You are on page 1of 13
 
Inhibitive properties, thermodynamic and quantum chemical studies of alloxazineon mild steel corrosion in H
2
SO
4
N.O. Obi-Egbedi
a
, I.B. Obot
b,
a
Department of Chemistry, University of Ibadan, Ibadan, Nigeria
b
Department of Chemistry, Faculty of Science, University of Uyo, P.M.B. 1017, Uyo, Akwa Ibom State, Nigeria
a r t i c l e i n f o
 Article history:
Received 30 April 2010Accepted 9 September 2010Available online 17 September 2010
Keywords:
A. AlloxazineB. Mild steelC. Sulphuric acidD. Density functional theory (DFT)
a b s t r a c t
Alloxazine (ALLOX) was tested as corrosion inhibitor for mild steel in 0.5M H
2
SO
4
 solution using non-electrochemical technique (gravimetric and UV–Visible spectrophotometric measurements) at 303–333K. ALLOX acts as inhibitor for mild steel in acidic medium. Inhibition efficiency increases withincrease in concentration of ALLOX but decrease with rise in temperature. The adsorption of ALLOXwas found to followTemkin adsorption isothermmodel. Both the activation andthermodynamic param-eters governing the adsorption process were calculated and discussed. The adsorption follows a first-order kinetics. DFT study gave further insight into the mechanism of inhibition action of ALLOX.
 2010 Elsevier Ltd. All rights reserved.
1. Introduction
Corrosioninhibitorshavebeenwidelyusedinstimulationoper-ations in petroleum wells [1,2]. In these operations acid solutionsat temperatures up to 333K are often employed to remove ironoxides and carbonated minerals [3]. In such aggressive medium,theuseofcorrosioninhibitorsisoneofthemostcommon,effectiveand economic methods to protect metals in acid media [4].The majority of the well-known inhibitors are organic com-pounds containing heteroatoms such as oxygen, nitrogen or sul-phur, and multiple bonds, which allow an adsorption on themetal surface [5–7]. It has been observed that the adsorption of these inhibitors depends on the physico-chemical properties of the functional groups and the electron density at the donor atom.The adsorption occurs due to the interaction of the lone pair and/or
 p
-orbitals of inhibitor with d-orbitals of the metal surfaceatoms, which evokes a greater adsorption of the inhibitor mole-cules onto the surface, leading to the formation of a corrosion pro-tection film [8–10]. Furthermore, adsorption is also influenced bythe structure and the charge of metal surface, and the type of test-ing electrolyte [11]. The choice of effective inhibitors is based ontheir mechanism of action and electron-donating ability. The sig-nificant criteria involved in this selection are molecular structure,electron density on the donor atoms, solubility and dispersibility[12–15].Recently, interest in alloxazines has intensified because of theirimportant role in a wide range of biological systems [16].Lumichrome (7,8-dimethylalloxazine), for example was found toinhibit flavin reductase in living
 Escherichia coli
 cells [17]. Anotherinteresting application is in an optical transistor device with a thinfilm of Lumichrome on conductive SnO
2
 glass [18]. A further pointof interest is the possibility of using alloxazines to sensitize thephotooxidation of substituted phenols in water [19]. However,there is no literature to date about the corrosion inhibitive effectof alloxazine on mild steel in H
2
SO
4
 solution.Theaimofthispaperthereforeistoexploretheuseofalloxazineasanacidcorrosioninhibitorformildsteelsurfaceinsulphuricacidsolution using gravimetric method. The effect of temperature oncorrosionandinhibitionprocessesarethoroughlyassessedanddis-cussed.Kineticandthermodynamicparameterswerecalculatedanddiscussedindetail.UV–Visiblespectroscopytogetherwithquantumchemical study using density functional theory were further em-ployed to provide additional insight into the mechanism of inhibi-toryaction.
2. Experimental method
 2.1. Material
Testwereperformedonafreshlypreparedsheetofmildsteelof the following composition (wt.%): 0.13% C, 0.18% Si, 0.39% Mn,0.40% P, 0.04% S, 0.025% Cu, and bal. Fe. Specimens used in theweight loss experiment were mechanically cut into 5.0cm
4.0cm
 0.8cm dimensions, then abraded with SiC abrasivepapers320, 400 and600grit, respectively, washedinabsoluteeth-anol and acetone, dried in roomtemperature and stored in a mois-ture free desiccator before their use in corrosion studies [5,6].
0010-938X/$ - see front matter
 
 2010 Elsevier Ltd. All rights reserved.doi:10.1016/j.corsci.2010.09.020
Corresponding author. Tel.: +234 8067476065.
E-mail address:
Contents lists available at ScienceDirect
Corrosion Science
 
 2.2. Inhibitor 
Alloxazine (ALLOX) was purchased from SIGMA–ALDRICH andusedasinhibitor.Stocksolutionwasmadein10:1water:methanolmixture to ensure solubility [20]. This stock solution was used forall experimental purposes. Fig. 1 shows the molecular structure of ALLOX. It is evident that ALLOX is a heterocyclic compound con-taining nitrogen and oxygen atoms, which could easily be proton-ated in acidic solution, and several
 p
-electrons exist in thismolecule.
 2.3. Solutions
The aggressive solutions, 0.5M H
2
SO
4
 were prepared by dilu-tion of analytical grade 98% H
2
SO
4
 with distilled water. The con-centration range of ALLOX was 2–10
l
M.
 2.4. Gravimetric measurements
The gravimetric method (weight loss) is probably the mostwidely used method of inhibition assessment [21–24]. The sim-plicity and reliability of the measurement offered by the weight
ab
Fig. 2.
 Variation of weight loss against time for mild steel corrosion in 0.5M H
2
SO
4
 in the presence of different concentrations of ALLOX at (a) 303 (b) 313 (c) 323 and (d)333K.
Fig. 1.
 Molecular structure of alloxazine (ALLOX).264
 N.O. Obi-Egbedi, I.B. Obot/Corrosion Science 53 (2011) 263–275
 
loss method is such that the technique forms the baseline methodof measurement in many corrosion monitoring programmes [25].Weight loss measurements were conducted under total immer-sion using 250mL capacity beakers containing 200mL test solu-tion at 303–333K maintained in a thermostated water bath.The mild steel coupons were weighed and suspended in the bea-ker with the help of rod and hook. The coupons were retrieved at2h interval progressively for 10h, washed thoroughly in 20%NaOH solution containing 200g/l of zinc dust [10] with bristlebrush, rinsed severally in deionized water, cleaned, dried in ace-tone, and re-weighed. The weight loss, in grammes, was takenas the difference in the weight of the mild steel coupons beforeand after immersion in different test solutions. Then the testswere repeated at different temperatures. In order to get goodreproducibility, experiments were carried out in triplicate. In thispresent study, the standard deviation values among parallel trip-licate experiments were found to be smaller than 5%, indicatinggood reproducibility.The corrosion rate (
q
) in mgcm
2
h
1
was calculated from thefollowing equation [26,27]:
q
¼
D
St 
 ð
1
Þ
where
 W 
 is the average weight loss of three mild steel sheets,
 S 
 thetotal area of one mild steel specimen, and
 t 
 is the immersion time(10h). With the calculated corrosion rate, the inhibition efficiency(%
) was calculated as follows [28,29]:
%
¼
 q
1
q
2
q
1
100
 ð
2
Þ
where
q
1
 and
q
2
 arethecorrosionratesof themildsteelcouponsinthe absence and presence of inhibitor, respectively.
 2.5. Spectrophotometric measurements
UV–Visible absorption spectrophotometric method was carriedout on the prepared mild steel samples after immersion in 0.5MH
2
SO
4
 with and without addition of 10
l
M of alloxazine at 303Kfor 3days. All the spectra measurements were carried out usinga Perkin-Elmer UV–Visible Lambda 2 spectrophotometer.
c d
Fig. 2
 (
continued
)
N.O. Obi-Egbedi, I.B. Obot/Corrosion Science 53 (2011) 263–275
 265

Reward Your Curiosity

Everything you want to read.
Anytime. Anywhere. Any device.
No Commitment. Cancel anytime.
576648e32a3d8b82ca71961b7a986505