Corrosion Science 50 (2008) 23102317

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Inhibitory action of Phyllanthus amarus extracts on the corrosion of mild steel in acidic media
P.C. Okafor a,*, M.E. Ikpi a, I.E. Uwah a, E.E. Ebenso a,b, U.J. Ekpe a, S.A. Umoren c
a

Department of Pure and Applied Chemistry, University of Calabar, PMB 1115, Calabar, Nigeria Department of Chemistry and Chemical Technology, National University of Lesotho, P.O. Roma 180, Lesotho, South Africa c Department of Chemistry, University of Uyo, PMB 1017, Uyo, Nigeria
b

a r t i c l e

i n f o

a b s t r a c t
The inhibitive action of leaves (LV), seeds (SD) and a combination of leaves and seeds (LVSD) extracts of Phyllanthus amarus on mild steel corrosion in HCl and H2SO4 solutions was studied using weight loss and gasometric techniques. The results indicate that the extracts functioned as a good inhibitor in both environments and inhibition efciency increased with extracts concentration. Temperature studies revealed an increase in inhibition efciency with rise in temperature and activation energies decreased in the presence of the extract. A mechanism of chemical adsorption of the plants components on the surface of the metal is proposed for the inhibition behaviour. The adsorption characteristics of the inhibitor were approximated by Temkin isotherm. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 30 January 2008 Accepted 15 May 2008 Available online 23 May 2008 Keywords: Mild steel Corrosion inhibition Phyllanthus amarus

1. Introduction Some investigations have in recent times been made into the corrosion inhibiting properties of natural products of plant origin, and have been found to generally exhibit good inhibition efciencies [115]. The signicance of this area of research is primarily due to the fact that natural products are environmentally friendly and ecologically acceptable. The yield of these natural products as well as the corrosion inhibition abilities of the plant extracts vary widely depending on the part of the plant [13,15,16] and its location [17]. Of importance also is the specicity of corrosion inhibiting compounds. One compound effective in a certain medium with a given metal may be ineffective for the same metal in another medium [11]. Nevertheless, the known hazardous effects of most synthetic organic inhibitors and the need to develop cheap, non-toxic and environmentally benign processes have now made researchers to focus on the use of natural products. These natural organic compounds are either synthesized or extracted from aromatic herbs, spices and medicinal plants. The use of natural products as corrosion inhibitors have been widely reported by several authors. Saleh et al. [18] reported that Opuntia extract, Aloe Vera leaves, orange and mango peels give adequate protection to steel in 5% and 10% HCl at 25 and 40 C. Srivatsava [19] found that tobacco, black pepper, castor oil seeds, acacia gum and lignin can be good inhibitors
* Corresponding author. Tel./fax: +234 803 429 5604. E-mail address: pcokafor@chemist.com (P.C. Okafor). 0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2008.05.009

for steel in acid medium. In fact, the rst patented corrosion inhibitors used were either natural product such as our, yeast etc., [20] or by products of food industries for restraining iron corrosion in acid media [21]. Cabrera et al. found that molasses treated in alkali solution inhibit the corrosion of steel in HCl used in acid cleaning [22]. Srivatsava and Sanyal studied the performance of caffeine [22] and nicotine [23] in the inhibition of steel corrosion in neutral media. Khamis et al. [24] has proved the use of herbs (such as coriander, hibiscus, anis, black cumin and garden cress) as new type of green inhibitors for acidic corrosion of steel. El-Etre [25] has studied the application of natural honey as corrosion inhibitor for copper in aqueous solution. Similar study has also been conducted on carbon steel [26]. Parikh et al. [27] studied the anticorrosion activity of onion, garlic and bitter gourd for mild steel in HCl media. Ethanolic extract of Ricimus communis leaves was studied for the corrosion inhibition of mild steel in acid media by Sathyanathan et al. [28]. Aqueous extract of Hibiscus ower and Agaricus has been studied as corrosion inhibitors for industrial cooling system by Minhaj et al. [29].The application of extracts of henna, thyme, bgugaine and inriine was investigated for their anticorrosion activity [3033]. The effect of addition of bgugaine on steel corrosion in HCl is patented [34]. Saleh et al. studied the peel of pomegranate [35] and beet root [36] as corrosion inhibitor for mild steel in acid media. Sanghvi et al. have investigated the anticorrosion activity of Embilica ofcianilis, Terminalia chebula, Terminalia belivia [37], Sapindus trifolianus and Accacia conicianna [38]. Corrosion inhibition has also been studied for the extracts of Swertia angustifolia [39], Eucalyptus leaves [40], Eugenia jambolans [41], Pongamia glabra,

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Annona squamosa [42], Accacia Arabica [43] and Vernonia amydalina [44] for steel in acid media. The anticorrosion effect of Andrographis paniculata [45] and tea wastes [46,47] have been reported too. Kliskic et al. analyzed aqueous extract of Rosmarinus ofcinalis [48] as corrosion inhibitor for aluminium alloy corrosion in chloride solution. Guar gum was analyzed for its anticorrosion activity by Abdallah et al. [49]. Martinez and Stern have studied the inhibitory mechanism of low carbon steel corrosion of Mimosa tannin in H2SO4 media [50]. Oguzie investigated the efciency of Telfaria occidentalis extract as corrosion inhibitor in both HCl and H2SO4 media [51]. The extracts of Chamomile, Halfabar, Black cumin and kidney bean were analyzed for their inhibitive action of corrosion of steel in acid media by Abdel-Gaber et al. [52]. El-Hosary et al. [53] studied the corrosion inhibition of aluminium and zinc in HCl using Hibiscus subdariffa extract. The inhibition effect of Zenthoxylum alatum extract on the corrosion of mild steel in aqueous orthophosphonic acid was investigated by Gunasekaran et al. [54]. Nypa fructicans wurmb [55] leaves were studied for the corrosion inhibition of mild steel in HCl media. Muller [56] investigated the effect of saccharides [reducing sugarsfructose and mannose] on the corrosion of aluminium and zinc in alkaline media. Hammouti et al. studied the extracts of Ginger [57], jojoba oil [57], eugenol, acetyl-eugenol [58], artemisia oil [59,60] and Mentha pulegium [61,62] for corrosion inhibition of steel in acid media.. El-Etre et al. investigated Khillah extract [63] for the corrosion inhibition of SX 316 steel in acid media, Lawsonia extract [64] was studied for its effect against acid induced corrosion of metals, Opuntia extract [65] was investigated for the corrosion of aluminium in acid medium and vanillin [66] for the corrosion of mild steel in acid media. Berberine, an alkaloid isolated from Captis was studied for its anticorrosion effect for mild steel corrosion in H2SO4 medium [67] by Yan Li et al. Zucchi and Omar [68] have found that Papaia, Poinciana pulcherrima, Cassia occidentalis and Datura stramonmium seeds, Calotropis procera, Azydracta indica and Auforpio turkiale sap are useful as acid corrosion inhibitors. Sethuraman et al. [69] have studied the acid extract of Datura metel as corrosion inhibitor for mild steel in acid medium. Quinine [70] has been studied for its anticorrosive effect of carbon steel in 1 M HCl by Mohamed Ismail Awad. Anthony et al. has studied the effect of caffeine against chloride corrosion of carbon steel [71]. An elaborate review has also been reported on natural products as corrosion inhibitors for metals in corrosive media [72].The corrosion inhibition activity in many of these plant extracts could be due to the presence of heterocyclic constituents like alkaloids, avonoids etc., Even the presence of tannins, cellulose and polycyclic compounds normally enhances the lm formation over the metal surface, thus aiding corrosion. A series of other reports have been highlighted in our laboratories on studies of other natural products (exudate gums) as corrosion inhibitors of mild steel and aluminium in acidic and basic media [7378]. In our continuous quest to explore more natural products of plant origin as corrosion inhibitors, the present study is on P. amarus. P. amarus is a plant that belongs to the family Euphorbiraceae and is widely distributed in tropical and subtropical countries and has long been used in folk medicine. It is the most prominent and widely used species of the genus Phyllanthus [79]. It was rst identied in central and southern India in the 18th century but is now found in many countries including Philippines, Cuba, and Nigeria etc. It is commonly called carry me seed, stone breaker, wind breaker, gulf leaf ower or gala of wind. P. amarus is an erect annual herb of not more than one and half feet tall and has small leaves and yellow owers. In folk medicine, it has allegedly been used to treat jaundice, diabetes, gonorrhoea, irregular menstruation etc. In Nigeria, the plant grows as weeds and every year large quantities of the plant are weeded and wasted. The extracts of this plant, which contains numerous naturally environmental

organic compounds, may be utilized as eco-friendly corrosion inhibitors. As a contribution to the current interest on environmentally friendly corrosion inhibitors, the present study investigates the inhibiting effect of extracts from the leaves (LV), seeds (SD) and a combination of leaves and seeds (LVSD) of P. amarus on mild steel corrosion in acidic solutions using the weight loss and gasometric techniques. 2. Experimental methods The mild steel sheets used for this study were obtained from Ejison Resources (Nigeria) Ltd and of the same composition as those reported previously [1315]. The test coupons were prepared, degreased and cleaned as previously described [1315]. All chemicals used were of Analar grade. 2.1. Preparation of plant extracts P. amarus leaves and seeds were collected from plants around the University of Calabar campus, Nigeria. These were dried in an N53C-Genlab Laboratory oven at 50 C, and ground to powder form. Four gram of the powder was digested in 1 l of 2 M and 5 M H2SO4 solutions (for weight loss and gasometric measurements, respectively). The resultant solution was kept for 24 h, ltered and stored. From the stock solution (4 g/l), plant extracts test solutions were prepared at concentrations of 0.1, 0.2, 0.5, 1.0 and 2.0 g/l.

10 9 8 7

Weight loss/(g)

6 5 4 3 2 1 0

Blank 0.1 g/l 0.2 g/l 0.5 g/l 1.0 g/l 2.0 g/l 4.0 g/l

b 10
9 8 Weight loss/(g ) 7 6 5 4 3 2 1 0 0 1 2 3 Time/(days)
Fig. 1. Variation of weight loss with time for mild steel coupons (of cross sectional area of 20 cm2) in 2 M: (a) HCl, and (b) H2SO4 solutions containing Phyllanthus amarus leaves (LV).

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2.2. Gravimetric and gasometric experiments The gravimetric (weight loss) and the gasometric technique (via the gasometric assembly) were determined as previously described [80,81]. However, experiments were conducted at 30 C for weight loss and 30 and 40 C for hydrogen evolution measurements.

3. Results and discussion 3.1. Gravimetric results The weight losses (gravimetric measurements) for the mild steel in 2 M HCl and 2 M H2SO4 containing different concentrations of the leaves (LV) of P. amarus extracts (PAE) as a function of time are presented in Fig. 1a and b, respectively. The results show that weight losses increase with increase in time but decrease with increase in concentration of PAE. Similar trends were obtained for the seeds (SD) and mixture (LVSD) extracts of the plant. The decrease is due to the inhibitive effects of PAE and these effects increase with increase in PAE concentration. From the weight loss data, the corrosion rates (CR) were calculated from

obtained are presented in Table 1 and show that the corrosion rates decreased with the increase in PAE concentration indicating that PAE inhibits the corrosion of mild steel in both 2 M HCl and 2 M H2SO4. It is also observed from Fig. 1 and Table 1 that the corrosion rates in HCl solutions is lower than that in H2SO4 and that the corrosion rates at all concentration of PAE used followed the trend: LV < LVSD < SD. From the weight loss data obtained, the inhibition efciencies (%I) for the corrosion of mild steel in 2 M HCl and 2 M H2SO4 containing different concentration of PAE were calculated using

%I

  CRblank CRinh 100 CRblank

CR

WL At

where WL is weight loss in mg, A is the specimen surface area (of 20 cm2) and t, the immersion period in hours (120 h). The results

where CRblank and CRinh are the corrosion rate in the absence and presence of the PAE, respectively. The results obtained are shown in Table 1 and indicate that PAE shows a signicant inhibitive effect on mild steel in HCl and H2SO4 solutions. Fig. 2 shows the variation of inhibition efciency with extracts concentration for mild steel in 2 M HCl and 2 M H2SO4 solutions containing PAE and indicates that the inhibition efciencies increase with increase in PAE concentration. Comparing the inhibition efciencies of the different parts of PAE shows that the efciencies followed the trend: LV < LVSD < SD. A plot of the logarithm of the measured weight (in g) of the mild steel after post treatment (Wf) against time (t) helps to explain the kinetics of the corrosion of mild steel in the acid media in the absence and presence of PAE. Linear plots were obtained (Fig. 3 for H2SO4), which reveal rst order kinetics. The values of the rate

Table 1 Calculated values of corrosion rate, inhibition efciency, rate constant and half-life for mild steel coupons (of cross sectional area of 20 cm2) in 2 M H2SO4 and HCl solutions containing extracts from Phyllanthus amarus (using the weight loss technique) Plants part Blank LV System 2 M H2SO4 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M H2SO4 + 0.2 g/l H2SO4 + 0.5 g/l H2SO4 + 1.0 g/l H2SO4 + 2.0 g/l H2SO4 + 4.0 g/l H2SO4 + 0.2 g/l H2SO4 + 0.5 g/l H2SO4 + 1.0 g/l H2SO4 + 2.0 g/l H2SO4 + 4.0 g/l H2SO4 + 0.1 g/l H2SO4 + 0.2 g/l H2SO4 + 0.5 g/l H2SO4 + 1.0 g/l H2SO4 + 2.0 g/l H2SO4 + 4.0 g/l extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract Corrosion rate (mg cm2 hr1) 3.59 2.87 2.14 1.70 1.10 0.41 3.56 3.25 2.83 2.00 1.27 4.09 3.79 3.04 2.56 1.68 0.86 1.34 extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract 0.18 0.13 0.12 0.10 0.10 0.08 0.52 0.26 0.19 0.32 0.27 0.27 0.37 0.16 0.11 0.08 0.11 0.17 Inhibition efciency (%) 20.0 40.4 52.6 69.3 88.6 0.7 9.5 21.0 44.1 64.6 14.0 5.6 15.3 28.7 53.3 76.1 86.3 90.0 91.0 92.5 92.8 94.1 61.1 68.7 73.0 76.3 79.8 80.1 72.6 88.2 91.9 93.8 91.9 87.2 Rate constant 101 (day1) 2.90 1.99 1.25 0.94 0.55 0.16 2.92 2.45 1.98 1.17 0.70 3.86 3.14 1.79 1.51 0.92 0.49 0.64 0.07 0.05 0.05 0.03 0.03 0.03 0.28 0.19 0.17 0.16 0.12 0.11 0.11 0.06 0.04 0.03 0.03 0.03 Half-life (days) 2.4 3.5 5.6 7.4 12.7 42.4 2.4 2.9 3.5 5.9 9.9 1.8 2.2 3.9 4.6 7.6 14.3 10.9 94.0 130.8 150.5 214.9 214.9 231.5 24.9 36.3 41.2 43.0 56.8 62.7 64.0 111.5 158.4 231.5 250.8 273.6

SD

LVSD

Blank LV

2 M HCl 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M 2M HCl + 0.1 g/l HCl + 0.2 g/l HCl + 0.5 g/l HCl + 1.0 g/l HCl + 2.0 g/l HCl + 4.0 g/l HCl + 0.1 g/l HCl + 0.2 g/l HCl + 0.5 g/l HCl + 1.0 g/l HCl + 2.0 g/l HCl + 4.0 g/l HCl + 0.1 g/l HCl + 0.2 g/l HCl + 0.5 g/l HCl + 1.0 g/l HCl + 2.0 g/l HCl + 4.0 g/l

SD

LVSD

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100 80

t 1=2

0:693 k

Inhibition efficiency/(%)

where k is the rate constant. t1/2, values are presented in Table 1 and were observed to increase with increase in concentration of PAE. 3.2. Gasometric results The acidic corrosion of mild steel is characterised by evolution of hydrogen and the rate of corrosion is proportional to the amount of hydrogen evolved [11]. The volume of hydrogen evolved, VH, during the corrosion of mild steel in 5 M HCl and H2SO4 solutions in the absence and presence of PAE at 30 and 40 C was measured as a function of time. The results obtained at 30 C are as depicted in Figs. 4 and 5 for HCl and H2SO4 solutions, respectively. Similar results were obtained at 40 C. The presence of leaves (LV) and seeds (SD) of PAE decreases the volume of hydrogen evolved compared to the blank. From the volume of hydrogen evolved during the corrosion reaction, the corrosion rate (CRH) was determined from

60 40 20 0 -20 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 LV (HCl) SD (HCl) LVSD (HCl) LV (H2SO4) SD (H2SO4) LVSD (H2SO4)

Extract concentration/(g/l)
Fig. 2. Variation of inhibition efciency with extract concentration for mild steel coupons (of cross sectional area of 20 cm2) in 2 M HCl and 2 M H2SO4 solutions containing the different parts of Phyllanthus amarus.

CRH

Vt Vi tt ti

1.2 1.1 1 0.9

Log Wf

Blank 0.2 g/l 0.5 g/l 1.0 g/l 2.0 g/l 4.0 g/l

where Vt and Vi are the volumes of hydrogen evolved at time tt and ti, respectively. The results obtained are presented in Table 2. The results show that the rate decreased with the increase in PAE concentration and increase in temperature for all systems. From the corrosion rate (deduced from the hydrogen evolved), the inhibition efciency was determined using Eq. (2). The results

0.8 0.7 0.6

20

25

0.5

VH/(cm3)

0.4

15

Blank 4.0 g/l

1.1 1 0.9

10

2.0 g/l 1.0 g/l

0.8 0.7 0.6 0.5 0.4

Blank 0.2 g/l 0.5 g/l 1.0 g/l 2.0 g/l 4.0 g/l

0.5 g/l 0.2 g/l

Log Wf

0.1 g/l

25

20

Time/(days)
Fig. 3. Plot of log Wf against time for mild steel coupons (of cross sectional area of 20 cm2) in 2 M H2SO4 solutions containing: (a) leaves (LV), and (b) seeds (SD) extracts of Phyllanthus amarus.

VH/(cm3)

15

10

0 0 10 20 30 40 50 60 70

constants, k, obtained from the slope in Fig. 3 are presented in Table 1. The results obtained reveal that the rate constant decreases with increase in PAE concentration. The values of half-life, t1/2, were calculated using the equation:

Time/(min.)
Fig. 4. Variation of volume of hydrogen evolved (VH) with time for mild steel coupons (of cross sectional area of 10 cm2) in 5 M HCl solutions containing: (a) leaves (LV), and (b) seeds (SD) extracts of Phyllanthus amarus at 30 C.

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obtained are as also shown in Table 2 and depicted in Fig. 6a and b for corrosion in HCl solutions. It is observed that inhibition efciency increases with increase in the PAE concentration and with increase in temperature. This suggests that the phytochemical components of PAE are adsorbed on the mild steel solution interface. The trend in temperature suggests chemical adsorption of the components of the PAE. A decrease in inhibition efciency with increasing temperature suggests physical adsorption. It is also quite clear that from what is known about dependence of adsorption as temperature decreases, that the quantity of equilibrium of adsorption increases and as a result, the plot of higher temperature is above the lower one [82]. This is clearly demonstrated in Fig. 6. Comparing the maximum inhibition efciencies of PAE (Fig. 7) shows that the efciencies followed the trend: LV > LVSD > SD in all systems. Similar trend were observed in 2 M H2SO4 from the weight loss measurements. 3.3. Inhibition mechanism The observed corrosion inhibition of mild steel in H2SO4 solution with increase in PAE concentration can be explained by the adsorption of the components of the PAE on the metal surface. In order to predict the type of adsorption, the corrosion mechanism of the iron must be known. According to the mechanism for the anodic dissolution of Fe in acidic sulphate solutions proposed initially by Bockris et al. [83], Fe electro-dissolution in acidic sulphate solutions depends primarily on the adsorbed intermediate FeOHads as follows:

Fe OH ( ) FeOHads H e FeOHads ! FeOH e ) Fe FeOH H (

2 rds

5a 5b

H2 O

5c

The cathodic hydrogen evolution follows the steps:

Fe H ( ) FeH ads FeH ads e ( ) FeHads FeHads H e ! Fe H2

6 7 8

The corrosion rate of iron in H2SO4 solutions is controlled by both hydrogen evolution reaction and dissolution reaction of iron. Another mechanism, involving two adsorbed intermediates has been used to account for the retardation of Fe anodic dissolution in the presence of an inhibitor [84]

Fe H2 O ( ) Fe H2 Oads ) Fe H2 Oads Y ( FeOH ads H Y

9a 9b 9c 9d 9e 9f 9g

) FeYads H2 O Fe H2 Oads Y ( FeOH ads ! FeOHads e ) FeYads ( FeY ads e

rds

FeOHads FeY ) FeYads FeOH ads ( ) Fe2 H2 O FeOH H (

a 40
35 30 25

20 15 10 5 0.5 g/l 0 0.2 g/l 0.1 g/l Blank 4.0 g/l 2.0 g/l 1.0 g/l

b 40
35 30 25 20 15 10 5 0 0 10 20 30 40 50 60 70

Time/(min.)
Fig. 5. Variation of volume of hydrogen evolved (VH) with time for mild steel coupons (of cross sectional area of 10 cm2) in 5 M H2SO4 solutions containing: (a) leaves (LV), and (b) seeds (SD) extracts of Phyllanthus amarus at 30 C.

where Y represents the inhibitor species. According to the detailed mechanism above, displacement of some adsorbed water molecules on the metal surface by inhibitor species to yield the adsorbed intermediate FeYads (Eq. (9c)) reduces the amount of the species FeOH ads available for the rate determining step. Such adsorbed intermediate could, depending on its relative solubility, either inhibit or catalyse further metal dissolution. PAE are viewed as an incredible rich source of naturally synthesized chemical compounds. These large numbers of different chemical compounds may form adsorbed intermediates (organo-metallic complexes) such as FePAE [5, 52 and 54] which may either inhibit or catalyse further metal dissolution. From the observed results it can be inferred that the insoluble FePAE complexes dominates the adsorbed intermediates and thus the resultant inhibitive effects. This conclusion is in line with those of Jaen et al. [85]. PAE is composed of numerous naturally occurring organic compounds [18]. This complex composition makes it rather difcult to attempt to assign the observed corrosion inhibitive effect to a particular constituent. Studies on the phytochemical constituents of PAE shows that it contains saponins (24.05%), tannins (17.05%), oxalates (5.47%), alkaloids (2.56%), cyanogenic glycosides (1.46%), carbohydrates (45.52%), bre (24.50%), protein (6.10%) and fat (6.03%) but the percentages are higher in the seeds than in the leaves especially of fat (24.80%), protein (34.20%), saponins (38.40%), tannins (29.40%) and alkaloids (19.42%). The high saponin and tannin, carbohydrate and bre contents explain its use in folk medicine for the treatment of liver problems, oedema etc and its use as corrosion inhibitors [86].However, further investigation to isolate the active ingredients and test their inhibition ability is being carried out in our laboratories. Other studies have reported the presence of phyllanthin and hypophyllanthin in PAE extracts. The presence of triterpenoids, steroids, alkaloids, sugar, tannins, glycosides, avonoids has also been reported in PAE depending on the type of extraction carried out [87]. Some of these components especially alkaloids, avonoids, tannins, fats, proteins were

VH/(cm3)

VH/(cm3)

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Table 2 Calculated values of corrosion rate, inhibition efciency, activation energy and heat of adsorption for mild steel coupons (of cross sectional area of 10 cm2) in the acid media containing extracts from Phyllanthus amarus (using the gasometric technique) Plants part System Corrosion rate (cm3 min1) 30 C 5 M H2SO4 LV 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M H2SO4 + 0.1 g/l H2SO4 + 0.2 g/l H2SO4 + 0.5 g/l H2SO4 + 1.0 g/l H2SO4 + 2.0 g/l H2SO4 + 4.0 g/l H2SO4 + 0.1 g/l H2SO4 + 0.2 g/l H2SO4 + 0.5 g/l H2SO4 + 1.0 g/l H2SO4 + 2.0 g/l H2SO4 + 4.0 g/l H2SO4 + 0.1 g/l H2SO4 + 0.2 g/l H2SO4 + 0.5 g/l H2SO4 + 1.0 g/l H2SO4 + 2.0 g/l H2SO4 + 4.0 g/l extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract 0.39 0.52 0.49 0.39 0.31 0.14 0.07 0.47 0.46 0.44 0.43 0.39 0.30 0.80 0.71 0.66 0.50 0.44 0.24 0.22 extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract extract 0.33 0.28 0.14 0.10 0.10 0.09 0.36 0.30 0.22 0.19 0.17 0.15 0.24 0.23 0.22 0.18 0.13 0.11 40 C 1.01 0.99 0.92 0.56 0.39 0.21 0.10 1.03 1.02 1.00 0.97 0.90 0.73 2.13 1.68 1.20 0.99 0.73 0.50 0.97 0.71 0.59 0.47 0.37 0.28 0.24 0.80 0.67 0.57 0.50 0.40 0.33 0.40 0.41 0.36 0.32 0.29 0.26 Inhibition efciency (%) 30 C 32.8 23.7 2.0 22.4 65.1 81.4 18.6 16.8 12.9 8.1 1.0 24.4 103.6 80.7 69.1 26.8 10.8 39.6 48.9 28.1 35.7 54.3 55.0 58.9 65.1 35.7 0.8 12.4 21.0 29.5 9.3 3.9 2.3 17.2 41.1 48.8 40 C 2.0 8.9 44.5 61.5 78.9 90.5 1.7 0.8 1.4 4.6 11.0 28.0 109.8 66.0 18.3 2.3 27.9 50.7 27.0 39.9 51.4 62.5 71.8 74.9 17.9 31.6 41.4 49.0 59.1 66.1 59.1 58.2 62.9 66.7 70.0 73.6 61.05 41.48 41.38 24.48 15.84 28.72 17.64 51.15 51.56 52.30 52.95 54.24 57.92 63.01 55.59 38.07 44.29 33.32 5.73 96.17 50.25 47.42 78.12 83.37 66.14 64.39 51.15 52.02 62.25 61.37 53.78 49.01 32.89 37.54 33.81 37.45 52.72 53.54 102.14 47.91 19.39 21.81 69.39 5.18 12.56 18.04 9.51 20.47 20.52 125.89 53.52 47.40 43.07 119.77 63.41 33.77 29.98 Activation energy (KJ mol1) Heat of adsorption (KJ mol1)

SD

LVSD

5 M HCl LV 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M 5M HCl + 0.1 g/l HCl + 0.2 g/l HCl + 0.5 g/l HCl + 1.0 g/l HCl + 2.0 g/l HCl + 4.0 g/l HCl + 0.1 g/l HCl + 0.2 g/l HCl + 0.5 g/l HCl + 1.0 g/l HCl + 2.0 g/l HCl + 4.0 g/l HCl + 0.1 g/l HCl + 0.2 g/l HCl + 0.5 g/l HCl + 1.0 g/l HCl + 2.0 g/l HCl + 4.0 g/l

SD

LVSD

higher in percentage in the seeds than in the leaves hence the reason why the seeds give rise to higher inhibition but further investigations to isolate the active ingredients and test their inhibition ability is going on in our laboratories. Increase in temperature increased the inhibition efciencies of the PAE suggesting chemisorption of PAE components on the surface of the metals [7,65,88]. In order to conrm this, the apparent activation energies, Ea, for the dissolution of mild steel in HCl and H2SO4 in the absence and presence of the PAE were calculated from the condensed Arrhenius equation as follows:

log

  R2 Ea 1 1 R1 2:303R T 1 T 2

10

where h1 and h2 are the degrees of surface coverage at temperatures T1 and T2 respectively. The calculated values are presented in Table 2. The positive values of the heat of adsorption are consistent with the phenomenon of inhibitor chemical adsorption [7]. The results obtained from this study have clearly showed that the inhibition efciency increases with extracts concentration and with temperature which indicated that the inhibition mechanism is due to chemical adsorption of the molecular components of PAE on the surface of the metal. The experimental data were applied to different adsorption isotherm equations. It was found that the experimental data tted the Temkin isotherm (Fig. 8) which may be formulated as:

exp2ah Kc

12

where R1 and R2 are the corrosion rates at temperatures T1 and T2, respectively. The calculated activated energy values are as listed in Table 2. The results indicate that Ea in the presence of the PAE decreases. This behaviour is an indication of chemical adsorption of the components of the PAE on the surface of the metal. An estimate of the heat of adsorption (Qad) was obtained from the trend of surface coverage with temperature as follows:

     h2 h1 T1T2 log x Q ad 2:303R log 1 h2 1 h2 T2 T1

11

where h is the surface coverage, c the extracts concentration, K the adsorption coefcient, which represents the adsorption-desorption equilibrium constant, and a is an interaction parameter. Calculated values of K and a are as shown in Table 3. Positive values of a indicates attraction forces between adsorbed molecules while negative values indicate repulsive forces between the adsorbed molecules [89]. It is seen in the table that the values of a in all cases are negative indicating that repulsion exists in the adsorption layer [90]. It is generally known that K denotes the strength between the adsorbate and adsorbent. Large values of K imply more efcient adsorp-

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P.C. Okafor et al. / Corrosion Science 50 (2008) 23102317

80 60 40 20 30 C 40 C

a 0.8
0.7 0.6 0.5

%I

0
0.4

-20
0.3

LV SD LVSD

-40 -60 -80 0 1 2 3 4 5

0 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 0.2 0.1

c/(g/l)

log c

b 100
80 30 C 60 40 40 C
1

b 1.5

%I

0.5

20 0 -20 -40 -60 0 1 2 3 4 5

-1.5 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 -1 0

LV SD LVSD

-0.5

c/(g/l)
Fig. 6. Variation of inhibition efciency with extract concentration for mild steel coupons (of cross sectional area of 10 cm2) in 5 M HCl solution containing: (a) LV, and (b) SD extracts from Phyllanthus amarus.

0.6

0.8

log c
Fig. 8. Temkin adsorption isotherm plot as h against log c for mild steel coupons (of cross sectional area of 10 cm2) in 5 M: (a) HCl, and (b) H2SO4 solutions containing PAE at 40 C.

90 80 Inhibition efficiency/(%) 70 60 50 40 30 20 10 0 LV LVSD Plant's part

Fig. 7. Maximum inhibition efciency for mild steel coupons (of cross sectional area of 10 cm2) in 5 M acid solutions containing 4 g/l PAE at 30 C. 5 M H2SO4 LV SD LVSD

HCl H2SO4

Table 3 Calculated values of the adsorption-desorption equilibrium constantK and the interaction parameter a for mild steel coupons (of cross sectional area of 10 cm2) in the acid media containing extracts from Phyllanthus amarus (using the gasometric technique) Plants part K 30 C 1.55 1.04 1.36 1.61 1.08 1.82 40 C 2.68 1.86 2.01 7.11 5.44 5.35 a 30 C 0.66 2.10 0.59 0.69 0.86 1.30 40 C 0.84 3.08 0.51 1.63 1.71 1.25

SD

5 M HCl LV SD LVSD

tion and hence better inhibition efciency [91]. K values are seen to increase with increase in temperature suggesting that the inhibitors are chemically adsorbed onto the mild steel surface. 4. Conclusions 1. P. amarus extracts (PAE) acts as inhibitor for mild steel corrosion in HCl and H2SO4 solutions and inhibition efciencies followed the trend: LV < LVSD < SD.

2. Inhibition efciency of PAE increases with increase in concentration of PAE and with increase in temperature suggesting chemical adsorption. 3. The corrosion process is inhibited by adsorption of PAE on the mild steel surface following the Temkin isotherm. 4. The presence of the extract decreased the corrosion activation energy in both media and the adsorption heats gave positive values.

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Acknowledgements The authors acknowledged Mr. Efremfon Edemidiong and Ochuko Djebah for assistance in performing some measurements. References
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