Anticorrosion Activity of Pheniramine Maleate on Mild

© 2018 JETIR December 2018, Volume 5, Issue 12

www.jetir.org (ISSN-2349-5162)

Anticorrosion Activity of Pheniramine Maleate on Mild Steel in Hydrochloric acid. Auxilia Christy1, Albin Aloysius1*, Rajajeyaganthan Ramanathan2, Noreen Anthony3, Ganapathi Sundaram4 1 Department of Chemistry, BWDA Arts & Science College, Kolliyangunam – 604304, Tamilnadu, India 2 Department of Chemistry, Kalasalingam Academy of Research and Education, Kalasalingam University, Krishnankoil 626126, Tamil Nadu, India 3 Department of Chemistry, Holy Cross College, Tiruchirappalli – 620002, Tamilnadu, India 3 Department of Chemistry, Faculty of Science and Humanities, Mahendra Engineering College (Autonomous), Mallasamudram, Namakkal, Tamilnadu-637503, India Abstract: Weight loss, electrochemical impedance and potentiodynamic polarization studies were done with the Mild steel in 0.5 M hydrochloric acid with the different concentration of pheniramine maleate (PM). The potentiodynamic polarization results showed as the concentration of pheniramine maleate increases the Icorr decreases and inhibition efficiency of Mild steel increases. From the result the good inhibition efficiency of pheniramine maleate is observed. The Surface analysis of mild steel in 0.5 M hydrochloric acid in the presence of pheniramine maleate was studied using scanning electron microscope. Keywords: Mild steel, 0.5 M hydrochloric acid, Pheniramine Maleate, Potentiodynamic polarization, Electrochemical impedance spectroscopy

1. INTRODUCTION Corrosion of metal is the most important drawbacks in most of the industry production process because of rusting of machineries, boilers, container, metal equipment’s and cooling Towers, there are so many types of corrosion out of that corrosion which is happened through acid is very important in the Chemical industry. the presence of acidic environment, Pitting and crevice corrosion occurs most frequently [1-3], Organic compounds and natural products are used as corrosion inhibitors for several metals [4-7], Unsaturated organic compounds and organic compounds with heteroatom like sulphur, Phosphorus, nitrogen and oxygen act as corrosion inhibitors of metal by surface adsorption [8-18], Heterocyclic compounds containing conjugated double bond and polar functional groups are used as an acidic inhibitor. Literature survey shows that most of the organic corrosion inhibitors control the corrosion through adsorption on the metal surface and it is depends upon the nature of metal surface, electronic structure of the inhibitor, mode of adsorption and temperature. The adsorption may be chemisorption or physisorption with the active polar functional groups of the in inhibitor, Present study deals with the corrosion inhibiting property of pheniramine maleate as corrosion inhibitors on Mild steel in 0.5 M hydrochloric acid solution, it is an drug which is having antihistamine with anticholinergic properties and it is used to treat heavy fever or urticarial. it is generally found in eye drops medicines which is used for the allergic conjunctivitis. pheniramine maleate structure is given in figure 1 , It contains heteroatoms like nitrogen, oxygen and aromatic 𝜋 electrons, in this research weight loss method, potentiodynamic polarization, electrochemical impedance and Scanning electron microscopy where used to analyse the corrosion inhibiting property and its mechanism.

Figure 1. Structure of Pheniramine Maleate 2. EXPERIMENTAL 2.1. Material and coupons The test material used was mild steel of composition 0.10% C, 0.06% P, 0.40% Mn, 0.026% S and the rest of iron. The size of the mild steel taken was 1 x 4 x 0.2 cm3 and their surfaces abraded by using 200-800 emery sheets. Before testing coupons

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were degreased with Acetone and washed with deionized water. Pheniramine maleate solution is prepared by dissolving one gram of pheniramine maleate in 100 ml SMF and made up to the mark using 0.5 M hydrochloric acid. Hydrochloric acid is prepared using double distilled water, various concentrations of inhibitors such as 100, 200, 300, 400 and 500 ppm were are used to find inhibition efficiency and corrosion rate. 2.2. Weight loss method In weight loss method all the test where carried out in 100 ml beaker containing 0.5 M hydrochloric acid, throughout the process room temperature was maintained, mild steel coupons were dipped in 100 ml 0.5 M hydrochloric acid solution or 0.5 M hydrochloric acid solution with inhibitor using plastic hooks the coupons which are immersed in solution taken out after 1 hour of immersion, rinsed with double distilled water dried and weighed. This method used to calculate the inhibition efficiency as IE, (%) and corrosion rate as CR, (mg.dm-2hr-1). CR (mg.dm-2.hr-1) = W =

M1−M2 𝑆𝑃

Where, W is the corrosion rate, M1 is the mass of the bare mild steel, M2 is the mass of the mild steel after corrosion, S is the surface area of the coupons in dm2 and P is the period of immersion in hours. The IE (%) was finding out using the subsequent equation: IE (%) =

(𝑊0 −𝑊𝑖 ) 𝑊0

× 100

Where Wi and Wo are the rate of corrosion of mild steel in the presence and absence of inhibitor respectively, In this study, the CR value is calculated using the formula, CR (mg.dm-2.day-1) = M1-M2 (mg)/ [0.096 (dm2) x 1 hr.] Where, the surface area S takes the value of 0.096 dm2. 2.3. Potentiodynamic polarization studies Conventional three electrode cell assembly is used to carry out electrochemical experiment. In this three electrode assembly mild steel coupon with exposed surface area 1 cm2 was used as working electrode and it was fitted to a holder and the remaining area was covered with epoxy resin coating, Platinum wire and saturated calomel electrode were used as counter and reference electrode, In the test medium working electrode was vertically immersed in the Princeton Applied Research (2 channels) analyzer, the open circuit potential were recorded at the scan rate of 0.5 mV/s. The corrosion current density (Icorr) and corrosion potential (Ecorr) were obtained from the tafel flat , using the Icorr value inhibition efficiency was calculated, Electrochemical impedance analyses were completed in the frequency range from 1 Hz to 1MHz with amplitude of 10 mV peakto-peak using AC signal at Ecorr. In this study the mild steel coupons of 1 cm2 surface area where exposed to the corrosion medium. The experiment were carried out in 0.5 M hydrochloric acid with various concentration of inhibitor at room temperature without stirring 2.4. Characterization of surface morphology Plane mild steel and mild steel immersed for 1 hour in 0.5 M hydrochloric acid with or without inhibitor were taken out and washed with double distilled water and dried and then it was taken photograph using TESCAN Vega 3 to study the surface morphology of the metal surface

3. RESULT AND DISCUSSION 3.1. Weight Loss Measurement Corrosion of mild steel in 0.5 M hydrochloric acid with and without various concentration of inhibitor in weight loss method given in Table 1, From the weight loss study it was observed that when the concentration of inhibitor increases IE (%) also increases, the maximum inhibition efficiency 75.34 % was obtained in 500 ppm of pheniramine maleate solution in the presence of corrosion medium after the immersion period of 1hr. In figure 2(a), the graph drawn between inhibitor concentration and inhibition efficiency clearly shows that the maximum inhibition efficiency is reached at 500 ppm inhibitor concentration, further addition of inhibitor concentration (600 and 700 ppm) never makes any remarkable change in the inhibition efficiency. The reason may be, the surface of the mild steel is completely adsorbed by the active sites of the inhibitor, and there is no empty surface for adoption of further addition of inhibitor concentration. In Figure 2(b), the graph drawn between inhibitor concentration and corrosion rate, it clearly shows that rate of corrosion decreases from 106.82 mgdm-2day-1 to 26.31 mgdm2 day-1, when increases the inhibitor concentration from 100 ppm to 500 ppm, corrosion inhibition by the inhibitor may be due to the heteroatoms like oxygen, nitrogen and ᴨ bond which is present in the pheniramine maleate, which makes an inhibitor

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molecule to adsorbed on the metal surface and forms the protective layer[19] which is insoluble in water due to this reason corrosion is prevented Table 1. Corrosion rate and inhibition efficiency obtained from weight loss method for mild steel immersed in 0.5 M hydrochloric acid in the absence and presence of various concentrations of pheniramine maleate Conc. of PM (ppm)

Weight loss (mg.dm-2)

CR (mg.dm-2.day-1)

Surface coverage (θ)

IE (%)

Blank

10.67

106.82

-

-

100

6.29

62.94

0.4103

41.03

200

4.79

47.99

0.5503

55.03

300

3.87

38.71

0.6373

63.73

400

3.29

32.91

0.6916

69.16

500

2.63

26.31

0.7534

75.34

Figure 2. Weight loss curves of different concentrations of pheniramine maleate in 0.5 M hydrochloric acid: (a) change of IE (%) with various concentration of pheniramine maleate and (b) change of corrosion rate with various concentration of pheniramine maleate 3.2. Potentiodynamic polarization Mild steel corrosion in 0.5 M hydrochloric acid is an electrochemical corrosion, it carries continuous anodic oxidation and cathodic reduction of mild steel, From the potentiaodynamic polarization curve (Figure 3) of mild steel immersed in 0.5 M hydrochloric acid with and without various concentration of pheniramine maleate at room temperature one can easily understand the mechanism, Figure 3 show both anodic and cathodic curve, the electrochemical parameters obtained from tafel plot such as anodic slope (βa), cathodic slope (βc), corrosion current (I corr), corrosion potential (Ecorr), surface coverage area (θ) and inhibition efficiency were summarised in Table 2, Inhibition efficiency in percentage were are calculated using the following formula[20]. IE% = (

I°corr−Icorr I°corr

) ×100

Where I°corr and Icorr are the corrosion current density values in the absence and presence of pheniramine maleate respectively, while increasing the inhibitor concentration of pheniramine maleate from 100 to 500 ppm in the 0.5 M hydrochloric acid solution, the corrosion current density values reduced (see Figure 3 and Table 2) at same time corrosion current density increased to a maximum value for 500 ppm of pheniramine maleate The Icorr value of blank 480.502µA/cm-2 is reduced and reached the minimum value of 120.219 µA/cm-2 for 500 ppm of Pheniramine maleate, it shows that both anodic dissolution of mild steel and cathodic reduction reactions were reduced by the addition of pheniramine maleate due to the formation of protective layer, In

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this study the percentage inhibition efficiency increases with increase in the inhibitor concentration of pheniramine maleate which is also agreed well with weight loss method, All the above shows that addition of pheniramine maleate prevent the corrosion by the formation of protective layer on the surface of mild steel. The type of inhibitor weather it is anodic inhibitors or cathodic inhibitor can be find out by relating the corrosion potential (Ecorr) values. Usually difference in Ecorr value between blank and inhibitor is greater than 85 mV/SCE, then the inhibitor is said to be cathodic or anodic type, but if the Ecorr value difference is less than 85 mV/SCE, then the inhibitor is said to be mixed type Inhibitor[21-24], in our case for pheniramine maleate Ecorr difference between blank and inhibitor is 13.64 mV/SCE (-453.609 mv/SCE to -467.252mV/SCE) it is less than 85 mV/SCE, it shows that pheniramine maleate is a mixed type of inhibitor in 0.5 M hydrochloric acid corrosion medium. Table 2. Potentiodynamic polarization data for mild steel in 0.5 M hydrochloric acid in the presence and absence of pheniramine maleate. Inhibitor concentration (ppm) Blank

Blank Icorr (µAcm-2) 480.502

Inhibitor Icorr (µAcm-2) -

Ecorr

βa

βc

(mV)/SCE -453.609

(mV dec-1) 70.877

100

480.502

223.964

-476.874

200

480.502

186.014

300

480.502

400 500

IEPDP

IEWL

(mV dec-1) 211.373

Surface coverage (θ) -

(%) -

(%) -

76.834

131.066

0.5338

53.38

41.03

-475.311

85.247

141.374

0.6128

61.28

55.03

172.932

-473.029

80.214

138.045

0.6401

64.01

63.73

480.502

159.146

-467.252

63.843

130.396

0.6687

66.87

69.16

480.502

120.291

-469.113

73.432

144.401

0.7496

74.96

75.34

Figure 3. Potentiodynamic polarization curves for mild steel in 0.5 M hydrochloric acid in the presence and absence of pheniramine maleate.

3.3. Electrochemical impedance spectroscopy Surface and Kinetic properties of mild steel in 0.5 M hydrochloric acid with and without inhibitor can be studied using electrochemical impedance spectroscopy, Figure 4 gives the Nyquist plots of mild steel immersed in 0.5 M hydrochloric acid with and without pheniramine maleate at room temperature, it gives the value of double layer capacitance (Cdl) and charge transfer resistance (Rct) which is given in the table 3. very simple electrical equivalent circuit[25-26] where used to explain the nature of Impedance, double layer capacitance (Cdl), charge transfer resistance (Rct) and the resistor (Rs) and it was shown in Figure. 5.

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Figure 4. Nyquist plots for mild steel in 0.5 M hydrochloric acid in the presence and absence of pheniramine maleate.

Figure 5. Equivalent electrical circuit used to fit the impedance spectra obtained for mild steel in 0.5 M hydrochloric acid in the presence and absence of pheniramine maleate Rct is the charge transfer resistance, CPEdl is the constant phase equivalent of double layer, and Rs is the solution resistance shown in the equivalent electrical circuit. From the nyquist plot when the concentration of inhibitor pheniramine maleate increases, the diameter of the semicircle (Rct) increases; it shows that there is a formation of protective layer on the mild steel surface. when the concentration of pheniramine maleate increases charge transfer resistance increases and the double layer capacitance decreases this is due to the formation of protective layer on the mild steel by the adsorption of pheniramine maleate and reduce dissolution reaction which further reduce the corrosion of mild steel [27], the degrease in the Cdl value is due to the increase in the thickness of the electrical double layer by the adsorption of pheniramine maleate on mild steel. The IE (%) was calculated from Rct values through the following equation. IE% = (

𝑅𝑐𝑡(𝑖) −𝑅𝑐𝑡(𝑏) 𝑅𝑐𝑡(𝑖)

× 100)

Where R ct(b) and R ct(i) are the uninhibited and inhibited charge transfer resistance respectively. From the table 3, the increase in the value of IE (%) with respect to the increase in the inhibitor concentration is due to the increase in the charge transfer resistance and corresponding degrees in the double layer capacitance value Double layer capacitance (Cdl) is related to the thickness of the adsorbed protective layer (d) by the equation [28], Cdl = (εεoA)/d Where ε - dielectric constant of the medium, εo - free space permittivity and A -surface area of the electrode. The decrease in the double layer capacitance value shows that there is an increase in the thickness of the double layer due to the strong adsorption of pheniramine maleate which prevent the mild steel disillusion in 0.5 M hydrochloric acid Table 3. Potentiodynamic polarization data for mild steel immersed in 0.5 M hydrochloric acid in the presence and absence of pheniramine maleate

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Inhibitor concentration (ppm) 100

Rct (blank) (Ω cm2)

Rct (i) (Ω cm2)

Ymax

Cdl (µ F cm-2)

IE (%)

θ(imp)

30.391

72.325

36.16

6.0883E-05

57.97

0.5797

200

30.391

85.421

42.71

4.3646E-05

64.42

0.6442

300

30.391

95.869

47.93

3.4651E-05

68.29

0.6829

400

30.391

111.2

55.6

2.5755E-05

72.66

0.7266

500

30.391

126.82

63.41

1.9801E-05

76.03

0.7603

3.4. Surface analysis Scanning electron microscopy (SEM) spectra is given in Figure 5. Figure 5(a) shows that the smooth surface of mild steel before immersion of corrosion medium, Figure 5(b) shows the rough surface of mild steel due to the pits observed after the immersion of 0.5 M hydrochloric acid for 1hr, but Figure 5(c) shows that there is smooth surface of metal when it was taken from 0.5 M hydrochloric acid with Pheniramine maleate, it is because of the adsorption of pheniramine maleate on the surface of the mild steel

Figure 5. SEM images of mild steel: a) polished mild steel, b) mild steel immersed in 0.5 M hydrochloric acid and c) mild steel immersed in 0.5 M hydrochloric acid in presence of pheniramine maleate. 4. CONCLUSION 1. 2. 3. 4.

Pheniramine maleate act as a good corrosion inhibitor for mild steel in 0.5 M hydrochloric acid corrosion medium, its maximum Inhibition efficiency is 67.12 % from weight class method. Potentiodynamic polarization studies show that pheniramine maleate act as a mixed type of inhibitor. Electrochemical impedance studies shows that when the concentration of pheniramine maleate increases, the thickness of electrical double layer also increases due to the adsorption of pheniramine maleate on the surface of the mild steel The formation of protective layer on the surface of the mild steel was confirmed by the smooth surface of SEM images

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