Chemistry and Technology of Fuels and Oils, Vol. 47, No. 1, March, 2011 (Russian Original No.

1, January-February, 2011)

ROSEMARY OIL AS A CORROSION INHIBITOR FOR CARBON STEEL IN 0.5 M SULFURIC ACID SOLUTION F. M. Al-Nowaiser, M. Abdallah, and E. H. El-Mossalamy

The possibility of using rosemary oil as a corrosion inhibitor of carbon steel in 0.5 M sulfuric acid solution was investigated by determination of weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy. It was shown that the inhibition effectiveness increases with an increase in the concentration of oil and a decrease in the temperature. The inhibiting effect of the investigated oil is due to its adsorption on the surface of the steel and complexation. Adsorption is described by a Langmuir isotherm. The effect of the temperature on the corrosion rate was studied in the presence and absence of the oil and the thermodynamic parameters of the corrosion process were calculated. Key words: hydrocarbon steel, rosemary oil, inhibitor, electrochemical impedance spectroscopy. Equipment made of carbon steel is widely used in the oil industry [1]. The main problem in using this steel is its low corrosion resistance in acid medium. Aqueous solutions of acids, primarily sulfuric acid, are used for scouring, cleaning boilers, descaling , and acid treatment of wells [2, 3]. These solutions are some of the most corrosive media. One method of protecting carbon steel from corrosion is to use organic inhibitors [4-8], which are heterocyclic compounds containing phosphorus, sulfur, oxygen, or nitrogen and have bonds [9, 10]. Almost all of these compounds are unfortunately very expensive and hazardous to the environment. For this reason, it is very important to select an inexpensive inhibitor that is safe to use. Some natural oils were previously investigated as corrosion inhibitors for metals and alloys [11-14]. We investigated the inhibition effectiveness of rosemary oil for carbon steel in 0.5 M sulfuric acid solution. Carbon steel L-52 of the following composition, wt. %, was used in the experiments: 0.26 carbon; 1.35 manganese; 1.04 phosphorus; 0.05 sulfur; 0.05 niobium; 0.02 vanadium; 0.03 titanium; remainder iron. The weight loss of steel plates with a total surface area of 4 cm 2 was determined with the method described in [15]. The samples were immersed in 0.5 M sulfuric acid solution (50 ml) with no inhibitor and with rosemary oil in different concentrations and held for 6 h. Cylindrical electrodes surrounded by Araldite with an open surface area of 0.64 cm 2 were used for the studies by potentiodynamic polarization and electrochemical impedance spectroscopy. Before conducting the experiments, the electrodes were polished with different types of emery paper, degreased ____________________________________________________________________________________________________ Chemistry Department, King Abdul-Aziz University, Jeddah, Saudi Arabia. Chemistry Department, Benha University, Benha, Egypt. Translated from Khimiya i Tekhnologiya Topliv i Masel , No. 1, pp. 49 53, January February, 2011. 66 0009-3092/11/47010066 2011 Springer Science+Business Media, Inc.

Table 1
C, ppm 100 200 300 400 500 600 IE, % 68.22 75.33 85.76 89.38 91.22 94.28

with acetone, washed with tap water, and dried with filter paper. All of the reagents used corresponded to the quality of analytical reagents. We used twice-distilled water to prepare the acid solutions. The electrolytic cell is described in [10]. The experiments were conducted at the temperature of 251C. The potentiodynamic polarization measurements were performed with a PS potentiostat with the PS6 software required for calculating the current density I curr and corrosion potential E corr , and anode b a and cathode b c Tafel constants. The corrosion current density was calculated with the intersection of the anode and cathode Tafel lines at a constant corrosion potential. The rate of measuring the potentiodynamic polarization was 10 mV/sec. Three cells, a calomel standard electrode, and an auxiliary platinum amalgam electrode were used for the measurements. A Volta Lab (model PGZ-301) potentiostat with Voltammeter 4 software was used for the electrochemical impedance spectroscopy. The measurements were performed with an alternating current signal (10 mV) at an open circuit potential in the 100-50 kHz frequency range. Rosemary and tannic acids are the basic components of rosemary oil [16]. The structural formula of rosemary acid is:

The method of determining the inhibition effectiveness with the weight loss is simple and reliable [17]. The inhibition effectiveness IE (in %) and parameter , which reflects the surface area of the steel coated with the inhibitor, were calculated with the equations:

IE = (1 Wadd / W free )100 = 1 W add / W free

where W free , W add are the weight losses of the carbon steel without and with the inhibitor. The calculated values of IE at different concentrations C of inhibitor are reported in Table 1. The inhibition effectiveness increases with the concentration of the inhibitor, which can be attributed to an increase in the surface area of the steel occupied by adsorbed molecules of rosemary oil. We believe that adsorption of the 67

C, ppm
Fig. 1. C/ as a function of C in adsorption of rosemary oil on the surface of carbon steel in 0.5 M sulfuric acid solution.

inhibitor on the metalsolution interface is the most important stage of inhibition. Four kinds of adsorption of organic compounds are possible on the surface of a metal: electrostatic attraction between the charged metal and inhibitor molecules, reaction of uncharged electron pairs in the inhibitor molecule with the metal, reaction of the electrons in the inhibitor molecule with the metal, and a combination of these kinds of adsorption [18]. Chemisorption includes charge separation or charge transfer from the inhibitor molecule from the surface of the metal with formation of a coordination bond. Electron transfer is characteristic of metal conductors with vacant electron orbitals with low energy. It can arise when compounds with relatively weakly bound electrons are involved [19]. We attempted to describe the values of with the Frumkin, Freundlich, Langmuir, and Temkin isotherm equations. These values are best described by the Langmuir isotherm equation:

C/ = 1 / K ads + C
where K ads is the adsorption equilibrium constant. The graph of C / as a function of C is a straight line (Fig. 1). This indicates that adsorption of rosemary oil on the surface of carbon steel in 0.5 M sulfuric acid solution is described by the Langmuir isotherm equation and consequently, the absence of a reaction between the adsorbed molecules. The adsorption equilibrium constant K ads calculated with Fig. 1 is 7.14 10 -3 . This constant is correlated with the adsorption free energy G by the expression in [20]

K ads =

1 G 0 exp RT 55.5

where R is the universal gas constant; T is the absolute temperature; 55.5 is the water content in the solution. The calculated value of G is 5.68 kJ/mole. The negative value of the adsorption free energy indicates that adsorption of rosemary oil on the surface of carbon steel is spontaneous. Values of G up to 20 kJ/mole are related to electrostatic interactions between charged molecules and the surface of the metal (physical adsorption), while values of G of less than 40 kJ/mole are related to separation or transfer of electrons from the 68

Fig. 2. log R corr of carbon steel as a function of reciprocal of the temperature 1/T in 0.5 M sulfuric acid solution: 1) without inhibitor; 2) with inhibitor.

Fig. 3.

log R corr/ T of carbon steel as a function of reciprocal of the temperature 1/ T

in 0.5 M sulfuric acid solution: 1) without inhibitor; 2) with inhibitor. inhibitor molecule to the metal surface with formation of a coordination bond (chemisorptions) [21]. As a consequence, for G = 5.68 kJ/mole, physical adsorption of rosemary oil primarily takes place on the surface of the steel. The effect of the temperature on the corrosion rate R corr of steel in 0.5 M sulfuric acid solution without and with rosemary oil in the concentration of 600 ppm was investigated by measuring the weight loss in the 30-70C temperature range. The results of the study are reported in Table 2. The corrosion rate increases and the inhibition effectiveness decreases with an increase in the temperature. This shows that inhibition consists of

(mg/cm 2min))

mg/cm 2min))

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Table 2
Temperature, C 30 40 50 60 70 30 40 50 60 70 R corr, mg/(cm2min) With no inhibitor 0.580 0.751 0.992 1.181 1.373 With 600 ppm rosemary oil 0.633 0.74 0.146 0.220 0.298 94.28 90.14 85.28 81.37 78.29 IE, %

adsorption of rosemary oil on the surface of the steel, since increasing the temperature causes desorption. The activation energy of the corrosion process was calculated with the equation in [22]

Rcorr = A exp( E a /RT )

where A is a pre-exponential factor; E a is the activation energy. The dependence of log R curr on the reciprocal of the temperature 1/ T in 0.5 M sulfuric acid solution uninhibited and inhibited by rosemary oil in the concentration of 600 ppm is shown in Fig. 2. The activation energy of the corrosion process, calculated with the slope of the lines for the uninhibited solution, is 26.72, versus 43.86 kJ/mol for the inhibited solution. The decrease in the activation energy with an increase in the temperature is due to a decrease in adsorption of the rosemary oil on the surface of the steel and a corresponding increase in the corrosion rate due to the fact that more of the surface of the metal is exposed to the acid [23]. The values of the enthalpy H and entropy S of activation of corrosion of carbon steel in 0.5 M sulfuric acid solution without and with rosemary oil in the concentration of 600 ppm were calculated with the transition equation of state [24]:

Rcorr = (RT/Nh ) exp( S 0 / R ) exp(H 0 / RT )

where N is Avogadros number; h is Plancks constant. The graph of log R corr/T as a function of 1/ T (Fig. 3) is a straight line with a slope of H / 2.303 R, which intersects segment log( R/Nh ) ( S /2.303 R ) at the coordinate axis. The values of H determined with the slope of the line are: in the uninhibited solution, 21.6 kJ/mol; in the inhibited solution, 38.2 kJ/mol. The positive values of H indicate the endothermic effect of dissolution of the carbon steel. The values of S calculated with the segments intersected by the lines on the coordinate axis for the uninhibited and inhibited solutions are respectively 223.4 and 245.34 J/(K mol). The negative values of S indicate that formation of an activated

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Table 3
Inhibitor content, ppm 0 100 200 300 400 500 600 Ecorr , mV (standard calomel electrode) 445 488 475 460 480 462 478 Icorr, A/cm2 566 172 142 102 72 53 34 bc, mV 101 188 176 178 166 172 163 162 ba, mV 101 152 144 150 152 138 144 135 IE, % 0,00 69,61 74,91 81,97 87,27 90,63 93,99

complex is the limiting stage, and association predominates over dissociation. This also shows that the ordering of the system increases in going from the reagents to the activated complex. The potentiodynamic polarization curves for the carbon steel electrode in 0.5 M sulfuric acid solution are shown in Fig. 4 in the absence of an inhibitor and in the presence of rosemary oil in different concentrations. The inhibition effectiveness was calculated with the equation

IE = (1 I corr add / I corr free )100

where I corr.add, I corr,free are the corrosion current density with and without the inhibitor. The effect of the concentration of rosemary oil on the kinetic corrosion parameters, I corr, E corr , ba , bc , and IE , determined as a result of measuring the polarization, is shown in Table 3. The anode and cathode Tafel constants are almost constant in the investigated range of concentrations, which indicates the inhibiting effect of the rosemary oil caused by its adsorption on the surface of the steel according to an adsorption blocking mechanism. The values of E corr , change insignificantly toward more negative values, the values of I corr decrease, and the inhibition effectiveness increases, which confirms the inhibiting effect of the rosemary oil. The Nyquist plot obtained in studying a steel electrode in 0.5 M sulfuric acid solution with different concentrations of rosemary oil is shown in Fig. 5. In almost all cases, the impedance diagram is not a true semicircumference, which can be attributed to frequency dispersion [25]. The electrochemical impedance parameters of carbon steel in 0.5 sulfuric acid solution was calculated before and after addition of the inhibitor. The charge-transfer resistance R i was calculated with the difference in the impedance at low and high frequencies [26]. The double-layer capacitance C dl was determined with the frequency F at which resistance Z is maximum:

F ( Z max ) = (2 C dl Rt )

The inhibition effectiveness was calculated with the charge-transfer resistance

IE = (1 Rt free / I t add )100

where R tadd , Rtfree are the charge-transfer resistance with and without the inhibitor. 71

Potential, V

A/cm 2
Fig. 4. Potentiodynamic polarization curves for a carbon-steel electrode in 0.5 M sulfuric acid solution without an inhibitor and with rosemary oil in the concentration of 100-600 ppm.

/cm 2

/cm 2
Fig. 5. Nyquist plot of carbon steel in 0.5 M sulfuric acid solution without and with inhibitor in different concentrations, ppm; 1) 0.5 M H2SO4 ; 2) 100; 3) 300; 4) 500; 5) 600. The results of electrochemical impedance spectroscopy are reported in Table 4. The charge-transfer resistance increases with the concentration of the inhibitor. The inhibitor effectiveness increases with the charge-transfer resistance. The decrease in the double-layer capacitance with an increase in the concentration of inhibitor can be attributed to substitution of molecules of water on the surface of the electrode by the inhibitor with a lower dielectric constant [27, 28]. This shows that the rosemary oil is adsorbed on the surface of the electrode.

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Table 4
Inhibitor content, ppm 0 100 300 500 600 Cdl, F/cm2 86.2 73.3 61.8 41.1 39.78 R r, /cm2 42 115 156 227 265 IE, % 63.78 73.07 81.49 84.15

The values of the inhibition effectiveness determined by electrochemical impedance spectroscopy and potentiodynamic polarization and the weight loss of the samples are satisfactorily correlated with each other (see Table 4). It is widely known that the molecules of organic substances of high molecular weight and bulky structure can occupy a large area of the surface of the metal. If such a molecule has the capacity for chemisorption, it can effectively inhibit corrosion. The inhibiting effect of the rosemary oil is due to its adsorption on the surface of the carbon steel with formation of a complex with charge transfer between the phenol groups in the inhibitor molecule and the surface of the steel. The size, shape, orientation, and electron charge of the molecule determine the degree of adsorption and the inhibition effectiveness. The rosemary acid molecule, the basic component of rosemary oil, contains groups that form a complex with bi- and trivalent metal ions [29]. The inhibiting effect of this compound is due to the fact that iron ions are coordinated with phenol groups on the ends of the molecule:

The presence of another active site in the rosemary acid molecule determines the horizontal position of the molecule relative to the surface of the steel, which increases the surface area occupied by the inhibitor and the high effectiveness of the inhibitor even at low concentrations. Based on the results of the study, we can form the following conclusions: rosemary oil is a good corrosion inhibitor of steel in 0.5 M sulfuric acid solution; the inhibiting effect of this oil is due to adsorption and the horizontal position of its molecule on the surface of the steel; adsorption of rosemary oil on the surface of the steel is described by a Langmuir adsorption isotherm; in the presence of rosemary oil, the double-layer capacitance decreases, due to adsorption of the oil on the surface of the steel. REFERENCES 1. M. A. Deyab, Corros. Sci. , 49, 2315 (2007). 2. 3. 4. 5. S. A. Abd El. Maksoud and A. S. Fouda, Mater. Chem. Phys., 93, 84 (2005). K. F. Khaled, Ibid. , 112, 90 (2008). J. Al Jourani, M. A. Golozar, and K. Roeissi, Ibid. , 121, 320 (2010). S. M. A. Hosseini, M. Salri, E. Jamalizadeh, et al., Ibid. , 119, 100. 73

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