solutions in comparison with it for the uninhibited
ones. Which has suggested the fact that in the case of moving from reactant to activated complex a
random increase has happened [11, 33].
Table 5. Activation conditions for mild steel dissolution in 1.0M HCl with a variety of the (EESA) concentrations.

Concentration Ea Δ H˚a ∆ S°a

Additive
(kJ/mol) (kJ/mol) (kJ/mol.K) Ea – Δ H˚ a
(g/L)
Blank 1 M HCl 23.5000 19.1020 -121.6490 2.2610
0.50 44.4510 41.8350 -60.0760 2.6160
1.0 51.0640 48.4490 -42.9410 2.6150
(EESA)
1.50 49.1630 46.5460 -51.3970 2.6170
2.0 45.6500 43.0330 -64.5990 2.6170

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

Figure 7. The arrhenius plots of (Ln CR vs. 1/T) in 1 M solution of the HCl with (EESA) for mild steel at
a variety of the concentration levels.

Figure 8. Ln (CR / T) vs. 1/T for mild steel in 1M solution of the HCl with the (EESA) at a variety of
hte concentration levels

CONCLUSIONS

From this analysis, the findings below may be derived:

1) The EESA has been discovered to be a highly sufficient inhibitor of the mild steel in 1M solution of
the HCl, which reaches about (94.07%) at 2 g / L at 25oC.

2) The efficiency of inhibition increases as concentration of the inhibitor increases and decreases as the
temperature rises.

3) EESA is an adsorptive agent and its adsorption opposes isothermic Langmuir adsorption.

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 Sonchus Asper Leaves Extract as a Corrosion Inhibitor for Mild Steel in Hydrochloric Acid Medium

4) The thermo-dynamic parameters have indicated the fact that inhibitors are adsorbed with a
spontaneous exothermic process and that an inhibitor could be proposed as physi-sorption.

5) EESA is a green, environmentally friendly, excellent, and inexpensive inhibitor of corrosion for mild
steel in 1.0M solution of HCl, which may be utilized for replacing the expensive toxic chemicals.

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