Research Letter Mild Steel Corrosion Inhibition by Acid Extract of Leaves of Hibiscus Sabdariffa As A Green Corrosion Inhibitor and Sorption Behavior
Research Letter Mild Steel Corrosion Inhibition by Acid Extract of Leaves of Hibiscus Sabdariffa As A Green Corrosion Inhibitor and Sorption Behavior
Research Letter Mild Steel Corrosion Inhibition by Acid Extract of Leaves of Hibiscus Sabdariffa As A Green Corrosion Inhibitor and Sorption Behavior
RESEARCH LETTER
Mild steel corrosion inhibition by acid extract of leaves of Hibiscus sabdariffa as a green corrosion
inhibitor and sorption behavior
Z.V.P. Murthy* and K. Vijayaragavan
A new corrosion inhibitor, namely acid extract of leaves of Hibiscus sabdariffa, has been synthesized, and its
inhibiting action on the corrosion of mild steel in acidic bath (1.2 N HCl and 1.2 N H2SO4) has been investigated
by corrosion-monitoring techniques. The results of the present study show that this compound has decent
inhibiting property for mild steel corrosion in 1.2 N H2SO4 than 1.2 N HCl. Four sorption isotherms are tested for
the data, namely Langmuir, Frumkin, Florry–Huggins, and Langmuir–Freundlich isotherms; of these the
Langmuir isotherm fits the data well having correlation coefficient over 0.99 in both the acid environments.
Keywords: corrosion inhibitor; Hibiscus sabdariffa; mild steel; acid bath; adsorption isotherm
100
90
80
Inhibition efficiency
70
60
50
40
30
20 Hydrochloric acid
Sulfuric acid
10
0
1 2 3 4 16 24
Time in hours
Figure 1. Effect of immersion period on inhibition efficiency of AELHS (5 g/100 mL) on mild steel in acid environment.
three hours and then decreases thereafter in the case increase in number of molecules occupied by the
of HCl. The reason behind this increase in inhibition inhibitor on the steel–acid solution interface. As the
efficiency initially may be attributed to the formation number of molecules increases, the corrosion reactions
of a barrier film. But, the weight loss experiments of are prevented from occurring over the active sites of the
mild steel in 1.2 N H2SO4 for 5 g inhibitor concen- mild steel surface covered by adsorbed inhibitor species,
tration per 100 mL of corrosive medium and at whereas the corrosion takes place on the surface not
temperature 30 ± 1°C are slightly different from covered by the inhibitor molecules. Thereby, one may
HCl as the inhibition efficiency decreases continu- conclude that the greater the surface coverage the
ously with time and stabilizes at a value of 66.67% greater the inhibition efficiency. This assumption has
after 24 hours. been applied to deduce the effect of concentration on the
adsorption of inhibitors. This is in total agreement with
the results of several investigators (11, 14).
Effect of inhibitor concentration on inhibition efficiency
From the inhibition efficiencies obtained from the
weight loss experiments for 1.2 N HCl and 1.2 N Effect of inhibitor concentration on corrosion rate
H2SO4, it is found that the inhibition efficiency In the present case, corrosion rate can be defined as
increases with increase in inhibitor concentration for the weight loss per unit area and unit time. To assess
both acidic media, which is evident from Figure 2. its protection value, AELHS is added in 2, 5, 10, and
Values of inhibition efficiency of AELHS for various 15 g/100 mL concentration in corrodent (1.2 N HCl
time periods and concentrations are shown in and H2SO4) at 30 ± 1°C. Figure 3 shows plot of
Tables 2 and 3. The increase in efficiency of the inhibitor corrosion rate of mild steel specimens as a function of
with increase in concentration may be attributed to concentration of the inhibitor. It is evident from the
Green Chemistry Letters and Reviews 211
100
90
80
70
Inhibition efficency
60
50
40
30 Hydrochloric acid
Sulfuric acid
20
10
0
2 5 10 15
Inhibitor concentration (g/100mL)
Figure 2. Effect of inhibitor concentration on inhibition efficiency in acid environment for a period of 24 hours.
Table 2. Inhibition efficiency of mild steel in 1.2 N HCl with AELHS for various time intervals.
2 50 61 64 65 36 39
5 60 62 67 69 42 40
10 65 67 70 70 53 49
15 68 69 73 71 55 51
Table 3. Inhibition efficiency of mild steel in 1.2 N H2SO4 with AELHS for various time intervals.
2 86 84 80 74 67 61
5 90 86 85 76 70 67
10 94 88 87 80 78 68
15 95 91 87 81 79 73
results, say for the exposure period of three hours the inhibition mechanism between Fe and inhibitor,
reported, that corrosion rate decreases with increase as given below:
in concentration. It is assumed that as the concentra-
tion of inhibitor increases, the number of inhibitor Fe þ Inh $ Fe-ðInhÞads $ Fenþ þ ne þ Inh ð1Þ
molecules occupying the active site increases, thereby
offering resistance to the activity of acid (i.e. decreases
the corrosion rate). The basis of assumption may be The adsorbed layer combats the action of acid and
explained, according to Bockris and Drazic (15), by enhances the protection of metal surface (16). When
212 Z.V.P. Murthy and K. Vijayaragavan
2.5
Corrosion rate (mg cm–2 h–1)
0.5
0
2 4 6 8 10 12 14 16
Inhibitor concentration (g/100mL)
Figure 3. Variation of corrosion rate with concentration of AELHS for the mild steel in 1.2 N hydrochloric acid and 1.2 N
sulfuric acid for a period of three hours.
35
30
15
10 HCl
5 H2SO4
0
0 2 4 6 8 10 12 14 16
Ci (g/100 mL)
Figure 5. Langmuir isotherm adsorption model on the mild steel surface of AELHS in acid environment.
Langmuir isotherm θ
According to the Langmuir isotherm (20, 21), θ is 0 0.2 0.4 0.6 0.8
related to the inhibitor concentration Ci (g/100 mL) 0
Table 4. Adsorption coefficients of corrosion inhibitor on mild steel in acid media based on different adsorption isotherm
models.
Kads Parameter R2
Figure 7. Florry–Huggins isotherm for corrosion inhibition of mild steel in acid environment.
Florry–Huggins isotherm
0.5
The substitution of water molecules by inhibitor
0.4
forms the basis of assumption in Florry–Huggins
isotherm (27). The equation of Florry–Huggins iso- 0.3
therm (shown in Figure 7) is given by: 0.2 Sulfuric acid
Hydrochloric acid
Log (θ/(1–θ))
h 0.1
¼ Kads C ð10Þ
½e ðx1Þ ð 1 hÞ x 0
0 0.5 1 1.5
–0.1
Data show in this case that x is 5.18 and 5.9 in the –0.2
case of H2SO4 and HCl, respectively, indicating that –0.3
5.18 (approximately) water molecules are substituted Log C (g/100 mL)
by one inhibitor molecule in sulfuric acid environment
and 5.9 water molecules in hydrochloric acid envir- Figure 8. Langmuir–Freundlich isotherm for corrosion
onment. This again reinforces the point that AELHS inhibition of mild steel in acid environment.
is a decent inhibitor.
on the surface can be calculated. Values of h are
tabulated in Table 4. All the results of isotherms
Langmuir–Freundlich isotherm calculations are shown in Table 4. The values of Kads
The Langmuir–Freundlich isotherm (28) (shown in in all the four isotherms used here clearly indicate that
Figure 8) is given by the equation: the adsorption of inhibitor on mild steel in sulfuric
acid environment is more than hydrochloric acid
1h environment.
h
¼ Kads C ð11Þ
1h
Specific reaction rate
where h is the heterogeneity parameter (0 < h < 1) and The rate equation that correlates specific reaction rate
a measure of the adsorption energy in different sites (k) with corrosion rate (r) is given by Mathur and
Green Chemistry Letters and Reviews 215
2
Sulfuric acid
Blank
1.5
ln r (mg cm–2 hr–1)
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5
Acid concentration in molarity
–0.5
Figure 10. Variation of ln(r) with concentration of H2SO4 for mild steel at 30 ± 1°C.
216 Z.V.P. Murthy and K. Vijayaragavan
Table 5. Results of corrosion rate, weight loss, inhibition efficiency, surface coverage of mild steel in acid environment (HCl and
H2SO4) for a period of three hours and for the area exposed for corrosion (Area = 18.25 cm2).
Corrosion rate (mg cm−2h−1) Inhibition efficiency (%) Surface coverage (θ)
1.2 N 1.2 N 1.2 N
Inhibitor Concentration (g/100 mL) HCl H2SO4 HCl H2SO4 HCl H2SO4
kept aside for 16 hours. The resultant mixture is with acetone and dried in atmospheric air for about
filtered and the filtered solution (AELHS) is directly 15 minutes. After each and every test, specimens are
used for experimental purpose. The schematic of the cleaned with 2 N NaOH to remove any corrosion
experimental setup and the flowchart of inhibitor products. The specimen is then cleaned with acetone
preparation process are shown in Figures 11 and 12, and stored in moisture-free desiccators (35).
respectively.
The chemical constituents that are likely to be
present in the leaves of H. sabdariffa are α-terpinyla- Solution
cetate, anisaldehyde, β-carotene, β-sitosterol, β-D- The aggressive solution used is made of analytical
galactoside, β-sitosteryl benzoate, niacin, fat, isoamyl reagent (AR)-grade HCl, H2SO4, and HNO3 (Merck).
alcohol, iso-propyl alcohol, methanol, 3-methyl- Appropriate concentration of acid is prepared using
1-butanol, benzyl alcohol, ethanol, malic acid, fiber, double-distilled water. Concentration range of inhib-
and ash (34). It is important to note that the informa- itor used for experimentation is between 2 and 15 g
tion on the level of extraction of these chemicals from per 100 mL of aggressive media.
leaves by acids is not available in the literature.
Table 6. The composition of mild steel used in the study. The percentage inhibition efficiency (I) of the
inhibitor is calculated (36) as:
Composition % Constituents
ðDMui DMi Þ
Carbon 0.12 I ¼ 100 ð13Þ
Magnesium 0.50
DMui
Silicon 0.14
where ΔMui and ΔMi are the weight loss of the metal
Sulfur 0.04
Iron 99.20
in uninhibited acid and inhibited acid solution,
respectively. The degree of surface coverage (θ) may
be calculated (11) as:
ðDMui DMi Þ
h¼ ð14Þ
DMui
machine. Requisite quantity of inhibitor is added to
250 mL plastic beakers containing 100 mL of syn- The corrosion rate (mg cm−2 h−1) may be obtained by
thetic corrosion medium and mild steel (33). The the following equation (35):
bottles are maintained at temperature 30 ± 1°C for all
weight loss
experiments. The contact time in the batch is varied Corrosion rate ¼ ð15Þ
from 1 to 24 hours (i.e. 1, 2, 3, 4, 16, and 24 hours) for ðarea timeÞ
a particular concentration of inhibitor. Further, where weight loss is expressed in mg, area in cm2 of
experiments are conducted for the same time period metal surface exposed, and time in hours.
by varying the concentration of inhibitor. At the end
of each test, the weight loss of the specimen is
measured using Mettler-weighing machine. A corro- Conclusions
sion inhibitor is a chemical substance which decreases The results clearly indicate that the AELHS is a
the corrosion rate when added in small concentration. decent corrosion inhibitor of mild steel. Out of
The corrosion efficiency of that inhibitor is thus the four sorption isotherms tested for the data,
expressed by a measure of this improvement. namely Langmuir, Frumkin, Florry–Huggins, and
218 Z.V.P. Murthy and K. Vijayaragavan
Langmuir–Freundlich isotherms, the Langmuir iso- HCI Solution. Int. J. Electrochem. Sci. 2008, 3,
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cient over 0.99 in both the acid (HCl and H2SO4) (11) Chowdhary, R.; Jain, T.; Rathoria, M.K.; Mathur, S.P.
Corrosion Inhibition of Mild Steel by Acid Extracts of
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