International Journal of CorrosionVolume 2012 (2012), Article ID 768729, 8 pagesdoi:10.1155/2012/768729

Research Article

Inhibitory Action of Artemisia annua Extracts and Artemisinin on the Corrosion of Mild Steel in Solution

P. C. Okafor,¹ V. E. Ebiekpe,¹ C. F. Azike,1,2 G. E. Egbung,³ E. A. Brisibe,⁴ and E. E. Ebenso⁵

¹Corrosion and Electrochemistry Research Group, Department of Pure and Applied Chemistry, University of Calabar, PMB 1115, Calabar, Nigeria²Headquarters Eastern Naval Command, Navy Road, Calabar, Nigeria³Department of Biochemistry, University of Calabar, PMB 1115, Calabar, Nigeria⁴Department of Genetics and Biotechnology, University of Calabar, PMB 1115, Calabar, Nigeria⁵Department of Chemistry, North-West University, Mafikeng Campus, Private Bag X2046, Mmabatho 2735, South Africa

Received 24 June 2011; Accepted 9 August 2011

Academic Editor: Ali Y. El-Etre

Copyright © 2012 P. C. Okafor et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

The action of ethanol (EEAA), acid (AEAA), and toluene (TEAA) extracts from Artemisia annua and Artemisinin (ATS) on mild steel corrosion in H₂SO₄ solutions was investigated using gravimetric and gasometric techniques. The extracts and ATS functioned as good inhibitors, and their inhibition efficiencies (%IE) followed the trend: EEAA > AEAA > TEAA > ATS. %IE increased with increase in inhibitors concentration and decreased with increase in temperature. The enhanced %IE values of the extracts were attributed to synergistic effect of the components of the plant extracts with ATS. The adsorption of the inhibitors was consistent with Langmuir isotherm. Physisorption is proposed as the mechanism of inhibition.

1. Introduction

Present trend in research on environmental friendly corrosion inhibitors is taking us back to exploring the use of natural products as possible sources of cheap, nontoxic, and ecofriendly corrosion inhibitors. These natural products are either synthesized or extracted from aromatic herbs, spices, and medicinal plants. Of increasing interest is the use of medicinal plant extracts as corrosion inhibitors for metals in acid solutions. This is because these plants serve as incredibly rich sources of naturally synthesized chemical compounds that are environmentally acceptable, inexpensive, readily available, and renewable sources of materials [1, 2]. These chemicals include alkaloids, flavonoids, terpenoids, glycosides, tannins, saponins, fats and oils, and carbohydrates, and so forth [3–11]. The complex composition of phytochemicals in plant extracts makes it difficult to attempt to assign the inhibition ability to a particular constituent. Some researchers have, however, ascribed the inhibition efficiency of these medicinal plants to their active components used for medical purposes [3]. We have recently attempted to assign the inhibition ability to some constituents by studying the inhibitive effect of different parts of a given plant with variable concentrations of the phytochemicals on acid corrosion [4–7]. Another most probable method would be the use of different solvents in the extraction process and comparing their inhibition efficiencies. This is yet to be explored in most of the reported work on corrosion inhibition of plant extracts.

Artemisia annua is native to Asia, most probably China, but is currently cultivated in many countries including Nigeria, mainly as a source of artemisinin, an important natural sesquiterpene lactone with antimalarial effect against susceptible and multidrug resistant Plasmodium spp. The plant is a large shrub often reaching more than 2.0 m in height, usually single-stemmed with alternate branches. The leaves are deeply dissected and range from 2.5 to 5 cm in length.

A. annua contains at least 20 known sesquiterpenes including artemisinin (arteannuin A), arteannuin B, artemisitene, and artemisinin acid. Artemisinin content varies from as low as 0.01 to 1.5% of plant dry weight depending on various factors such as the plant's origin, its stage of development, and the cultivation conditions [12–14]. This compound, isolated more than 50 years ago from A. annua by Chinese scientists searching for novel antimalarial drugs, has an unusual trioxane structure with seven stereogenic centers and tetracyclic framework (Figure 1) but lacks a nitrogen containing heterocyclic ring which is found in most antimalarial compounds. A. annua has also been shown to have a high content of flavonoid compounds, including the newly reported C-glycosyl flavonoids as a possible component of the antioxidant and antiviral activity [15].

Figure 1: Structure of artemisinin.

In view of our interest in environmentally friendly corrosion inhibitor, the present study reports the inhibitory effect of acid (AEAA), ethanol (EEAA), and toluene (TEAA) extracts from A. annua and artemisinin (ATS) on mild steel corrosion in H₂SO₄ solutions using the weight loss and gasometric techniques.

2. Experimental Methods

The mild steel sheets used in this present work have the composition presented in Table 1. Before measurements, the mild steel coupons were mechanically polished with series of emery paper of variable grades starting with the coarsest and proceeding in steps to the finest (600) grade, degreased with absolute ethanol, dipped into acetone, and air-dried. The hydrogen evolution experiments were conducted on mild steel coupons of dimension 1.33 × 0.08 × 5.0 cm (with a surface area of 14.008 cm²), and, for the weight loss study, mild steel specimens of size 4.0 × 0.08 × 5.0 cm (with a surface area of 41.44 cm²) were used.

Table 1: Chemical composition of the mild steel.

Element
C
Si
Mn
S
P
Ni
Cr
Mo
Cu
Fe

Composition
0.19
0.26
0.64
0.05
0.06
0.09
0.08
0.02
0.27
Balance

2.1. Preparation of Inhibitor Solutions

Dried leaves of Artemisia annua and artemisinin (ATS) used for this work were gotten from the Department of Genetics and Biotechnology, University of Calabar, Calabar, Nigeria. The leaves were ground into powder form. 80.0 g of the powder was extracted continually with 250 cm³ of the appropriate solvent (ethanol and toluene for the ethanol and toluene extracts, resp.) in a soxhlet extractor for 24 hours. After recovering most of the solvents, the extracts were heated on a water bath (at 60°C) until most of the solvents evaporated. 4.0 g of the extracts were soaked in 1 liter of 5 M H₂SO₄ and 1 M H₂SO₄ solutions for hydrogen evolution and weight loss measurements, respectively. The resultant solutions were kept for 24 hours, filtered, and stored. From the stock solutions (4.0 gL⁻¹), test solutions (concentrations of 0.1, 0.5, 1.0, 2.0 and 4.0 gL⁻¹) were prepared. Similar procedure was also carried out with 4.0 g of the powdered form of the leaves. For the ATS-H₂SO₄ solutions, 20, 50, 100, 200, and 400 mgL⁻¹ ATS solutions were prepared in 5.0 M H₂SO₄ and 1.0 M H₂SO₄ solutions for hydrogen evolution and weight loss measurements, respectively.

2.2. Phytochemical Screening

Phytochemical screening was carried out on the extracts from A. annua following the methods described by Harbone [16], Sofowora [17], and Trease and Evans [18]. The plant extracts were screened for alkaloids, saponins, tannins, flavonoids, cardiac glycosides, and anthraquinones.

2.3. Weight Loss and Gasometric Measurements

The weight loss and gasometric measurements were carried out as previously described [19, 20]. However, experiments were conducted at 30°C for weight loss, and at 30°, 40°, 50°, and 60°C for gasometric measurements.

For the weight loss measurements, the mild steel coupons were each suspended and completely immersed in the test solutions (1 M H₂SO₄) with and without different concentrations of the plant extracts and artemisinin (ATS) with the help of glass hooks and rods for 7 days at 30 ± 1°C. The coupons were retrieved at 24-hour intervals, washed several times in 20% sodium hydroxide solution containing 200 gL⁻¹ of zinc dust until clean, dipped into acetone, air-dried, and reweighed [19, 20].

Gasometric technique is based on the principle that corrosion reactions in aqueous media are characterized by the evolution of gas resulting from the cathodic reaction of the corrosion process, which is proportional to the rate of corrosion [21]. The rate of evolution of the gas () was determined from the slope of the graph of volume of gas evolved per surface area versus immersion time and efficiencies (%IE) determined using where and are the rates of hydrogen evolution per surface area in the absence and presence of the inhibiting molecules, respectively.

In determining the rate of hydrogen evolution per surface area, the contribution of other gases, including water vapour at especially higher temperature is assumed to be insignificant. This gasometric technique has been corroborated by other well-established corrosion rate determination techniques, including weight loss, thermometric, and electrochemical techniques [22–24]. The data presented in this work represents the average of two to three measurements from the weight loss and gasometric techniques.

3. Results and Discussion

3.1. Weight Loss Results

The variation of the weight loss (in mg cm⁻²) of mild steel with immersion time in 1 M H₂SO₄ solutions in the absence and presence of ATS and EEAA at 30°C is as shown in Figure 2. The weight loss was observed to increase with increase in time but decrease with increase in the concentration of the inhibitors. This behaviour reflects the inhibitive effect of the inhibitors toward the acid corrosion of the steel. Similar trend was observed in the presence of the other plant extracts. The rate of corrosion (in mg cm−2 h⁻¹) of the mild steel in the acid medium determined from the slope of the plots is given in Table 2. It is clearly seen that the corrosion rate decreases with increase in the inhibitors concentration. This observed trend may result from the fact that adsorption and surface coverage increase with the increase in concentration; thus, the surface is separated from the medium. From the corrosion rate values, the inhibition efficiency (%IE) was determined using where Ro and Ri are the corrosion rates in the absence and presence of the inhibiting molecules, respectively. The data are given in Table 2. It is observed that the inhibition efficiency increases as the added inhibitors concentrations are increased. It reaches 96% for 4.0 gL⁻¹ EEAA, 93% for, 4.0 gL⁻¹ AEAA, and 24% for 400 mgL⁻¹ ATS.

Table 2: Calculated values of the corrosion rate and inhibition efficiency for mild steel coupons in 1.0 M H₂SO₄ solutions in the absence and presence of inhibitors (using the weight loss technique).

Inhibitor
System
Corrosion rates (mg cm⁻² hr⁻¹)
Inhibition efficiency (%)

Blank
1.406
—

EEAA
0.1 gL⁻¹ EEAA + 5 M H₂SO₄
1.040
26.00

0.5 gL⁻¹ EEAA + 5 M H₂SO₄
0.886
37.02

1.0 gL⁻¹ EEAA + 5 M H₂SO₄
0.703
50.01

2.0 gL⁻¹ EEAA + 5 M H₂SO₄
0.366
74.00

4.0 gL⁻¹ EEAA + 5 M H₂SO₄
0.064
95.48

AEAA
0.1 gL⁻¹ AEAA + 5 M H₂SO₄
0.886
37.02

0.5 gL⁻¹ AEAA + 5 M H₂SO₄
0.515
63.35

1.0 gL⁻¹ AEAA + 5 M H₂SO₄
0.414
70.55

2.0 gL⁻¹ AEAA + 5 M H₂SO₄
0.206
85.36

4.0 gL⁻¹ AEAA + 5 M H₂SO₄
0.105
92.54

ATS
20 mgL⁻¹ ATS + 5 M H₂SO₄
1.266
9.97

50 mgL⁻¹ ATS + 5 M H₂SO₄
1.172
16.61

100 mgL⁻¹ ATS + 5 M H₂SO₄
1.159
17.55

200 mgL⁻¹ ATS + 5 M H₂SO₄
1.153
17.98

400 mgL⁻¹ ATS + 5 M H₂SO₄
1.071
23.81

(a)

(b)

Figure 2: Variation of weight loss per surface area with time for mild steel in 1.0 M H₂SO₄ containing (a) ATS and (b) EEAA.

3.2. Gasometric Technique

The effect of addition of the tested extracts (EEAA, AEAA, and TEAA) and ATS at different concentrations and temperatures on the corrosion of mild steel in 5 M H₂SO₄ was studied in more detail using the gas evolution method. The gas evolution technique is more suitable at a high corrodent concentration, while the weight loss method suffices for a low corrodent concentration [19]. Table 3 groups the corresponding values of rate of hydrogen evolved per surface area of the mild steel and the inhibition efficiency. It is clear that the presence of all tested extracts and ATS reduced the rate of hydrogen evolution per surface area and consequently the corrosion attack is inhibited. It is clearly seen that the rate of hydrogen evolution per surface area decreases with increase in the extracts and ATS concentrations. This trend as noted earlier may result from the fact that adsorption and surface coverage increases with the increase in the inhibitors concentration, thus, separating the surface of the metal from the medium [25–27]. It is also observed from Table 3 that the inhibition efficiencies follow the trend: EEAA>AEAA>TEAA>ATS. Similar trend was obtained at lower concentration of the acid via the weight loss method. The inhibition efficiency increases with the extracts and ATS concentrations to reach 96.73, 94.01, 86.10 and 44.41% for EEAA, AEAA, TEAA, and ATS, respectively. Figure 3 illustrates the comparison of the inhibition efficiencies of the extracts and ATS on the corrosion of mild steel in H₂SO₄ at 30°C.

Table 3: Kinetics and activation parameters for mild steel coupons in 5.0 M H₂SO₄ solutions in the absence and presence of inhibitors (using the gasometric technique).

System
Rate of hydrogen evolution (cm min⁻¹)
Inhibition efficiency (%)
(KJmol⁻¹)
Δ* (KJmol⁻¹)
Δ*(Jmol⁻¹ K⁻¹)

30°C
40°C
50°C
60°C
30°C
40°C
50°C
60°C

5 M H₂SO₄ (blank)
0.037
0.096
0.174
0.311
—
—
—
—
58.96
56.32
−86.00

0.1 gL⁻¹ EEAA + 5 M H₂SO₄
0.017
0.060
0.119
0.257
54.50
37.70
31.70
17.27
74.83
72.19
−39.82

0.5 gL⁻¹ EEAA + 5 M H₂SO₄
0.015
0.041
0.078
0.144
60.49
56.96
55.22
53.72
63.30
60.66
−79.28

1.0 gL⁻¹ EEAA + 5 M H₂SO₄
0.008
0.023
0.064
0.120
77.93
75.71
63.40
61.27
76.55
73.91
−40.73

2.0 gL⁻¹ EEAA + 5 M H₂SO₄
0.006
0.015
0.038
0.082
84.74
84.40
77.93
73.66
75.52
72.88
−47.53

4.0 gL⁻¹ EEAA + 5 M H₂SO₄
0.001
0.005
0.014
0.039
96.73
94.97
91.82
87.33
97.12
94.48
11.34

0.1 gL⁻¹ AEAA + 5 M H₂SO₄
0.014
0.037
0.090
0.256
62.40
60.84
48.41
17.59
80.78
78.14
−23.05

0.5 gL⁻¹ AEAA + 5 M H₂SO₄
0.011
0.032
0.082
0.168
68.94
66.18
52.91
46.06
75.58
72.94
−41.17

1.0 gL⁻¹ AEAA + 5 M H₂SO₄
0.007
0.028
0.070
0.132
79.84
70.68
59.54
57.67
80.49
77.84
−27.76

2.0 gL⁻¹ AEAA + 5 M H₂SO₄
0.005
0.018
0.047
0.090
86.38
81.05
73.20
70.96
81.03
78.39
−29.39

4.0 gL⁻¹ AEAA + 5 M H₂SO₄
0.002
0.008
0.034
0.071
94.01
91.73
80.58
77.10
99.91
97.27
25.45

0.1 gL⁻¹ TEAA + 5 M H₂SO₄
0.027
0.079
0.149
0.286
26.43
17.17
14.18
7.91
64.93
62.29
−68.71

0.5 gL⁻¹ TEAA + 5 M H₂SO₄
0.023
0.066
0.123
0.263
36.24
31.41
29.34
15.37
66.27
63.63
−65.75

1.0 gL⁻¹ TEAA + 5 M H₂SO₄
0.019
0.052
0.102
0.204
47.68
45.86
41.10
34.26
65.37
62.73
−70.39

2.0 gL⁻¹ TEAA + 5 M H₂SO₄
0.012
0.035
0.067
0.145
67.57
63.66
61.21
53.39
68.59
65.95
−63.65

4.0 gL⁻¹ TEAA + 5 M H₂SO₄
0.005
0.016
0.039
0.079
86.10
83.66
77.75
74.69
76.65
74.01
−44.14

20 mgL⁻¹ ATS + 5 M H₂SO₄
0.035
0.092
0.167
0.306
5.18
3.98
3.57
1.67
59.90
57.26
−83.33

50 mgL⁻¹ ATS + 5 M H₂SO₄
0.032
0.087
0.159
0.286
12.26
9.01
8.53
7.91
60.23
57.59
−82.80

100 mgL⁻¹ ATS + 5 M H₂SO₄
0.031
0.083
0.151
0.279
16.35
13.19
13.26
10.20
60.74
58.10
−81.57

200 mgL⁻¹ ATS + 5 M H₂SO₄
0.026
0.071
0.145
0.265
28.61
25.86
16.54
14.73
64.42
61.79
−70.80

400 mgL⁻¹ ATS + 5 M H₂SO₄
0.020
0.054
0.125
0.233
44.41
43.04
27.72
25.06
68.46
65.82
−59.73

Figure 3: Variation of inhibition efficiency with extract concentration for mild steel in 5 M H₂SO₄ containing the inhibitors at 30°C.

3.3. Activation Parameters

Temperature can affect mild steel corrosion in acidic media in the presence and absence of inhibitor. To determine the action energy of the corrosion process, gasometric measurements were taken at various temperatures (30–60°C) in the presence and absence of the extracts and ATS. The corresponding results are also given in Table 3. From these results, we can deduce that the rate of hydrogen evolution per surface area increases with the rise of temperature. The inhibitive efficiencies of the inhibitors decrease with the rise of temperature.

Figure 4 shows Arrhenius plots for the mild steel in 5 M H₂SO₄ solutions in the absence and presence of EEAA. Similar plots were obtained in the presence of AEAA, TEAA, and ATS. The activation energies () can be expressed by the Arrhenius equation: where is the absolute temperature, is the Arrhenius constant, and is the universal gas constant. The values of were taken to be equal to the rate of hydrogen evolution per surface area [4, 28–30]. The activation energies are given in Table 3. It is evident that the presence of inhibitor increases the activation energy. This may indicate the physical nature of adsorption mechanism [31, 32].

Figure 4: Arrhenius plots for the mild steel in 5 M H₂SO₄ in the absence (Blank) and presence of EEAA.

The enthalpy () and entropy of activation () were determined using the Eyring transition state equation (Figure 5 for EEAA): where is the Avogadro’s number, is the Plank’s constant, and and are the standard enthalpy and entropy of activation, respectively. The data are given in Table 3. Inspection of Table 3 shows higher values for in the presence of the inhibitors, indicative of the higher protection efficiency observed for the system [28]. The values in the absence and presence of the inhibitors are negative. This implies that the activation complex in the rate determining step represents association rather than dissociation step, meaning that a decrease in disordering takes place on going from reactants to the activated complex [33].

Figure 5: Eyring transition state equation for the mild steel in 5 M H₂SO₄ in the absence (Blank) and presence of EEAA.

3.4. Adsorption Parameters

The inhibitive action of the plant extracts toward the acid corrosion of steel is attributed to the adsorption of ATS and the other components of the plant on the surface of the mild steel. The adsorbed layer acts as a barrier for mass and charge transfers, leading to a decrease in the corrosion rate. Thus, it follows that the inhibition efficiency (%IE) is directly proportional to the fraction of the surface covered by the adsorbed molecules (θ). Therefore, θ is calculated using the relation θ= %IE/100 [3]. The mode of variation of θ with the extract concentration specifies the adsorption isotherm that describes the system. The obtained θ values were applied to different adsorption isotherm equations and found to fit the Langmuir adsorption isotherm (Figure 6 for AEAA) with values of up to 0.9962 for EEAA, 0.9995 for AEAA, 0.9688 for TEAA, and 0.9026 for ATS. The Langmuir adsorption isotherm may be formulated as where c is inhibitor concentration, θ is the fraction of the surface covered by the adsorbed molecules, and equals the equilibrium constant. The values of obtained from the intercept of the isotherm plots are given in Table 4. values are seen to decrease with increase in temperature suggesting that the inhibitors are physically adsorbed on the surface of the metal. From the dependence of the values on temperature, the thermodynamic parameters and were obtained by linear least squares fits of the log data against 1/T (Figure 7): The resultant values are given in Table 4. Generally, negative values of were obtained indicating an exothermic adsorption process. The exothermic adsorption process signifies either physical or chemical adsorption, while endothermic adsorption process is attributable to chemisorption. In an exothermic process, physical adsorption is distinguished from chemisorption by considering the absolute value of adsorption enthalpy. Typically, enthalpy of physical adsorption process is lower than 80 KJmol⁻¹, while the enthalpy of chemisorption process approaches 100 KJmol⁻¹ [32]. The values of the obtained enthalpy therefore suggest physical adsorption of the inhibitors on the surface of the metal. Comparing the values of obtained in this work with the values of (enthalpy of activation), it is observed that the latter are very much larger than those of . This has been interpreted to indicate physical adsorption rather than chemisorption [28].

Table 4: Thermodynamic parameters for the adsorption of EEAA, AEAA, TEAA, and ATS on mild steel in 5 M H₂SO₄ (using the gasometric technique).

Inhibitor
Equilibrium constant
(KJmol⁻¹)
(Jmol⁻¹)

30°C
40°C
50°C
60°C

EEAA
3.97
3.31
2.48
1.94
−20.37
−55.51

AEAA
5.92
4.42
3.27
2.03
−29.41
−81.89

TEAA
1.35
1.08
0.97
0.50
−25.50
−81.01

ATC
0.32
0.23
0.24
0.16
−17.22
−66.45

Figure 6: Langmuir adsorption isotherm for AEAA on mild steel in 5 M H₂SO₄.

Figure 7: Curve fitting of log K data against 1/T.

3.5. Mechanism of Inhibition

The adsorption of an organic adsorbate on a metal surface is generally regarded as a substitutional adsorption process between the organic molecule in the aqueous solution () and water molecules adsorbed on the metallic surface () [34]: where x is the size ratio representing the number of water molecules replaced by one molecule of organic adsorbate. The adsorption of organic compounds can be described by two main types of interaction: physical adsorption and chemisorption. In general, the proceeding of physical adsorption requires the presence of both electrically charged surface of the metal and charged species in the bulk of the solution. Chemisorption process involves charge sharing or charge-transfer from the inhibitor molecules to the metal surface to form a coordinate type of bond. This is possible in case of a positive as well as a negative charge on the surface. The presence of a transition metal, having vacant, low-energy electron orbital and of an inhibitor with molecules having relatively loosely bound electrons or heteroatoms with lone pair of electrons is necessary [35, 36].

The plant extracts under investigation contain ATS in variable concentrations (0.01 to 1.5% of plant dry weight) [12–15]. The compound inhibits the corrosion reaction to an appreciable extent as shown in Tables 2 and 3. ATS is a slightly polar compound [12] and can adsorb directly on the positively charged mild steel surface. ATS has an unusual trioxane structure with seven stereogenic centers and tetracyclic framework (Figure 1). It is probable that the adsorbed molecule is oriented with three of the tetracyclic ring structures parallel to the metal surface, thereby creating a barrier for mass and charge transfers. This situation leads to the protection of the mild steel from the acid corrosive ions. Comparing the inhibition efficiencies of ATS with those of the plant extracts, it is evident that ATS has the least efficiency. In addition to ATS, the plant extracts contain other known sesquiterpenes (over 20) including arteannuin B, artemisitene and artemisinin acid, flavonoid compounds, and other naturally occurring organic compounds [12–15]. This large number of different chemical compounds may form adsorbed intermediates which may either inhibit (forming insoluble Fe-phytochemical complex) or catalyse further metal dissolution. From the observed results, it can be inferred that the insoluble Fe-phytochemical complexes dominate the adsorbed intermediates and thus the resultant inhibitive effects. Synergistic inhibition of the components of the plant extracts may also contribute to the enhanced inhibition efficiency when compared to that of ATS. In addition to the physical adsorption mechanism of inhibition of ATS and other components of the extracts, there could be chemical adsorption of some components of the extracts which may also enhance the inhibition ability of the plant extracts. However, from the study, it is evident that physical adsorption is the dominant mechanism of inhibition.

The results from the phytochemical screening of the extracts are shown in Table 5. It revealed that the composition of the extracts is dependent on the type of solvents used for the extraction process. EEAA is observed to contain alkaloids, appreciable quantities of flavonoids, tannins, and glycosides. Flavonoids and glycosides were detected in AEAA while tannins and glycosides were present in TEAA. The presence of more phytochemicals in EEAA, especially the alkaloids (which are nitrogen containing organic bases) and flavonoids compared to the other extracts may be responsible for the observed highest inhibition efficiency of EEAA. Comparing the phytochemical components of AEAA and TEAA, and relating them to their inhibition efficiencies, it could be inferred that the flavonoids inhibit better than the tannins thus the higher efficiency observed for AEAA. From the observed phytochemical screening results and inhibition efficiencies, it could be concluded that the flavonoids are the principal phytochemicals in the extracts responsible for the inhibition ability of the plant. Synergism effects with other components of the plants, especially the alkaloids and tannins, may increase the inhibition efficiency to an appreciable extent, as observed for EEAA.

Table 5: Phytochemical screening of the extracts from A. Annua.

Chemical constituent
Screening

EEAA
AEAA
TEAA

Alkaloids
+
−
−

Saponins
−
−
−

Flavonoids
++
+
−

Tannins
+
−
+

Glycosides
+
+
+

Anthraquinones
−
−
−

Notes: +: present in the extracts, −: absent in the extracts.

4. Conclusions

The ethanol (EEAA), acid (AAEE), and toluene (TEAA) extracts from the leaves of Artemisia annua and artemisinin (ATS) act as inhibitors for the corrosion of mild steel in H₂SO₄ solutions and the maximum inhibition efficiencies followed the trend: EEAA > AEAA > TEAA > ATS. The inhibition efficiency values increase with increase in concentration of the inhibitors and decrease with increase in temperature. The composition of the extracts as well as its inhibition efficiency is dependent on the type of solvents used for the extraction process. Synergistic inhibition of the components of the plant extracts with ATS is attributed to the enhanced inhibition efficiencies of the extracts. The adsorption of the inhibitors molecules was consistent with Langmuir adsorption isotherm, and physical adsorption is proposed as the dominant mechanism of inhibition.

References

R. M. Saleh, A. A. Ismail, and A. H. El Hosary, “Corrosion inhibition by naturally occurring substances. vii. the effect of aqueous extracts of some leaves and fruit peels on the corrosion of steel, Al, Zn and Cu in acids,” British Corrosion Journal, vol. 17, no. 3, pp. 131–135, 1982.

O. K. Abiola and A. O. James, “The effects of Aloe vera extract on corrosion and kinetics of corrosion process of zinc in HCl solution,” Corrosion Science, vol. 52, no. 2, pp. 661–664, 2010.

A. Y. El-Etre, “Inhibition of acid corrosion of carbon steel using aqueous extract of olive leaves,” Journal of Colloid and Interface Science, vol. 314, no. 2, pp. 578–583, 2007.

P. C. Okafor and E. E. Ebenso, “Inhibitive action of Carica papaya extracts on the corrosion of mild steel in acidic media and their adsorption characteristics,” Pigment and Resin Technology, vol. 36, no. 3, pp. 134–140, 2007.

P. C. Okafor, M. E. Ikpi, I. E. Uwah, E. E. Ebenso, U. J. Ekpe, and S. A. Umoren, “Inhibitory action of Phyllanthus amarus extracts on the corrosion of mild steel in acidic media,” Corrosion Science, vol. 50, no. 8, pp. 2310–2317, 2008.

I. E. Uwah, P. C. Okafor, and V. E. Ebiekpe, “Inhibitive action of ethanol extracts from Nauclea latifolia on the corrosion of mild steel in H₂SO₄ solutions and their adsorption characteristics,” Arabian Journal of Chemistry. In press

P. C. Okafor, E. E. Ebenso, and U. J. Ekpe, “Azadirachta indica extracts as corrosion inhibitor for mild steel in acid medium,” International Journal of Electrochemical Science, vol. 5, no. 7, pp. 978–993, 2010.

I. B. Obot, S. A. Umoren, and N. O. Obi-Egbedi, “Corrosion inhibition and adsorption behaviour for aluminuim by extract of Aningeria robusta in HCl solution: synergistic effect of iodide ions,” Journal of Materials and Environmental Science, vol. 2, no. 1, pp. 60–71, 2011.

M. Lebrini, F. Robert, and C. Roos, “Alkaloids extract from Palicourea guianensis plant as corrosion inhibitor for C38 steel in 1 M hydrochloric acid medium,” International Journal of Electrochemical Science, vol. 6, no. 3, pp. 847–859, 2011.

M. Lebrini, F. Robert, P. A. Blandinières, and C. Roos, “Corrosion inhibition by Isertia coccinea plant extract in hydrochloric acid solution,” International Journal of Electrochemical Science, vol. 6, no. 7, pp. 2443–2460, 2011.

A. O. James and O. Akaranta, “Inhibition of corrosion of zinc in hydrochloric acid solution by red onion skin acetone extract,” Research Journal of Chemical Sciences, vol. 1, no. 1, pp. 31–37, 2011.

M. Kohler, W. Haerdi, P. Christen, and J.-L. Veuthey, “Extraction of artemisinin and artemisinic acid from Artemisia annua L. using supercritical carbon dioxide,” Journal of Chromatography A, vol. 785, no. 1-2, pp. 353–360, 1997.

P. S. Covello, “Making artemisinin,” Phytochemistry, vol. 69, no. 17, pp. 2881–2885, 2008.

J. Ferreira and J. Janick, “Annual Wormwood (Artemisia annua L.) New Crop FactSHEET,” 2009, www.hort.purdue.edu/newcrop/cropfactsheets/artemisia.pdf, 23rd March, 2010

J. Han, M. Ye, X. Qiao, M. Xu, B.-R. Wang, and D.-A. Guo, “Characterization of phenolic compounds in the Chinese herbal drug Artemisia annua by liquid chromatography coupled to electrospray ionization mass spectrometry,” Journal of Pharmaceutical and Biomedical Analysis, vol. 47, no. 3, pp. 516–525, 2008.

J. B. Harbone, Phytochemical Methods : A Guide to Modern Techniques of Plant Analysis, Chapman and Hill, London ,UK, 1973.

E. R. Sofowora, “Guidelines for research promotion and development in traditional medicine,” Nigeria Journal of Pharmacy, vol. 11, pp. 117–118, 1980.

G. E. Trease and W. C. Evans, A Textbook of Pharmacology, Baillier Tidally, London ,UK, 1996.

U. J. Ekpe, U. J. Ibok, B. I. Ita, O. E. Offiong, and E. E. Ebenso, “Inhibitory action of methyl and phenyl thiosemicarbazone derivatives on the corrosion of mild steel in hydrochloric acid,” Materials Chemistry and Physics, vol. 40, no. 2, pp. 87–93, 1995.

B. I. Ita and O. E. Offiong, “Inhibition of steel corrosion in hydrochloric acid by pyridoxal, 4-methylthiosemicarbazide, pyridoxal-(4-methylthiosemicarbazone) and its Zn(II) complex,” Materials Chemistry and Physics, vol. 48, no. 2, pp. 164–169, 1997.

P. C. Okafor, U. J. Ekpe, E. E. Ebenso, E. M. Umoren, and K. E. Leizou, “Inhibition of mild steel corrosion in acidic medium by Allium sativum extracts,” Bulletin of Electrochemistry, vol. 21, no. 8, pp. 347–352, 2005.

A. Y. El-Etre, “The inhibitive action of the mucilage extracted from the modified stems of prickly pears, toward acid corrosion of aluminum,” Corrosion Science, vol. 45, no. 11, pp. 2485–2495, 2003.

M. Abdallah, “Antibacterial drugs as corrosion inhibitors for corrosion of aluminium in hydrochloric solution,” Corrosion Science, vol. 46, no. 8, pp. 1981–1996, 2004.

P. C. Okafor, U. J. Ekpe, E. E. Ebenso, E. E. Oguzie, N. S. Umo, and A. R. Etor, “Extract of Allium cepa and Allium sativum as corrosion inhibitors of mild steel in HCl solution,” Transactions of the SAEST, vol. 41, no. 2, pp. 82–87, 2006.

T. Zhao and G. Mu, “The adsorption and corrosion inhibition of anion surfactants on aluminium surface in hydrochloric acid,” Corrosion Science, vol. 41, no. 10, pp. 1937–1944, 1999.

M. Abdallah, E. A. Helal, and A. S. Fouda, “Aminopyrimidine derivatives as inhibitors for corrosion of 1018 carbon steel in nitric acid solution,” Corrosion Science, vol. 48, no. 7, pp. 1639–1654, 2006.

S. S. Rehim, O. A. Hazzazi, M. A. Amin, and K. F. Khaled, “On the corrosion inhibition of low carbon steel in concentrated sulphuric acid solutions. Part I: chemical and electrochemical (AC and DC) studies,” Corrosion Science, vol. 50, no. 8, pp. 2258–2271, 2008.

A. A. El-Awady, B. A. Abd-El-Nabey, and S. G. Aziz, “Kinetic-thermodynamic and adsorption isotherms analyses for the inhibition of the acid corrosion of steel by cyclic and open-chain amines,” Journal of the Electrochemical Society, vol. 139, no. 8, pp. 2149–2154, 1992.

P. C. Okafor, V. I. Osabor, and E. E. Ebenso, “Eco-friendly corrosion inhibitors: inhibitive action of ethanol extracts of Garcinia kola for the corrosion of mild steel in H₂SO₄ solutions,” Pigment and Resin Technology, vol. 36, no. 5, pp. 299–305, 2007.

E. E. Oguzie, G. N. Onuoha, and A. I. Onuchukwu, “The inhibition of aluminium corrosion in potassium hydroxide by "Congo Red" dye, and synergistic action with halide ions,” Anti-Corrosion Methods and Materials, vol. 52, no. 5, pp. 293–298, 2005.

K. Gomma and M. H. Wahdan, “Effect of temperature on the acidic dissolution of copper in the presence of amino acids,” Materials Chemistry and Physics, vol. 32, no. 2, pp. 142–148, 1994.

S. Martinez and I. Stern, “Thermodynamic characterization of metal dissolution and inhibitor adsorption processes in the low carbon steel/mimosa tannin/sulfuric acid system,” Applied Surface Science, vol. 199, no. 1–4, pp. 83–89, 2002.

S. S. Abd El Rehim, M. A. M. Ibrahim, and K. F. Khalid, “The inhibition of 4-(2'-amino-5'-methylphenylazo) antipyrine on corrosion of mild steel in HCl solution,” Materials Chemistry and Physics, vol. 70, no. 3, pp. 268–273, 2001.

B. B. Damaskin, O. A. Petrii, and B. Batraktov, Adsorption of Organic Compounds on Electrodes, Plenum Press, New York, NY, USA, 1971.

A. Le Mehaute and G. Grepy, “Introduction to transfer and motion in fractal media: the geometry of kinetics,” Solid State Ionics, vol. 9-10, no. 17, pp. 17–30, 1983.

G. Reinhard and U. Rammet, in Proceedings of the Proceedings of the 6th European Symposium on Corrosion Inhibitors, p. 831, Ferrara, Italy, 1985.