INHIBITION OF MILD STEEL CORROSION IN HYDROCHLORIC ACID SOLUTION BY ACETAZOLAMIDE DRUG

S.Mani megalai*, M.Eswari , R.Ramesh, and P.Manjula1

*

PG and Researsh Department of Chemistry, Arulmigu Palaniandavar College of Arts & Culture, Palani-624601, Tamilnadu, India.
1

Arulmigu Palaniandavar College for Women,Palani-624601,Tamilnadu, India.

Abstract
The effect of a Acetazolamide is studied for use as a low cost and ecofriendly corrosion inhibitor for mild steel in acidic environment. The corrosion inhibition effect is investigated using weight loss, Tafel polarization, and electrochemical impedance spectroscopy and studies. The inhibitor showed 86.4% inhibition efficiency at 10.10-4M concentration of Acetazolamide. Potentiodynamic polarization suggests that it is a mixed type of inhibitor. Electrochemical impedance spectroscopy was used to investigate the mechanism of corrosion inhibition. The adsorption of this compound on mild steel surface obeys Temkins adsorption isotherm. Key words: Acetazolamide, mild steel, weight loss, corrosion inhibition, polarization and EIS, Adsorption

1.INTRODUCTION Mild steel is an important category of materials due to their wide range of industrial applications. It is used in many industries due to its excellent mechanical properties. These are used in industries as pipelines for petroleum industries, storage tanks, reaction vessels and chemical batteries (1). Acids are widely used for Pickling, Descaling, Acid Cleaning, Oil Well acidizing and other applications. Due to their high corrosive nature acids may cause damage to the system components. Various methods are used to decrease the corrosion rate of metals in acids, among the different methods use of inhibitors is most commonly used (2-7). The use of corrosion inhibitors is most economical and practical method to reduce electrochemical corrosion. Heterocyclic compounds containing hetero atoms such as S, N & O act as effective corrosion inhibitors for mild steel in acid media and have been the subject of many publications (8-11). Organic compounds have been widely used as corrosion inhibitors for metals in acidic media (12-18). The effective and efficient corrosion inhibitors were those compounds which have bonds and contains hetero atoms such as sulphur, nitrogen, oxygen and phosphorous which allows the adsorption of compounds on the metal surface(19-23). The organic inhibitors decrease the

corrosion rate by adsorbing on the metal surface and blocking the active sites by displacing water molecules and form a compact barrier film on the metal surface. The most of the organic inhibitors are toxic, highly expensive and environment unfriendly. Research activities . in recent times are geared towards developing the cheap, non-toxic and environment friendly corrosion inhibitors. The present paper describes a study of corrosion protection action of Acetazolamide on mild steel in 1M HCl using weight loss, electrochemical techniques. Acetazolamide is a _____________ with -electrons, heteroatoms S, N & O. The molecule is big enough (Molecular Mass; 222.245) and sufficiently planar to block more surface area (due to adsorption) on mild steel. These factors favour the interaction of Acetazolamide with the metal. As far as we know no concrete report has been published so for Acetazolamide in 1N HCl with use of weight loss electrochemical techniques, hydrogen permeation and diffuse reflectance spectra. Hence the present study. The structure of the Acetazolamide is shown in the fig.1. Different concentrations of inhibitor were prepared and there inhibition efficiency in acidic media was investigated. 2. EXPERIMENTAL METHODS 2.1 Materials preparation All the tests were performed on mild steel of following composition (wt %) : 0.076% C, 0.192% Mn, 0.012% P, 0.026% Si, 0.050% Cr, 0023% Al, 0.123% Cu and balance Fe. Mild steel specimens with dimensions of 1.0 x 4.0 x 0.2 cm were used for weight loss and electrochemical studies. The surface of each specimen was abraded with different emery papers (600-1200) and washed with acetone. The cleaned samples were then washed with double distilled water and finally dried. Electrochemical experiments were performed using a three electrode cell assembly with mild steel samples as working electrode, platinum as counter electrode and saturated calomel (SCE) as the reference electrode. The mild steel electrode of 1.0 x 4.0 x 0.2 cm sizes with an exposed area of 1cm2 and rest being covered by epoxy resin was used as working electrode for electrochemical study. AR grade hydrochloric acid and doubly distilled water were used to prepare lM acid for all experiments. 2.2 Inhibitor Acetazolamide tablets are commercially obtained as a trade name Diamox manufactured by the Sun Pharmaceuticals Ltd.The compound is in its purest state, having molecular formula (C4H6N4O3S2) and melting point (258261C). Its chemical structure is shown in Fig (1)

Acetazolamide is a N-S heterocyclic compound containing three oxygen atoms, four nitrogen atoms and two sulphur atoms. Hence it is expected to act as a good inhibitor. Acetazolamide is a ______________________ with -electrons, heteroatoms such as S,N and O.The molecule molecular mass is 222.245 g/mol. Acetazolamide, tablet are commercially obtained as a manufactured by the sun pharmaceuticals trade name Diamox, is a carbonic an hydrase inhibitor that is used to treat glaucoma , epileptic seizures, idiopathic intracranial hypertension (pseudotumor cerbri), altitude sickness, cystinuria, periodic paralysis and dural ectasia. Acetazolamide is available as a generic drug and is also a diuretic. The range of the concentrations of inhibitor used for the inhibition is from 1.1 x 10-4 M to 10.10 x 10-4 M. 2.3 Weight Loss Measurements The MS specimens used had a rectangular shape of 1.0 x 4.0 x 0.2 cm were abraded with series of emery paper (600-1200) and then washed with distilled water and finally washed with acetone. After weighing accurately, the specimens were immersed in beaker which contained 100ml of 1M HCl in the absence and presence of different concentration of inhibitor at room temperature. After 3h the specimens were taken out, washed, dried and weighed accurately. Triplicate experiments were performed in weight loss test for each concentration of inhibitor and without inhibitor and average of weight loss is reported. The corrosion rate CR was calculated from the following equation. 87.6W CR (mm/y) = ---------atD ---------------> (1)

Where W is the average weight loss of mild steel specimens, a is the total area of one mild steel specimen, t is the immersion time (3h) and D is density of mild steel in (gcm-3). The inhibition efficiency (IE%) and surface coverage () of inhibitor on the corrosion of MS was calculated as follows. W1-W2 IE(%) = --------- x 100 W1 W1-W2 = --------W1 ----------------> (2)

Surface coverage

---------------->

(3)

Where W1 and W2 are the weight losses of mild steel without and with the inhibitor respectively.

2.4 Electrochemical Measurements Three electrochemical techniques, namely DC-Tafel slope, linear polarization resistance (LPR), and ACelectrochemical impedance spectroscopy (EIS), were used to study the corrosion behaviour. All experiments were performed in conventional three electrode cell. Three electrodes connected to potentiostat/galvanostat G 300-45050 (Gamry instruments inc., USA) Echem Analyst 5.0 software package was used for data fitting. 2.4.1 Tafel polarization and linear polarization studies The MS was the working electrode, and platinum electrode was used as an auxiliary electrode. All potentials were measured versus a saturated calomel electrode (SCE) ie. Reference electrode. Before recording the polarization curves the solution was deaerated for 20 min and the working electrode was maintained at its corrosion potential for 10 min. until a steady state was obtained. The mild steel surface was exposed to various concentrations of Acetazolamide in 100ml of 1M Hcl at room temperature. The inhibition efficiency (IE%) was calculated using the equation. Icorr Icorr(inh) Inhibition efficiency (IE%) = ---------------------- x 100 -------> (4) Icorr (Rct(inh) Rct Inhibition efficiency (IE%) = Rct(inh) x 100 -------> (5)

Where Rct (inh) and Rct are the values of charge transfer resistance in presence and absence of inhibitor in lM HCl respectively. All experiments were measured after immersion period for 30min of mild steel in lM HCl in the absence and presence of different concentrations of inhibitor. 3. RESULTS AND DISCUSSION 3.1. Weight Loss Studies The values of inhibition efficiency (IE%) and the corrosion rate (CR) obtained from weight loss method at different concentrations of Acetazolamide are summarized in Table 1. It follows from the data that the weight loss decreased and therefore corrosion inhibition increased with increase in inhibitor concentration. It was also observed that corrosion rate decreased with increase in inhibitor concentration.

It is evident from the table that Acetazolamide inhibits the corrosion of mild steel in HCl solution at all the concentrations used in the study i.e. 1.1.x 10-4M to 10.10 x 10-4M. Maximum inhibition efficiency was obtained at the concentration 10.10 x 10-4M. The increased inhibition efficiency and decreased corrosion rate might be due to the increased adsorption and increased surface coverage () of inhibitor on mild steel surface with increase in concentration. The variation of inhibition efficiency with increase in inhibitor concentrations is shown in Fig 2. 3.2 Effect of immersion time The effect of immersion time was investigated by using optimum concentration 10.10 x 10-4 M of Acetazolamide for 2 to 8 hrs. The effect of immersion time on the inhibition efficiency is shown in Fig.3. It is a round that the inhibition efficiency decreases from 88.2% to 81.4% with increase in immersion time from 2 to 8 hrs. 3.3 Tafel polarization Polarization curves for mild steel in 1M HCl at various concentrations of Acetazolamide are shown in the Fig.4 The values of corrosion potential (Ecorr), current densities (Icorr), anodic tafel slopes (ba), cathodic tafel slopes (bc), surface coverage () and inhibition efficiency(%) of Acetazolamide concentration were calculated from the curves are shown in Table 2. It is evident from the figure that both reactions where suppressed with the addition of the Acetazolamide inhibitor. The suggest that Acetazolamide reduced the anodic dissolution reactions as well as retarded the hydrogen evolution reaction on the cathodic sites. (24,25). It is observed that the inhibition efficiency increased with increasing ampicillin concentration and exhibited both cathodic and anodic inhibition through adsorption on the mild steel surface blocking active sites (26). According to Riggs (27) and others if the displacement in E (i) is >85mV,with respect to E, the inhibitor can be seen as a cathodic or anodic type (ii) if displacement in E is < 85,the inhibitor can be seen as mixed type. In our study the maximum displacement is less than 85, which indicates that acetazolamide is a mixed type inhibitor. It is evident from the data that inhibition efficiency (IE), surface coverage () increases with increase in concentration of the inhibitor. The corrosion current density (Icorr) decreases with increase in inhibitor concentration. The maximum inhibition efficiency of 83.25% is obtained at 10.10 x 10-4 M solution of Acetazolamide.

3.4 Electrochemical Impedance Spectroscopy (EIS) Studies Corrosion inhibition of mild steel in 1M HCl solution with and without inhibitor was investigated by electrochemical impedance spectroscopy measurements. The Nyquist representations of impedance behavior of mild steel in 1M HCl with and without addition of different concentrations of Acetazolamide are shown in the Fig.5 It is observed from the figure that at all concentrations range of Acetazolamide one large capacitive loop at higher frequency range followed by the one small inductive loop at lower frequency range. The diameter of the circle increased with increase in inhibitor concentration. The higher frequency capacitive loop is due to the adsorption of inhibitor molecule (28). This can be interpreted by Rs-Rp Cdl equivalent circuit, commonly known as Randle circuit . which was previously used to model the iron-acid interface (29) .Many workers also explained the results by using randle circuit (29-34) in the following figure. The deviation from the perfect semi circle shape (depression) is often referred to the frequency dispersion of interfacial impedance. This behavior is due to the in homogeneity of the metal surface arising from surface roughness or interfacial phenomena (35-37). It is observed that addition of inhibitor increases the values of Rct and reduces the Cdl value. The decrease in Cdl is due to increase in thickness of the electronic double layer (38). The increase in Rct values is due to the formation of protective film on the metal / solution interface (39,40). This observation suggests that Acetazolamide molecules function by adsorption on metal surface and thereby causing the decrease in Cdl values and increase in Rct values. The charge transfer resistance (Rct) values and the interfacial double layer capacitance (Cdl) values calculated from the cures are shown in the Table 3. 3.5. Adsorption Isotherm The degree of surface coverage () for different concentrations of inhibitor in 1M HCl has been calculated from weight loss, polarization and electrochemical impedance studies. The obtained data was tested graphically for fitting suitable isotherm. Almost a straight line was obtained by plotting surface coverage () Vs log C shown in Fig. 7, which proves that the adsorption of this compound obeys Temkin isotherm. 3.6. Mechanism of Corrosion Inhibition Corrosion inhibition mechanism in acidic medium is based on the adsorption of inhibitor on the metal surface. The process of adsorption is influenced by the nature and charge of the metal, chemical structure of the inhibitor and the type of the aggressive electrolyte. The charge of the metal

surface can be determined from the potential zero charge (Pzc) on the correlative scale (c) (41) by the equation. c = Ecorr Eq = o Where Eq=o is the potential of zero charge. He value of Ecorr obtained in Hcl is 470mv versus SCE. In HCl solution Acetazolanide acts as a protonated species. This protonated species are adsorbed on the metal surface through chloride bridge and reduces the corrosion. Benerijee and malhotra (42) reported the Pzc of iron in hydrochloric acid solution is -530 versus SCE. Therefore the value of is +60mV versus SCE, so the metal surface acquires slight positive charge. The adsorption of cationic Acetazolamide species does not take place and the adsorption of chloride ions occurs and surface becomes negatively charged. Now due to the electrostatic attraction, the protonated Acetazolamide molecules physically adsorbed on the metal surface and thereby giving high inhibition by Acetazolamide molecules. 4. CONCLUSION Acetazolanide acts as a good inhibitor for the corrosion of mild steel in 1M HCl. Potentiodynamic curves reveal that Acetazolamide is a mixed type of inhibitor. EIS measurements also indicates that the inhibitor performance increase due to the adsorption of molecule on metal surface. The result obtained from weight loss, impedance and polarization studies are in good agreement with each other. The adsorption of Acetazolamide on mild steel surface obeyed Temkins adsorption isotherm.

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Fig 1. Molecular structure of Acetazolamide N-(5 sulfamoyl 1,3,4 thiadiazol 2-yl) acetamide.

Fig 2 Variation of Inhibition Efficiency in 1 M HCl on mild steel at different concentration of inhibitor

Inhibitio n efficiency (%)

Inhibitor Concentration

Fig 3: Variation of I.E. in 1M HCL on mild steel at different immersion time.

89 88 87
IE (%)

86 85 84 83 82 81 0 1 2 3 4 5 6 7 8 9

Immersion time

Fig 4: Potentiodynamic polarization curves for mild steel in 1 M HCl in the absence and present of different concentration of Acetazolamilde

Fig.5-Randle Circuit

1.1 X 10-4 M 2.2 X 10-4M 4.4 X 10-4M 6.6 X 10-4M 8.8 X 10-4M 10.10 X 10-4 M

Fig.6: Nyquist plot of mild steel in 1M HCl in the absence & presence of different concentrations of Acetazolamide drug.

Surface Coverage

log C x 10-4

Fig 7. Temkin adsorption isotherm for different concentrations of Acetazolamide in 1M HCl

Table 1. Weight loss measurements for mild steel in 1M HCl at different concentrations of Acetazolamide drug. Inhibitor concentration x 10-4 M Blank Weight loss (mg cm-2) Surface coverage -

IE%

CR (mm/y)

37.52

131.12

1.1

26.49

29.39%

92.579

0.2939

2.2

22.69

39.52%

79.299

0.3952

4.4

19.86

47.06%

69.408

0.4706

6.6

18.13

51.67%

63.362

0.5167

8.8

14.17

62.23%

49.522

0.6223

10.10

5.10

86.40%

17.823

0.8640

Table 2: Electrochemical parameters and inhibition efficiency for corrosion of mild steel in lM HCl obtained by polarization method.

Conc (M)

Ecorr mV vs SCE

Icorr (A/cm2)

ba mV/dec

bc mV/dec

Surface coverage ( )

IE (%)

Blank

-472.3

598.5

82

130

1.1

-474.6

466.5

80

141

0.2205

22.05

2.2

-477.2

341.1

66

145

0.4300

43.00

4.4

-479.1

230.2

64

149

0.6153

61.53

6.6

-483.4

222.4

54

157

0.6284

62.84

8.8

-487.6

220.1

52

161

0.6322

63.22

10.10

-493.4

100.2

50

165

0.8325

83.25

Table 3. Electrochemical parameters and inhibition efficiency for corrosion of mild steel in 1M HCl obtained by impedance method .

Concentrations (M) Blank

Rct ( cm2)

Cdl (F Cm-2)

Surface coverage ()

Inhibition efficiency (%) -

46.68

619

1.1

151.72

535

0.6923

69.23

2.2

154.7

493

0.6982

69.82

4.4

158.14

479

0.7048

70.48

6.6

166.72

449

0.7200

72.00

8.8

173.0

410

0.7301

73.01

10.10

198.2

402

0.8272

82.72